CN106145101A - A kind of bigger serface nitrogen-doped graphene and preparation method thereof - Google Patents
A kind of bigger serface nitrogen-doped graphene and preparation method thereof Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention uses microwave vacuum high-temperature heater to provide the preparation method of a kind of bigger serface nitrogen-doped graphene, including following two step: (1) Hummers method is prepared graphene oxide (2) and is carried out the microwave treatment of graphene oxide, thermal reduction and chemical gaseous phase deposition (CVD) doping in situ.The method that the present invention proposes, it is on the basis of improved voluntarily to equipment, before realizing graphene oxide thermal reduction, after microwave prestripping, thermal reduction and thermal reduction, chemical gaseous phase deposits the manipulation in situ of doping three steps, improves combined coefficient, reduces synthesis energy consumption, it is adaptable to big batch metaplasia is produced.Synthesis gained doped graphene can be used for the field such as electrochemical catalysis, ultracapacitor.
Description
Technical field
The invention belongs to technical field of inorganic material, be specifically related to a kind of bigger serface nitrogen-doped graphene and preparation side thereof
Method.
Background technology
Day by day serious with the constantly exhausted of the non-renewable resources such as coal, oil, natural gas and environmental pollution, grinds
Studying carefully and develop can provide novel energy storage device renewable, green, clean energy resource to seem particularly urgent and heavy for the mankind
Want.In numerous energy substitution schemes, ultracapacitor and novel battery suffer from huge potentiality and market.
But, present stage, these energy substitution schemes still had respective deficiency.Anode material for lithium-ion batteries, super capacitor
The capacity of device electrode material is not high, and fuel cell is fast to dependence, the Cathodic oxygen reduction of expensive noble metal electrode catalyst
Rate is all bottleneck problem far below anode evolving hydrogen reaction speed.The excellent character of Graphene provides very for solving these problems
Big possibility.Therefore, Graphene rapidly becomes one of research topic the most popular in material science in recent years.
For lithium ion battery and electrode of super capacitor, the bigger serface Graphene through N doping shows
More preferable capacity.For fuel cell, the adsorption activation doped with beneficially oxygen of nitrogen, and then promote going back of oxygen
Former, become the contenders substituting platinum catalyst.
Content of the invention
The purpose of the present invention is to propose to a kind of bigger serface nitrogen-doped graphene and preparation method thereof.
The technical scheme realizing the object of the invention is:
The preparation method of a kind of bigger serface Graphene, comprises the following steps:
A.Hummers method prepares graphene oxide:
(1) aoxidize: weigh graphite raw material and potassium permanganate, subsequently the concentrated sulfuric acid is joined graphite raw material and mix with potassium permanganate
Stirring in compound, during stirring, temperature is maintained at 0-2 DEG C, after stirring 60-120 minute, adjusts temperature to 30-40 DEG C, then
Insulated and stirred 60-120 minute；Add deionized water first, stir, temperature is increased to 90-95 DEG C, Heat preservation 5-15
Minute, add hydrogen peroxide, again add deionized water dilution, obtain graphite oxide dilution；
(2) ultrasonic: the graphite oxide dilution of gained to be carried out ultrasonically treated, obtains suspension；
(3) washing and drying: described suspension is carried out settling, removes supernatant；Use hydrochloric acid, ethanol pair more respectively successively
Suspension carries out washing, settles, removes supernatant operation；Reusability deionized water carries out washing and depositing, goes to suspension again
Except supernatant operation, final until suspension in neutrality, subsequently freeze-drying process is carried out to described suspension, it is thus achieved that pale brown
Look powder, i.e. graphene oxide powder；
B. the microwave treatment of graphene oxide, thermal reduction and chemical gaseous phase deposition doping:
(1) microwave treatment: under vacuum, carries out microwave treatment, described graphene oxide powder to described graphene oxide powder
Volumetric expansion 2-3 times after the microwave treatment of end, weight is 40-60% before expansion；
(2) thermal reduction: carry out in-situ annealing to the graphene oxide powder after microwave treatment: heating rate 4-8 DEG C/minute,
Temperature is incubated 20-60 minute after rising to 800 DEG C；
(3) chemical gaseous phase deposition: after 800 DEG C of insulation 20-60 minutes, start to be passed through ammonia, keep the flow of 1-30torr
Ventilation 30-180 minute, naturally cools to room temperature with final vacuum, i.e. can get bigger serface nitrogen-doped graphene, and tail gas uses
Water is collected.
Use above-mentioned preparation method, the available Graphene that specific surface area is big, nitrogen content is high.
Preferably, in described A (1) graphite raw material be natural flake graphite, graphous graphite powder, the one in expanded graphite or
Any combination；Described natural flake graphite and the low price of described graphous graphite powder, low cost；The price of described expanded graphite
Slightly higher, but during follow-up A (3) washing and drying, the speed of sedimentation is fast, saves the time thus reduces time cost.When
So above-mentioned three kinds of raw materials all can meet the needs of preparation.
Preferably, in described A (1), graphite raw material and the mass ratio of potassium permanganate are 3:5.57-7, and every gram of graphite raw material
Corresponding concentrated sulfuric acid consumption is 20-30mL；The corresponding hydrogen peroxide consumption of every gram of graphite raw material is 2-3mL.
Preferably, after described A (1) insulated and stirred 60-120 minute, the temperature adding deionized water first is 0-2 DEG C, first
Secondary addition deionized water is 2:1 with described concentrated sulfuric acid volume ratio.
Preferably, after described A (1) adds deionized water dilution again, graphite oxide concentration in graphite oxide dilution
For 6-10mg/mL.
Preferably, carrying out ultrasonically treated to described graphite oxide dilution in described A (2), ultrasonic machine power is 100-
1000W, frequency is 10-5000Hz, and ultrasonic time is 5-120 minute.And the ultrasonic time is longer, described bigger serface nitrogen
The proterties of doped graphene is better, but since it is considered that the relation of energy consumption, it is impossible to lengthening time simply, technique parameter
It is chosen as taking into account of the two.
Preferably, suspension described in described A (3) finally wash to solution be gel form.
Preferably, in described B (1), microwave treatment power is 600-850W, and the microwave time is the 5-60 second.
Preferably, described B (1) microwave treatment, B (2) thermal reduction and B (3) chemical gaseous phase deposition are carried out all in position.
Above-mentioned preferred technical parameter, if no special instructions, is for ensureing more stable preparation result.
Present invention also offers a kind of Graphene, described Graphene is prepared by above-mentioned preparation method.
The beneficial effects of the present invention is:
1st, use Graphene specific surface area prepared by the preparation method in the present invention high, can reach 500-1000m2/ g, N contain
Amount, at 5-8%, can meet capacity requirement completely for electrode material.
2nd, microwave treatment in the preparation method in the present invention, thermal reduction and and chemical gaseous phase deposition doping three steps all in position
Carrying out, time and energy consumption cost are substantially reduced.
Brief description
Fig. 1 is graphene preparation method process chart of the present invention；
Fig. 2 is the bigger serface nitrogen-doped graphene typical scan Electronic Speculum figure of embodiment 3 preparation.
Detailed description of the invention
Detailed description below is used for illustrating the present invention, but should not be construed as limitation of the present invention.
In embodiment, if no special instructions, technological means used is this area conventional technique means.
In embodiment, graphite raw material is general commercial graphite raw material, and wherein, expanded graphite is purchased from triumphant abundant industry, and particle is average
Granularity is 10-30 micron.
Embodiment 1:
A.Hummers method prepares graphene oxide:
(1) aoxidize: weigh natural flake graphite 3g, potassium permanganate 7g, wherein a diameter of 1-of natural flake graphite particle
200 microns, two kinds of raw materials are slowly added to the concentrated sulfuric acid that 60ml mass concentration is 98% after mixing, and concentrated sulfuric acid temperature is 2 DEG C.
After mixture keeps 0-2 DEG C of stirring 60 minutes, temperature is adjusted to 30 DEG C, then insulated and stirred 60 minutes.It is slowly added to first
150ml temperature is the deionized water of 2 DEG C, improves mixing speed simultaneously.Temperature is increased to 95 DEG C, Heat preservation 15 minutes, with
Rear addition 6ml mass fraction is the hydrogen peroxide of 30%, add the dilution of 250ml deionized water, graphite oxide concentration is about 6mg/
Ml, obtains graphite oxide dilution.
(2) ultrasonic: gained graphite oxide solution is carried out ultrasonically treated, ultrasonic machine power be 100W, frequency be 10Hz, super
The sound time is 5 minutes, obtains suspension.
(3) washing and drying: after described suspension being carried out settle, removing supernatant liquor, add salt acid elution；And again sink
Fall, it is thus achieved that lower floor's colloid.Use 100ml hydrochloric acid to washed once, then settle once, washed once again, then with 100ml ethanol
Settle once, then Reusability deionized water is washed and settled, repeatedly operate to the aobvious neutrality of solution, now occur that hydrogel is existing
As.Hydrogel is carried out freeze-drying, and sample lasts 72 hours and is warmed to room temperature by-35 DEG C under 1Pa air pressure, it is thus achieved that brown color is done
Dry thing powder 3.4g, i.e. graphene oxide powder.
B. the microwave treatment of graphene oxide, thermal reduction and chemical gaseous phase deposition doping:
(1) microwave treatment: in vacuum 1 × 10-3Under the conditions of torr, microwave treatment is carried out to 3.4g graphene oxide powder,
Power 600W, 5 seconds microwave time.Color sample is transferred to black by brown color, occurs substantially expanding, before weight is for expanding
60%；
(2) thermal reduction: keep 1 × 10-3Torr vacuum, is incubated 20 minutes after rising to 800 DEG C with 4 DEG C/min.
(3) chemical gaseous phase deposition: after 800 DEG C are incubated 20 minutes, being passed through ammonia, flow is 30sccm, and in storehouse, pressure is about
1torr, ventilates 30 minutes.Naturally cool to room temperature with final vacuum.I.e. can get bigger serface nitrogen-doped graphene, tail gas makes
It is collected with water.
Record the present embodiment through BET method to prepare gained Graphene specific surface area and be about 500m2/g.N content is about 5%.
Embodiment 2:
A.Hummers method prepares graphene oxide:
(1) aoxidize: weigh graphous graphite powder 3.5g, potassium permanganate 6.5g, wherein a diameter of 1-of Delanium powder particles
200 microns, two kinds of raw materials are slowly added to the concentrated sulfuric acid that 105ml concentration is 98% after mixing, and concentrated sulfuric acid temperature is 2 DEG C.Mixed
After compound keeps 0-2 DEG C of stirring 120 minutes, temperature is adjusted to 40 DEG C, then insulated and stirred 120 minutes.It is slowly added to first
230ml temperature is the deionized water of 2 DEG C, improves mixing speed simultaneously.Temperature is increased to 90 DEG C, Heat preservation 15 minutes, with
Rear addition 11ml mass fraction is the hydrogen peroxide of 30%, add 200ml deionized water dilution acid solution, graphite oxide concentration is about
For 10mg/ml, obtain graphite oxide dilution.
(2) ultrasonic: to carry out ultrasonically treated to gained graphite oxide solution, ultrasonic machine power is that 1000W, frequency are
5000Hz, ultrasonic time is 120 minutes, obtains suspension.
(3) washing and drying: after described suspension being carried out settle, removing supernatant liquor, add salt acid elution；And again sink
Fall, it is thus achieved that lower floor's colloid.Use 150ml hydrochloric acid to washed once, then settle once, washed once again, then with 150ml ethanol
Once, then Reusability deionized water is washed and is settled in sedimentation, repeatedly operates and shows neutrality to solution and hydrogel phenomenon occur.By water
Gel carries out freeze-drying, and sample lasts 72 hours and is warmed to room temperature by-35 DEG C under 1Pa air pressure, it is thus achieved that brown color dried object powder
End 6g, i.e. graphene oxide powder.
B. the microwave treatment of graphene oxide, thermal reduction and chemical gaseous phase deposition doping:
(1) microwave treatment: in vacuum 9 × 10-4Under the conditions of torr, microwave treatment, work(are carried out to 6g graphene oxide powder
Rate 850W, 60 seconds microwave time.Color sample is transferred to black by brown color, occurs substantially expanding, and weight is before expansion 40%.
(2) thermal reduction: keep 9 × 10-4Torr vacuum, is incubated 60 minutes after rising to 800 DEG C with 8 DEG C/min.
(3) chemical gaseous phase deposition: after 800 DEG C are incubated 60 minutes, being passed through ammonia, flow is 50sccm, and in storehouse, pressure is about
30torr, ventilates 180 minutes.Naturally cool to room temperature with final vacuum.I.e. can get bigger serface nitrogen-doped graphene, tail gas
Water is used to be collected.
Record the present embodiment through BET method to prepare gained Graphene specific surface area and be about 1000m2/g.N content is about 8%.
Embodiment 3:
A.Hummers method prepares graphene oxide:
(1) aoxidize: weighing expanded graphite 10g, potassium permanganate 20g, wherein a diameter of 1-200 of expanded graphite particles is micro-
Rice, two kinds of raw materials are slowly added to the concentrated sulfuric acid that 250ml concentration is 98% after mixing, concentrated sulfuric acid temperature is 2 DEG C.Mixture is protected
After holding 0-2 DEG C of stirring 90 minutes, temperature is adjusted to 35 DEG C, then insulated and stirred 90 minutes.Being slowly added to 500ml temperature first is
The deionized water of 2 DEG C, improves mixing speed simultaneously.Temperature is increased to 93 DEG C, Heat preservation 10 minutes, it is subsequently added 25ml matter
Amount fraction is the hydrogen peroxide of 30%, add 700ml deionized water dilution acid solution, graphite oxide concentration is about 8mg/ml, obtains
Graphite oxide dilution.
(2) ultrasonic: gained graphite oxide solution is carried out ultrasonically treated, ultrasonic machine power be 550W, frequency be 2500Hz,
Ultrasonic time is 60 minutes.
(3) washing and drying: after described suspension being carried out settle, removing supernatant liquor, add salt acid elution；And again sink
Fall, it is thus achieved that lower floor's colloid.. use 250ml hydrochloric acid to washed once, then settle once, washed once again, so with 250ml ethanol
Once, then Reusability deionized water is washed and is settled in rear sedimentation, repeatedly operates and shows neutrality to solution and hydrogel phenomenon occur.Will
Hydrogel carries out freeze-drying, and sample lasts 96 hours and is warmed to room temperature by-35 DEG C under 1Pa air pressure, it is thus achieved that brown color dried object
Powder 12g, i.e. graphene oxide powder.
B. the microwave treatment of graphene oxide, thermal reduction and chemical gaseous phase deposition doping:
(1) microwave treatment: in vacuum 2 × 10-3Under the conditions of torr, microwave treatment, work(are carried out to 12g graphene oxide powder
Rate 725W, 30 seconds microwave time.Color sample is transferred to black by brown color, occurs substantially expanding, and weight is before expansion 50%.
(2) thermal reduction: keep 2 × 10-3Torr vacuum, is incubated 40 minutes after rising to 800 DEG C with 6 DEG C/min.
(3) chemical gaseous phase deposition: after 800 DEG C are incubated 40 minutes, being passed through ammonia, flow is 60sccm, and in storehouse, pressure is about
15torr, ventilates 105 minutes.Naturally cool to room temperature with final vacuum.I.e. can get bigger serface nitrogen-doped graphene, tail gas
Water is used to be collected.
Record the present embodiment through BET method to prepare gained Graphene specific surface area and be about 850m2/g.N content is about 7%.
Above embodiment is only that the detailed description of the invention to the present invention is described, and not enters the scope of the present invention
Row limits, and those skilled in the art also can do numerous modifications and variations on the basis of existing technology, set without departing from the present invention
On the premise of meter spirit, the various modification that technical scheme is made by this area ordinary skill technical staff and improvement,
All should fall in the protection domain that claims of the present invention determines.
Claims (10)
1. a preparation method for bigger serface nitrogen-doped graphene, comprises the following steps:
A.Hummers method prepares graphene oxide:
(1) aoxidize: weigh graphite raw material and potassium permanganate, subsequently the concentrated sulfuric acid is joined graphite raw material and potassium permanganate mixture
In stir, during stirring, temperature is maintained at 0-2 DEG C, stirring 60-120 minute after, adjust temperature to 30-40 DEG C, then be incubated
Stirring 60-120 minute；Adding deionized water first, stirring, temperature is increased to 90-95 DEG C, Heat preservation 5-15 divides
Clock, adds hydrogen peroxide, again adds deionized water dilution, obtain graphite oxide dilution；
(2) ultrasonic: the graphite oxide dilution of gained to be carried out ultrasonically treated, obtains suspension；
(3) washing and drying: described suspension is carried out settling, removes supernatant；Use respectively hydrochloric acid, ethanol to suspended more successively
Liquid carries out washing, settles, removes supernatant operation；Reusability deionized water carries out washing and depositing, in removal to suspension again
Clear liquid operates, final until suspension in neutrality, subsequently freeze-drying process is carried out to described suspension, it is thus achieved that pale brown toner
End, i.e. graphene oxide powder；
B. the microwave treatment of graphene oxide, thermal reduction and chemical gaseous phase deposition doping:
(1) microwave treatment: under vacuum, carries out microwave treatment to described graphene oxide powder, and described graphene oxide powder is micro-
Volumetric expansion 2-3 times after ripple process, weight is 40-60% before expansion；
(2) thermal reduction: carry out in-situ annealing to the graphene oxide powder after microwave treatment: heating rate 4-8 DEG C/minute, temperature
It is incubated 20-60 minute after rising to 800 DEG C；
(3) chemical gaseous phase deposition: after 800 DEG C of insulation 20-60 minutes, start to be passed through ammonia, keeps the flow ventilation of 1-30torr
30-180 minute, naturally cools to room temperature with final vacuum, i.e. can get bigger serface nitrogen-doped graphene.
2. preparation method according to claim 1, it is characterised in that in described A (1), graphite raw material is natural scale stone
One in ink, graphous graphite powder, expanded graphite or any combination.
3. preparation method according to claim 1, it is characterised in that the matter of graphite raw material and potassium permanganate in described A (1)
Amount is than being 3:5.57-7, and the corresponding concentrated sulfuric acid consumption of every gram of graphite raw material is 20-30mL；The corresponding dioxygen of every gram of graphite raw material
Water consumption is 2-3mL.
4. preparation method according to claim 1, it is characterised in that after described A (1) insulated and stirred 60-120 minute, first
The temperature of secondary addition deionized water is 0-2 DEG C, adds deionized water and described concentrated sulfuric acid volume ratio to be 2:1 first.
5. preparation method according to claim 1, it is characterised in that again add deionized water to dilute in described A (1)
After, in graphite oxide dilution, graphite oxide concentration is 6-10mg/mL.
6. preparation method according to claim 1, it is characterised in that in described A (2), described graphite oxide dilution is entered
Row is ultrasonically treated, and ultrasonic machine power is 100-1000W, and frequency is 10-5000Hz, and ultrasonic time is 5-120 minute.
7. preparation method according to claim 1, it is characterised in that suspension described in described A (3) finally washs to molten
Liquid is gel form.
8. preparation method according to claim 1, it is characterised in that in described B (1), microwave treatment power is 600-
850W, the microwave time is the 5-60 second.
9. preparation method according to claim 1, it is characterised in that described B (1) microwave treatment, B (2) thermal reduction and B
(3) chemical gaseous phase deposition is carried out all in position.
10. a Graphene, it is characterised in that described Graphene is prepared into by the arbitrary described preparation method of claim 1-9
Arrive.
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| CN109179387A (en) * | 2018-11-16 | 2019-01-11 | 重庆大学 | A kind of method preparing graphene and its graphene obtained |
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| CN110217782A (en) * | 2019-07-05 | 2019-09-10 | 郑州新世纪材料基因组工程研究院有限公司 | Application and electro-magnetic wave absorption-reflecting material adjusting method of the redox graphene in electro-magnetic wave absorption-reflecting material |
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