CN104743551A - Method for preparing reduced graphene oxide heat conductive film - Google Patents
Method for preparing reduced graphene oxide heat conductive film Download PDFInfo
- Publication number
- CN104743551A CN104743551A CN201510139841.5A CN201510139841A CN104743551A CN 104743551 A CN104743551 A CN 104743551A CN 201510139841 A CN201510139841 A CN 201510139841A CN 104743551 A CN104743551 A CN 104743551A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- deionized water
- gained
- film
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a method for preparing a reduced graphene oxide heat conductive film. The method comprises the following steps: adding graphite oxide into the deionized water to perform ultrasonic treatment, centrifuging the obtained suspension solution for 5-20 min at the speed of 2000-3000 rpm, getting a supernate, drying and grinding to obtain the graphene oxide; and adding the obtained graphene oxide into a solvent to perform ultrasonic treatment to obtain a graphene oxide dispersed solution with the concentration of 1-5 mg/ml, performing vacuum filtration by a millipore filter, drying the obtained filter cake with the filter membrane, stripping the filter cake from the filter membrane, exerting the pressure of 0-10 MPa to the obtained graphene oxide, under the atmosphere of nitrogen, argon or helium, and processing for 2-8h at the temperature of 600-1000 DEG C to obtain the reduced graphene oxide heat conductive film with high heat conductivity, high reduction degree, high graphene lamellar surface inner orientation degree, smooth surface, good flexibility, wide curl degree without crack and small interlamellar spacing. The preparation method is simple and the reduced graphene oxide heat conductive film is easy for realization of industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of redox graphene heat conduction film, belong to carbon material field.
Background technology
Graphene is a kind of novel material of the individual layer sheet structure be made up of carbon atom close-packed arrays, and since being found, its special structure and excellent performance cause the extensive concern of material educational circles and community of physicists.Research in recent years shows, thermal conductivity in the face that Graphene has a superelevation, its value, up to 4800-6000W/mK, in the heat dissipation problem improving superpower, integrated micro-/ nano device, has a good application prospect.Two-dimensional film based on graphene sheet layer NW-TFT 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 heat management.How to prepare the graphene film material that heat dispersion is good, be successfully applied in power device field of radiating and come to be a technical barrier urgently to be resolved hurrily.The method preparing Graphene has a lot, wherein, peels off graphite oxide and obtains a kind of method that graphene oxide is large-scale production Graphene again through reduction.And prepare graphene film by graphene oxide/graphene solution and have a lot of method, comprise spraying method, spin-coating method, vacuum filtration method, gas/liquid self-assembly method, Langmuir – Blodgett self-assembly method etc.Vacuum filtration method is the method adopting graphene oxide/graphene sheet layer to carry out NW-TFT film forming layer by layer under the flowing of solution.When direct suction filtration graphene solution prepares graphene film, can reunion be produced because graphene oxide is reduced in the process of Graphene, not easily form stable graphene dispersing solution, form the film of flat smooth compared with hard-pumped filter; And contain a large amount of oxygen-containing functional group due to surface of graphene oxide, form stable dispersions in Yi Shui, ethanol isopolarity solution, adopt the easy film forming of suction method, then can oxidation graphene film be prepared through reduction treatment.But adopt in usual chemical reduction or high-temperature heat treatment reduction process; the integrity of graphene film is difficult to keep; or though film is more regular; its snappiness is poor, can not higher curvature curling; and space is many, density is low; in film, graphene sheet layer is low along the orientation degree in face, causes thermal conductivity of thin film low.
Summary of the invention
The object of the invention is to be difficult to keep that big area is complete, snappiness is poor, space is many after solving the reduction of above-mentioned graphene oxide film, graphene sheet layer provides a kind of redox graphene heat conduction film preparation method along technical problems such as orientation degree in face are low, the oxidation graphene film of described preparation method's gained has that big area is complete, snappiness good, space is few, graphene sheet layer is high along orientation degree in face, thermal conductivity high.
Technical scheme of the present invention
A preparation method for redox graphene heat conduction film, specifically comprises the steps:
(1), by graphite oxide join in deionized water, ultrasonic 10min-1h, to the centrifugal 5-20min of suspension control 2000-3000rpm of ultrasonic rear gained, get supernatant liquor, after drying, grinding, obtain graphene oxide;
Graphite oxide and deionized water consumption, in graphite oxide: deionized water is that the ratio of 1g:500-1000mL calculates; Described graphite oxide is standby by the Hummers legal system improved;
(2), the graphene oxide of step (1) gained is joined in solvent, supersound process 0.5-1.5h under 100W, 40KHz, be preferably 1h, obtain the dispersion liquid that concentration is 1-5mg/mL graphene oxide;
Described solvent is the mixing solutions that deionized water, ethanol or deionized water and ethanol form;
(3), the dispersion liquid of the graphene oxide of step (2) gained is adopted millipore filtration vacuum filtration, the filter cake obtained is 60-100 DEG C together with filter membrane control temperature, be preferably 80 DEG C carry out drying after, peeled off from filter membrane by filter cake and obtain graphene oxide film, its thickness is preferably 10-55 μm;
Described millipore filtration to be aperture the be cellulose mixture millipore filtration of 0.45 μm;
(4), the graphene oxide film of step (3) gained is folded between ganoid superalloy mould, be placed in tube furnace, in the atmosphere of nitrogen, argon gas or helium, adopt oil press to apply the pressure of 0-7.5MPa, simultaneously with the temperature rise rate of 1-5 DEG C/min, be warming up to 600-1000 DEG C, under the thermal expansion effects of superalloy, system is from boosting to 20-40MPa, insulation 2-8h, then naturally cools to room temperature, obtains redox graphene heat conduction film.
Beneficial effect of the present invention
The preparation method of a kind of redox graphene heat conduction film of the present invention compares with prior art, owing to being that graphene oxide film is applied certain pressure in high-temperature hot reduction, after therefore effectively overcoming graphene oxide film reduction, be difficult to keep that big area is complete, snappiness is poor, space is many, graphene sheet layer is along technical problems such as orientation degree in face are low.Graphene oxide film redox graphene heat conduction film of gained after reduction is become the grey having metalluster by black, and integrity is preserved, smooth surface and also snappiness fine, can by a relatively large margin curling not rupture.The interlamellar spacing of reduction rear oxidation graphene film obviously reduces, and has that reducing degree is higher simultaneously, graphene sheet layer is along orientation degree high in face.
Further, the thermal conductivity of the redox graphene heat conduction film of preparation method's gained of a kind of redox graphene heat conduction film of the present invention is higher, its thermal conductivity is 1784-2636W/mK, has potential actual application value in heat dissipation from microelectronic devices field.
Further, the preparation method of a kind of redox graphene heat conduction film of the present invention, its preparation technology is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
The measuring principle schematic diagram of orientation degree in the face of Fig. 1, graphene oxide film and oxidation graphene film;
The SEM of Fig. 2, embodiment 1 step (3) gained graphene oxide film and step (4) gained oxidation graphene film cross section schemes;
The XRD figure of Fig. 3, embodiment 1 step (3) gained graphene oxide film and step (4) gained oxidation graphene film is composed;
Orientation degree in the face of Fig. 4, embodiment 1 step (3) gained graphene oxide film and step (4) gained oxidation graphene film;
The x-ray photoelectron energy spectrogram of Fig. 5, embodiment 1 step (3) gained graphene oxide film and step (4) gained oxidation graphene film.
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 Quanta200 FEG, FEI Co. of the U.S. produces.
X-ray diffractometer used, model D/max2200PC(CuK α, λ=0.15406 nm), 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 graphene oxide film and oxidation graphene film 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.
In embodiments of the invention, the Electronic Structure analysis of graphene oxide film and oxidation graphene film adopts PHI 5000 VersaProbe type x-ray photoelectron spectroscopy, excitation of X-rays source is Al K α (1486.6 eV), vacuum tightness 2 × 10
-9pa, adopts electron binding energy 284.6 eV of sample surfaces carbon C1s as interior mark.
Thermal diffusivity (α, mm in embodiments of the invention in graphene oxide film and oxidation graphene film plane
2/ s) adopt the LFA447 flicker method heat transfer analysis instrument of German Nai Chi company to test, apparent density (ρ, g/cm
3) calculated divided by volume by film quality, the specific heat capacity (C of sample
p, J/gK) recorded by TA Q2000 type differential scanning calorimetry instrument, thermal conductivity (λ, W/mK) is by λ=α × ρ × C
pcalculate.
The Hummers legal system improved is for graphite oxide, and concrete steps are as follows:
Measure the 96mL vitriol oil and be placed in drying receptacle, 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 1.5h, whole process adopts ice bath to make system remain on 0-5 DEG C, then temperature rises to 35 DEG C of reaction 2.5h, then in reaction system, slowly adds 80mL deionized water, reaction 10min, slowly add 200mL deionized water more afterwards, add 10mL H more subsequently
2o
2, continue reaction 10min, the reaction solution suction filtration of gained, gained filter cake 800mL mass percent concentration is the HCl solution washing of 5%, to go out metal ion, then with deionized water wash until the pH of effluent liquid is neutral, then control temperature is 120 DEG C of dryings, obtains graphite oxide.
embodiment 1
A preparation method for redox graphene heat conduction film, specifically comprises the steps:
(1), by graphite oxide join in deionized water, ultrasonic 10min under 80W, 40KHz, to the centrifugal 5min of suspension control 3000rpm of ultrasonic rear gained, get supernatant liquor and grind after 80 DEG C of dry 24h in vacuum drying oven, obtain graphene oxide;
Graphite oxide and deionized water consumption, in graphite oxide: deionized water is that the ratio of 1g:500mL calculates; Described graphite oxide is standby by the Hummers legal system improved;
(2), the graphene oxide of 400mg step (1) gained is joined in 200mL solvent, supersound process 1h under 100W, 40KHz, obtain the dispersion liquid that concentration is 2mg/mL graphene oxide;
Described solvent is deionized water and ethanol is mixing solutions that 1:1 forms by volume;
(3), aperture is adopted to be the cellulose mixture millipore filtration vacuum filtration of 0.45 μm the dispersion liquid of the graphene oxide of 30mL step (2) gained, after the filter cake obtained is 80 DEG C of dry 24h together with filter membrane control temperature, peeled off from filter membrane by filter cake and obtain graphene oxide film, its thickness is 31 μm;
(4), the graphene oxide film of step (3) gained is folded between ganoid superalloy mould, be placed in tube furnace, oil press is adopted to apply the pressure of 7.5MPa, in nitrogen atmosphere, with the temperature rise rate of 4 DEG C/min, be warming up to 600 DEG C, system is from boosting to 35MPa, after insulation 2h, naturally cool to room temperature, namely obtain redox graphene heat conduction film;
Above-mentioned graphene oxide film redox graphene heat conduction film of gained after reduction is become the grey having metalluster by black, and integrity is preserved, smooth surface and also snappiness fine, can by a relatively large margin curling not rupture.
The SEM figure of above-mentioned graphene oxide film and redox graphene heat conduction film cross section as shown in Figure 2, in Fig. 2, a is graphene oxide film, b is redox graphene heat conduction film, as can be drawn from Figure 2, the thickness of graphene oxide heat conduction film is about 31 μm, and the thickness of oxidation graphene film obviously reduces, it is about 14 μm.
The graphene oxide film of above-mentioned gained and the XRD figure of redox graphene heat conduction film are composed as shown in Figure 3, and in Fig. 3, a is graphene oxide film, and b is redox graphene heat conduction film, and as can be drawn from Figure 3, graphene oxide heat conduction film is 10.6
ooccur diffraction peak, after reduction, the diffraction peak of the redox graphene heat conduction film of gained moves on to 26.4
o, illustrate that the interlamellar spacing of reduction rear oxidation graphene film obviously reduces.
In the graphene oxide film of above-mentioned gained and redox graphene heat conduction film, the orientation degree of graphene sheet layer as shown in Figure 4, and as can be drawn from Figure 4, graphene oxide film deflection angle accounts for about 56% within 10 °, accounts for about 95% within 30 °; And oxidation graphene film deflection angle accounts for about 59% within 10 °, about 98% is accounted within 30 °, compared with graphene oxide film, orientation degree significantly improves, and the oxidation graphene film indicating gained of the present invention thus has graphene sheet layer along the high feature of orientation degree in face.
The graphene oxide film of above-mentioned gained and the x-ray photoelectron energy spectrogram of redox graphene heat conduction film are as shown in Figure 5, in Fig. 5, a is graphene oxide film, b is redox graphene heat conduction film, as can be drawn from Figure 5, the carbon Sauerstoffatom ratio (C/O) on graphene oxide film surface is 2.45, after reduction, the carbon Sauerstoffatom ratio (C/O) of the redox graphene heat conduction film of gained brings up to 11.0, and the oxidation graphene film indicating gained of the present invention thus has the higher feature of reducing degree.
After tested, the apparent density of the redox graphene heat conduction film of above-mentioned gained is 1.96g/cm
3, thermal diffusivity is 1703mm
2/ s, specific heat capacity is 0.726J/gK, and thermal conductivity is 2423W/mK.
embodiment 2
A preparation method for redox graphene heat conduction film, specifically comprises the steps:
(1), by graphite oxide join in deionized water, ultrasonic 30min(80W, 40KHz), to the centrifugal 10min of suspension control 2500rpm of ultrasonic rear gained, get supernatant liquor and grind after 80 DEG C of dry 24h in vacuum drying oven, obtain graphene oxide;
Graphite oxide and deionized water consumption, in graphite oxide: deionized water is that the ratio of 1g:800mL calculates; Described graphite oxide is standby by the Hummers legal system improved;
(2), the graphene oxide of 200mg step (1) gained is joined in 200mL solvent, supersound process 1h (100W, 40KHz), obtain the dispersion liquid that concentration is 1mg/mL graphene oxide;
Described solvent is deionized water and ethanol is mixing solutions that 1:1 forms by volume;
(3), aperture is adopted to be the cellulose mixture millipore filtration vacuum filtration of 0.45 μm the dispersion liquid of the graphene oxide of 20mL step (2) gained, after the filter cake obtained is 80 DEG C of dry 24h together with filter membrane control temperature, peeled off from filter membrane by filter cake and obtain graphene oxide film, its thickness is 12 μm;
(4), the graphene oxide film of step (3) gained is folded between ganoid superalloy mould, be placed in tube furnace, oil press is adopted to apply the pressure of 0MPa, in nitrogen atmosphere, with the temperature rise rate of 4 DEG C/min, be warming up to 600 DEG C, system is from boosting to 24MPa, after insulation 2h, naturally cool to room temperature, obtain the redox graphene heat conduction film that thickness is 5 μm;
After tested, the apparent density of the redox graphene heat conduction film of above-mentioned gained is 1.92g/cm
3, thermal diffusivity is 1280mm
2/ s, specific heat capacity is 0.726J/gK, and thermal conductivity is 1784W/mK.
embodiment 3
A preparation method for redox graphene heat conduction film, specifically comprises the steps:
(1), by graphite oxide join in deionized water, ultrasonic 10min under 80W, 40KHz, to the centrifugal 20min of suspension control 2000rpm of ultrasonic rear gained, get supernatant liquor and grind after 80 DEG C of dry 24h in vacuum drying oven, obtain graphene oxide;
Graphite oxide and deionized water consumption, in graphite oxide: deionized water is that the ratio of 1g:1000mL calculates; Described graphite oxide is standby by the Hummers legal system improved; ;
(2), the graphene oxide of 400mg step (1) gained is joined in 200mL solvent, supersound process 1h under 100W, 40KHz, obtain the dispersion liquid that concentration is 2mg/mL graphene oxide;
Described solvent is deionized water and ethanol is mixing solutions that 1:1 forms by volume;
(3), aperture is adopted to be the cellulose mixture millipore filtration vacuum filtration of 0.45 μm the dispersion liquid of the graphene oxide of 40mL step (2) gained, after the filter cake obtained is 80 DEG C of dry 24h together with filter membrane control temperature, peeled off from filter membrane by filter cake and obtain graphene oxide film, its thickness is 42 μm;
(4), the graphene oxide heat conduction film-clamp of step (3) gained is placed between ganoid superalloy mould, be placed in tube furnace, oil press is adopted to apply the pressure of 5MPa, in nitrogen atmosphere, with the temperature rise rate of 4 DEG C/min, be warming up to 600 DEG C, system is from boosting to 34MPa, after insulation 2h, naturally cool to room temperature, obtain the redox graphene heat conduction film that thickness is 17 μm;
After measured, the apparent density of the redox graphene heat conduction film of above-mentioned gained is 1.95g/cm
3, thermal diffusivity is 1476mm
2/ s, specific heat capacity is 0.726J/gK, and thermal conductivity is 2089W/mK.
embodiment 4
A preparation method for redox graphene heat conduction film, specifically comprises the steps:
(1), by graphite oxide join in deionized water, ultrasonic 10min under 80W, 40KHz, to the centrifugal 10min of suspension control 3000rpm of ultrasonic rear gained, get supernatant liquor and grind after 80 DEG C of dry 24h in vacuum drying oven, obtain graphene oxide;
Graphite oxide and deionized water consumption, in graphite oxide: deionized water is that the ratio of 1g:500mL calculates; Described graphite oxide is standby by the Hummers legal system improved;
(2), the graphene oxide of 500mg step (1) gained is joined in 100mL solvent, supersound process 1h under 100W, 40KHz, obtain the dispersion liquid that concentration is 5mg/mL graphene oxide;
Described solvent is deionized water and ethanol is mixing solutions that 1:1 forms by volume;
(3), aperture is adopted to be the cellulose mixture millipore filtration vacuum filtration of 0.45 μm the dispersion liquid of the graphene oxide of 20mL step (2) gained, after the filter cake obtained is 80 DEG C of dry 24h together with filter membrane control temperature, peeled off from filter membrane by filter cake and obtain graphene oxide film, its thickness is 55 μm;
(4), the graphene oxide film of step (3) gained is folded between ganoid superalloy mould, be placed in tube furnace, oil press is adopted to apply the pressure of 0MPa, in nitrogen atmosphere, with the temperature rise rate of 4 DEG C/min, be warming up to 1000 DEG C, system is from boosting to 40MPa, after insulation 2h, naturally cool to room temperature, obtain the redox graphene heat conduction film that thickness is 15 μm.
After measured, the apparent density of the redox graphene heat conduction film of above-mentioned gained is 1.94g/cm
3, thermal diffusivity is 1890mm
2/ s, specific heat capacity is 0.719J/gK, and thermal conductivity is 2636W/mK.
embodiment 5
A preparation method for redox graphene heat conduction film, specifically comprises the steps:
(1), by graphite oxide join in deionized water, ultrasonic 1h under 80W, 40KHz, to the centrifugal 10min of suspension control 3000rpm of ultrasonic rear gained, get supernatant liquor and grind after 80 DEG C of dry 24h in vacuum drying oven, obtain graphene oxide;
Graphite oxide and deionized water consumption, in graphite oxide: deionized water is that the ratio of 1g:500mL calculates; Described graphite oxide is standby by the Hummers legal system improved;
(2), the graphene oxide of 400mg step (1) gained is joined in 200mL solvent, supersound process 1h under 100W, 40KHz, obtain the dispersion liquid that concentration is 2mg/mL graphene oxide;
Described solvent is deionized water and ethanol is mixing solutions that 1:1 forms by volume;
(3), aperture is adopted to be the cellulose mixture millipore filtration vacuum filtration of 0.45 μm the dispersion liquid of the graphene oxide of 40mL step (2) gained, after the filter cake obtained is 80 DEG C of dry 24h together with filter membrane control temperature, peeled off from filter membrane by filter cake and obtain graphene oxide film, its thickness is 42 μm;
(4), the graphene oxide film of step (3) gained is folded between ganoid superalloy mould, be placed in tube furnace, oil press is adopted to apply the pressure of 0MPa, in nitrogen atmosphere, with the temperature rise rate of 4 DEG C/min, be warming up to 600 DEG C, system is from boosting to 24MPa, after insulation 2h, naturally cool to room temperature, obtain the redox graphene heat conduction film that thickness is 18 μm;
After measured, the apparent density of the redox graphene heat conduction film of above-mentioned gained is 1.92g/cm
3, thermal diffusivity is 1298mm
2/ s, specific heat capacity is 0.726J/gK, and thermal conductivity is 1809W/mK.
embodiment 6
A preparation method for redox graphene heat conduction film, specifically comprises the steps:
(1), by graphite oxide join in deionized water, ultrasonic 10min under 80W, 40KHz, to the centrifugal 10min of suspension control 3000rpm of ultrasonic rear gained, get supernatant liquor and grind after 80 DEG C of dry 24h in vacuum drying oven, obtain graphene oxide;
Graphite oxide and deionized water consumption, in graphite oxide: deionized water is that the ratio of 1g:500mL calculates; Described graphite oxide is standby by the Hummers legal system improved;
(2), the graphene oxide of 400mg step (1) gained is joined in 200mL solvent, supersound process 1h under 100W, 40KHz, obtain the dispersion liquid that concentration is 2mg/mL graphene oxide;
Described solvent is deionized water and ethanol is mixing solutions that 1:1 forms by volume;
(3), aperture is adopted to be the cellulose mixture millipore filtration vacuum filtration of 0.45 μm the dispersion liquid of the graphene oxide of 40mL step (2) gained, after the filter cake obtained is 80 DEG C of dry 24h together with filter membrane control temperature, peeled off from filter membrane by filter cake and obtain graphene oxide film, its thickness is 42 μm;
(4), the graphene oxide film of step (3) gained is folded between ganoid superalloy mould, be placed in tube furnace, oil press is adopted to apply the pressure of 2.5MPa, in nitrogen atmosphere, with the temperature rise rate of 4 DEG C/min, be warming up to 600 DEG C, system is from boosting to 33MPa, after insulation 2h, naturally cool to room temperature, obtain the redox graphene heat conduction film that thickness is 16 μm;
After measured, the apparent density of the redox graphene heat conduction film of above-mentioned gained is 1.93g/cm
3, thermal diffusivity is 1323mm
2/ s, specific heat capacity is 0.726J/gK, and thermal conductivity is 1854W/mK.
In sum, the thickness of the redox graphene heat conduction film of preparation method's gained of a kind of redox graphene heat conduction film of the present invention is 5-18 μm, and apparent density is 1.92-1.96g/cm
3, thermal diffusivity is 1280-1890mm
2/ s, specific heat capacity is 0.719-0.726J/gK, and thermal conductivity is 1784-2636W/mK, and its preparation technology is simple, is easy to suitability for industrialized production, has potential actual application value in heat dissipation from microelectronic devices field.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement, these improvement also should be considered as protection scope of the present invention.
Claims (5)
1. a preparation method for redox graphene heat conduction film, is characterized in that specifically comprising the steps:
(1), by graphite oxide join in deionized water, ultrasonic 10min-1h, to the centrifugal 5-20min of suspension control 2000-3000rpm of ultrasonic rear gained, get supernatant liquor, after drying, grinding, obtain graphene oxide;
Graphite oxide and deionized water consumption, in graphite oxide: deionized water is that the ratio of 1g:500-1000mL calculates;
(2), the graphene oxide of step (1) gained is joined in solvent, supersound process 0.5-1.5h, obtain the dispersion liquid that concentration is 1-5mg/mL graphene oxide;
Described solvent is the mixing solutions that deionized water, ethanol or deionized water and ethanol form;
(3), by the dispersion liquid of the graphene oxide of step (2) gained adopt millipore filtration vacuum filtration, the filter cake obtained together with filter membrane control temperature be 60-100 DEG C carry out drying after, filter cake is peeled off from filter membrane and obtains graphene oxide film;
(4), the graphene oxide film of step (3) gained is folded between ganoid superalloy mould, be placed in tube furnace, oil press is adopted to apply the pressure of 0-10MPa, adopt in any one atmosphere in nitrogen, argon gas and helium, with the temperature rise rate of 1-5 DEG C/min, be warming up to 600-1000 DEG C, under the thermal expansion effects of superalloy, system is from boosting to 20-40MPa, after insulation 2-8h, then naturally cool to room temperature, obtain redox graphene heat conduction film.
2. the preparation method of redox graphene heat conduction film as claimed in claim 1, it is characterized in that the graphite oxide described in step (1) is standby by the Hummers legal system improved, concrete steps are as follows:
Measure the 96mL vitriol oil and be placed in drying receptacle, 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 1.5h, whole process adopts ice bath to make system remain on 0-5 DEG C, then temperature rises to 35 DEG C of reaction 2.5h, then in reaction system, slowly adds 80mL deionized water, reaction 10min, slowly add 200mL deionized water more afterwards, add 10mL H more subsequently
2o
2, continue reaction 10min, the reaction solution suction filtration of gained, gained filter cake 800mL mass percent concentration is the HCl solution washing of 5%, to go out metal ion, then with deionized water wash until the pH of effluent liquid is neutral, then control temperature is 120 DEG C of dryings, obtains graphite oxide.
3. the preparation method of redox graphene heat conduction film as claimed in claim 1, is characterized in that the pressure described in step (4) is 0-7.5MPa.
4. the preparation method of redox graphene heat conduction film as claimed in claim 1, is characterized in that the pressure described in step (4) is 2.5-7.5Mpa.
5. the preparation method of redox graphene heat conduction film as claimed in claim 1, it is characterized in that the mixing solutions that the deionized water described in step (2) and ethanol form, wherein deionized water and ethanol are 1:1 by volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510139841.5A CN104743551B (en) | 2015-03-27 | 2015-03-27 | A kind of preparation method of redox graphene heat conduction thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510139841.5A CN104743551B (en) | 2015-03-27 | 2015-03-27 | A kind of preparation method of redox graphene heat conduction thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104743551A true CN104743551A (en) | 2015-07-01 |
| CN104743551B CN104743551B (en) | 2017-03-01 |
Family
ID=53583925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510139841.5A Expired - Fee Related CN104743551B (en) | 2015-03-27 | 2015-03-27 | A kind of preparation method of redox graphene heat conduction thin film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104743551B (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038222A (en) * | 2015-08-11 | 2015-11-11 | 河南科技大学 | Graphene/PEI (polyethyleneimine) gas barrier composite membrane and preparing method of graphene/PEI gas barrier composite membrane |
| CN105254302A (en) * | 2015-10-12 | 2016-01-20 | 上海应用技术学院 | Preparing method for graphene heat conduction sheet |
| CN105914429A (en) * | 2016-04-21 | 2016-08-31 | 中国第汽车股份有限公司 | Flexible heat conductive film based on functional group graphene reduction and preparation method of same |
| CN106938845A (en) * | 2017-03-10 | 2017-07-11 | 华南理工大学 | A kind of graphite oxide positive electrode and preparation method for lithium ion battery, the preparation method of lithium ion cell positive |
| CN108910863A (en) * | 2018-06-26 | 2018-11-30 | 中科钢研节能科技有限公司 | A kind of intelligence graphene heat conducting film and preparation method thereof |
| CN109455708A (en) * | 2018-12-12 | 2019-03-12 | 中国科学院新疆理化技术研究所 | A kind of preparation method of super-hydrophobic three-dimensional grapheme film |
| CN109467078A (en) * | 2017-09-07 | 2019-03-15 | 常州富烯科技股份有限公司 | Graphene heat conducting film and preparation method thereof, production equipment |
| CN109585185A (en) * | 2018-11-16 | 2019-04-05 | 郑州轻工业学院 | The confinement the preparation method and its stored energy application of a kind of nitrogen, sulphur codope graphene film |
| CN109694055A (en) * | 2018-12-28 | 2019-04-30 | 常州富烯科技股份有限公司 | High-density graphite alkene foam film and preparation method thereof |
| CN109755027A (en) * | 2019-01-10 | 2019-05-14 | 中国科学院金属研究所 | Composite graphite alkene film, high-energy ultracapacitor and intelligent flexible device |
| CN109860577A (en) * | 2019-03-07 | 2019-06-07 | 上海电气集团股份有限公司 | A kind of carbon/ferriferous oxide composite and flexible electrode material and preparation method thereof |
| CN109913185A (en) * | 2019-03-11 | 2019-06-21 | 中国科学院合肥物质科学研究院 | A kind of multilayered structure heat-conductive composite material and preparation method thereof containing heat conducting film |
| CN110204214A (en) * | 2019-06-13 | 2019-09-06 | 浙江吉利控股集团有限公司 | A kind of preparation method of graphene-based film |
| CN110255538A (en) * | 2019-06-26 | 2019-09-20 | 东旭光电科技股份有限公司 | A kind of preparation method of graphene cooling fin |
| CN111003706A (en) * | 2019-11-25 | 2020-04-14 | 苏州盈顺绝缘材料有限公司 | Preparation method of graphene heat conduction and dissipation material |
| CN112645683A (en) * | 2020-12-24 | 2021-04-13 | 广东工业大学 | Processing device and method for graphene film with thermal control function |
| CN113759145A (en) * | 2021-09-08 | 2021-12-07 | 华东师范大学 | Thermal type wind speed and wind direction sensor and preparation method of graphene film |
| CN113896190A (en) * | 2021-11-08 | 2022-01-07 | 中国人民解放军国防科技大学 | Nitrogen-doped pre-reduced graphene oxide film and preparation method and application thereof |
| CN113929074A (en) * | 2021-10-30 | 2022-01-14 | 华为技术有限公司 | Carbon material and application thereof |
| CN114411080A (en) * | 2021-12-29 | 2022-04-29 | 钢铁研究总院 | Thermal protection composite coating and manufacturing method thereof |
| CN115784706A (en) * | 2022-11-21 | 2023-03-14 | 中国电子科技集团公司第十八研究所 | Self-supporting reduced graphene oxide film, lithium-free negative current collector and application thereof |
| CN116216701A (en) * | 2023-03-06 | 2023-06-06 | 大连交通大学 | Method for preparing graphene oxide film with high reduction rate in situ |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145124A (en) * | 2013-03-27 | 2013-06-12 | 北京大学 | High-performance graphene paper and preparation method thereof |
| CN104030275A (en) * | 2014-05-30 | 2014-09-10 | 上海应用技术学院 | Preparation method of reduction graphene oxide heat-conducting film |
-
2015
- 2015-03-27 CN CN201510139841.5A patent/CN104743551B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145124A (en) * | 2013-03-27 | 2013-06-12 | 北京大学 | High-performance graphene paper and preparation method thereof |
| CN104030275A (en) * | 2014-05-30 | 2014-09-10 | 上海应用技术学院 | Preparation method of reduction graphene oxide heat-conducting film |
Non-Patent Citations (1)
| Title |
|---|
| FEI LIU ET AL.: "folded structured graphene paper for high performance electrode materials", 《ADVANCED MATERIALS》 * |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038222A (en) * | 2015-08-11 | 2015-11-11 | 河南科技大学 | Graphene/PEI (polyethyleneimine) gas barrier composite membrane and preparing method of graphene/PEI gas barrier composite membrane |
| CN105254302A (en) * | 2015-10-12 | 2016-01-20 | 上海应用技术学院 | Preparing method for graphene heat conduction sheet |
| CN105254302B (en) * | 2015-10-12 | 2017-05-03 | 上海应用技术学院 | Preparing method for graphene heat conduction sheet |
| CN105914429A (en) * | 2016-04-21 | 2016-08-31 | 中国第汽车股份有限公司 | Flexible heat conductive film based on functional group graphene reduction and preparation method of same |
| CN105914429B (en) * | 2016-04-21 | 2018-10-23 | 中国第一汽车股份有限公司 | A kind of flexible heat conducting film and preparation method based on functional group's graphene reduction |
| CN106938845A (en) * | 2017-03-10 | 2017-07-11 | 华南理工大学 | A kind of graphite oxide positive electrode and preparation method for lithium ion battery, the preparation method of lithium ion cell positive |
| CN109467078A (en) * | 2017-09-07 | 2019-03-15 | 常州富烯科技股份有限公司 | Graphene heat conducting film and preparation method thereof, production equipment |
| CN108910863A (en) * | 2018-06-26 | 2018-11-30 | 中科钢研节能科技有限公司 | A kind of intelligence graphene heat conducting film and preparation method thereof |
| CN108910863B (en) * | 2018-06-26 | 2020-05-15 | 中科钢研节能科技有限公司 | Graphene heat-conducting film and preparation method thereof |
| CN109585185A (en) * | 2018-11-16 | 2019-04-05 | 郑州轻工业学院 | The confinement the preparation method and its stored energy application of a kind of nitrogen, sulphur codope graphene film |
| CN109455708A (en) * | 2018-12-12 | 2019-03-12 | 中国科学院新疆理化技术研究所 | A kind of preparation method of super-hydrophobic three-dimensional grapheme film |
| CN109694055B (en) * | 2018-12-28 | 2021-12-03 | 常州富烯科技股份有限公司 | High-density graphene foam film and preparation method thereof |
| CN109694055A (en) * | 2018-12-28 | 2019-04-30 | 常州富烯科技股份有限公司 | High-density graphite alkene foam film and preparation method thereof |
| CN109755027A (en) * | 2019-01-10 | 2019-05-14 | 中国科学院金属研究所 | Composite graphite alkene film, high-energy ultracapacitor and intelligent flexible device |
| CN109755027B (en) * | 2019-01-10 | 2021-01-19 | 中国科学院金属研究所 | Composite graphene film, high-energy supercapacitor and intelligent flexible device |
| CN109860577A (en) * | 2019-03-07 | 2019-06-07 | 上海电气集团股份有限公司 | A kind of carbon/ferriferous oxide composite and flexible electrode material and preparation method thereof |
| CN109913185A (en) * | 2019-03-11 | 2019-06-21 | 中国科学院合肥物质科学研究院 | A kind of multilayered structure heat-conductive composite material and preparation method thereof containing heat conducting film |
| CN110204214A (en) * | 2019-06-13 | 2019-09-06 | 浙江吉利控股集团有限公司 | A kind of preparation method of graphene-based film |
| CN110255538A (en) * | 2019-06-26 | 2019-09-20 | 东旭光电科技股份有限公司 | A kind of preparation method of graphene cooling fin |
| CN111003706A (en) * | 2019-11-25 | 2020-04-14 | 苏州盈顺绝缘材料有限公司 | Preparation method of graphene heat conduction and dissipation material |
| CN112645683B (en) * | 2020-12-24 | 2021-07-27 | 广东工业大学 | Processing method of graphene film with thermal control function |
| CN112645683A (en) * | 2020-12-24 | 2021-04-13 | 广东工业大学 | Processing device and method for graphene film with thermal control function |
| US11331689B1 (en) | 2020-12-24 | 2022-05-17 | Guangdong University Of Technology | Method for producing graphene film with thermal management function |
| CN113759145A (en) * | 2021-09-08 | 2021-12-07 | 华东师范大学 | Thermal type wind speed and wind direction sensor and preparation method of graphene film |
| CN113929074A (en) * | 2021-10-30 | 2022-01-14 | 华为技术有限公司 | Carbon material and application thereof |
| CN113929074B (en) * | 2021-10-30 | 2022-08-23 | 华为技术有限公司 | Carbon material and application thereof |
| CN113896190A (en) * | 2021-11-08 | 2022-01-07 | 中国人民解放军国防科技大学 | Nitrogen-doped pre-reduced graphene oxide film and preparation method and application thereof |
| CN113896190B (en) * | 2021-11-08 | 2022-11-25 | 中国人民解放军国防科技大学 | Nitrogen-doped pre-reduced graphene oxide film and preparation method and application thereof |
| CN114411080A (en) * | 2021-12-29 | 2022-04-29 | 钢铁研究总院 | Thermal protection composite coating and manufacturing method thereof |
| CN114411080B (en) * | 2021-12-29 | 2022-11-11 | 钢铁研究总院 | Thermal protection composite coating and manufacturing method thereof |
| CN115784706A (en) * | 2022-11-21 | 2023-03-14 | 中国电子科技集团公司第十八研究所 | Self-supporting reduced graphene oxide film, lithium-free negative current collector and application thereof |
| CN116216701A (en) * | 2023-03-06 | 2023-06-06 | 大连交通大学 | Method for preparing graphene oxide film with high reduction rate in situ |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104743551B (en) | 2017-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104743551A (en) | Method for preparing reduced graphene oxide heat conductive film | |
| Chen et al. | 2D sandwich-like carbon-coated ultrathin TiO2@ defect-rich MoS2 hybrid nanosheets: Synergistic-effect-promoted electrochemical performance for lithium ion batteries | |
| CN104916826B (en) | A kind of graphene coated silicium cathode material and preparation method thereof | |
| Zhao et al. | Porous MXene monoliths with locally laminated structure for enhanced pseudo-capacitance and fast sodium-ion storage | |
| Zhao et al. | In-situ generated nano-Fe3C embedded into nitrogen-doped carbon for high performance anode in lithium ion battery | |
| Zhou et al. | Microwave-assisted synthesis of hollow CuO–Cu2O nanosphere/graphene composite as anode for lithium-ion battery | |
| Li et al. | Scalable synthesis of a novel structured graphite/silicon/pyrolyzed-carbon composite as anode material for high-performance lithium-ion batteries | |
| Wang et al. | Achieving high-rate capacitance of multi-layer titanium carbide (MXene) by liquid-phase exfoliation through Li-intercalation | |
| Ma et al. | Superior cycle stability of nitrogen-doped graphene nanosheets for Na-ion batteries | |
| CN104876213A (en) | Graphene material and preparation method of electrode material of graphene material | |
| Bai et al. | Supercapacitor performance of 3D-graphene/MnO2 foam synthesized via the combination of chemical vapor deposition with hydrothermal method | |
| Shi et al. | One-pot solvothermal synthesis of ZnFe2O4 nanospheres/graphene composites with improved lithium-storage performance | |
| CN106783230A (en) | A kind of titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof | |
| CN105254302A (en) | Preparing method for graphene heat conduction sheet | |
| Liu et al. | Synthesis of MnO2-graphene composites with enhanced supercapacitive performance via pulse electrodeposition under supergravity field | |
| Ren et al. | Γ-MnS/reduced graphene oxide nanocomposites with great lithium storage capacity | |
| Yang et al. | In situ synthesis of Mn3O4 on Ni foam/graphene substrate as a newly self-supported electrode for high supercapacitive performance | |
| CN106384807A (en) | Lithium ion battery positive electrode plate and preparation method thereof | |
| CN107275114B (en) | A kind of preparation method of graphene composite film | |
| Peng et al. | Propelling electrochemical kinetics of transition metal oxide for high-rate lithium-ion battery through in situ deoxidation | |
| Du et al. | Interconnected sandwich structure carbon/Si-SiO2/carbon nanospheres composite as high performance anode material for lithium-ion batteries | |
| Chai et al. | Ultrahigh photothermal temperature in a graphene/conducting polymer system enables contact thermochemical reaction | |
| Li et al. | Controlled synthesis of Ni (OH) 2/graphene composites and their transformation to NiO/graphene for energy storage | |
| Xu et al. | Encapsulating iron oxide@ carbon in carbon nanofibers as stable electric conductive network for lithium-ion batteries | |
| Wang et al. | Controlled synthesis of three-dimensional interconnected graphene-like nanosheets from graphite microspheres as high-performance anodes for lithium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170301 Termination date: 20200327 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |