CN105254302B - Preparing method for graphene heat conduction sheet - Google Patents
Preparing method for graphene heat conduction sheet Download PDFInfo
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- CN105254302B CN105254302B CN201510657888.0A CN201510657888A CN105254302B CN 105254302 B CN105254302 B CN 105254302B CN 201510657888 A CN201510657888 A CN 201510657888A CN 105254302 B CN105254302 B CN 105254302B
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Abstract
The invention discloses a preparing method for a graphene heat conduction sheet. The preparing method includes the steps that graphene nanosheet powder and high-softening-point coal pitch powder are added into absolute ethyl alcohol in proportion, and the mixture is subjected to ultrasonic processing, suction filtration and drying; obtained mixed powder is guided into a mold and subjected to cold pressing for 3 min to 5 min at 15 MPa to 20 MPa to achieve forming, a cold-pressed sheet is clamped between high-temperature alloy molds, pressure is applied, the sheet is processed for 1 h to 3 h at the temperature of 500 DEG C to 800 DEG C in nitrogen or argon or helium atmosphere, and a hot-rolled sheet is obtained; the hot-rolled sheet is arranged in a high-temperature tube furnace and processed for 1 h to 3 h at the temperature of 900 DEG C to 1,200 DEG C in nitrogen or argon or helium atmosphere, and a carbonized sheet is obtained; the carbonized sheet is arranged in a high-temperature graphitizing furnace and processed for 0.5 h to 2 h at the temperature of 2,300 DEG C to 2,700 DEG C in nitrogen or argon or helium atmosphere, and the graphitized graphene sheet is obtained. The prepared graphitized graphene sheet has high heat conduction anisotropism, the preparing method of the graphitized graphene sheet is simple, and industrial production is facilitated.
Description
Technical field
The invention belongs to materialogy field, is related to a kind of material with carbon element, a kind of specifically system of Graphene thermal sheet
Preparation Method.
Background technology
At present, Graphene is because of its unique structure and excellent performance, such as high heat conduction（Thermal conductivity is up to 4800- in face
6000W/m·K）, the ability such as high connductivity, receive significant attention, in high power heat dissipation from microelectronic devices, heat-resistant seal material, send out
The technical fields such as hot body, have a good application prospect.The two-dimentional thermal sheet aligned based on graphene sheet layer can be fully
Its structural advantage is played, also can provide heat-insulated in thickness direction while radiating in piece aspect, be conducive to it to lead in heat management
The application in domain.
Since separating Graphene by micro- adhesive tape stripping method from Man Chesidun universities in 2004, people are extensively by notice
Concentrate on optimization for the Graphene or graphene preparation method for how obtaining high-quality high yield etc..Now, existing Graphene
Preparation method is numerous, and such as micro- adhesive tape stripping method, chemical vapour deposition technique, epitaxial growth method, epitaxy method, solvent are peeled off
Method, chemistry redox method.The volume production of Graphene has also tentatively been realized, but how to realize the industrial application value of Graphene still
It is a difficult problem urgently to be resolved hurrily.People also did multiple trial, as being taken out using vacuum filtration method, spraying process, spin-coating method, vacuum
The graphene film of the preparations such as filter method, gas/liquid self-assembly method, Langmuir-Blodgett self-assembly methods, but prepared film
It is difficult to keep its integrality, broken, space is more, the low shortcoming of mechanical strength, and production cost is high, trivial operations.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of preparation side of Graphene thermal sheet
Method, the preparation method of described this Graphene thermal sheet solves the side for preparing Graphene thermal sheet of the prior art
Film prepared by method is difficult to keep that its integrality, broken, space be more, mechanical strength is low and production cost height, trivial operations
Technical problem.
The invention provides a kind of preparation method of Graphene thermal sheet, comprises the steps：
1) graphene nanometer sheet powder and high softening-point coal tar pitch powder, described graphene nano are weighed according to mass ratio
The mass ratio of piece powder and high softening-point coal tar pitch powder is 5:0 ~ 0.5, graphene nanometer sheet powder and high softening-point coal are dripped
Blue or green powder mixing, is then added to 0.5 ~ 2h of ultrasound, suction filtration in absolute ethyl alcohol, after drying, obtains mixed-powder；Described is anhydrous
The consumption of ethanol, by graphene powder：Absolute ethyl alcohol is 1g:The ratio of 350 ~ 500 mL is calculated；
2) by step（1）The mixed-powder of gained is imported in mould, and it is 15 ~ 20MPa to adjust hydraulic press pressure, and the time is
3 ~ 5min, mixed-powder is directly colded pressing and is laminated；
3) by step（2）The thin slice of colding pressing of gained is folded between the smooth high temperature alloy mould in surface, is placed in tube furnace
In, 0 ~ 5MPa pressure is applied using hydraulic press, adopt in nitrogen, argon gas or helium atmosphere under any one atmosphere, with 3 ~ 5
DEG C/heating rate of min, and it is warming up to 420 ~ 450 DEG C, 0.5 ~ 1.5h of constant temperature, then with the heating rate of 1 ~ 5 DEG C/min, rise to 500
~ 800 DEG C, system after 1 ~ 3h of constant temperature, is then naturally cooled to from 21 ~ 34MPa is boosted under the thermal expansion effects of high temperature alloy
Room temperature, that is, obtain hot pressing graphene platelet；The thickness of hot pressing graphene platelet is 179 ~ 211 μm.
Further, by step（3）The hot pressing graphene platelet of gained is placed in high temperature process furnances, using in nitrogen, argon
In gas or helium atmosphere under any one atmosphere, 900 ~ 1200 DEG C of 1 ~ 3h of charing process are carried out, that is, obtain charing black lead alkene thin slice.
Further, the charing black lead alkene thin slice of gained is placed in high temperature graphitization stove, using in nitrogen, argon gas or helium
In gas atmosphere under any one atmosphere, 2300 ~ 2700 DEG C of 0.5 ~ 2h of graphitization processing are carried out, that is, obtain graphitization Graphene thin
Piece.
Further, described graphene nanometer sheet powder is prepared via a method which：
1) concentrated sulfuric acid of measured amounts is placed in a reaction vessel, is added thereto to sodium nitrate, and stirring makes sodium nitrate
After dissolving, crystalline flake graphite is added, after crystalline flake graphite is uniformly dispersed, be slowly added to potassium permanganate reaction, whole process is adopted
Ice bath makes system be maintained at 0 ~ 5 DEG C of 1 ~ 2h of reaction, and then temperature rises to 30 ~ 45 DEG C and reacts 1 ~ 3 hour, then in reaction system
First deionized water is slowly added to, 20 ~ 40min is reacted, second batch deionized water is slowly added into again afterwards, is subsequently added
H2O2, continuing to react 5 ~ 20min, the reacting liquor while hot suction filtration of gained, gained filter cake mass percent concentration is 3 ~ 10% HCl
Solution washing, to remove metal ion；
2) and then by deionized water it is added in filter cake, centrifuge washing is carried out after stirring, until during the pH of colloid is
Property, 5 ~ 15min of ultrasound obtains final product graphene oxide colloid；
3) graphene oxide colloid is taken in a polytetrafluoroethylcontainer container, it is 11 that addition ammoniacal liquor adjusts PH, stirring is lower slow
Slow addition mass percent concentration is that the mass ratio of 30 ~ 60% hydrazine hydrate solution, graphene oxide colloid and hydrazine hydrate solution is
1:8 ~ 12, then carry out microwave treatment；20s heating using microwaves, 20s takes out stirring and circulates for 1, repeats 3 ~ 8 circulations, takes out afterwards
Filter, freeze-drying obtains final product graphene nanometer sheet powder.
Further, the mass percent concentration of the described concentrated sulfuric acid is 60 ~ 98%.
Further, the described concentrated sulfuric acid, sodium nitrate, crystalline flake graphite, potassium permanganate, first deionized water, second batch
Deionized water, H2O2, HCl/water solution material ratio 96mL：2g：2g：12g：80mL：200mL：10mL：1000mL.
Further, step（1）Described in high softening-point coal tar pitch powder, its softening point at 270 ~ 300 DEG C, TI contents
In 50 ~ 70%, QI contents 10 ~ 30%, 150 ~ 300 mesh sieves are crossed.
Specifically, step 1）In, the condition of ultrasound is 100W, 40KHz.
A kind of preparation method of Graphene thermal sheet of the present invention, non-environmental-pollution, the absolute ethyl alcohol after suction filtration can be returned
Receive and recycle, the preparation of thermal sheet, its operating process is easy, low cost can be used for high-volume industrial production.The one of the present invention
Plant the Graphene thermal sheet obtained by the preparation method of Graphene thermal sheet and there is high anisotropic heat conductivity, obtained stone
Black graphite alkene thin slice has a high heat conduction anisotropy, plane thermal conductivity in 300 ~ 405 W/mK, axial thermal conductivity 0.89 ~
1.20W/m·K；Graphitization graphene platelet has high intensity, its tensile strength in 7.76 ~ 10.94MPa, deflection 1.13 ~
1.25%, there is potential actual application value in field of radiating.
The present invention is compared with prior art, and its technological progress is significant.The present invention peels off reduction system using microwave assistant
The graphene nanometer sheet for obtaining is raw material, and it is binding agent to introduce high softening-point coal tar pitch, thin using Graphene obtained in heat pressing process
Piece, its high mechanical strength, not cracky, excellent thermal conductivity, low cost of manufacture, preparation process is simple, with huge potential
Using value and industrial production basis.Have that surface is smooth, tensile strength using the high heat conduction graphene platelet obtained by the present invention
High, space is few, graphene sheet layer is the features such as the degree of orientation is high along face, thermal conductivity is high.
Description of the drawings
Fig. 1 is the measuring principle schematic diagram of the degree of orientation in the face of graphene platelet.
Fig. 2 is the step of embodiment 1（1）The xrd figures of middle graphene nanometer sheet（a）And step（5）Gained graphitization Graphene
Thin slice xrd schemes (b).
Fig. 3 is the step of embodiment 1（3）Gained hot pressing graphene platelet optical photograph（a）And plane（b）And cross section（c）
SEM figure.
Fig. 4 is the step of embodiment 1（3）Gained hot pressing graphene platelet, step（4）Gained charing black lead alkene thin slice and step
（5）The degree of orientation in the face of gained graphitization graphene platelet.
Fig. 5 is the step of embodiment 1（5）The tensile property of gained graphitization graphene platelet.
Specific embodiment
Below by embodiment and combine accompanying drawing the present invention is further elaborated, but be not intended to limit the present invention.
SEM used in the embodiment of the present invention, model Phenom Pro.
X-ray diffractometer used, model D/max2200PC（CuK α, λ=0.15406 nm）, the life of Rigaku company
Produce.
The pole figure of sample by the multi-functional texture testing board on the D/max2200PC type X-ray diffractometers,
Reflective observing is made using Schulz bounce techniques to (002) crystal face of different samples.
In embodiments of the invention in the face of hot pressing graphene platelet, charing black lead alkene thin slice and graphitization graphene platelet
The measure of the degree of orientation, needs sample to rotate in three dimensions, and test philosophy schematic diagram is as shown in figure 1, wherein α is sample deflection
Angle, β be sample rotation angle, α=0 ~ 70 °, β=0 ~ 360 °, sample rotational velocity be 10 °/min.Surveyed by prescan first
The accurate Bragg angle of fixed difference sample difference crystal face, then carries out three-dimensional rotation to sample, and Prague is met in rotary course
The crystal face at angle can occur diffraction, and the intensity distribution of diffraction maximum can characterize the orientation of the sample crystal face.
Thermal diffusion coefficient (α, the mm of graphene platelet in embodiments of the invention2/ s) using Nai Chi companies of Germany
LFA447 Flicker method heat transfer analysis instruments are tested, bulk density (ρ, g/cm3) calculated divided by volume by thin slice quality, the specific heat of sample
Hold (Cp, J/gK) measured by TA Q2000 type differential scanning calorimetry instrument, thermal conductivity (λ, W/mK) is by λ=α × ρ × CpCalculate.
Embodiment 1
A kind of preparation method of Graphene thermal sheet, specifically includes following steps：
（1）, 0.5g graphene nanometer sheet powders and 0.03g high softening-point coal tar pitch powder mixed, be added to anhydrous
In ethanol, the ultrasonically treated 1h under 100W, 40KHz, suction filtration after 70 DEG C of drying, obtains mixed-powder；
Absolute ethyl alcohol consumption, by graphene powder：Absolute ethyl alcohol is 1g:The ratio of 350mL is calculated；Described Graphene powder
End is obtained by the multiple intercalation lift-off technology of catalysis oxidation；
（2）, by step（1）The mixed-powder of gained is imported in mould, and it is 20MPa to adjust hydraulic press pressure, and the time is
3min, mixed-powder is directly colded pressing and is laminated；
（3）, by step（2）The thin slice of colding pressing of gained is folded between the smooth high temperature alloy mould in surface, is placed in tubular type
In stove, hydraulic press piston is in contact mould upper surface but does not apply under pressure, in nitrogen atmosphere, with the intensification speed of 5 DEG C/min
Rate, is warming up to 450 DEG C, constant temperature 1.5h, then with the heating rate of 5 DEG C/min, rises to 600 DEG C, imitates in the thermal expansion of high temperature alloy
System should be descended from 23MPa is boosted to, after constant temperature 1h, room temperature is then naturally cooled to, that is, obtain hot pressing graphene platelet, its thickness
For 202 μm；
（4）, by step（3）The hot pressing graphene platelet of gained is placed in high temperature process furnances, in a nitrogen atmosphere, is carried out
1000 DEG C of charing process 3h, that is, obtain charing black lead alkene thin slice；
（5）, by step（4）The charing black lead alkene thin slice of gained is placed in high temperature graphitization stove, under an argon atmosphere, is carried out
2700 DEG C of graphitization processings 1h, that is, obtain graphitization graphene platelet；
Above-mentioned hot pressing graphene platelet surface is smooth, the grey of metal luster, with certain hardness and tensile strength.
The xrd of above-mentioned graphene nanometer sheet is shown in shown in Fig. 2 (a), from Fig. 2 (a) it can be seen that graphene nanometer sheet is on 26 ° of left sides
One wide diffraction maximum of right appearance, illustrates that graphene oxide forms graphene nanometer sheet Jing after microwave assistant peels off reduction.Fig. 2 (b)
Xrd for graphitization graphene platelet schemes, and a sharp diffraction maximum can be substantially observed at 26.5 °, illustrates graphite graphite
The dramatic reduction of interlamellar spacing in alkene thin slice between Graphene.
The optical photograph of above-mentioned hot pressing graphene platelet and the SEM figures of plane and cross section are as shown in figure 3, a is heat in Fig. 3
Laminated flake optical photograph, b is hot pressing laminae plane SEM figures, and c is hot pressing thin slice cross section SEM figures, as can be drawn from Figure 3, stone
The plane of black alkene thin slice and cross-sectional structure are presented significant difference.
The degree of orientation of graphene sheet layer is shown in Fig. 4 institutes in the hot pressing of above-mentioned gained, charing and graphitization Graphene thermal sheet
Show, as can be drawn from Figure 4, hot pressing graphene platelet deflection angle accounts for 41% or so within 5 °, within 20 ° to account for 91% left
It is right；Charing black lead alkene thin slice deflection angle accounts for 39% or so within 5 °, and within 20 ° 90% or so is accounted for；And graphite graphite
Alkene thin slice thin slice deflection angle accounts for 42% or so within 5 °, and within 20 ° 93% or so is accounted for, compared with hot pressing, charing thin slice,
The graphitized sheets degree of orientation substantially it is a little higher than the above two, the graphene platelet for being indicated above gained of the present invention has graphene film
Layer is the characteristics of the degree of orientation is high along face.
Jing is tested, and the graphitization graphene platelet bulk density of above-mentioned gained is 1.382 g/cm3, plane thermal conductivity is
405 W/mK, axial thermal conductivity is 1.19 W/mK；The maximum tensile stress of graphitized sheets can reach 10.94MPa, become
Shape amount is 1.21%.
Embodiment 2
A kind of preparation method of Graphene thermal sheet, specifically includes following steps：
（1）, 0.5g graphene nanometer sheet powders and 0.01g high softening-point coal tar pitch powder mixed, be added to anhydrous
In ethanol, the ultrasonically treated 1h under 100W, 40KHz, suction filtration after 70 DEG C of drying, obtains mixed-powder；
Absolute ethyl alcohol consumption, by graphene powder：Absolute ethyl alcohol is 1g:The ratio of 400mL is calculated；Described Graphene powder
End is obtained by the multiple intercalation lift-off technology of catalysis oxidation；
（2）, by step（1）The mixed-powder of gained is imported in mould, and it is 15MPa to adjust hydraulic press pressure, and the time is
5min, mixed-powder is directly colded pressing and is laminated；
（3）, by step（2）The thin slice of colding pressing of gained is folded between the smooth high temperature alloy mould in surface, is placed in tubular type
In stove, 3MPa pressure is applied using hydraulic press, in a nitrogen atmosphere, with the heating rate of 3 DEG C/min, be warming up to 450 DEG C, constant temperature
1h, then with the heating rate of 1 DEG C/min, 600 DEG C are risen to, system boosts to 30MPa certainly under the thermal expansion effects of high temperature alloy,
After constant temperature 2h, room temperature is then naturally cooled to, that is, obtain hot pressing graphene platelet, its thickness is 187 μm；
（4）, by step（3）The hot pressing graphene platelet of gained is placed in high temperature process furnances, in a nitrogen atmosphere, is carried out
900 DEG C of charing process 2h, that is, obtain charing black lead alkene thin slice；
（5）, by step（4）The charing black lead alkene thin slice of gained is placed in high temperature graphitization stove, under an argon atmosphere, is carried out
2300 DEG C of graphitization processings 2h, that is, obtain graphitization graphene platelet；
Jing is tested, and the graphitization graphene platelet bulk density of above-mentioned gained is 1.327 g/cm3, plane thermal conductivity is
325 W/mK, axial thermal conductivity is 1.16 W/mK；The maximum tensile stress of graphitized sheets can reach 8.96MPa, deformation
Measure as 1.25%.
Embodiment 3
A kind of preparation method of Graphene thermal sheet, specifically includes following steps：
（1）, 0.5g graphene nanometer sheet powders and 0.02g high softening-point coal tar pitch powder mixed, be added to anhydrous
In ethanol, the ultrasonically treated 1h under 100W, 40KHz, suction filtration after 70 DEG C of drying, obtains mixed-powder；
Absolute ethyl alcohol consumption, by graphene powder：Absolute ethyl alcohol is 1g:The ratio of 500mL is calculated；Described Graphene powder
End is obtained by the multiple intercalation lift-off technology of catalysis oxidation；
（2）, by step（1）The mixed-powder of gained is imported in mould, and it is 20MPa to adjust hydraulic press pressure, and the time is
5min, mixed-powder is directly colded pressing and is laminated；
（3）, by step（2）The thin slice of colding pressing of gained is folded between the smooth high temperature alloy mould in surface, is placed in tubular type
In stove, 5MPa pressure is applied using hydraulic press, in a nitrogen atmosphere, with the heating rate of 3 DEG C/min, be warming up to 420 DEG C, constant temperature
0.5h, then with the heating rate of 1 DEG C/min, 500 DEG C are risen to, system is boosted to certainly under the thermal expansion effects of high temperature alloy
32MPa, after constant temperature 3h, then naturally cools to room temperature, that is, obtain hot pressing graphene platelet, and its thickness is 182 μm；
（4）, by step（3）The hot pressing graphene platelet of gained is placed in high temperature process furnances, in a nitrogen atmosphere, is carried out
1200 DEG C of charing process 1h, that is, obtain charing black lead alkene thin slice；
（5）, by step（4）The charing black lead alkene thin slice of gained is placed in high temperature graphitization stove, under an argon atmosphere, is carried out
2500 DEG C of graphitization processings 1.5h, that is, obtain graphitization graphene platelet；
Jing is tested, and the graphitization graphene platelet bulk density of above-mentioned gained is 1.447g/cm3, plane thermal conductivity is
377W/mK, axial thermal conductivity is 1.20W/mK；The maximum tensile stress of graphitized sheets can reach 8.27MPa, deflection
For 1.13%.
Embodiment 4
A kind of preparation method of Graphene thermal sheet, specifically includes following steps：
（1）, under without asphalt powder, 0.5g graphene nanometer sheet powders are added in absolute ethyl alcohol, in 100W,
Ultrasonically treated 1h under 40KHz, suction filtration, 70 DEG C of drying；
Absolute ethyl alcohol consumption, by graphene powder：Absolute ethyl alcohol is 1g:The ratio of 450mL is calculated；Described Graphene powder
End is obtained by the multiple intercalation lift-off technology of catalysis oxidation；
（2）, by step（1）The powder of gained is imported in mould, and it is 20MPa to adjust hydraulic press pressure, and the time is 5min,
Powder is directly colded pressing and is laminated；
（3）, by step（2）The thin slice of colding pressing of gained is folded between the smooth high temperature alloy mould in surface, is placed in tubular type
In stove, hydraulic press piston is in contact mould upper surface but does not apply under pressure, in nitrogen atmosphere, with the intensification speed of 5 DEG C/min
Rate, is warming up to 450 DEG C, constant temperature 1.5h, then with the heating rate of 1 DEG C/min, rises to 500 DEG C, imitates in the thermal expansion of high temperature alloy
System should be descended from 21MPa is boosted to, after constant temperature 1h, room temperature is then naturally cooled to, that is, obtain hot pressing graphene platelet, its thickness
For 198 μm；
（4）, by step（3）The hot pressing graphene platelet of gained is placed in high temperature process furnances, in a nitrogen atmosphere, is carried out
1000 DEG C of charing process 3h, that is, obtain charing black lead alkene thin slice；
（5）, by step（4）The charing black lead alkene thin slice of gained is placed in high temperature graphitization stove, under an argon atmosphere, is carried out
2700 DEG C of graphitization processings 1h, that is, obtain graphitization graphene platelet；
Jing is tested, and the graphitization graphene platelet bulk density of above-mentioned gained is 1.329g/cm3, plane thermal conductivity is
300W/mK, axial thermal conductivity is 1.20W/mK；The maximum tensile stress of graphitized sheets can reach 7.76MPa, deflection
For 1.16%.
Embodiment 5
A kind of preparation method of Graphene thermal sheet, specifically includes following steps：
（1）, 0.5g graphene nanometer sheet powders and 0.04g high softening-point coal tar pitch powder mixed, be added to anhydrous
In ethanol, the ultrasonically treated 1h under 100W, 40KHz, suction filtration after 70 DEG C of drying, obtains mixed-powder；
Absolute ethyl alcohol consumption, by graphene powder：Absolute ethyl alcohol is 1g:The ratio of 350mL is calculated；Described Graphene powder
End is obtained by the multiple intercalation lift-off technology of catalysis oxidation；
（2）, by step（1）The mixed-powder of gained is imported in mould, and it is 15MPa to adjust hydraulic press pressure, and the time is
3min, mixed-powder is directly colded pressing and is laminated；
（3）, by step（2）The thin slice of colding pressing of gained is folded between the smooth high temperature alloy mould in surface, is placed in tubular type
In stove, hydraulic press piston is in contact mould upper surface but does not apply under pressure, in nitrogen atmosphere, with the intensification speed of 3 DEG C/min
Rate, is warming up to 450 DEG C, constant temperature 1h, then with the heating rate of 5 DEG C/min, rises to 800 DEG C, in the thermal expansion effects of high temperature alloy
Lower system after constant temperature 1h, then naturally cools to room temperature from 29MPa is boosted to, that is, obtain hot pressing graphene platelet, and its thickness is
211μm；
（4）, by step（3）The hot pressing graphene platelet of gained is placed in high temperature process furnances, in a nitrogen atmosphere, is carried out
1200 DEG C of charing process 3h, that is, obtain charing black lead alkene thin slice；
（5）, by step（4）The charing black lead alkene thin slice of gained is placed in high temperature graphitization stove, under an argon atmosphere, is carried out
2300 DEG C of graphitization processings 1.5h, that is, obtain graphitization graphene platelet；
Jing is tested, and the graphitization graphene platelet bulk density of above-mentioned gained is 1.411g/cm3, plane thermal conductivity is 369
W/mK, axial thermal conductivity is 0.98 W/mK；The maximum tensile stress of graphitized sheets can reach 9.56MPa, and deflection is
1.19%。
Embodiment 6
A kind of preparation method of Graphene thermal sheet, specifically includes following steps：
（1）, 0.5g graphene nanometer sheet powders and 0.01g high softening-point coal tar pitch powder mixed, be added to anhydrous
In ethanol, the ultrasonically treated 1h under 100W, 40KHz, suction filtration after 70 DEG C of drying, obtains mixed-powder；
Absolute ethyl alcohol consumption, by graphene powder：Absolute ethyl alcohol is 1g:The ratio of 400mL is calculated；Described Graphene powder
End is obtained by the multiple intercalation lift-off technology of catalysis oxidation；
（2）, by step（1）The mixed-powder of gained is imported in mould, and it is 18MPa to adjust hydraulic press pressure, and the time is
3min, mixed-powder is directly colded pressing and is laminated；
（3）, by step（2）The thin slice of colding pressing of gained is folded between the smooth high temperature alloy mould in surface, is placed in tubular type
In stove, 5MPa pressure is applied using hydraulic press, in a nitrogen atmosphere, with the heating rate of 5 DEG C/min, be warming up to 450 DEG C, constant temperature
1.5h, then with the heating rate of 4 DEG C/min, 600 DEG C are risen to, system is boosted to certainly under the thermal expansion effects of high temperature alloy
34MPa, after constant temperature 2h, then naturally cools to room temperature, that is, obtain hot pressing graphene platelet, and its thickness is 179 μm；
（4）, by step（3）The hot pressing graphene platelet of gained is placed in high temperature process furnances, in a nitrogen atmosphere, is carried out
1000 DEG C of charing process 1h, that is, obtain charing black lead alkene thin slice；
（5）, by step（4）The charing black lead alkene thin slice of gained is placed in high temperature graphitization stove, under an argon atmosphere, is carried out
2500 DEG C of graphitization processings 2h, that is, obtain graphitization graphene platelet；
Jing is tested, and the graphitization graphene platelet bulk density of above-mentioned gained is 1.331g/cm3, plane thermal conductivity is 330
W/mK, axial thermal conductivity is 0.98 W/mK；The maximum tensile stress of graphitized sheets can reach 8.31MPa, and deflection is
1.18%。
Embodiment 7
A kind of preparation method of Graphene thermal sheet, specifically includes following steps：
（1）, 0.5g graphene nanometer sheet powders and 0.03g high softening-point coal tar pitch powder mixed, be added to anhydrous
In ethanol, the ultrasonically treated 1h under 100W, 40KHz, suction filtration after 70 DEG C of drying, obtains mixed-powder；
Absolute ethyl alcohol consumption, by graphene powder：Absolute ethyl alcohol is 1g:The ratio of 500mL is calculated；Described Graphene powder
End is obtained by the multiple intercalation lift-off technology of catalysis oxidation；
（2）, by step（1）The mixed-powder of gained is imported in mould, and it is 20MPa to adjust hydraulic press pressure, and the time is
5min, mixed-powder is directly colded pressing and is laminated；
（3）, by step（2）The thin slice of colding pressing of gained is folded between the smooth high temperature alloy mould in surface, is placed in tubular type
In stove, hydraulic press piston is in contact mould upper surface but does not apply under pressure, in nitrogen atmosphere, with the intensification speed of 3 DEG C/min
Rate, is warming up to 420 DEG C, constant temperature 0.5h, then with the heating rate of 1 DEG C/min, rises to 500 DEG C, imitates in the thermal expansion of high temperature alloy
System should be descended from 21MPa is boosted to, after constant temperature 3h, room temperature is then naturally cooled to, that is, obtain hot pressing graphene platelet, its thickness
For 208 μm；
（4）, by step（3）The hot pressing graphene platelet of gained is placed in high temperature process furnances, in a nitrogen atmosphere, is carried out
900 DEG C of charing process 1h, that is, obtain charing black lead alkene thin slice；
（5）, by step（4）The charing black lead alkene thin slice of gained is placed in high temperature graphitization stove, under an argon atmosphere, is carried out
2500 DEG C of graphitization processings 2h, that is, obtain graphitization graphene platelet；
Jing is tested, and the graphitization graphene platelet bulk density of above-mentioned gained is 1.374g/cm3, plane thermal conductivity is 388
W/mK, axial thermal conductivity is 0.96 W/mK；The maximum tensile stress of graphitized sheets can reach 10.56MPa, deflection
For 1.20%.
Embodiment 8
A kind of preparation method of Graphene thermal sheet, specifically includes following steps：
（1）, 0.5g graphene nanometer sheet powders and 0.04g high softening-point coal tar pitch powder mixed, be added to anhydrous
In ethanol, the ultrasonically treated 1h under 100W, 40KHz, suction filtration after 70 DEG C of drying, obtains mixed-powder；
Absolute ethyl alcohol consumption, by graphene powder：Absolute ethyl alcohol is 1g:The ratio of 400mL is calculated；Described Graphene powder
End is obtained by the multiple intercalation lift-off technology of catalysis oxidation；
（2）, by step（1）The mixed-powder of gained is imported in mould, and it is 20MPa to adjust hydraulic press pressure, and the time is
3min, mixed-powder is directly colded pressing and is laminated；
（3）, by step（2）The thin slice of colding pressing of gained is folded between the smooth high temperature alloy mould in surface, is placed in tubular type
In stove, 3MPa pressure is applied using hydraulic press, in a nitrogen atmosphere, with the heating rate of 5 DEG C/min, be warming up to 420 DEG C, constant temperature
1.5h, then with the heating rate of 5 DEG C/min, 600 DEG C are risen to, system is boosted to certainly under the thermal expansion effects of high temperature alloy
30MPa, after constant temperature 1h, then naturally cools to room temperature, that is, obtain hot pressing graphene platelet, and its thickness is 209 μm；
（4）, by step（3）The hot pressing graphene platelet of gained is placed in high temperature process furnances, in a nitrogen atmosphere, is carried out
900 DEG C of charing process 1h, that is, obtain charing black lead alkene thin slice；
（5）, by step（4）The charing black lead alkene thin slice of gained is placed in high temperature graphitization stove, under an argon atmosphere, is carried out
2500 DEG C of graphitization processings 2h, that is, obtain graphitization graphene platelet；
Jing is tested, and the graphitization graphene platelet bulk density of above-mentioned gained is 1.407g/cm3, plane thermal conductivity is
358W/mK, axial thermal conductivity is 0.89W/mK；The maximum tensile stress of graphitized sheets can reach 9.03MPa, deflection
For 1.23%.
A kind of preparation method of the graphene nanometer sheet powder of embodiment 9
Measure the 96mL concentrated sulfuric acids and be placed in and be dried in round-bottomed flask, be added thereto to 2g sodium nitrate, stirring dissolves sodium nitrate
Afterwards, 2g crystalline flake graphites are added, after crystalline flake graphite is uniformly dispersed, 12g potassium permanganate is slowly added to, 1.45h, whole mistake is reacted
Cheng Caiyong ice baths make system be maintained at 0 ~ 5 DEG C, and then temperature rises to 35 DEG C of reaction 2h, is then slowly added to in reaction system
80mL deionized waters, react 30min, are slowly added into 200mL deionized waters again afterwards, subsequently add 10mL H2O2, continue anti-
10min, the reacting liquor while hot suction filtration of gained, gained filter cake is answered to be washed with the HCl/water solution that 1000mL mass percent concentrations are 5%
Wash, to remove metal ion.Then appropriate amount of deionized water is added in filter cake, centrifuge washing is carried out after stirring, until
The pH of colloid is neutrality, and ultrasonic 10min obtains final product graphene oxide colloid；
The graphene oxide colloid of 40mL1.5mg/mL is taken in polytetrafluoroethylcontainer container, it is 11 that addition ammoniacal liquor adjusts PH,
The hydrazine hydrate solutions of 0.6g 50% are slowly added under stirring, then container is placed in the micro-wave oven that power is 800W, carry out microwave；
20s heating using microwaves, 20s takes out stirring and circulates for 1, repeats 5 circulations, afterwards suction filtration, freezes under -50 DEG C, 1Pa vacuums
It is dried, obtains final product graphene nanometer sheet powder.
Claims (7)
1. a kind of preparation method of Graphene thermal sheet, it is characterised in that comprise the steps：
1）Graphene nanometer sheet powder and high softening-point coal tar pitch powder, described graphene nanometer sheet powder are weighed according to mass ratio
The mass ratio of end and high softening-point coal tar pitch powder is 5:0 ~ 0.5, by graphene nanometer sheet powder and high softening-point pitch powder
End mixing, is then added to 0.5 ~ 2h of ultrasound, suction filtration in absolute ethyl alcohol, after drying, obtains mixed-powder；Described absolute ethyl alcohol
Consumption, by graphene nanometer sheet powder：Absolute ethyl alcohol is 1g:The ratio of 350 ~ 500 mL is calculated；
2）By step（1）The mixed-powder of gained is imported in mould, and it is 15 ~ 20MPa to adjust hydraulic press pressure, and the time is 3 ~
5min, mixed-powder is directly colded pressing and is laminated；
3）By step（2）The thin slice of colding pressing of gained is folded between the smooth high temperature alloy mould in surface, in being placed in tube furnace, is adopted
Apply 0 ~ 5MPa pressure with hydraulic press, adopt in nitrogen, argon gas or helium atmosphere under any one atmosphere, with 3 ~ 5 DEG C/min
Heating rate, be warming up to 420 ~ 450 DEG C, 0.5 ~ 1.5h of constant temperature, then with the heating rate of 1 ~ 5 DEG C/min, rise to 500 ~ 800
DEG C, system after 1 ~ 3h of constant temperature, then naturally cools to room from 21 ~ 34MPa is boosted under the thermal expansion effects of high temperature alloy
Temperature, that is, obtain hot pressing graphene platelet；The thickness of hot pressing graphene platelet is 179 ~ 211 μm.
2. the preparation method of Graphene thermal sheet as claimed in claim 1, it is characterised in that：By step（3）The heat of gained
Pressure graphene platelet is placed in high temperature process furnances, and adopt under any one atmosphere, is carried out in nitrogen, argon gas or helium atmosphere
900 ~ 1200 DEG C of 1 ~ 3h of charing process, that is, obtain charing black lead alkene thin slice.
3. the preparation method of Graphene thermal sheet as claimed in claim 2, it is characterised in that：By the charing black lead alkene of gained
Thin slice is placed in high temperature graphitization stove, using under any one atmosphere, carrying out 2300 in nitrogen, argon gas or helium atmosphere ~
2700 DEG C of 0.5 ~ 2h of graphitization processing, that is, obtain graphitization graphene platelet.
4. the preparation method of Graphene thermal sheet as claimed in claim 1, it is characterised in that：Described graphene nanometer sheet
Powder is prepared via a method which：
1）The concentrated sulfuric acid of measured amounts is placed in a reaction vessel, is added thereto to sodium nitrate, and stirring dissolves sodium nitrate
Afterwards, crystalline flake graphite is added, after crystalline flake graphite is uniformly dispersed, potassium permanganate reaction is slowly added to, whole process adopts ice bath
System is set to be maintained at 0 ~ 5 DEG C of 1 ~ 2h of reaction, then temperature rises to 30 ~ 45 DEG C and reacts 1 ~ 3 hour, then slow in reaction system
First deionized water is added, 20 ~ 40min is reacted, second batch deionized water is slowly added into again afterwards, H is subsequently added2O2, after
5 ~ 20min of continuous reaction, the reacting liquor while hot suction filtration of gained, gained filter cake mass percent concentration is 3 ~ 10% HCl/water solution
Washing, to remove metal ion；
2）Then deionized water is added in filter cake, centrifuge washing is carried out after stirring, until the pH of colloid is neutrality, surpassed
5 ~ 15min of sound, obtains final product graphene oxide colloid；
3）Graphene oxide colloid is taken in a polytetrafluoroethylcontainer container, addition ammoniacal liquor regulation pH is 11, slow under stirring to add
The mass ratio for entering the hydrazine hydrate solution that mass percent concentration is 30 ~ 60%, graphene oxide colloid and hydrazine hydrate solution is 1:8~
12, then carry out microwave treatment；20s heating using microwaves, 20s takes out stirring and circulates for 1, repeats 3 ~ 8 circulations, afterwards suction filtration,
Freeze-drying, obtains final product graphene nanometer sheet powder.
5. the preparation method of Graphene thermal sheet as claimed in claim 4, it is characterised in that：The quality of the described concentrated sulfuric acid
Percent concentration is 60 ~ 98%.
6. the preparation method of Graphene thermal sheet as claimed in claim 4, it is characterised in that：The concentrated sulfuric acid, sodium nitrate, scale
Graphite, potassium permanganate, first deionized water, second batch deionized water, H2O2, HCl/water solution material ratio 96mL：2g：2g：
12g：80mL：200mL：10mL：1000mL.
7. the preparation method of Graphene thermal sheet as claimed in claim 1, it is characterised in that:Step（1）Described in height
Softening point coal tar pitch powder, at 270 ~ 300 DEG C, TI contents, 10 ~ 30%, cross 150 ~ 300 to its softening point in 50 ~ 70%, QI contents
Mesh sieve.
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| CN105885906A (en) * | 2016-04-12 | 2016-08-24 | 方大炭素新材料科技股份有限公司 | Preparation method of oxidized graphene modified medium-temperature coal tar pitch |
| CN106833083B (en) * | 2016-12-21 | 2020-03-20 | 福建科华中盈新材料有限公司 | Graphene composite microchip for conductive coating and preparation method thereof |
| CN108329030B (en) * | 2017-01-20 | 2020-12-15 | 株洲晨昕中高频设备有限公司 | Heat-conducting graphite sheet and preparation method thereof |
| CN109860524A (en) * | 2017-11-30 | 2019-06-07 | 宝武炭材料科技有限公司 | A kind of method of solid asphalt low temperature cladding preparation negative electrode material |
| CN110776319A (en) * | 2018-07-31 | 2020-02-11 | 天津大学 | All-carbon heat-conducting composite material and preparation method thereof |
| CN110745019A (en) * | 2019-10-09 | 2020-02-04 | 浙江绿源电动车有限公司 | Radiating electric vehicle charger of graphite alkene heat conduction plastic construction |
| CN110775966B (en) * | 2019-11-21 | 2021-07-27 | 秦皇岛中科瀚祺科技有限公司 | Flexible graphene film and application thereof |
| CN112430115B (en) * | 2020-12-01 | 2021-12-28 | 江苏星途新材料科技有限公司 | Preparation process of high-performance carbon fiber graphene |
| CN116553533A (en) * | 2023-05-09 | 2023-08-08 | 浙江道明超导科技有限公司 | Preparation method of graphene sealing material |
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| CN104743551A (en) * | 2015-03-27 | 2015-07-01 | 上海应用技术学院 | Method for preparing reduced graphene oxide heat conductive film |
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