CN103723717B - A kind of preparation method of nitrogen-doped graphene film - Google Patents
A kind of preparation method of nitrogen-doped graphene film Download PDFInfo
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- CN103723717B CN103723717B CN201410001619.4A CN201410001619A CN103723717B CN 103723717 B CN103723717 B CN 103723717B CN 201410001619 A CN201410001619 A CN 201410001619A CN 103723717 B CN103723717 B CN 103723717B
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Abstract
A kind of preparation method of nitrogen-doped graphene film hands over the graphite oxide aqueous solution to obtain the graphene oxide water-sol through supersound process; Hydrazine hydrate solution is mixed the mixing solutions of obtained hydrazine hydrate, second alcohol and water with ethanolic soln; 0.5 ~ 1.5h are reacted at 80 ~ 95 DEG C by after above-mentioned two solution mixing, then the solution for vacuum suction filtration processed is obtained the graphene film of N doping, through drying at room temperature, thermal anneal process 1 ~ 3h under vacuum, afterwards by it at ambient temperature, 0.5 ~ 2h. is pressed thus obtained high heat conduction nitrogen-doped graphene film with the pressure of 1000 ~ 4000Psi.The present invention has high heat conduction, advantage that mechanical property is good.
Description
Technical field
The present invention relates to a kind of preparation method of high heat conduction nitrogen-doped graphene film.
Background technology
In recent years along with the fast development of science and technology, the design of instrument, equipment is made more and more significantly to present feature that is light, thin, short, little and high efficiency.But simultaneously adjoint one important problem is that plant and instrument creates a large amount of heats in operational process, if these heats are got rid of not in time, will badly influence job stability and the safe reliability of electron device.Therefore the thin-film material developing a kind of high heat conduction is imperative.The more heat conduction thin-film material occurred in life and scientific research at present is then mainly nano graphite flakes paper; wherein according to existing reported in literature: in the largest face of stripping graphite nano plate paper, thermal conductivity is 178W/ (mK) [Xiang J, Drzal LT. Thermal conductivity of exfoliated graphite nanoplatelet paper. Carbon. 2011; 49 (3): 773-8.]; the maximum heat conductance of business-like stripping graphite products is 1500 W/ (mK) [Leng Y; Gu J; Cao W, Zhang T. Influences of density and flake size on the mechanical properties of flexible graphite. Carbon. 1998; 36:875-81.].Since producing Graphene first from the peace moral of University of Manchester in 2004 strong K sea nurse, Graphene is as a kind of novel two dimensional surface nano material, the monoatomic layer structure special because of it and the physicals of the novelty showed, make it all to show good application prospect in every field.Single-layer graphene thermal conductivity has at room temperature been recorded for (4.84 ± 0.44) × 10 at Alexander A. Balandin in 2008, Suchismita Ghosh etc.
3-(5.30 ± 0.48) × 10
3w/(m K).The method that current preparation has the graphene film of good conductive energy mainly comprises two kinds: (1) thermal reduction, but the obtained thin film material mechanics performance of this kind of method is extremely bad, easily present the performance of embrittlement, (2) chemical reduction, after chemical reduction, in graphene sheet layer, the content of contained oxygen element is still higher, can reduce raw-material conductive performance.If a kind of thin-film material of high heat conduction will be prepared as you know, need the reducing degree controlling Graphene on the one hand, also need to control its density on the other hand.Therefore a kind of new method has been invented by this seminar, first chemical reduction and thermal reduction is combined, improves its reducing degree; And then colded pressing, improve its density; Thus the obtained graphene film material with good conductive energy.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of high heat conduction, high heat conduction nitrogen-doped graphene laminated film that mechanical property is good.
In line with the aim improving Graphene composite thin film material thermal conductivity, its thermal diffusivity to be improved on the one hand, have employed the method that graphene oxide solution and hydrazine hydrate solution mixed mutually to reach redox graphene and to realize the object of N doping further; Its density to be improved on the other hand, have employed the later stage to its method of colding pressing to realize making stacking object more closely between its lamella.
Preparation method of the present invention, mainly comprises the following steps:
(1) configuration concentration is 2 ~ 6mg/mL graphite oxide aqueous solution, is 100 ~ 200W through power, and supersound process 0.5 ~ 1.5h obtains graphene oxide (GO) water-sol;
(2) ethanolic soln be hydrazine hydrate solution and the ethanol massfraction of 50-80% by hydrazine hydrate massfraction being 50% to dehydrated alcohol mixes, obtained concentration of hydrazine hydrate is 10 ~ 20mg/mL, and the concentration of ethanol is the mixing solutions of the hydrazine hydrate of 300mg/mL-700 mg/mL, second alcohol and water;
(3) R is designated as by the mass ratio of hydrazine hydrate and graphene oxide
hydrazine hydrate/ R
gO, by the solution mixing in (1) and (2), wherein R in gained mixing solutions
hydrazine hydrate/ R
gO=2.4 ~ 4.4
(4) mixing solutions prepared in step (3) is reacted 0.5 ~ 1.5h at 80 ~ 95 DEG C, then the solution for vacuum suction filtration processed is obtained the graphene film of N doping, through drying at room temperature;
(5) by the graphene film thermal anneal process 1 ~ 3h under vacuum of gained in step (4), afterwards by it at ambient temperature, 0.5 ~ 2h. is pressed thus obtained high heat conduction nitrogen-doped graphene film with the pressure of 1000 ~ 4000Psi.
Described graphite oxide can be prepared by Hummers method, Brodie method, Staudenmaier method or electrochemical oxidation process.
Graphite oxide can be selected prepared by Shanxi coal chemical research, also can select commercially available graphite oxide slurry or powder (wherein oxidized graphite flake layer size is 1-10 μm, and thickness is 0.7-1.5nm).
Described protective atmosphere is nitrogen, argon gas, helium, or vacuum protection.
Graphene film prepared by the present invention is a kind of brand-new functional materials, can conduct heat as one, dispel the heat, equal hot materials, for eliminating local pyrexia point, smoothed temperature gradient, it is lightweight, thickness is thin, good toughness, can with various gum and the good compound of insulation paper, and be die-cut to easily and variously need shape and size, thus well fit together with various metal, plastics.The fields such as smart mobile phone, panel computer, LED illumination device, intelligent television, pick up camera, digital camera, semiconductor manufacturing facility, vehicle electronics can be widely used in.
Beneficial effect of the present invention is:
The present invention can according to the demand to the different thermal conductivity of product, by controlling the mass ratio of hydrazine hydrate and GO, the two temperature of reaction, reaction times, vacuum treated temperature and time and the conditions such as institute's applied pressure of colding pressing, realize the control to its N doping ratio and density, thus control the size of its thermal conductivity.
Owing to being adopt multi-step to regulate and control it, so be more prone to realize to the regulation and control of its performance subtle change, simple to operate, energy-conservation, while, is also easy to industrially carry out amplification production.
Embodiment
Embodiment 1:
Be mixed in water by the graphite oxide standby by Hummers legal system, be made into the graphite oxide aqueous solution of 2mg/mL, then ultrasonic 1.5 hours, ultrasonic power was 100W, obtained graphene oxide water solution (being designated as solution 1).Then by massfraction be 80% hydrazine hydrate solution and massfraction be 70% ethanol mixes, obtain the ethanolic soln (concentration of hydrazine hydrate is 7.1mg/mL, and the concentration of ethanol is 700 mg/mL) (being designated as solution 2) of hydrazine hydrate.Then mixed with solution 2 by solution 1, wherein the mass ratio of hydrazine hydrate and graphene oxide is 2.4, reacts 1.5 hours, obtain the ethanolic soln of nitrogen-doped graphene in the environment of 95 DEG C.Vacuum filtration obtains the graphene film of N doping.At ambient temperature by the film drying of gained.Then 200 DEG C of vacuum heat treatment 3 hours.Afterwards gained film is colded pressing 2 hours under the pressure of 2000psi.The finally graphene film of the N doping of obtained high heat conduction.The thermal conductivity obtaining this film is as calculated 1503 W/(mK), tensile strength is 1.15MPa, and Young's modulus is 0.4GPa.
Embodiment 2:
Be mixed in water by the graphite oxide standby by Brodie legal system, be made into the graphite oxide aqueous solution of 3mg/mL, then ultrasonic 1.2 hours, ultrasonic power was 120W, obtained graphene oxide water solution (being designated as solution 1).Then through being that the hydrazine hydrate solution of 50% mixes with dehydrated alcohol by massfraction, the ethanol solution (concentration of hydrazine hydrate is 8.1mg/mL, and the concentration of ethanol is 750 mg/mL) (being designated as solution 2) of hydrazine hydrate is obtained.Then mixed with solution 2 by solution 1, wherein the mass ratio of hydrazine hydrate and graphene oxide is 2.9, reacts 1.2 hours, obtain the ethanolic soln of nitrogen-doped graphene in the environment of 93 DEG C.Vacuum filtration obtains the graphene film of N doping.At the film drying of room temperature by gained.Then 200 DEG C of vacuum heat treatment 2.5 hours.Afterwards gained film is colded pressing 1.5 hours under the pressure of 3000psi.The finally graphene film of the N doping of obtained high heat conduction.The thermal conductivity obtaining this film is as calculated 1650.31 W/(mK), tensile strength is 4.9MPa, and Young's modulus is 1.5GPa.
Embodiment 3:
Be mixed in water by graphite oxide standby for Staudenmaier legal system, be made into the graphite oxide aqueous solution of 4mg/mL, then ultrasonic 1 hour, ultrasonic power was 140W, obtained graphene oxide water solution (being designated as solution 1).Then through being that the ethanolic soln that hydrazine hydrate solution and the massfraction of 65% are 90% mixes by massfraction, the ethanolic soln (concentration of hydrazine hydrate is 9.1mg/mL, and the concentration of ethanol is 650 mg/mL) (being designated as solution 2) of hydrazine hydrate is obtained.Then mixed with solution 2 by solution 1, wherein the mass ratio of hydrazine hydrate and graphene oxide is 3.4, reacts 1 hour, obtain the ethanolic soln of nitrogen-doped graphene in the environment of 90 DEG C.Vacuum filtration obtains the graphene film of N doping.At the film drying of room temperature by gained.Then 200 DEG C of vacuum heat treatment 2 hours.Afterwards gained film is colded pressing 2 hours under the pressure of 3000psi.The finally graphene film of the N doping of obtained high heat conduction.The thermal conductivity obtaining this film is as calculated 4800W/(mK), tensile strength is 20.72MPa, and Young's modulus is 4.1GPa.
Embodiment 4:
Be mixed in water by the graphite oxide standby by Hummers legal system, be made into the graphite oxide aqueous solution of 5mg/mL, then ultrasonic 0.8 hour, ultrasonic power was 160W, obtained graphene oxide water solution (being designated as solution 1).Then through being that the hydrazine hydrate solution of 80% mixes with dehydrated alcohol by massfraction, the ethanol solution (concentration of hydrazine hydrate is 9.1mg/mL, and the concentration of ethanol is 750 mg/mL) (being designated as solution 2) of hydrazine hydrate is obtained.Then mixed with solution 2 by solution 1, wherein the mass ratio of hydrazine and graphene oxide is 3.9, reacts 1 hour, obtain the ethanolic soln of nitrogen-doped graphene in the environment of 85 DEG C.Vacuum filtration obtains the graphene film of N doping.At the film drying of room temperature by gained.Then thermal treatment 1.5 hours under 200 DEG C of argon gas atmosphere.Afterwards gained film is colded pressing 0.5 hour under the pressure of 2000psi.The finally graphene film of the N doping of obtained high heat conduction.The thermal conductivity obtaining this film is as calculated 1544.13W/(mK), tensile strength is 8.47MPa, and Young's modulus is 1.6GPa.
Embodiment 5:
Be mixed in water by the graphite oxide prepared by electrochemical oxidation process, be made into the graphite oxide aqueous solution of 6mg/mL, then ultrasonic 0.6 hour, ultrasonic power was 180W, obtained graphene oxide water solution (being designated as solution 1).Then through being that the hydrazine hydrate solution of 80% mixes with dehydrated alcohol by massfraction, the ethanol solution (concentration of hydrazine hydrate is 10.1mg/mL, and the concentration of ethanol is 400 mg/mL) (being designated as solution 2) of hydrazine hydrate is obtained.Then mixed with solution 2 by solution 1, wherein the mass ratio of hydrazine and graphene oxide is 4.4, reacts 0.5 hour, obtain the ethanolic soln of nitrogen-doped graphene in the environment of 82 DEG C.Vacuum filtration obtains the graphene film of N doping.At the film drying of room temperature by gained.Then thermal treatment 2 hours under 200 DEG C of nitrogen atmospheres.Afterwards gained film is colded pressing 0.5 hour under the pressure of 2000psi.The finally graphene film of the N doping of obtained high heat conduction.The thermal conductivity obtaining this film is as calculated 1657.83W/(mK), tensile strength is 5.2MPa, and Young's modulus is 1.1GPa.
Embodiment 6:
Be mixed in water by the graphite oxide standby by Hummers legal system, be made into the graphite oxide aqueous solution of 2mg/mL, then ultrasonic 0.5 hour, ultrasonic power was 200W, obtained graphene oxide water solution (being designated as solution 1).Then through being that the hydrazine hydrate solution of 80% mixes with dehydrated alcohol by massfraction, the ethanol solution (concentration of hydrazine hydrate is 11.1mg/mL, and the concentration of ethanol is 300 mg/mL) (being designated as solution 2) of hydrazine hydrate is obtained.Then mixed with solution 2 by solution 1, wherein the mass ratio of hydrazine and graphene oxide is 4.4, reacts 1 hour, obtain the ethanolic soln of nitrogen-doped graphene in the environment of 87 DEG C.Vacuum filtration obtains the graphene film of N doping.At the film drying of room temperature by gained.The finally graphene film of the N doping of obtained high heat conduction.The thermal conductivity obtaining this film is as calculated 1996.6W/(mK), tensile strength is 3.18MPa, and Young's modulus is 0.66GPa.
Embodiment 7:
Be mixed in water by the graphite oxide standby by Hummers legal system, be made into the graphite oxide aqueous solution of 3mg/mL, then ultrasonic 1.1 hours, ultrasonic power was 140W, obtained graphene oxide water solution (being designated as solution 1).Then through being that the hydrazine hydrate solution of 80% mixes with dehydrated alcohol by massfraction, the ethanol solution (concentration of hydrazine hydrate is 11.1mg/mL, and the concentration of ethanol is 550 mg/mL) (being designated as solution 2) of hydrazine hydrate is obtained.Then mixed with solution 2 by solution 1, wherein the mass ratio of hydrazine hydrate and graphene oxide is 4.4, reacts 1 hour, obtain the ethanolic soln of nitrogen-doped graphene in the environment of 80 DEG C.Vacuum filtration obtains the graphene film of N doping.At the film drying of room temperature by gained.The finally graphene film of the N doping of obtained high heat conduction.The thermal conductivity obtaining this film is as calculated 1884.98W/(mK), tensile strength is 8.48MPa, and Young's modulus is 1.32GPa.
Embodiment 8:
Be mixed in water by the graphite oxide standby by Hummers legal system, be made into the graphite oxide aqueous solution of 4mg/mL, then ultrasonic 0.9 hour, ultrasonic power was 100W, obtained graphene oxide water solution (being designated as solution 1).Then through being that the hydrazine hydrate solution of 80% mixes with dehydrated alcohol by massfraction, the ethanol solution (concentration of hydrazine hydrate is 9.1mg/mL, and the concentration of ethanol is 600 mg/mL) (being designated as solution 2) of hydrazine hydrate is obtained.Then mixed with solution 2 by solution 1, wherein the mass ratio of hydrazine and graphene oxide is 3.4, reacts 1 hour, obtain the ethanolic soln of nitrogen-doped graphene in the environment of 93 DEG C.Vacuum filtration obtains the graphene film of N doping.At the film drying of room temperature by gained.Then the graphene film of the N doping of high heat conduction within 2 hours, is finally obtained 200 DEG C of vacuum heat treatment.The thermal conductivity obtaining this film is as calculated 3428.24W/ (mK), and tensile strength is 20.82MPa, and Young's modulus is 3.8GPa.
Claims (2)
1. a preparation method for nitrogen-doped graphene film, is characterized in that comprising the following steps:
(1) configuration concentration is 2 ~ 6mg/mL graphite oxide aqueous solution, is 100 ~ 200W through power, and supersound process 0.5 ~ 1.5h, obtains the graphene oxide water-sol;
(2) ethanolic soln be hydrazine hydrate solution and the ethanol massfraction of 50-80% by hydrazine hydrate massfraction being 50% to dehydrated alcohol mixes, obtained concentration of hydrazine hydrate is 10 ~ 20mg/mL, and the concentration of ethanol is the mixing solutions of the hydrazine hydrate of 300mg/mL-700 mg/mL, second alcohol and water;
(3) R is designated as by the mass ratio of hydrazine hydrate and graphene oxide
hydrazine hydrate/ R
gO, by the solution mixing in step (1) and step (2), wherein R in gained mixing solutions
hydrazine hydrate/ R
gO=2.4 ~ 4.4;
(4) mixing solutions prepared in step (3) is reacted 0.5 ~ 1.5h at 80 ~ 95 DEG C, then the solution for vacuum suction filtration processed is obtained the graphene film of N doping, through drying at room temperature;
(5) by the graphene film thermal anneal process 1 ~ 3h under vacuum of gained in step (4), afterwards by it at ambient temperature, with the pressure pressure 0.5 ~ 2h of 1000 ~ 4000Psi, thus obtained high heat conduction nitrogen-doped graphene film;
Described oxidized graphite flake layer size is 1-10 μm, and thickness is 0.7-1.5nm.
2. the preparation method of a kind of nitrogen-doped graphene film as claimed in claim 1, is characterized in that described graphite oxide is prepared by Hummers method, Brodie method, Staudenmaier method or electrochemical oxidation process.
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| CN103935994B (en) * | 2014-04-28 | 2015-09-09 | 上海交通大学 | A kind of self-supporting redox graphene paper and preparation method thereof |
| CN104229781B (en) * | 2014-09-09 | 2016-01-27 | 东莞市翔丰华电池材料有限公司 | A kind of method preparing high itrogen content of getter with nitrogen doped nitrogen-doped graphene |
| CN104817078B (en) * | 2015-05-07 | 2017-01-25 | 常州大学 | Preparation method of a sulfur- and nitrogen-doped graphene sheet |
| CN104986754A (en) * | 2015-06-11 | 2015-10-21 | 中国科学院山西煤炭化学研究所 | Graphene-based thermal conductive film preparing method |
| CN104973873A (en) * | 2015-06-11 | 2015-10-14 | 中国科学院山西煤炭化学研究所 | High temperature oxidization-resistant graphene-based composite film and preparation method thereof |
| CN106335899B (en) * | 2016-08-11 | 2018-03-20 | 安徽省宁国天成电工有限公司 | A kind of nitrating graphene oxide membrane preparation method and applications |
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| CN102689896A (en) * | 2012-03-15 | 2012-09-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene oxide through simultaneously performing reduction and nitrogen doping functionalization |
| CN103145122A (en) * | 2013-03-25 | 2013-06-12 | 西北工业大学 | Preparation method of nitrogen-doped graphene |
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| CN102689896A (en) * | 2012-03-15 | 2012-09-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene oxide through simultaneously performing reduction and nitrogen doping functionalization |
| CN103145122A (en) * | 2013-03-25 | 2013-06-12 | 西北工业大学 | Preparation method of nitrogen-doped graphene |
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