CN103723717A - Preparation method of nitrogen-doped graphene thin film - Google Patents
Preparation method of nitrogen-doped graphene thin film Download PDFInfo
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- CN103723717A CN103723717A CN201410001619.4A CN201410001619A CN103723717A CN 103723717 A CN103723717 A CN 103723717A CN 201410001619 A CN201410001619 A CN 201410001619A CN 103723717 A CN103723717 A CN 103723717A
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Abstract
The invention discloses a preparation method of a nitrogen-doped graphene thin film. The preparation method comprises the steps of implementing ultrasonic treatment to a graphite oxide water solution to obtain graphite oxide hydrosol; mixing a hydrazine hydrate solution with an ethanol solution to obtain a mixing solution of hydrazine hydrate, ethanol and water; mixing the two solutions and implementing reaction for 0.5-1.5 hours at 80-95 DEG C, carrying out vacuum filtration on the treated solution to obtain nitrogen-doped graphene thin film, drying at room temperature, implementing thermal annealing for 1-3 hours under a vacuum condition, and pressing for 0.5-2 hours under 1000-4000Psi to obtain high thermal-conductivity nitrogen-doped graphene thin film. The nitrogen-doped graphene thin film prepared by the preparation method has the advantages of high thermal conductivity and good mechanical property.
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 scientific and technical fast development, make the design of instrument, equipment more and more significantly present the feature of light, thin, short, little and high efficiency.Yet an important problem of following is that plant and instrument has produced a large amount of heats in operational process simultaneously, 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 of developing a kind of high heat conduction is imperative.The more heat conduction thin-film material occurring in life and scientific research at present is mainly nano graphite flakes paper; wherein according to existing reported in literature: the interior thermal conductivity of largest face of peeling off graphite nano plate paper is 178W/ (mK) [Xiang J, Drzal LT. Thermal conductivity of exfoliated graphite nanoplatelet paper. Carbon. 2011; 49 (3): 773-8.]; the business-like maximum heat conductance of peeling off 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 strong K of the peace moral of University of Manchester in 2004 sea nurse, Graphene is as a kind of novel two dimensional surface nano material, novel physicals because its special monoatomic layer structure shows, makes it all to have shown good application prospect in every field.At Alexander A. Balandin in 2008, Suchismita Ghosh etc. recorded single-layer graphene thermal conductivity at room temperature for (4.84 ± 0.44) * 10
3-(5.30 ± 0.48) * 10
3w/(m K).The method that preparation at present has the graphene film of good conductive energy mainly comprises two kinds: (1) thermal reduction, yet the thin film material mechanics performance that this kind of method makes 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 prepare a kind of thin-film material of high heat conduction, need to control on the one hand the reducing degree of Graphene as you know, also need on the other hand to control its density.Therefore a kind of new method has been invented by this seminar, first chemical reduction and thermal reduction is combined, and improves its reducing degree; And then colded pressing, improve its density; Thereby make the 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 that improves graphene composite film material thermal conductivity, to improve its thermal diffusivity on the one hand, adopted the method that graphene oxide solution is mixed mutually with hydrazine hydrate solution to reach redox graphene and further to realize the object that nitrogen adulterates; To improve its density on the other hand, adopt the method that the later stage colds pressing to it to make stacking object more closely between its lamella to realize.
Preparation method of the present invention, mainly comprises the following steps:
(1) configuration concentration is 2～6mg/mL graphite oxide aqueous solution, through power, is 100～200W, and supersound process 0.5～1.5h obtains graphene oxide (GO) water-sol;
(2) hydrazine hydrate solution that is 50-80% by hydrazine hydrate massfraction is that 50% ethanolic soln to dehydrated alcohol mixes with ethanol massfraction, making hydrazine hydrate concentration is 10～20mg/mL, and the concentration of ethanol is the hydrazine hydrate of 300mg/mL-700 mg/mL, the mixing solutions of second alcohol and water;
(3) by the mass ratio of hydrazine hydrate and graphene oxide, be designated as R
hydrazine hydrate/ R
gO, the solution in (1) and (2) is mixed, wherein R in gained mixing solutions
hydrazine hydrate/ R
gO=2.4～4.4
(4) mixing solutions preparing in step (3) is reacted to 0.5～1.5h at 80～95 ℃, then the solution for vacuum suction filtration of processing is obtained to the graphene film of nitrogen doping, through drying at room temperature;
(5), by graphene film thermal anneal process 1～3h under vacuum condition of gained in step (4), afterwards by it at ambient temperature, thereby press 0.5～2h. to make 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 select Shanxi coal chemical research prepared, also can select commercially available graphite oxide slurry or powder (wherein oxidized graphite flake layer size is 1-10 μ m, 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 be used as a kind of heat transfer, heat radiation, equal hot material, be used for eliminating local pyrexia point, smoothed temperature gradient, it is lightweight, thin thickness, good toughness, can be well compound with various gums and insulation paper, and be die-cut to easily the various shape and size that need, thus well fit together with various metals, plastics.Can be widely used in the fields such as smart mobile phone, panel computer, LED set lights, intelligent television, pick up camera, digital camera, semiconductor manufacturing facility, vehicle electronics.
Beneficial effect of the present invention is:
The present invention can be according to the demand to the different thermal conductivities of product, by controlling hydrazine hydrate and the mass ratio of GO, temperature of reaction, reaction times, the vacuum treated temperature and time of the two and the conditions such as institute's applied pressure of colding pressing, the control of realization to its nitrogen doping ratio and density, thus the size of its thermal conductivity controlled.
Because being adopts multi-step to regulate and control it, thus the regulation and control of its performance subtle change are more prone to realize, simple to operate, energy-conservation, be also easy to amplify production industrial simultaneously.
Embodiment
Embodiment 1:
To be mixed in water by the standby graphite oxide of Hummers legal system, be made into the graphite oxide aqueous solution of 2mg/mL, then ultrasonic 1.5 hours, ultrasonic power was 100W, made graphite oxide aqueous solution (being designated as solution 1).Then the hydrazine hydrate solution that is 80% by massfraction mixes with the ethanol that massfraction is 70%, obtains 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 solution 1 is mixed with solution 2, wherein the mass ratio of hydrazine hydrate and graphene oxide is 2.4, reacts 1.5 hours in the environment of 95 ℃, obtains the ethanolic soln of nitrogen-doped graphene.Vacuum filtration obtains the graphene film of nitrogen doping.At ambient temperature by the film drying of gained.Then 200 ℃ of vacuum heat treatment 3 hours.Afterwards gained film is colded pressing 2 hours under the pressure of 2000psi.Finally make the graphene film of the nitrogen doping of high heat conduction.The thermal conductivity that obtains as calculated this film is 1503 W/(mK), tensile strength is 1.15MPa, Young's modulus is 0.4GPa.
Embodiment 2:
To be mixed in water by the standby graphite oxide of Brodie legal system, be made into the graphite oxide aqueous solution of 3mg/mL, then ultrasonic 1.2 hours, ultrasonic power was 120W, made graphite oxide aqueous solution (being designated as solution 1).Then the hydrazine hydrate solution that process is 50% by massfraction mixes with dehydrated alcohol, obtains 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.Then solution 1 is mixed with solution 2, wherein the mass ratio of hydrazine hydrate and graphene oxide is 2.9, reacts 1.2 hours in the environment of 93 ℃, obtains the ethanolic soln of nitrogen-doped graphene.Vacuum filtration obtains the graphene film of nitrogen doping.In room temperature by the film drying of gained.Then 200 ℃ of vacuum heat treatment 2.5 hours.Afterwards gained film is colded pressing 1.5 hours under the pressure of 3000psi.Finally make the graphene film of the nitrogen doping of high heat conduction.The thermal conductivity that obtains as calculated this film is 1650.31 W/(mK), tensile strength is 4.9MPa, Young's modulus is 1.5GPa.
Embodiment 3:
The standby graphite oxide of Staudenmaier legal system is mixed in water, is made into the graphite oxide aqueous solution of 4mg/mL, then ultrasonic 1 hour, ultrasonic power was 140W, made graphite oxide aqueous solution (being designated as solution 1).Then the ethanolic soln that the hydrazine hydrate solution that process is 65% by massfraction is 90% with massfraction mixes, and obtains 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.Then solution 1 is mixed with solution 2, wherein the mass ratio of hydrazine hydrate and graphene oxide is 3.4, reacts 1 hour in the environment of 90 ℃, obtains the ethanolic soln of nitrogen-doped graphene.Vacuum filtration obtains the graphene film of nitrogen doping.In room temperature by the film drying of gained.Then 200 ℃ of vacuum heat treatment 2 hours.Afterwards gained film is colded pressing 2 hours under the pressure of 3000psi.Finally make the graphene film of the nitrogen doping of high heat conduction.The thermal conductivity that obtains as calculated this film is 4800W/(mK), tensile strength is 20.72MPa, Young's modulus is 4.1GPa.
Embodiment 4:
To be mixed in water by the standby graphite oxide of Hummers legal system, be made into the graphite oxide aqueous solution of 5mg/mL, then ultrasonic 0.8 hour, ultrasonic power was 160W, made graphite oxide aqueous solution (being designated as solution 1).Then the hydrazine hydrate solution that process is 80% by massfraction mixes with dehydrated alcohol, obtains 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.Then solution 1 is mixed with solution 2, wherein the mass ratio of hydrazine and graphene oxide is 3.9, reacts 1 hour in the environment of 85 ℃, obtains the ethanolic soln of nitrogen-doped graphene.Vacuum filtration obtains the graphene film of nitrogen doping.In room temperature by the film drying of gained.Then thermal treatment 1.5 hours under 200 ℃ of argon gas atmosphere.Afterwards gained film is colded pressing 0.5 hour under the pressure of 2000psi.Finally make the graphene film of the nitrogen doping of high heat conduction.The thermal conductivity that obtains as calculated this film is 1544.13W/(mK), tensile strength is 8.47MPa, Young's modulus is 1.6GPa.
Embodiment 5:
The graphite oxide of being prepared by electrochemical oxidation process is mixed in water, is made into the graphite oxide aqueous solution of 6mg/mL, then ultrasonic 0.6 hour, ultrasonic power was 180W, made graphite oxide aqueous solution (being designated as solution 1).Then the hydrazine hydrate solution that process is 80% by massfraction mixes with dehydrated alcohol, obtains 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.Then solution 1 is mixed with solution 2, wherein the mass ratio of hydrazine and graphene oxide is 4.4, reacts 0.5 hour in the environment of 82 ℃, obtains the ethanolic soln of nitrogen-doped graphene.Vacuum filtration obtains the graphene film of nitrogen doping.In room temperature by the film drying of gained.Then thermal treatment 2 hours under 200 ℃ of nitrogen atmospheres.Afterwards gained film is colded pressing 0.5 hour under the pressure of 2000psi.Finally make the graphene film of the nitrogen doping of high heat conduction.The thermal conductivity that obtains as calculated this film is 1657.83W/(mK), tensile strength is 5.2MPa, Young's modulus is 1.1GPa.
Embodiment 6:
To be mixed in water by the standby graphite oxide of Hummers legal system, be made into the graphite oxide aqueous solution of 2mg/mL, then ultrasonic 0.5 hour, ultrasonic power was 200W, made graphite oxide aqueous solution (being designated as solution 1).Then the hydrazine hydrate solution that process is 80% by massfraction mixes with dehydrated alcohol, obtains 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.Then solution 1 is mixed with solution 2, wherein the mass ratio of hydrazine and graphene oxide is 4.4, reacts 1 hour in the environment of 87 ℃, obtains the ethanolic soln of nitrogen-doped graphene.Vacuum filtration obtains the graphene film of nitrogen doping.In room temperature by the film drying of gained.Finally make the graphene film of the nitrogen doping of high heat conduction.The thermal conductivity that obtains as calculated this film is 1996.6W/(mK), tensile strength is 3.18MPa, Young's modulus is 0.66GPa.
Embodiment 7:
To be mixed in water by the standby graphite oxide of Hummers legal system, be made into the graphite oxide aqueous solution of 3mg/mL, then ultrasonic 1.1 hours, ultrasonic power was 140W, made graphite oxide aqueous solution (being designated as solution 1).Then the hydrazine hydrate solution that process is 80% by massfraction mixes with dehydrated alcohol, obtains 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.Then solution 1 is mixed with solution 2, wherein the mass ratio of hydrazine hydrate and graphene oxide is 4.4, reacts 1 hour in the environment of 80 ℃, obtains the ethanolic soln of nitrogen-doped graphene.Vacuum filtration obtains the graphene film of nitrogen doping.In room temperature by the film drying of gained.Finally make the graphene film of the nitrogen doping of high heat conduction.The thermal conductivity that obtains as calculated this film is 1884.98W/(mK), tensile strength is 8.48MPa, Young's modulus is 1.32GPa.
Embodiment 8:
To be mixed in water by the standby graphite oxide of Hummers legal system, be made into the graphite oxide aqueous solution of 4mg/mL, then ultrasonic 0.9 hour, ultrasonic power was 100W, made graphite oxide aqueous solution (being designated as solution 1).Then the hydrazine hydrate solution that process is 80% by massfraction mixes with dehydrated alcohol, obtains 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.Then solution 1 is mixed with solution 2, wherein the mass ratio of hydrazine and graphene oxide is 3.4, reacts 1 hour in the environment of 93 ℃, obtains the ethanolic soln of nitrogen-doped graphene.Vacuum filtration obtains the graphene film of nitrogen doping.In room temperature by the film drying of gained.Then 200 ℃ of vacuum heat treatment, within 2 hours, finally make the graphene film of the nitrogen doping of high heat conduction.The thermal conductivity that obtains as calculated this film is 3428.24W/ (mK), and tensile strength is 20.82MPa, and Young's modulus is 3.8GPa.
Claims (4)
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, through power, is 100～200W, and supersound process 0.5～1.5h, obtains the graphene oxide water-sol;
(2) hydrazine hydrate solution that is 50-80% by hydrazine hydrate massfraction is that 50% ethanolic soln to dehydrated alcohol mixes with ethanol massfraction, making hydrazine hydrate concentration is 10～20mg/mL, and the concentration of ethanol is the hydrazine hydrate of 300mg/mL-700 mg/mL, the mixing solutions of second alcohol and water;
(3) by the mass ratio of hydrazine hydrate and graphene oxide, be designated as R
hydrazine hydrate/ R
gO, the solution in step (1) and step (2) is mixed, wherein R in gained mixing solutions
hydrazine hydrate/ R
gO=2.4～4.4
(4) mixing solutions preparing in step (3) is reacted to 0.5～1.5h at 80～95 ℃, then the solution for vacuum suction filtration of processing is obtained to the graphene film of nitrogen doping, through drying at room temperature;
(5), by graphene film thermal anneal process 1～3h under vacuum condition of gained in step (4), afterwards by it at ambient temperature, thereby press 0.5～2h. to make high heat conduction nitrogen-doped graphene film with the pressure of 1000～4000Psi.
2. the preparation method of a kind of nitrogen-doped graphene film as claimed in claim 1, is characterized in that described graphite oxide prepared by Hummers method, Brodie method, Staudenmaier method or electrochemical oxidation process.
3. the preparation method of a kind of nitrogen-doped graphene film as claimed in claim 2, is characterized in that described oxidized graphite flake layer size is 1-10 μ m, and thickness is 0.7-1.5nm.
4. the preparation method of a kind of nitrogen-doped graphene film as claimed in claim 1, is characterized in that described protective atmosphere is nitrogen, argon gas, helium, or vacuum protection.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103935994A (en) * | 2014-04-28 | 2014-07-23 | 上海交通大学 | Self-supported reduced graphene oxide paper and preparation method thereof |
| CN104229781A (en) * | 2014-09-09 | 2014-12-24 | 东莞市翔丰华电池材料有限公司 | Method for preparing nitrogen-doped graphene with high nitrogen doping amount |
| CN104817078A (en) * | 2015-05-07 | 2015-08-05 | 常州大学 | Preparation method of a sulfur- and nitrogen-doped graphene sheet |
| 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 |
| 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 |
| CN106335899A (en) * | 2016-08-11 | 2017-01-18 | 安徽省宁国天成电工有限公司 | Preparation method and application of nitrogen-doped graphene oxide film |
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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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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103935994A (en) * | 2014-04-28 | 2014-07-23 | 上海交通大学 | Self-supported reduced graphene oxide paper and preparation method thereof |
| 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 |
| CN104229781A (en) * | 2014-09-09 | 2014-12-24 | 东莞市翔丰华电池材料有限公司 | Method for preparing nitrogen-doped graphene with high nitrogen doping amount |
| 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 |
| CN104817078A (en) * | 2015-05-07 | 2015-08-05 | 常州大学 | Preparation method of a sulfur- and nitrogen-doped graphene sheet |
| 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 |
| 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 |
| CN106335899A (en) * | 2016-08-11 | 2017-01-18 | 安徽省宁国天成电工有限公司 | Preparation method and application of nitrogen-doped graphene oxide film |
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