CN105254302A - Preparing method for graphene heat conduction sheet - Google Patents
Preparing method for graphene heat conduction sheet Download PDFInfo
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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, relate to a kind of carbon material, specifically a kind of preparation method of Graphene thermal sheet.
Background technology
At present, the structure of Graphene because of its uniqueness and the performance of excellence, as abilities such as high heat conduction (in face, thermal conductivity is up to 4800-6000W/mK), high connductivity, be subject to extensive concern, in technical fields such as superpower heat dissipation from microelectronic devices, heat-resistant seal material, heating elements, have a good application prospect.The two-dimentional thermal sheet aligned based on graphene sheet layer can give full play to its structural advantage, also can at thickness direction provide heat insulation while dispelling the heat in sheet aspect, is conducive to its application in field of heat management.
Since Man Chesidun university in 2004 separates Graphene by micro-tape stripping method, how people extensively obtain the Graphene of high quality high yield or the optimization etc. of graphene preparation method by concentrating on.Now, existing graphene preparation method is numerous, as micro-tape stripping method, chemical Vapor deposition process, epitaxial growth method, epitaxy method, solvent stripping method, chemistry redox method.The volume production of Graphene also tentatively realizes, but the industrial application value how realizing Graphene is still a difficult problem urgently to be resolved hurrily.People also did and repeatedly attempted, picture adopts the graphene film of the preparations such as vacuum filtration method, spraying method, spin-coating method, vacuum filtration method, gas/liquid self-assembly method, Langmuir – Blodgett self-assembly method, but prepared film is difficult to keep its integrity, easy fragmentation, space is many, the shortcomings such as physical strength is low, and production cost is high, trivial operations.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of preparation method of Graphene thermal sheet, preparation method's film solved prepared by the method preparing Graphene thermal sheet of the prior art of described this Graphene thermal sheet is difficult to keep its integrity, easily fragmentation, space is many, physical strength is low and production cost is high, the technical problem of trivial operations.
The invention provides a kind of preparation method of Graphene thermal sheet, comprise the steps:
1) graphene nanometer sheet powder and high softening-point coal-tar pitch powder is taken according to mass ratio, the mass ratio of described graphene nanometer sheet powder and high softening-point coal-tar pitch powder is 5:0 ~ 0.5, by graphene nanometer sheet powder and the mixing of high softening-point coal-tar pitch powder, then ultrasonic 0.5 ~ 2h in dehydrated alcohol is joined, suction filtration, after oven dry, obtain mixed powder; The consumption of described dehydrated alcohol, in graphene powder: dehydrated alcohol is that the ratio of 1g:350 ~ 500mL calculates;
2) import in mould by the mixed powder of step (1) gained, regulate oil press pressure to be 15 ~ 20MPa, the time is 3 ~ 5min, by direct for mixed powder cold compaction flakiness;
3) thin slice of colding pressing of step (2) gained is folded between ganoid superalloy mould, be placed in tube furnace, oil press is adopted to apply 0 ~ 5MPa pressure, adopt in nitrogen, argon gas or helium atmosphere under any one atmosphere, with the temperature rise rate of 3 ~ 5 DEG C/min, be warming up to 420 ~ 450 DEG C, constant temperature 0.5 ~ 1.5h, again with the temperature rise rate of 1 ~ 5 DEG C/min, rise to 500 ~ 800 DEG C, under the thermal expansion effects of superalloy, system is from boosting to 21 ~ 34MPa, after constant temperature 1 ~ 3h, then naturally cool to room temperature, namely obtain hot pressing graphene platelet; The thickness of hot pressing graphene platelet is 179 ~ 211 μm.
Further, the hot pressing graphene platelet of step (3) gained is placed in high temperature process furnances, adopts in nitrogen, argon gas or helium atmosphere under any one atmosphere, carry out 900 ~ 1200 DEG C of charing process 1 ~ 3h, namely obtain charing black lead alkene thin slice.
Further, the charing black lead alkene thin slice of gained is placed in high temperature graphitization stove, adopts in nitrogen, argon gas or helium atmosphere under any one atmosphere, carry out 2300 ~ 2700 DEG C of graphitization processing 0.5 ~ 2h, namely obtain greying graphene platelet.
Further, described graphene nanometer sheet powder is prepared by the following method:
1) vitriol oil of measured amounts is placed in a reaction vessel, add SODIUMNITRATE wherein, after stirring makes SODIUMNITRATE dissolve, add crystalline flake graphite again, after crystalline flake graphite is uniformly dispersed, slowly add potassium permanganate reaction, whole process adopts ice bath to make system remain on 0 ~ 5 DEG C of reaction 1 ~ 2h, then temperature rises to 30 ~ 45 DEG C of reactions 1 ~ 3 hour, then in reaction system, first deionized water is slowly added, reaction 20 ~ 40min, slowly adds second batch deionized water more afterwards, adds H more subsequently
2o
2, continue reaction 5 ~ 20min, the reacting liquor while hot suction filtration of gained, gained filter cake mass percent concentration is the HCl solution washing of 3 ~ 10%, to remove metal ion;
2) then join in filter cake by deionized water, carry out centrifuge washing after stirring, until the pH of colloid is neutral, ultrasonic 5 ~ 15min, obtains graphene oxide colloid;
3) graphene oxide colloid is got in a polytetrafluoroethylcontainer container, adding ammoniacal liquor regulates PH to be 11, slowly add the hydrazine hydrate solution that mass percent concentration is 30 ~ 60% under stirring, the mass ratio of graphene oxide colloid and hydrazine hydrate solution is 1:8 ~ 12, then carries out microwave treatment; 20s microwave heating, it is 1 circulation that 20s takes out stirring, and repetitive operation 3 ~ 8 circulates, and suction filtration afterwards, lyophilize, obtains graphene nanometer sheet powder.
Further, the mass percent concentration of the described vitriol oil is 60 ~ 98%.
Further, the described vitriol oil, SODIUMNITRATE, crystalline flake graphite, potassium permanganate, first deionized water, second batch deionized water, H
2o
2, the HCl aqueous solution material ratio 96mL:2g:2g:12g:80mL:200mL:10mL:1000mL.
Further, the high softening-point coal-tar pitch powder described in step (1), its softening temperature is at 270 ~ 300 DEG C, and TI content 10 ~ 30%, crosses 150 ~ 300 mesh sieves at 50 ~ 70%, QI content.
Concrete, in step 1), ultrasonic condition is 100W, 40KHz.
The preparation method of a kind of Graphene thermal sheet of the present invention, non-environmental-pollution, the recyclable recycling of the dehydrated alcohol after suction filtration, the preparation of thermal sheet, its operating process is easy, and cost is low, can be used for industrial production in enormous quantities.The Graphene thermal sheet of preparation method's gained of a kind of Graphene thermal sheet of the present invention has high anisotropic heat conductivity, obtained greying graphene platelet has high anisotropic heat conductivity, plane thermal conductivity is at 300 ~ 405W/mK, and axial thermal conductivity is at 0.89 ~ 1.20W/mK; Greying graphene platelet has high strength, and its tensile strength is at 7.76 ~ 10.94MPa, and deflection, 1.13 ~ 1.25%, has potential actual application value at field of radiating.
The present invention compares with prior art, and its technical progress is significant.The graphene nanometer sheet that the present invention utilizes microwave assistant to peel off reduction obtained is raw material, introducing high softening-point coal-tar pitch is binding agent, adopt the graphene platelet that heat pressing process is obtained, its physical strength is high, not cracky, excellent thermal conductivity, low cost of manufacture, preparation technology is simple, has huge potential using value and industrial production basis.Adopt gained of the present invention high thermal conductivity graphene thin slice has smooth surface, tensile strength is high, space is few, graphene sheet layer is high along orientation degree in face, thermal conductivity high.
Accompanying drawing explanation
Fig. 1 be graphene platelet face in the measuring principle schematic diagram of orientation degree.
Fig. 2 is that the xrd of graphene nanometer sheet in embodiment 1 step (1) schemes (a) and step (5) gained greying graphene platelet xrd figure (b).
Fig. 3 is that embodiment 1 step (3) gained hot pressing graphene platelet optical photograph (a) and plane (b) are schemed with the SEM of cross section (c).
Fig. 4 be embodiment 1 step (3) gained hot pressing graphene platelet, step (4) gained charing black lead alkene thin slice and step (5) gained greying graphene platelet face in orientation degree.
Fig. 5 is the tensile property of embodiment 1 step (5) gained greying graphene platelet.
Embodiment
Below by embodiment, also the present invention is further elaborated by reference to the accompanying drawings, but do not limit the present invention.
Scanning electronic microscope used in the embodiment of the present invention, model PhenomPro.
X-ray diffractometer used, model D/max2200PC(CuK α, λ=0.15406nm), Rigaku company produces.
The pole figure of sample, by being arranged on the multi-functional texture testing board on D/max2200PC type X-ray diffractometer, adopts Schulz reflection method to make reflective observing to (002) crystal face of different sample.
In embodiments of the invention hot pressing graphene platelet, charing black lead alkene thin slice and greying graphene platelet face in the mensuration of orientation degree, sample is needed to rotate in three-dimensional space, test philosophy schematic diagram as shown in Figure 1, wherein α is sample deflection angle, β is sample rotation angle, α=0 ~ 70 °, β=0 ~ 360 °, sample rotational velocity is 10 °/min.First measured the accurate Bragg angle of the different crystal face of different sample by prescan, then carrying out three-dimensional rotation to sample, can there is diffraction in the crystal face meeting Bragg angle in rotary course, and the intensity distribution of diffraction peak can the orientation of this crystal face of characterizing sample.
Thermal diffusivity (α, the mm of graphene platelet in embodiments of the invention
2/ s) adopt the LFA447 flicker method heat transfer analysis instrument of German Nai Chi company to test, volume density (ρ, g/cm
3) calculated divided by volume by thin slice quality, the specific heat capacity (C of sample
p, J/gK) recorded by TAQ2000 type differential scanning calorimetry instrument, thermal conductivity (λ, W/mK) is by λ=α × ρ × C
pcalculate.
embodiment 1
A preparation method for Graphene thermal sheet, specifically comprises the steps:
(1), by 0.5g graphene nanometer sheet powder mix mutually with 0.03g high softening-point coal-tar pitch powder, join in dehydrated alcohol, supersound process 1h under 100W, 40KHz, suction filtration, after 70 DEG C of oven dry, obtain mixed powder;
Dehydrated alcohol consumption, in graphene powder: dehydrated alcohol is that the ratio of 1g:350mL calculates; Repeatedly intercalation lift-off technology is obtained by catalyzed oxidation for described graphene powder;
(2), import in mould by the mixed powder of step (1) gained, regulate oil press pressure to be 20MPa, the time is 3min, by direct for mixed powder cold compaction flakiness;
(3), the thin slice of colding pressing of step (2) gained is folded between ganoid superalloy mould, be placed in tube furnace, oil press piston is at contact mould upper surface but under not applying pressure, in nitrogen atmosphere, with the temperature rise rate of 5 DEG C/min, be warming up to 450 DEG C, constant temperature 1.5h, again with the temperature rise rate of 5 DEG C/min, rise to 600 DEG C, under the thermal expansion effects of superalloy, system is from boosting to 23MPa, after constant temperature 1h, then naturally cool to room temperature, namely obtain hot pressing graphene platelet, its thickness is 202 μm;
(4), by the hot pressing graphene platelet of step (3) gained be placed in high temperature process furnances, in a nitrogen atmosphere, carry out 1000 DEG C of charing process 3h, namely obtain charing black lead alkene thin slice;
(5), by the charing black lead alkene thin slice of step (4) gained be placed in high temperature graphitization stove, under an argon atmosphere, carry out 2700 DEG C of graphitization processing 1h, namely obtain greying graphene platelet;
Above-mentioned hot pressing graphene platelet smooth surface, the grey of metal luster, has certain hardness and tensile strength.
The xrd of above-mentioned graphene nanometer sheet is shown in shown in Fig. 2 (a), can find out that graphene nanometer sheet occurs a wide diffraction peak at about 26 ° from Fig. 2 (a), illustrates that graphene oxide is peeled off after reduction through microwave assistant and forms graphene nanometer sheet.The xrd that Fig. 2 (b) is greying graphene platelet schemes, and obviously can observe a sharp-pointed diffraction peak, illustrate that the interlamellar spacing pole in greying graphene platelet between Graphene is reduced sharply little at 26.5 °.
The optical photograph of above-mentioned hot pressing graphene platelet and the SEM figure of plane and cross section are as shown in Figure 3, in Fig. 3, a is hot pressing leaf optical photo, b is that hot pressing laminae plane SEM schemes, c is that hot pressing thin slice cross section SEM schemes, as can be drawn from Figure 3, the plane of graphene platelet and cross-sectional structure present significant difference.
In the hot pressing of above-mentioned gained, charing and greying Graphene thermal sheet, the orientation degree of graphene sheet layer as shown in Figure 4, and as can be drawn from Figure 4, hot pressing graphene platelet deflection angle accounts for about 41% within 5 °, accounts for about 91% within 20 °; Charing black lead alkene thin slice deflection angle accounts for about 39% within 5 °, accounts for about 90% within 20 °; And greying graphene platelet thin slice deflection angle accounts for about 42% within 5 °, about 93% is accounted within 20 °, with hot pressing, carbonize compared with thin slice, graphitized sheets orientation degree obviously a little higher than the above two, the graphene platelet indicating gained of the present invention thus has graphene sheet layer along the high feature of orientation degree in face.
After tested, the greying graphene platelet volume density of above-mentioned gained is 1.382g/cm
3, plane thermal conductivity is 405W/mK, and axial thermal conductivity is 1.19W/mK; The maximum tensile stress of graphitized sheets can reach 10.94MPa, and deflection is 1.21%.
embodiment 2
A preparation method for Graphene thermal sheet, specifically comprises the steps:
(1), by 0.5g graphene nanometer sheet powder mix mutually with 0.01g high softening-point coal-tar pitch powder, join in dehydrated alcohol, supersound process 1h under 100W, 40KHz, suction filtration, after 70 DEG C of oven dry, obtain mixed powder;
Dehydrated alcohol consumption, in graphene powder: dehydrated alcohol is that the ratio of 1g:400mL calculates; Repeatedly intercalation lift-off technology is obtained by catalyzed oxidation for described graphene powder;
(2), import in mould by the mixed powder of step (1) gained, regulate oil press pressure to be 15MPa, the time is 5min, by direct for mixed powder cold compaction flakiness;
(3), by the thin slice of colding pressing of step (2) gained be folded between ganoid superalloy mould, be placed in tube furnace, adopt oil press to apply 3MPa pressure, in a nitrogen atmosphere, with the temperature rise rate of 3 DEG C/min, be warming up to 450 DEG C, constant temperature 1h, again with the temperature rise rate of 1 DEG C/min, rise to 600 DEG C, under the thermal expansion effects of superalloy, system is from boosting to 30MPa, after constant temperature 2h, then naturally cool to room temperature, namely obtain hot pressing graphene platelet, its thickness is 187 μm;
(4), by the hot pressing graphene platelet of step (3) gained be placed in high temperature process furnances, in a nitrogen atmosphere, carry out 900 DEG C of charing process 2h, namely obtain charing black lead alkene thin slice;
(5), by the charing black lead alkene thin slice of step (4) gained be placed in high temperature graphitization stove, under an argon atmosphere, carry out 2300 DEG C of graphitization processing 2h, namely obtain greying graphene platelet;
After tested, the greying graphene platelet volume density of above-mentioned gained is 1.327g/cm
3, plane thermal conductivity is 325W/mK, and axial thermal conductivity is 1.16W/mK; The maximum tensile stress of graphitized sheets can reach 8.96MPa, and deflection is 1.25%.
embodiment 3
A preparation method for Graphene thermal sheet, specifically comprises the steps:
(1), by 0.5g graphene nanometer sheet powder mix mutually with 0.02g high softening-point coal-tar pitch powder, join in dehydrated alcohol, supersound process 1h under 100W, 40KHz, suction filtration, after 70 DEG C of oven dry, obtain mixed powder;
Dehydrated alcohol consumption, in graphene powder: dehydrated alcohol is that the ratio of 1g:500mL calculates; Repeatedly intercalation lift-off technology is obtained by catalyzed oxidation for described graphene powder;
(2), import in mould by the mixed powder of step (1) gained, regulate oil press pressure to be 20MPa, the time is 5min, by direct for mixed powder cold compaction flakiness;
(3), by the thin slice of colding pressing of step (2) gained be folded between ganoid superalloy mould, be placed in tube furnace, adopt oil press to apply 5MPa pressure, in a nitrogen atmosphere, with the temperature rise rate of 3 DEG C/min, be warming up to 420 DEG C, constant temperature 0.5h, again with the temperature rise rate of 1 DEG C/min, rise to 500 DEG C, under the thermal expansion effects of superalloy, system is from boosting to 32MPa, after constant temperature 3h, then naturally cool to room temperature, namely obtain hot pressing graphene platelet, its thickness is 182 μm;
(4), by the hot pressing graphene platelet of step (3) gained be placed in high temperature process furnances, in a nitrogen atmosphere, carry out 1200 DEG C of charing process 1h, namely obtain charing black lead alkene thin slice;
(5), by the charing black lead alkene thin slice of step (4) gained be placed in high temperature graphitization stove, under an argon atmosphere, carry out 2500 DEG C of graphitization processing 1.5h, namely obtain greying graphene platelet;
After tested, the greying graphene platelet volume density of above-mentioned gained is 1.447g/cm
3, plane thermal conductivity is 377W/mK, and axial thermal conductivity is 1.20W/mK; The maximum tensile stress of graphitized sheets can reach 8.27MPa, and deflection is 1.13%.
embodiment 4
A preparation method for Graphene thermal sheet, specifically comprises the steps:
(1), do not adding under asphalt powder, 0.5g graphene nanometer sheet powder is being joined in dehydrated alcohol, supersound process 1h under 100W, 40KHz, suction filtration, 70 DEG C of oven dry;
Dehydrated alcohol consumption, in graphene powder: dehydrated alcohol is that the ratio of 1g:450mL calculates; Repeatedly intercalation lift-off technology is obtained by catalyzed oxidation for described graphene powder;
(2), import in mould by the powder of step (1) gained, regulate oil press pressure to be 20MPa, the time is 5min, by direct for powder cold compaction flakiness;
(3), the thin slice of colding pressing of step (2) gained is folded between ganoid superalloy mould, be placed in tube furnace, oil press piston is at contact mould upper surface but under not applying pressure, in nitrogen atmosphere, with the temperature rise rate of 5 DEG C/min, be warming up to 450 DEG C, constant temperature 1.5h, again with the temperature rise rate of 1 DEG C/min, rise to 500 DEG C, under the thermal expansion effects of superalloy, system is from boosting to 21MPa, after constant temperature 1h, then naturally cool to room temperature, namely obtain hot pressing graphene platelet, its thickness is 198 μm;
(4), by the hot pressing graphene platelet of step (3) gained be placed in high temperature process furnances, in a nitrogen atmosphere, carry out 1000 DEG C of charing process 3h, namely obtain charing black lead alkene thin slice;
(5), by the charing black lead alkene thin slice of step (4) gained be placed in high temperature graphitization stove, under an argon atmosphere, carry out 2700 DEG C of graphitization processing 1h, namely obtain greying graphene platelet;
After tested, the greying graphene platelet volume density of above-mentioned gained is 1.329g/cm
3, plane thermal conductivity is 300W/mK, and axial thermal conductivity is 1.20W/mK; The maximum tensile stress of graphitized sheets can reach 7.76MPa, and deflection is 1.16%.
embodiment 5
A preparation method for Graphene thermal sheet, specifically comprises the steps:
(1), by 0.5g graphene nanometer sheet powder mix mutually with 0.04g high softening-point coal-tar pitch powder, join in dehydrated alcohol, supersound process 1h under 100W, 40KHz, suction filtration, after 70 DEG C of oven dry, obtain mixed powder;
Dehydrated alcohol consumption, in graphene powder: dehydrated alcohol is that the ratio of 1g:350mL calculates; Repeatedly intercalation lift-off technology is obtained by catalyzed oxidation for described graphene powder;
(2), import in mould by the mixed powder of step (1) gained, regulate oil press pressure to be 15MPa, the time is 3min, by direct for mixed powder cold compaction flakiness;
(3), the thin slice of colding pressing of step (2) gained is folded between ganoid superalloy mould, be placed in tube furnace, oil press piston is at contact mould upper surface but under not applying pressure, in nitrogen atmosphere, with the temperature rise rate of 3 DEG C/min, be warming up to 450 DEG C, constant temperature 1h, again with the temperature rise rate of 5 DEG C/min, rise to 800 DEG C, under the thermal expansion effects of superalloy, system is from boosting to 29MPa, after constant temperature 1h, then naturally cool to room temperature, namely obtain hot pressing graphene platelet, its thickness is 211 μm;
(4), by the hot pressing graphene platelet of step (3) gained be placed in high temperature process furnances, in a nitrogen atmosphere, carry out 1200 DEG C of charing process 3h, namely obtain charing black lead alkene thin slice;
(5), by the charing black lead alkene thin slice of step (4) gained be placed in high temperature graphitization stove, under an argon atmosphere, carry out 2300 DEG C of graphitization processing 1.5h, namely obtain greying graphene platelet;
After tested, the greying graphene platelet volume density of above-mentioned gained is 1.411g/cm
3, plane thermal conductivity is 369W/mK, and axial thermal conductivity is 0.98W/mK; The maximum tensile stress of graphitized sheets can reach 9.56MPa, and deflection is 1.19%.
embodiment 6
A preparation method for Graphene thermal sheet, specifically comprises the steps:
(1), by 0.5g graphene nanometer sheet powder mix mutually with 0.01g high softening-point coal-tar pitch powder, join in dehydrated alcohol, supersound process 1h under 100W, 40KHz, suction filtration, after 70 DEG C of oven dry, obtain mixed powder;
Dehydrated alcohol consumption, in graphene powder: dehydrated alcohol is that the ratio of 1g:400mL calculates; Repeatedly intercalation lift-off technology is obtained by catalyzed oxidation for described graphene powder;
(2), import in mould by the mixed powder of step (1) gained, regulate oil press pressure to be 18MPa, the time is 3min, by direct for mixed powder cold compaction flakiness;
(3), by the thin slice of colding pressing of step (2) gained be folded between ganoid superalloy mould, be placed in tube furnace, adopt oil press to apply 5MPa pressure, in a nitrogen atmosphere, with the temperature rise rate of 5 DEG C/min, be warming up to 450 DEG C, constant temperature 1.5h, again with the temperature rise rate of 4 DEG C/min, rise to 600 DEG C, under the thermal expansion effects of superalloy, system is from boosting to 34MPa, after constant temperature 2h, then naturally cool to room temperature, namely obtain hot pressing graphene platelet, its thickness is 179 μm;
(4), by the hot pressing graphene platelet of step (3) gained be placed in high temperature process furnances, in a nitrogen atmosphere, carry out 1000 DEG C of charing process 1h, namely obtain charing black lead alkene thin slice;
(5), by the charing black lead alkene thin slice of step (4) gained be placed in high temperature graphitization stove, under an argon atmosphere, carry out 2500 DEG C of graphitization processing 2h, namely obtain greying graphene platelet;
After tested, the greying graphene platelet volume density of above-mentioned gained is 1.331g/cm
3, plane thermal conductivity is 330W/mK, and axial thermal conductivity is 0.98W/mK; The maximum tensile stress of graphitized sheets can reach 8.31MPa, and deflection is 1.18%.
embodiment 7
A preparation method for Graphene thermal sheet, specifically comprises the steps:
(1), by 0.5g graphene nanometer sheet powder mix mutually with 0.03g high softening-point coal-tar pitch powder, join in dehydrated alcohol, supersound process 1h under 100W, 40KHz, suction filtration, after 70 DEG C of oven dry, obtain mixed powder;
Dehydrated alcohol consumption, in graphene powder: dehydrated alcohol is that the ratio of 1g:500mL calculates; Repeatedly intercalation lift-off technology is obtained by catalyzed oxidation for described graphene powder;
(2), import in mould by the mixed powder of step (1) gained, regulate oil press pressure to be 20MPa, the time is 5min, by direct for mixed powder cold compaction flakiness;
(3), the thin slice of colding pressing of step (2) gained is folded between ganoid superalloy mould, be placed in tube furnace, oil press piston is at contact mould upper surface but under not applying pressure, in nitrogen atmosphere, with the temperature rise rate of 3 DEG C/min, be warming up to 420 DEG C, constant temperature 0.5h, again with the temperature rise rate of 1 DEG C/min, rise to 500 DEG C, under the thermal expansion effects of superalloy, system is from boosting to 21MPa, after constant temperature 3h, then naturally cool to room temperature, namely obtain hot pressing graphene platelet, its thickness is 208 μm;
(4), by the hot pressing graphene platelet of step (3) gained be placed in high temperature process furnances, in a nitrogen atmosphere, carry out 900 DEG C of charing process 1h, namely obtain charing black lead alkene thin slice;
(5), by the charing black lead alkene thin slice of step (4) gained be placed in high temperature graphitization stove, under an argon atmosphere, carry out 2500 DEG C of graphitization processing 2h, namely obtain greying graphene platelet;
After tested, the greying graphene platelet volume density of above-mentioned gained is 1.374g/cm
3, plane thermal conductivity is 388W/mK, and axial thermal conductivity is 0.96W/mK; The maximum tensile stress of graphitized sheets can reach 10.56MPa, and deflection is 1.20%.
embodiment 8
A preparation method for Graphene thermal sheet, specifically comprises the steps:
(1), by 0.5g graphene nanometer sheet powder mix mutually with 0.04g high softening-point coal-tar pitch powder, join in dehydrated alcohol, supersound process 1h under 100W, 40KHz, suction filtration, after 70 DEG C of oven dry, obtain mixed powder;
Dehydrated alcohol consumption, in graphene powder: dehydrated alcohol is that the ratio of 1g:400mL calculates; Repeatedly intercalation lift-off technology is obtained by catalyzed oxidation for described graphene powder;
(2), import in mould by the mixed powder of step (1) gained, regulate oil press pressure to be 20MPa, the time is 3min, by direct for mixed powder cold compaction flakiness;
(3), by the thin slice of colding pressing of step (2) gained be folded between ganoid superalloy mould, be placed in tube furnace, adopt oil press to apply 3MPa pressure, in a nitrogen atmosphere, with the temperature rise rate of 5 DEG C/min, be warming up to 420 DEG C, constant temperature 1.5h, again with the temperature rise rate of 5 DEG C/min, rise to 600 DEG C, under the thermal expansion effects of superalloy, system is from boosting to 30MPa, after constant temperature 1h, then naturally cool to room temperature, namely obtain hot pressing graphene platelet, its thickness is 209 μm;
(4), by the hot pressing graphene platelet of step (3) gained be placed in high temperature process furnances, in a nitrogen atmosphere, carry out 900 DEG C of charing process 1h, namely obtain charing black lead alkene thin slice;
(5), by the charing black lead alkene thin slice of step (4) gained be placed in high temperature graphitization stove, under an argon atmosphere, carry out 2500 DEG C of graphitization processing 2h, namely obtain greying graphene platelet;
After tested, the greying graphene platelet volume density of above-mentioned gained is 1.407g/cm
3, plane thermal conductivity is 358W/mK, and axial thermal conductivity is 0.89W/mK; The maximum tensile stress of graphitized sheets can reach 9.03MPa, and deflection is 1.23%.
embodiment 9a kind of preparation method of graphene nanometer sheet powder
Measure the 96mL vitriol oil and be placed in dry round-bottomed flask, add 2g SODIUMNITRATE wherein, stir after SODIUMNITRATE is dissolved, add 2g crystalline flake graphite again, after crystalline flake graphite is uniformly dispersed, slowly add 12g potassium permanganate, reaction 1.45h, whole process adopts ice bath to make system remain on 0 ~ 5 DEG C, then temperature rises to 35 DEG C of reaction 2h, then in reaction system, slowly adds 80mL deionized water, reaction 30min, slowly add 200mL deionized water more afterwards, add 10mLH more subsequently
2o
2, continue reaction 10min, the reacting liquor while hot suction filtration of gained, gained filter cake 1000mL mass percent concentration is the HCl solution washing of 5%, to remove metal ion.Then join in filter cake by appropriate amount of deionized water, carry out centrifuge washing after stirring, until the pH of colloid is neutral, ultrasonic 10min, obtains graphene oxide colloid;
Get the graphene oxide colloid of 40mL1.5mg/mL in polytetrafluoroethylcontainer container, add ammoniacal liquor and regulate PH to be 11, slowly add 0.6g50% hydrazine hydrate solution under stirring, then container is placed in the microwave oven that power is 800W, carries out microwave; 20s microwave heating, it is 1 circulation that 20s takes out stirring, and repetitive operation 5 circulates, afterwards suction filtration, in-50 DEG C, lyophilize under 1Pa vacuum tightness, obtains graphene nanometer sheet powder.
Claims (7)
1. a preparation method for Graphene thermal sheet, is characterized in that comprising the steps:
1) graphene nanometer sheet powder and high softening-point coal-tar pitch powder is taken according to mass ratio, the mass ratio of described graphene nanometer sheet powder and high softening-point coal-tar pitch powder is 5:0 ~ 0.5, by graphene nanometer sheet powder and the mixing of high softening-point coal-tar pitch powder, then ultrasonic 0.5 ~ 2h in dehydrated alcohol is joined, suction filtration, after oven dry, obtain mixed powder; The consumption of described dehydrated alcohol, in graphene powder: dehydrated alcohol is that the ratio of 1g:350 ~ 500mL calculates;
2) import in mould by the mixed powder of step (1) gained, regulate oil press pressure to be 15 ~ 20MPa, the time is 3 ~ 5min, by direct for mixed powder cold compaction flakiness;
3) thin slice of colding pressing of step (2) gained is folded between ganoid superalloy mould, be placed in tube furnace, oil press is adopted to apply 0 ~ 5MPa pressure, adopt in nitrogen, argon gas or helium atmosphere under any one atmosphere, with the temperature rise rate of 3 ~ 5 DEG C/min, be warming up to 420 ~ 450 DEG C, constant temperature 0.5 ~ 1.5h, again with the temperature rise rate of 1 ~ 5 DEG C/min, rise to 500 ~ 800 DEG C, under the thermal expansion effects of superalloy, system is from boosting to 21 ~ 34MPa, after constant temperature 1 ~ 3h, then naturally cool to room temperature, namely 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 characterized in that: the hot pressing graphene platelet of step (3) gained is placed in high temperature process furnances, adopt in nitrogen, argon gas or helium atmosphere under any one atmosphere, carry out 900 ~ 1200 DEG C of charing process 1 ~ 3h, namely obtain charing black lead alkene thin slice.
3. the preparation method of Graphene thermal sheet as claimed in claim 2, it is characterized in that: the charing black lead alkene thin slice of gained is placed in high temperature graphitization stove, adopt in nitrogen, argon gas or helium atmosphere under any one atmosphere, carry out 2300 ~ 2700 DEG C of graphitization processing 0.5 ~ 2h, namely obtain greying graphene platelet.
4. the preparation method of Graphene thermal sheet as claimed in claim 1, is characterized in that: described graphene nanometer sheet powder is prepared by the following method:
1) vitriol oil of measured amounts is placed in a reaction vessel, add SODIUMNITRATE wherein, stir after SODIUMNITRATE is dissolved, then add crystalline flake graphite, after crystalline flake graphite is uniformly dispersed, slowly add potassium permanganate reaction, whole process adopts ice bath to make system remain on 0 ~ 5 DEG C of reaction 1 ~ 2h, and then temperature rises to 30 ~ 45 DEG C of reactions 1 ~ 3 hour, then in reaction system, first deionized water is slowly added, reaction 20 ~ 40min, slowly adds second batch deionized water more afterwards, adds H more subsequently
2o
2, continue reaction 5 ~ 20min, the reacting liquor while hot suction filtration of gained, gained filter cake mass percent concentration is the HCl solution washing of 3 ~ 10%, to remove metal ion;
2) then join in filter cake by deionized water, carry out centrifuge washing after stirring, until the pH of colloid is neutral, ultrasonic 5 ~ 15min, obtains graphene oxide colloid;
3) graphene oxide colloid is got in a polytetrafluoroethylcontainer container, adding ammoniacal liquor regulates PH to be 11, slowly add the hydrazine hydrate solution that mass percent concentration is 30 ~ 60% under stirring, the mass ratio of graphene oxide colloid and hydrazine hydrate solution is 1:8 ~ 12, then carries out microwave treatment; 20s microwave heating, it is 1 circulation that 20s takes out stirring, and repetitive operation 3 ~ 8 circulates, and suction filtration afterwards, lyophilize, obtains graphene nanometer sheet powder.
5. the preparation method of Graphene thermal sheet as claimed in claim 4, is characterized in that: the mass percent concentration of the described vitriol oil is 60 ~ 98%.
6. the preparation method of Graphene thermal sheet as claimed in claim 4, is characterized in that: the vitriol oil, SODIUMNITRATE, crystalline flake graphite, potassium permanganate, first deionized water, second batch deionized water, H
2o
2, the HCl aqueous solution material ratio 96mL:2g:2g:12g:80mL:200mL:10mL:1000mL.
7. the preparation method of Graphene thermal sheet as claimed in claim 1, is characterized in that: the high softening-point coal-tar pitch powder described in step (1), and its softening temperature is at 270 ~ 300 DEG C, and TI content 10 ~ 30%, crosses 150 ~ 300 mesh sieves at 50 ~ 70%, QI content.
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