CN104743551B - A kind of preparation method of redox graphene heat conduction thin film - Google Patents
A kind of preparation method of redox graphene heat conduction thin film Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of redox graphene heat conduction thin film, will be added to ultrasonic in deionized water by graphite oxide, gained suspension controls 2000 3000rpm to be centrifuged 5 20min, takes supernatant, be dried, grind after graphene oxide；Gained graphene oxide is added to supersound process in solvent, obtain the dispersion liquid that concentration is 1 5mg/mL graphene oxide and adopt microporous filter membrane vacuum filtration, after gained filter cake is dried together with filter membrane, filter cake is peeled off from filter membrane the pressure that the graphene oxide film obtaining applies 0 10MPa, in nitrogen, under argon or helium atmosphere, 600 1000 DEG C of process 2 8h, obtain final product thermal conductivity high, reducing degree is higher, graphene sheet layer degree of orientation along along face is high, smooth surface and pliability is good, can significantly crimp and not rupture, the redox graphene heat conduction thin film that interlamellar spacing is obviously reduced.Its preparation method simple it is easy to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of redox graphene heat conduction thin film, belong to material with carbon element field.
Background technology
Graphene is a kind of new material of the monolayer laminated structure being made up of carbon atom close-packed arrays, since be found with
Come, its special structure and excellent performance cause the extensive concern of material educational circles and community of physicists.Research table in recent years
Bright, Graphene has thermal conductivity in the face of superelevation, and its value is up to 4800-6000W/m K, is improving high power, integrated
The heat dissipation problem aspect of micro-/ nano device, has a good application prospect.Two-dimensional film based on graphene sheet layer NW-TFT
Its structural advantage can be given full play to, also can provide in thickness direction heat-insulated while radiating in piece aspect, be conducive to it in heat
Managerial application.How to prepare the good graphene film material of heat dispersion, be successfully applied to power device
It to be a technical barrier urgently to be resolved hurrily in field of radiating.The method preparing Graphene has a lot, wherein, peels off graphite oxide
Obtain graphene oxide again through reduction be a kind of method of large-scale production Graphene.And by graphene oxide/graphene solution
Preparing graphene film has a lot of methods, including spraying process, spin-coating method, vacuum filtration method, gas/liquid self-assembly method, Langmuir
Blodgett self-assembly method etc..Vacuum filtration method is to carry out layer under the flowing of solution using graphene oxide/graphene sheet layer
The method of layer NW-TFT film forming.When directly sucking filtration graphene solution prepares graphene film, because graphene oxide is reduced to stone
Reunion can be produced during black alkene, be difficult to form stable graphene dispersing solution it is more difficult to sucking filtration forms the thin film of flat smooth；
And because surface of graphene oxide contains a large amount of oxygen-containing functional groups, in Yi Shui, ethanol isopolarity solution, form stable dispersions,
Using the easy film forming of suction method, then oxidation graphene film can be prepared through reduction treatment.But using generally chemistry also
In former or high-temperature heat treatment reduction process, the integrity of graphene film is difficult to keep, though or thin film more regular, its pliability
Difference, it is unable to higher curvature curling, and space is many, density is low, in thin film, graphene sheet layer is low along the degree of orientation in face, leads to thin film
Thermal conductivity is low.
Content of the invention
The invention aims to being difficult to keep large area complete, soft after solving above-mentioned graphene oxide film reduction
Poor toughness, space are many, the low technical problem of graphene sheet layer degree of orientation along along face and a kind of redox graphene heat conduction is provided
The preparation method of thin film, the oxidation graphene film of described preparation method gained has that large area is complete, pliability is good,
The features such as space is few, graphene sheet layer degree of orientation along along face is high, thermal conductivity is high.
Technical scheme
A kind of preparation method of redox graphene heat conduction thin film, specifically includes following steps：
（1）, graphite oxide is added in deionized water, ultrasonic 10min-1h, the suspension of ultrasonic rear gained is controlled
2000-3000rpm is centrifuged 5-20min, takes supernatant, after drying, grinding, obtains graphene oxide；
Graphite oxide and deionized water consumption, by graphite oxide：Deionized water is 1g:The ratio of 500-1000mL calculates；
Described graphite oxide is prepared by improved Hummers method；
（2）, by step（1）The graphene oxide of gained is added in solvent, supersound process 0.5- under 100W, 40KHz
1.5h, preferably 1h, obtain the dispersion liquid that concentration is 1-5mg/mL graphene oxide；
Described solvent is deionized water, ethanol or deionized water and the mixed solution of ethanol composition；
（3）, by step（2）The dispersion liquid of the graphene oxide of gained adopts microporous filter membrane vacuum filtration, the filter cake obtaining
Controlling temperature together with filter membrane is 60-100 DEG C, after preferably 80 DEG C are dried, filter cake are peeled off from filter membrane and obtains oxygen
Graphite alkene thin film, its thickness is preferably 10-55 μm；
The cellulose mixture microporous filter membrane that described microporous filter membrane is 0.45 μm for aperture；
（4）, by step（3）The graphene oxide film of gained is folded between the high temperature alloy mould of smooth surface, puts
In tube furnace, in the atmosphere of nitrogen, argon or helium, apply the pressure of 0-7.5MPa using hydraulic press, simultaneously with 1-5
DEG C/heating rate of min, it is warming up to 600-1000 DEG C, system is from boosting to 20- under the thermal expansion effects of high temperature alloy
40MPa, is incubated 2-8h, then naturally cools to room temperature, obtain final product redox graphene heat conduction thin film.
Beneficial effects of the present invention
A kind of preparation method of redox graphene heat conduction thin film of the present invention is compared with prior art, due to being by oxygen
Graphite alkene thin film applies certain pressure in high temperature thermal reduction, therefore effectively overcomes hardly possible after graphene oxide film reduction
To keep, large area is complete, pliability is poor, space is many, the low technical problem of graphene sheet layer degree of orientation along along face.Graphite oxide
The redox graphene heat conduction thin film of gained is become by black and has the Lycoperdon polymorphum Vitt of metallic luster alkene thin film after carrying out reduction, and completely
Property preserved, smooth surface and pliability very well, can not rupture in curling by a relatively large margin.Reduction rear oxidation Graphene is thin
The interlamellar spacing of film is obviously reduced, and has that reducing degree is higher, graphene sheet layer is the features such as the degree of orientation is high along along face simultaneously.
Further, the reduction-oxidation graphite of the preparation method gained of a kind of redox graphene heat conduction thin film of the present invention
The thermal conductivity of alkene heat conduction thin film is higher, and its thermal conductivity is 1784-2636W/m K, has potential in heat dissipation from microelectronic devices field
Actual application value.
Further, the preparation method of a kind of redox graphene heat conduction thin film of the present invention, its preparation process is simple, easily
In industrialized production.
Brief description
The measuring principle schematic diagram of the degree of orientation in the face of Fig. 1, graphene oxide film and oxidation graphene film；
Fig. 2, embodiment 1 step（3）Gained graphene oxide film and step（4）Gained oxidation graphene film is horizontal
The SEM figure in section；
Fig. 3, embodiment 1 step（3）Gained graphene oxide film and step（4）Gained oxidation graphene film
XRD spectrum；
Fig. 4, embodiment 1 step（3）Gained graphene oxide film and step（4）Gained oxidation graphene film
The degree of orientation in face；
Fig. 5, embodiment 1 step（3）Gained graphene oxide film and step（4）Gained oxidation graphene film
X-ray photoelectron energy spectrum diagram.
Specific embodiment
Below by embodiment and combine accompanying drawing the present invention is further elaborated, but it is not intended to limit the present invention.
Scanning electron 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 gives birth to
Produce.
The pole figure of sample by the multi-functional texture testing board being arranged on D/max2200PC type X-ray diffractometer,
Using Schulz bounce technique, reflective observing is made to (002) crystal face of different samples.
The mensure of the degree of orientation in the face of graphene oxide film and oxidation graphene film in embodiments of the invention,
Sample is needed to rotate in three dimensions, as shown in figure 1, wherein α is sample deflection angle, β is sample to test philosophy schematic diagram
Rotation angle, α=0-70 °, β=0-360 °, sample rotational velocity is 10 °/min.First pass through prescan and measure different samples not
With the accurate Bragg angle of crystal face, then three-dimensional rotation is carried out to sample, the crystal face meeting Bragg angle in rotary course can be sent out
Raw diffraction, the intensity distributions of diffraction maximum can characterize the orientation of this crystal face of sample.
In embodiments of the invention, graphene oxide film and the Electronic Structure of oxidation graphene film are analyzed
Using PHI 5000 VersaProbe type x-ray photoelectron spectroscopy, excitation of X-rays source is Al K α (1486.6 eV), very
Reciprocal of duty cycle 2 × 10-9Pa, using sample surfaces carbon C1s electron binding energy 284.6 eV as internal standard.
Thermal diffusion coefficient in graphene oxide film and oxidation graphene film plane in embodiments of the invention
(α,mm2/ s) tested using the LFA447 Flicker method heat transfer analysis instrument of German Nai Chi company, apparent density (ρ, g/cm3) by thin film
Quality calculates divided by volume, the specific heat capacity (C of samplep, J/gK) recorded by TA Q2000 type differential scanning calorimetry instrument, thermal conductivity
Rate (λ, W/mK) is by λ=α × ρ × CpCalculate.
Improved Hummers method prepares graphite oxide, comprises the following steps that：
Measure 96mL concentrated sulphuric acid to be placed in drying receptacle, be added thereto to 2g sodium nitrate, after stirring makes sodium nitrate dissolve, then
Add 2g crystalline flake graphite, after crystalline flake graphite is uniformly dispersed, be slowly added to 12g potassium permanganate, react 1.5h, whole process adopts
Ice bath makes system be maintained at 0-5 DEG C, and then temperature rises to 35 DEG C of reaction 2.5h, is then slowly added to 80mL in reaction system and goes
Ionized water, reacts 10min, is slowly added into 200mL deionized water afterwards again, subsequently adds 10mL H2O2, continue reaction
10min, the reactant liquor sucking filtration of gained, the HCl/water solution that gained filter cake is 5% with 800mL mass percent concentration washs, to go out
Remove metal ion, be then washed with deionized until the pH of effluent is neutrality, then control temperature to be 120 DEG C of dryings, that is,
Obtain graphite oxide.
Embodiment 1
A kind of preparation method of redox graphene heat conduction thin film, specifically includes following steps：
（1）, graphite oxide is added in deionized water, ultrasonic 10min under 80W, 40KHz, ultrasonic rear gained is hanged
Supernatant liquid controls 3000rpm centrifugation 5min, take supernatant in the vacuum drying oven 80 DEG C 24h is dried after grind, obtain graphite oxide
Alkene；
Graphite oxide and deionized water consumption, by graphite oxide：Deionized water is 1g:The ratio of 500mL calculates；Described
Graphite oxide is prepared by improved Hummers method；
（2）, by 400mg step（1）The graphene oxide of gained is added in 200mL solvent, ultrasonic under 100W, 40KHz
Process 1h, obtain the dispersion liquid that concentration is 2mg/mL graphene oxide；
Described solvent is deionized water is 1 with ethanol by volume:The mixed solution of 1 composition；
（3）, by 30mL step（2）The cellulose mixture that the dispersion liquid of the graphene oxide of gained is 0.45 μm using aperture
Microporous filter membrane vacuum filtration, the filter cake obtaining controls temperature to be 80 DEG C together with filter membrane to be dried after 24h, by filter cake from filter membrane
Stripping obtains graphene oxide film, and its thickness is 31 μm；
（4）, by step（3）The graphene oxide film of gained is folded between the high temperature alloy mould of smooth surface, puts
In tube furnace, apply the pressure of 7.5MPa using hydraulic press, in nitrogen atmosphere, with the heating rate of 4 DEG C/min, be warming up to
600 DEG C, system, from boosting to 35MPa, after insulation 2h, naturally cools to room temperature, that is, obtains redox graphene heat conduction thin film；
The redox graphene heat conduction thin film of gained is become by black and has gold above-mentioned graphene oxide film after carrying out reduction
Belong to the Lycoperdon polymorphum Vitt of gloss, and integrity preserved, smooth surface and pliability very well, can curling by a relatively large margin continuous
Split.
The SEM figure of above-mentioned graphene oxide film and redox graphene heat conduction thin film cross section is as shown in Fig. 2 Fig. 2
Middle a is graphene oxide film, and b is redox graphene heat conduction thin film, as can be drawn from Figure 2, graphene oxide heat conduction
The thickness of thin film is 31 μm about, and the thickness of oxidation graphene film is obviously reduced, and is 14 μm about.
The XRD spectrum of the graphene oxide film of above-mentioned gained and redox graphene heat conduction thin film as shown in Figure 3, is schemed
In 3, a is graphene oxide film, and b is redox graphene heat conduction thin film, as can be drawn from Figure 3, graphene oxide heat conduction
Thin film is 10.6oDiffraction maximum occurs, after reduction, the diffraction maximum of the redox graphene heat conduction thin film of gained moves on to 26.4o, explanation
The interlamellar spacing of reduction rear oxidation graphene film is obviously reduced.
The degree of orientation of graphene sheet layer in the graphene oxide film of above-mentioned gained and redox graphene heat conduction thin film
As shown in Figure 4, as can be drawn from Figure 4, graphene oxide film deflection angle accounts for 56% about, within 30 ° within 10 °
Account for 95% about；And oxidation graphene film deflection angle accounts for 59% about within 10 °, within 30 ° to account for 98% left
The right side, compared with graphene oxide film, the degree of orientation significantly improves, and the redox graphene being indicated above gained of the present invention is thin
Film has the characteristics that graphene sheet layer degree of orientation along along face is high.
The x-ray photoelectron energy spectrum diagram of the graphene oxide film of above-mentioned gained and redox graphene heat conduction thin film is shown in
Shown in Fig. 5, in Fig. 5, a is graphene oxide film, and b is redox graphene heat conduction thin film, as can be drawn from Figure 5, oxidation
The carbon oxygen atom ratio on graphene film surface（C/O）For 2.45, the carbon of the redox graphene heat conduction thin film of gained after reduction
Oxygen atom ratio（C/O）Bring up to 11.0, the oxidation graphene film being indicated above gained of the present invention has reducing degree
Higher feature.
After tested, the apparent density of the redox graphene heat conduction thin film of above-mentioned gained is 1.96g/cm3, thermal diffusion system
Number is 1703mm2/ s, specific heat capacity is 0.726J/g K, and thermal conductivity is 2423W/m K.
Embodiment 2
A kind of preparation method of redox graphene heat conduction thin film, specifically includes following steps：
（1）, graphite oxide is added in deionized water, ultrasonic 30min（80W, 40KHz）, ultrasonic rear gained is hanged
Supernatant liquid controls 2500rpm centrifugation 10min, take supernatant in the vacuum drying oven 80 DEG C 24h is dried after grind, obtain graphite oxide
Alkene；
Graphite oxide and deionized water consumption, by graphite oxide：Deionized water is 1g:The ratio of 800mL calculates；Described
Graphite oxide is prepared by improved Hummers method；
（2）, by 200mg step（1）The graphene oxide of gained is added in 200mL solvent, supersound process 1h (100W,
40KHz), obtain the dispersion liquid that concentration is 1mg/mL graphene oxide；
Described solvent is deionized water is 1 with ethanol by volume:The mixed solution of 1 composition；
（3）, by 20mL step（2）The cellulose mixture that the dispersion liquid of the graphene oxide of gained is 0.45 μm using aperture
Microporous filter membrane vacuum filtration, the filter cake obtaining controls temperature to be 80 DEG C together with filter membrane to be dried after 24h, by filter cake from filter membrane
Stripping obtains graphene oxide film, and its thickness is 12 μm；
（4）, by step（3）The graphene oxide film of gained is folded between the high temperature alloy mould of smooth surface, puts
In tube furnace, apply the pressure of 0MPa using hydraulic press, in nitrogen atmosphere, with the heating rate of 4 DEG C/min, be warming up to
600 DEG C, system, from boosting to 24MPa, after insulation 2h, naturally cools to room temperature, obtains final product the redox graphene that thickness is 5 μm
Heat conduction thin film；
After tested, the apparent density of the redox graphene heat conduction thin film of above-mentioned gained is 1.92g/cm3, thermal diffusion system
Number is 1280mm2/ s, specific heat capacity is 0.726J/g K, and thermal conductivity is 1784W/m K.
Embodiment 3
A kind of preparation method of redox graphene heat conduction thin film, specifically includes following steps：
（1）, graphite oxide is added in deionized water, ultrasonic 10min under 80W, 40KHz, ultrasonic rear gained is hanged
Supernatant liquid controls 2000rpm centrifugation 20min, take supernatant in the vacuum drying oven 80 DEG C 24h is dried after grind, obtain graphite oxide
Alkene；
Graphite oxide and deionized water consumption, by graphite oxide：Deionized water is 1g:The ratio of 1000mL calculates；Described
Graphite oxide prepared by improved Hummers method；；
（2）, by 400mg step（1）The graphene oxide of gained is added in 200mL solvent, ultrasonic under 100W, 40KHz
Process 1h, obtain the dispersion liquid that concentration is 2mg/mL graphene oxide；
Described solvent is deionized water is 1 with ethanol by volume:The mixed solution of 1 composition；
（3）, by 40mL step（2）The cellulose mixture that the dispersion liquid of the graphene oxide of gained is 0.45 μm using aperture
Microporous filter membrane vacuum filtration, the filter cake obtaining controls temperature to be 80 DEG C together with filter membrane to be dried after 24h, by filter cake from filter membrane
Stripping obtains graphene oxide film, and its thickness is 42 μm；
（4）, by step（3）The graphene oxide heat conduction thin film of gained be folded in smooth surface high temperature alloy mould it
Between, it is placed in tube furnace, applies the pressure of 5MPa using hydraulic press, in nitrogen atmosphere, with the heating rate of 4 DEG C/min, rise
To 600 DEG C, system, from boosting to 34MPa, after insulation 2h, naturally cools to room temperature, obtains final product the reduction-oxidation that thickness is 17 μm temperature
Graphene heat conduction thin film；
After measured, the apparent density of the redox graphene heat conduction thin film of above-mentioned gained is 1.95g/cm3, thermal diffusion system
Number is 1476mm2/ s, specific heat capacity is 0.726J/g K, and thermal conductivity is 2089W/m K.
Embodiment 4
A kind of preparation method of redox graphene heat conduction thin film, specifically includes following steps：
（1）, graphite oxide is added in deionized water, ultrasonic 10min under 80W, 40KHz, ultrasonic rear gained is hanged
Supernatant liquid controls 3000rpm centrifugation 10min, take supernatant in the vacuum drying oven 80 DEG C 24h is dried after grind, obtain graphite oxide
Alkene；
Graphite oxide and deionized water consumption, by graphite oxide：Deionized water is 1g:The ratio of 500mL calculates；Described
Graphite oxide is prepared by improved Hummers method；
（2）, by 500mg step（1）The graphene oxide of gained is added in 100mL solvent, ultrasonic under 100W, 40KHz
Process 1h, obtain the dispersion liquid that concentration is 5mg/mL graphene oxide；
Described solvent is deionized water is 1 with ethanol by volume:The mixed solution of 1 composition；
（3）, by 20mL step（2）The cellulose mixture that the dispersion liquid of the graphene oxide of gained is 0.45 μm using aperture
Microporous filter membrane vacuum filtration, the filter cake obtaining controls temperature to be 80 DEG C together with filter membrane to be dried after 24h, by filter cake from filter membrane
Stripping obtains graphene oxide film, and its thickness is 55 μm；
（4）, by step（3）The graphene oxide film of gained is folded between the high temperature alloy mould of smooth surface, puts
In tube furnace, apply the pressure of 0MPa using hydraulic press, in nitrogen atmosphere, with the heating rate of 4 DEG C/min, be warming up to
1000 DEG C, system, from boosting to 40MPa, after insulation 2h, naturally cools to room temperature, obtains final product the reduction-oxidation graphite that thickness is 15 μm
Alkene heat conduction thin film.
After measured, the apparent density of the redox graphene heat conduction thin film of above-mentioned gained is 1.94g/cm3, thermal diffusion system
Number is 1890mm2/ s, specific heat capacity is 0.719J/g K, and thermal conductivity is 2636W/m K.
Embodiment 5
A kind of preparation method of redox graphene heat conduction thin film, specifically includes following steps：
（1）, graphite oxide is added in deionized water, ultrasonic 1h under 80W, 40KHz, the suspension to ultrasonic rear gained
Control 3000rpm centrifugation 10min, take supernatant in the vacuum drying oven 80 DEG C 24h is dried after grind, obtain graphene oxide；
Graphite oxide and deionized water consumption, by graphite oxide：Deionized water is 1g:The ratio of 500mL calculates；Described
Graphite oxide is prepared by improved Hummers method；
（2）, by 400mg step（1）The graphene oxide of gained is added in 200mL solvent, ultrasonic under 100W, 40KHz
Process 1h, obtain the dispersion liquid that concentration is 2mg/mL graphene oxide；
Described solvent is deionized water is 1 with ethanol by volume:The mixed solution of 1 composition；
（3）, by 40mL step（2）The cellulose mixture that the dispersion liquid of the graphene oxide of gained is 0.45 μm using aperture
Microporous filter membrane vacuum filtration, the filter cake obtaining controls temperature to be 80 DEG C together with filter membrane to be dried after 24h, by filter cake from filter membrane
Stripping obtains graphene oxide film, and its thickness is 42 μm；
（4）, the graphene oxide film of step (3) gained is folded between the high temperature alloy mould of smooth surface, put
In tube furnace, apply the pressure of 0MPa using hydraulic press, in nitrogen atmosphere, with the heating rate of 4 DEG C/min, be warming up to
600 DEG C, system, from boosting to 24MPa, after insulation 2h, naturally cools to room temperature, obtains final product the reduction-oxidation graphite that thickness is 18 μm
Alkene heat conduction thin film；
After measured, the apparent density of the redox graphene heat conduction thin film of above-mentioned gained is 1.92g/cm3, thermal diffusion system
Number is 1298mm2/ s, specific heat capacity is 0.726J/g K, and thermal conductivity is 1809W/m K.
Embodiment 6
A kind of preparation method of redox graphene heat conduction thin film, specifically includes following steps：
（1）, graphite oxide is added in deionized water, ultrasonic 10min under 80W, 40KHz, ultrasonic rear gained is hanged
Supernatant liquid controls 3000rpm centrifugation 10min, take supernatant in the vacuum drying oven 80 DEG C 24h is dried after grind, obtain graphite oxide
Alkene；
Graphite oxide and deionized water consumption, by graphite oxide：Deionized water is 1g:The ratio of 500mL calculates；Described
Graphite oxide is prepared by improved Hummers method；
（2）, by 400mg step（1）The graphene oxide of gained is added in 200mL solvent, ultrasonic under 100W, 40KHz
Process 1h, obtain the dispersion liquid that concentration is 2mg/mL graphene oxide；
Described solvent is deionized water is 1 with ethanol by volume:The mixed solution of 1 composition；
（3）, by 40mL step（2）The cellulose mixture that the dispersion liquid of the graphene oxide of gained is 0.45 μm using aperture
Microporous filter membrane vacuum filtration, the filter cake obtaining controls temperature to be 80 DEG C together with filter membrane to be dried after 24h, by filter cake from filter membrane
Stripping obtains graphene oxide film, and its thickness is 42 μm；
（4）, the graphene oxide film of step (3) gained is folded between the high temperature alloy mould of smooth surface, put
In tube furnace, apply the pressure of 2.5MPa using hydraulic press, in nitrogen atmosphere, with the heating rate of 4 DEG C/min, be warming up to
600 DEG C, system, from boosting to 33MPa, after insulation 2h, naturally cools to room temperature, obtains final product the reduction-oxidation graphite that thickness is 16 μm
Alkene heat conduction thin film；
After measured, the apparent density of the redox graphene heat conduction thin film of above-mentioned gained is 1.93g/cm3, thermal diffusion system
Number is 1323mm2/ s, specific heat capacity is 0.726J/g K, and thermal conductivity is 1854W/m K.
In sum, the oxygen reduction fossil of the preparation method gained of a kind of redox graphene heat conduction thin film of the present invention
The thickness of black alkene heat conduction thin film is 5-18 μm, and apparent density is 1.92-1.96g/cm3, thermal diffusion coefficient is 1280-1890mm2/
S, specific heat capacity is 0.719-0.726J/g K, and thermal conductivity is 1784-2636W/m K, and its preparation process is simple is it is easy to industrialization
Produce, in heat dissipation from microelectronic devices field, there is potential actual application value.
The above is only the citing of embodiments of the present invention it is noted that ordinary skill for the art
For personnel, on the premise of without departing from the technology of the present invention principle, some improvement can also be made, these improvement also should be regarded as this
The protection domain of invention.
Claims (3)
1. a kind of preparation method of redox graphene heat conduction thin film is it is characterised in that specifically include following steps：
（1）, graphite oxide is added in deionized water, ultrasonic 10min-1h, 2000- is controlled to the suspension of ultrasonic rear gained
3000rpm is centrifuged 5-20min, takes supernatant, after drying, grinding, obtains graphene oxide；
Graphite oxide and deionized water consumption, by graphite oxide：Deionized water is 1g:The ratio of 500-1000mL calculates；
（2）, by step（1）The graphene oxide of gained is added in solvent, supersound process 0.5-1.5h, and obtaining concentration is 1-
The dispersion liquid of 5mg/mL graphene oxide；
Described solvent is deionized water, ethanol or deionized water and the mixed solution of ethanol composition；
（3）, by step（2）The dispersion liquid of the graphene oxide of gained adopt microporous filter membrane vacuum filtration, the filter cake obtaining together with
Filter membrane control together temperature be 60-100 DEG C be dried after, filter cake is peeled off from filter membrane and obtains graphene oxide film；
（4）, by step（3）The graphene oxide film of gained is folded between the high temperature alloy mould of smooth surface, is placed in pipe
In formula stove, apply the pressure of 2.5-7.5MPa using hydraulic press, using any one atmosphere in nitrogen, argon and helium
In, with the heating rate of 1-5 DEG C/min, it is warming up to 600-1000 DEG C, system is from boosting under the thermal expansion effects of high temperature alloy
To 20-40MPa, after being incubated 2-8h, then naturally cool to room temperature, obtain final product redox graphene heat conduction thin film.
2. the preparation method of redox graphene heat conduction thin film as claimed in claim 1 is it is characterised in that step（1）Middle institute
The graphite oxide stated is prepared by improved Hummers method, comprises the following steps that：
Measure 96mL concentrated sulphuric acid to be placed in drying receptacle, be added thereto to 2g sodium nitrate, after stirring makes sodium nitrate dissolve, add
2g crystalline flake graphite, after crystalline flake graphite is uniformly dispersed, is slowly added to 12g potassium permanganate, reacts 1.5h, whole process adopts ice bath
System is made to be maintained at 0-5 DEG C, then temperature rises to 35 DEG C of reaction 2.5h, is then slowly added to 80mL deionization in reaction system
Water, reacts 10min, is slowly added into 200mL deionized water afterwards again, subsequently adds 10mL H2O2, continue reaction 10min, institute
Reactant liquor sucking filtration, the HCl/water solution that gained filter cake is 5% with 800mL mass percent concentration washs, with go out metal from
Son, is then washed with deionized until the pH of effluent is neutrality, then controls temperature to be 120 DEG C of dryings, obtain final product oxidation stone
Ink.
3. the preparation method of redox graphene heat conduction thin film as claimed in claim 1 is it is characterised in that step（2）Middle institute
The mixed solution that the deionized water stated is formed with ethanol, wherein deionized water and ethanol are 1 by volume:1.
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| 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 |
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| CN103145124B (en) * | 2013-03-27 | 2015-01-14 | 北京大学 | High-performance graphene paper and preparation method thereof |
| CN104030275B (en) * | 2014-05-30 | 2016-08-24 | 上海应用技术学院 | A kind of preparation method of redox graphene heat conduction thin film |
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