CN105645403B - A kind of preparation method of high-performance N doping three-dimensional grapheme - Google Patents
A kind of preparation method of high-performance N doping three-dimensional grapheme Download PDFInfo
- Publication number
- CN105645403B CN105645403B CN201610184640.1A CN201610184640A CN105645403B CN 105645403 B CN105645403 B CN 105645403B CN 201610184640 A CN201610184640 A CN 201610184640A CN 105645403 B CN105645403 B CN 105645403B
- Authority
- CN
- China
- Prior art keywords
- dimensional grapheme
- doping
- dimensional
- graphite
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to the synthesis technical fields of grapheme material, provide a kind of preparation method of nitrogen-doped graphene.The method specifically comprises the following steps：Continuous large stretch of graphene oxide is prepared using Hummers methods are improved；Graphene oxide is prepared into porous three-dimensional structure graphite alkene using hydro-thermal method；It will be in the acid solution of porous three-dimensional graphene ultrasonic disperse to pH value 1~5, then aniline is added in stir evenly, it is subsequently added into ammonium persulfate to continue to stir evenly, gained mixed liquor is transferred in the container of polytetrafluoroethylene (PTFE) and carries out hydro-thermal reaction, obtain porous three-dimensional graphene Polyaniline；Under nitrogen protection, high-temperature process, polyaniline decomposite nitrogen source, obtain N doping porous three-dimensional graphene.Nitrogen-doped graphene of the above method in addition to high nitrogen content can be prepared, the structure of three-dimensional grapheme can also be kept, gained N doping porous three-dimensional graphene has good chemical property, is very suitable for preparing ultracapacitor, and it is easy to operation, be conducive to industrialization promotion.
Description
Technical field
The present invention relates to the synthesis technical field of grapheme material, more particularly to a kind of system of high-performance nitrogen-doped graphene
Preparation Method.
Background technology
Graphene is the bi-dimensional cellular shape network structure being made of the monoatomic layer of carbon, is the base for forming other graphite materials
Member.The basic structural unit of graphene is benzene hexatomic ring, is current optimal two-dimension nano materials.Graphene has approached perfection
Substance, but to extend its practical application in fields such as the energy, environment and biologies, the graphene two dimension is needed to be self-assembled into
For three-dimensional graphene-structured.Such three-dimensional structure is in addition to some performances of graphene in itself are possessed, also with oneself solely
The characteristics of special.
Three-dimensional grapheme is formed by the monoatomic layer stacking of carbon, with electric conductivity more superior than two-dimensional graphene, greatly
Specific surface area and porous structure.Unique three-dimensional structure make graphene assembly have porosity, flexibility, lamination type,
The properties such as mass transfer performances.Although the surface of two-dimensional graphene can be higher, easily reunite, and three-dimensional netted graphene stability
Preferably, large specific surface area and utilization rate height, can increase wellability of the electrolyte to electrode material, and improve the storing up electricity energy of electrode
Power.Three-dimensional grapheme and its composite material have property more superior than two-dimensional graphene material in the energy, environment, catalysis etc.
Energy and broader practice.Based on this, we introduce nitrogen in three-dimensional grapheme, former using the carbon on nitrogen substitution graphene
Son prepares N doping three-dimensional grapheme, can greatly improve the energy-storage property of three-dimensional grapheme.At present, people mix nitrogen
The research of the preparation method of miscellaneous three-dimensional grapheme mainly includes following several directions, including vapour deposition process, solvent-thermal method, Re Chu
Logos, plasma method etc..Vapour deposition process can generate more uniform large area film and adulterate more uniform N doping stone
Black alkene, controllability is preferable, but air source and residual air generally have toxicity, operating process is cumbersome, and equipment requirement is more harsh, yield compared with
Few, production cost is high.Solvent-thermal method is easy to operate, and mild condition, safety is higher, and yield is big and most wide for everybody at present
A kind of method of general application.But the homogeneity of N doping is poor, the controllability of doping rate is poor.Heat treating process is a kind of letter
It is clean, the method for the miscellaneous graphenes of nitrogen Erbium-doped is efficiently produced, but obtained nitrogen content is relatively low, to the control of temperature and reaction time more
It is harsh.For plasma method to equipment, experiment condition has harsh requirement.
But the N doping limited amount on current three-dimensional grapheme, this strongly limits answering for N doping three-dimensional grapheme
With.It can be seen that it is that the technology that technical field is badly in need of solving is asked to prepare the higher N doping three-dimensional grapheme of nitrogen content
Topic.The present invention provides a kind of preparation methods, can obtain the higher high performance N doping three-dimensional grapheme of nitrogen content.
Invention content
In view of above-mentioned technical problem exists in the prior art, the present invention proposes a kind of higher N doping three-dimensional stone of nitrogen content
The preparation method of black alkene, the preparation method by first removing expanded graphite into graphene oxide, utilize simple hydro-thermal method
Prepare three-dimensional grapheme, and oxidation three-dimensional grapheme-Polyaniline be prepared into aniline, make oxygen in three-dimensional grapheme with
Nitrogen in aniline forms chemical combination key, then three-dimensional grapheme-Polyaniline is cracked at high temperature, nitrogen then with carbon
Element forms bonding, at the same time, moreover it is possible to play part skeleton function, the hole of three-dimensional grapheme is supported to keep former at high temperature
Sample obtains porous N doping three-dimensional grapheme structure.The technical solution adopted in the present invention is specific as follows：
A kind of high-performance N doping porous three-dimensional graphene of present invention offer and preparation method thereof, the method packet
Include following steps：
Step S1：Graphene oxide is prepared using graphite；
Step S2：Three-dimensional grapheme hydrogel is prepared using graphene oxide：It is 1~2mg according to mass volume ratio:1ml,
It adds graphene oxide into deionized water, by being ultrasonically treated, is configured to graphene oxide water solution, then will aoxidize stone
Black aqueous solution is transferred in the container of polytetrafluoroethylene (PTFE), is put and is carried out hydro-thermal reaction in a kettle, three-dimensional stone is obtained after cooling
Black alkene hydrogel；
Step S3：Three-dimensional grapheme-polyaniline composite material is prepared using three-dimensional grapheme hydrogel：According to three-dimensional graphite
Alkene and acid solution mass volume ratio 1mg：The three-dimensional grapheme hydrogel is immersed in acid solution by the amount of 20~50ml
In, it is 1 according to three-dimensional grapheme and aniline mass ratio:5~10 amount, oxytropism solution instill quantitative aniline and stirring, allow
Aniline is then 5 by aniline and ammonium persulfate mass ratio well into the microcellular structure to three-dimensional grapheme:3~5 amount,
Ammonium persulfate is quantitatively adding, and is stirred, mixed liquor is transferred to polytetrafluoroethylcontainer container again, is put into reaction kettle and continues hydro-thermal
Product is filtered and cleaned, dry three-dimensional grapheme-polyaniline composite material is obtained by freeze-drying by reaction；
Step S4：N doping three-dimensional grapheme is prepared using three-dimensional grapheme-polyaniline composite material：It is protected in inert gas
Under shield, gained three-dimensional grapheme-Polyaniline is heated to 750~1000 DEG C, keeps the temperature 1~2h, high property is obtained through cooling
It can N doping three-dimensional grapheme.
In further technical solution, above-mentioned steps S1：Graphene oxide is prepared using graphite；Improvement may be used
Hummers methods are prepared, and specific step includes：(1) it is 5g according to mass volume ratio：200ml, by expansible graphite plus
Enter to by volume ratio be 3:In the mixed liquor that 1 concentrated sulfuric acid is formed with concentrated nitric acid, and pre-expansion is stirred at room temperature, uses deionization
Water dilute reaction solution, collected by suction product simultaneously dry, and are heated with microwave 1800W, the microwave time, 40~60s made graphite completely swollen
It is swollen；
(2) it is 5g by expanded graphite and concentrated sulfuric acid mass volume ratio：Expanded graphite is added in the concentrated sulfuric acid, then pressed by 300ml
Expanded graphite：Potassium peroxydisulfate：Phosphorus pentoxide mass ratio is 5:4.2:6.2 amount is separately added into potassium peroxydisulfate and five oxidations two
Phosphorus stirs 3~5h at 60~80 DEG C, has reacted and has used deionized water dilute reaction solution, then is washed with deionized and filters and dry in the air
It is dry, obtain pre-oxidation graphite；
(3) it is 5g according to the mass volume ratio of pre-oxidation graphite and the concentrated sulfuric acid:200ml, by the pre- oxygen obtained by step (2)
Graphite is added in the concentrated sulfuric acid, is then heated to 35~40 DEG C, and 1~2h of stirring is removed and intercalation, then uses deionization
Water dilutes, and the hydrogen peroxide that 10ml volume fractions are 3% is instilled into dilution, is stirred continuously to solution and golden yellow occurs, is stood
Afterwards, solution supernatant is removed, golden yellow mixed liquor is left, then distinguish centrifugal treating with hydrochloric acid, deionized water, obtains graphite oxide
Alkene dispersion liquid, is finally lyophilized, and obtains golden yellow solid oxide graphene.
Above-mentioned graphite should choose expansible graphite, the inflatable 300 mesh graphite that preferably purity is 99.7%.It is above-mentioned dense
Sulfuric acid refers to the sulfuric acid that mass fraction is 98%；Above-mentioned concentrated nitric acid refers to the fuming nitric aicd that mass fraction is 65%.
In step (3), need slowly to be added to potassium permanganate in the mixed solution of pre-oxidation graphite and the concentrated sulfuric acid.
In above-mentioned steps S2, when carrying out the hydro-thermal reaction, reaction temperature is 140~180 DEG C, and the time is 8~12h.Together
When, obtained three-dimensional porous graphene hydrogel needs to clean two to three times with deionized water, and hydrogel should be immersed in water
In property solution, it is sure not convection drying, otherwise destroys three-dimensional appearance.
In above-mentioned steps S3, the pH value of the acid flux material is 1~5, can be hydrochloric acid, sulfuric acid or perchloric acid etc.；Benzene
Amine aqueous solution should be slowly added to and need magnetic agitation 1-2h；When adding in ammonium persulfate, need first that the ammonium persulfate of solid is molten
Solution stirs 10~30min in above-mentioned acid solution；, when carrying out hydro-thermal reaction again, reaction temperature is 120~160 DEG C,
Time is 10~12h.
Polymerisation is carried out by adding in ammonium persulfate, it is therefore an objective to using ammonium persulfate as initiator, cause aniline hair
Raw polymerisation, so as to obtain polyaniline.Gained mixed liquor is put and is reacted under hydrothermal conditions, is to accelerate the poly- of aniline
It closes.Aniline monomer polymerize under the action of ammonium persulfate derivant, generates polyaniline, is grown in inside three-dimensional grapheme,
Obtain three-dimensional grapheme-polyaniline mixed liquor.
In above-mentioned steps S3, after the filtered cleaning of three-dimensional grapheme-Polyaniline of gained, under freeze drier
Freeze-drying 12~for 24 hours, moisture is extracted out under the three-dimensional structure for keeping graphene.
In above-mentioned steps S4, the heating condition by the graphene oxide-polyaniline mixture is：With 5~10 DEG C/min
Heating rate rise to 750~1000 DEG C, by the uniform velocity heating up, polyaniline in three-dimensional grapheme is made thoroughly to decompose；High temperature point
The process of solution can be with inert atmospheres such as helium, argon gas in addition to nitrogen atmosphere；The condition of inert gas shielding is, by three-dimensional graphite
Alkene-polyaniline mixture is placed in high temperature resistant tube furnace, first by tubular type stove evacuation, removes air, then with 100~300ml/
The rate of min is passed through inert gas, forms oxygen-free environment..
Nitrogen in N doping three-dimensional grapheme prepared by the preparation method according to N doping three-dimensional grapheme of the present invention
Mass percentage is 5.4~10.8%, and nitrogen content reaches as high as 10.8%；The capacitance of the N doping three-dimensional grapheme is
145~228C, capacitance highest reach 228C.
Graphite oxide is first removed into graphene oxide by step S1, passes through step by preparation method provided by the invention
S2 is prepared into three-dimensional grapheme hydrogel, and by step S3, it is multiple that three-dimensional grapheme with aniline prepares three-dimensional grapheme-polyaniline
Condensation material makes the nitrogen in the functional group and polyaniline in three-dimensional grapheme form chemical combination key, makes it in height by step S4
After anneal crack solution, nitrogen is then bonded with carbon formation, is played the skeleton function of part, is supported the three-dimensional shaped of three-dimensional grapheme
Looks so that N doping three-dimensional grapheme prepared by the above method has higher nitrogen content, and the mass percentage highest of nitrogen
Up to 10.8% and porous three-dimensional structure.Wherein, three-dimensional grapheme is prepared into oxidation three-dimensional grapheme-polyaniline with aniline
During compound, for aniline monomer with ammonium persulfate under conditions of hydro-thermal, aniline polymerization generation polyaniline is grown in three-dimensional stone
In the endoporus and lamella of black alkene, three-dimensional grapheme-polyaniline composite material is obtained.
N doping three-dimensional grapheme produced by the present invention has porous structure and high nitrogen doped structure simultaneously, both with porous
The structure and performance characteristics of three-dimensional grapheme, specific surface area are up to 580m2/ g, BJH desorption accumulation internal surface of hole product 474.86
(m2/ g), porous structure is presented, and there is higher nitrogen content, the mass percentage of nitrogen reaches as high as 10.8% so that
The capacitance of N doping three-dimensional grapheme prepared by this method is up to 228C, has excellent chemical property, is highly suitable as
Prepare the similar energy-storage travelling wave tube such as ultracapacitor.And above-mentioned preparation method is simple, is conducive to industrialized production.
In more specifical technical solution, the preparation method of nitrogen-doped graphene includes the following steps：
A kind of high-performance N doping porous three-dimensional graphene of present invention offer and preparation method thereof, the method includes such as
Lower step：
Step S1：Graphene oxide is prepared using graphite；
Using graphite prepare graphene oxide may be used improve Hummers methods be prepared, specific step includes：
(1) it is 5g according to mass volume ratio：200ml, it is 3 that expansible graphite, which is added to by volume ratio,:1 concentrated sulfuric acid with
In the mixed liquor of concentrated nitric acid composition, and mixing is stirred at room temperature and is pre-expanded for 24 hours, form mixed solution, mixed solution is diluted
Into 1L deionized waters, and 3 filtering and washings are carried out, collect product and dry, be dried to obtain pre-expansion graphite；Graphite will be pre-expanded
1800w microwave heatings are carried out, 40~60s of microwave time obtains complete expanded graphite；
(2) it is 5g by expanded graphite and concentrated sulfuric acid mass volume ratio：Expanded graphite is added in the concentrated sulfuric acid, then pressed by 300ml
Expanded graphite：Potassium peroxydisulfate：Phosphorus pentoxide mass ratio is 5:4.2:6.2 amount is separately added into potassium peroxydisulfate and five oxidations two
Phosphorus is stirred to react 3~5h, then by the deionized water of product dilution to 2L, filtering and washing finally dries 1 at 60~80 DEG C
My god, obtain pre-oxidation graphite；
(3) it is 5g according to the mass volume ratio of pre-expansion graphite and the concentrated sulfuric acid:200ml, by the pre- oxygen obtained by step (2)
Graphite is added in the concentrated sulfuric acid, is 5 according to the mass volume ratio of pre-expansion graphite and potassium permanganate:15 amount adds in permanganic acid
Potassium is then heated to 35~40 DEG C, keeps the temperature 30~60min, and 1~2h of stirring is removed and intercalation, then that product is dilute
It releases in 2L deionized waters, obtains reaction solution, instill the hydrogen peroxide that 10ml volume fractions are 3% while stirring in reaction solution,
It is stirred continuously to solution and golden yellow occurs, through standing 12h, remove supernatant, leave bottom golden yellow liquid, and use successively
1mol/L dilute hydrochloric acid and deionized water centrifugal treating obtain large stretch of continuous oxidation graphene dispersing solution；Finally freeze-drying 12~locate for 24 hours
Reason obtains golden yellow graphene oxide solid.
In step (3), need slowly to be added to potassium permanganate in the mixed solution of pre-expansion graphite and the concentrated sulfuric acid.
Step S2：Three-dimensional grapheme hydrogel is prepared using graphene oxide；It is 1~2mg according to mass volume ratio:1ml,
It adds graphene oxide into deionized water, 1~2h configuration graphene oxide water solutions is ultrasonically treated, by graphene oxide water
Solution is transferred in the container of polytetrafluoroethylene (PTFE), is put into reaction kettle and is carried out hydro-thermal reaction, and reaction temperature is 120~180 DEG C, when
Between for 8~12h, obtain three-dimensional porous graphene hydrogel；
Three-dimensional porous graphene hydrogel obtained above needs to clean two to three times with deionized water, and hydrogel should
It is immersed in aqueous solution, is sure not convection drying, otherwise destroys three-dimensional appearance.
Step S3：Three-dimensional grapheme-polyaniline composite material is prepared using three-dimensional grapheme hydrogel；According to three-dimensional graphite
Alkene and acid solution mass volume ratio 1mg：It is 1~5 that the three-dimensional grapheme hydrogel is immersed in PH by the amount of 20~50ml
It is 1 according to three-dimensional grapheme and aniline mass ratio in acid solution:5~10 amount instills quantitative aniline in acid solution,
1~2h of magnetic agitation makes aniline uniformly disperse in an acidic solution, and enters in three-dimensional grapheme endoporus, then by aniline
It is 5 with ammonium persulfate mass ratio:3~5 amount, is quantitatively adding ammonium persulfate, continues 10~30min of stirring, by above-mentioned mixed liquor
It is transferred in the container of polytetrafluoroethylene (PTFE), is placed in reaction kettle and carries out hydro-thermal reaction, 120~160 DEG C of reaction temperature, the reaction time
8~12h.Aniline monomer polymerize under the action of ammonium persulfate derivant, generates polyaniline, is grown in three-dimensional grapheme
Inside obtains three-dimensional grapheme-polyaniline mixed liquor, and three-dimensional grapheme-polyaniline mixed liquor is filtered, and with ethyl alcohol and goes successively
Ionized water cleans extra impurity, using the method for freeze-drying, the precipitation point extraction under the premise of graphene three-dimensional structure is kept, most
Dry three-dimensional grapheme-polyaniline composite material is obtained eventually.
Above-mentioned aniline is liquid, adds in excessively and should be slowly added to simultaneously 1~2h of magnetic agitation.
When adding in ammonium persulfate, need that the dissolving of the ammonium persulfate of solid is first then added to mixed liquor in an acidic solution
In, and stir 10~30min.
Step S4：N doping three-dimensional grapheme is prepared using three-dimensional grapheme-polyaniline composite material.By the three-dimensional stone
Black alkene-polyaniline composite material is heated to 750~1000 DEG C, and keep the temperature under nitrogen protection, with 5~10 DEG C/min of heating rate
1~2h is reacted, cooled to room temperature obtains N doping three-dimensional grapheme.
In the particular embodiment, three-dimensional grapheme-polyaniline mixture is placed in high temperature resistant tube furnace, first by tubular type
Stove evacuation removes air, then is passed through inert gas with the rate of 100~300ml/min, forms oxygen-free environment.
The present invention has the advantages that：1st, the N doping three-dimensional grapheme prepared by the method for the invention has
Higher nitrogen content makes it have high capacitance and excellent chemical property；2nd, above-mentioned N doping three-dimensional grapheme has porous knot
Structure has the characteristics that high-specific surface area, high BJH desorption accumulation internal surface of hole products；3rd, N doping three-dimensional grapheme of the present invention
Preparation method it is simple for process, it is easy to operation, be conducive to industrialized production.
Description of the drawings
Fig. 1 is the high power scanning electron microscope (SEM) photograph of the three-dimensional grapheme of embodiment 3；
Fig. 2 is the high power scanning electron microscope (SEM) photograph of three-dimensional grapheme-polyaniline of embodiment 3；
Fig. 3 is the high power scanning electron microscope (SEM) photograph of three-dimensional grapheme-polyaniline of embodiment 3；
Fig. 4 is the high power scanning electron microscope (SEM) photograph after the high-temperature process of the N doping three-dimensional grapheme of embodiment 3.
Specific embodiment
Nitrogen-doped graphene and preparation method thereof is made mainly in combination with drawings and the specific embodiments below further details of
Explanation.
Embodiment 1
Preparing for the N doping three-dimensional grapheme of the present embodiment is as follows：
Step S1：Graphene oxide is prepared using graphite；It is prepared using Hummers methods are improved, specific step
Including：
(1) 5g300 mesh expansible graphites are taken, it is each to add in the 150ml concentrated sulfuric acids and 50ml fuming nitric aicds, it is stirred at room temperature
It is pre-expanded for 24 hours, obtains the dilution of mixed liquor 1L deionized waters, by dilute solution filtering and washing 3 times, collect product and dry, then use
Microwave 1800W heating 60s makes graphite expand completely.
(2) graphite that 5g expands is taken to add in the 300ml concentrated sulfuric acids, 4.2g potassium peroxydisulfates, 6.2g phosphorus pentoxides are stirred at 60 DEG C
Reaction 5h is mixed, has reacted and has been filtered with deionized water water washing, it is drying for one day, obtain pre-oxidation graphite.
(3) it will obtain adding in the 200ml concentrated sulfuric acids, 15g potassium permanganate with pre-oxidation graphite, 1h stirred at 40 DEG C and is carried out
Stripping and intercalation, then diluted with 2L deionized waters, the hydrogen peroxide that 10ml volume fractions are 3% is instilled into dilution, no
Disconnected stirring to solution occurs golden yellow, stands 12h, removes solution supernatant, leave bottom golden yellow mixed liquor, with hydrochloric acid,
Deionized water distinguishes centrifugal treating, obtains graphene oxide dispersion, is finally lyophilized 12~obtains golden yellow solid oxygen fossil for 24 hours
Black alkene.
Step S2：Three-dimensional grapheme hydrogel is prepared using graphene oxide；It is 1mg according to mass volume ratio:1ml will consolidate
State graphene oxide is added in deionized water, is ultrasonically treated 1h configuration graphene oxide water solutions；Graphene oxide is water-soluble
Liquid is transferred in the container of polytetrafluoroethylene (PTFE), is put into reaction kettle and is carried out hydro-thermal reaction, and reaction temperature is 120 DEG C, and the time is
12h obtains three-dimensional grapheme hydrogel.
Step S3：Three-dimensional grapheme-polyaniline composite material is prepared using three-dimensional grapheme hydrogel；By three-dimensional grapheme
Hydrogel adds in the hydrochloric acid solution of 1mol/L, according still further to three-dimensional grapheme and aniline mass ratio 1:5, it is molten toward three-dimensional grapheme acidity
Quantitative aniline is added in liquid, 2h is stirred, according still further to aniline and ammonium persulfate mass ratio 5:3 add in ammonium persulfate, continue to stir
10min is transferred in the container of polytetrafluoroethylene (PTFE), is placed on hydro-thermal reaction in reaction kettle, and reaction temperature is 120 DEG C, and the time is
Polymerisation occurs under these conditions for 10h, aniline monomer, is grown in inside three-dimensional grapheme, filters product after cooling, according to
It is secondary that extra impurity is cleaned with ethyl alcohol and deionized water, using the method for freeze-drying, it is multiple to obtain dry three-dimensional grapheme-polyaniline
Condensation material.
Step S4：N doping three-dimensional grapheme is prepared using three-dimensional grapheme-polyaniline composite material.By three-dimensional graphite
Alkene-polyaniline mixture is placed in nitrogen (being passed through rate as 200ml/min) atmosphere, is first vacuumized removing air and is being passed through nitrogen
Gas, is then heated to 750 DEG C of insulation reaction 2h with the heating rate of 5 DEG C/min, and cooled to room temperature obtains N doping three-dimensional
Graphene.
The mass percentage of each element of N doping three-dimensional grapheme manufactured in the present embodiment is shown in Table 1.The present embodiment system
The chemical property of standby N doping three-dimensional grapheme is shown in Table 2.
Embodiment 2
Preparing for the N doping three-dimensional grapheme of the present embodiment is as follows：
Step S1：Graphene oxide is prepared using graphite；It is prepared using Hummers methods are improved, specific step
Including：
(1) 5g300 mesh expansible graphites are taken, it is each to add in the 150ml concentrated sulfuric acids and 50ml fuming nitric aicds, it is stirred at room temperature
It is pre-expanded for 24 hours, obtains the dilution of mixed liquor 1L deionized waters, by dilute solution filtering and washing 3 times, collect product and dry, then use
Microwave 1800W heating 40s makes graphite expand completely.
(2) graphite that 5g expands is taken to add in the 300ml concentrated sulfuric acids, 4.2g potassium peroxydisulfates, 6.2g phosphorus pentoxides are stirred at 80 DEG C
3h is mixed, has reacted and has been filtered with deionized water water washing, it is drying for one day, collect pre-oxidation graphite.
(3) it will obtain adding in the 200ml concentrated sulfuric acids, 15g potassium permanganate with pre-oxidation graphite, 2h stirred at 35 DEG C and is carried out
Stripping and intercalation, then diluted with 2L deionized waters, the hydrogen peroxide that 10ml volume fractions are 3% is instilled into dilution, no
Disconnected stirring to solution occurs golden yellow, stands 12h, removes solution supernatant, leave bottom golden yellow mixed liquor, with hydrochloric acid,
Deionized water distinguishes centrifugal treating, obtains graphene oxide dispersion, is finally lyophilized 12~obtains solid oxide graphene for 24 hours.
Step S2：Three-dimensional grapheme hydrogel is prepared using graphene oxide；It is 1.5mg according to mass volume ratio:1ml will
Graphene oxide is added in deionized water, is ultrasonically treated 2h configuration graphene oxide water solutions；By graphene oxide water solution
It is transferred in the container of polytetrafluoroethylene (PTFE), is put into reaction kettle and carries out hydro-thermal reaction, reaction temperature is 180 DEG C, and time 8h is obtained
To three-dimensional grapheme hydrogel.
Step S3：Three-dimensional grapheme-polyaniline composite material is prepared using three-dimensional grapheme hydrogel；By three-dimensional grapheme
Hydrogel adds in the sulfuric acid solution of 1mol/L, according still further to three-dimensional grapheme and aniline mass ratio 1:8, it is molten toward three-dimensional grapheme acidity
Quantitative aniline is added in liquid, 1h is stirred, according still further to aniline and ammonium persulfate mass ratio 5:4 add in ammonium persulfate, continue to stir
30min is transferred in the container of polytetrafluoroethylene (PTFE), is placed on hydro-thermal reaction in reaction kettle, and reaction temperature is 160 DEG C, time 8h,
Polymerisation occurs under these conditions for aniline monomer, is grown in inside three-dimensional grapheme, filters product after cooling, uses successively
Ethyl alcohol and deionized water clean extra impurity, using the method for freeze-drying, obtain dry three-dimensional grapheme-polyaniline composite wood
Material.
Step S4：N doping three-dimensional grapheme is prepared using three-dimensional grapheme-polyaniline composite material.By three-dimensional graphite
Alkene-polyaniline mixture is placed in argon gas (being passed through rate as 200ml/min) atmosphere, is first vacuumized removing air and is being passed through argon
Gas, is then heated to 1000 DEG C of insulation reaction 1h with the heating rate of 10 DEG C/min, and cooled to room temperature obtains N doping three
Tie up graphene.
The mass percentage of each element of N doping three-dimensional grapheme manufactured in the present embodiment is shown in Table 1.The present embodiment system
The chemical property of standby N doping three-dimensional grapheme is shown in Table 2.
Embodiment 3
Preparing for the N doping three-dimensional grapheme of the present embodiment is as follows：
Step S1：Graphene oxide is prepared using graphite；It is prepared using Hummers methods are improved, specific step
Including：
(1) 5g300 mesh expansible graphites are taken, it is each to add in the 150ml concentrated sulfuric acids and 50ml fuming nitric aicds, it is stirred at room temperature
It is pre-expanded for 24 hours, obtains the dilution of mixed liquor 1L deionized waters, by dilute solution filtering and washing 3 times, collect product and dry, then use
Microwave 1800W heating 40s makes graphite expand completely.
(2) graphite that 5g expands is taken to add in the 300ml concentrated sulfuric acids, 4.2g potassium peroxydisulfates, 6.2g phosphorus pentoxides are stirred at 80 DEG C
5h is mixed, has reacted and has been filtered with deionized water water washing, it is drying for one day, obtain pre-oxidation graphite.
(3) it will obtain adding in the 200ml concentrated sulfuric acids, 15g potassium permanganate with pre-oxidation graphite, 2h stirred at 35 DEG C and is carried out
Stripping and intercalation, then diluted with 2L deionized waters, the hydrogen peroxide that 10ml volume fractions are 3% is instilled into dilution, no
Disconnected stirring to solution occurs golden yellow, stands 12h, removes solution supernatant, leave bottom golden yellow mixed liquor, with hydrochloric acid,
Deionized water distinguishes centrifugal treating, obtains graphene oxide dispersion, is finally lyophilized 12~obtains golden yellow solid oxygen fossil for 24 hours
Black alkene.
Step S2：Three-dimensional grapheme hydrogel is prepared using graphene oxide；It is 2mg according to mass volume ratio:1ml is by oxygen
Graphite alkene is added in deionized water, is ultrasonically treated 1.5h configuration graphene oxide water solutions；By graphene oxide water solution
It being transferred in the container of polytetrafluoroethylene (PTFE), is put into reaction kettle and carries out hydro-thermal reaction, reaction temperature is 180 DEG C, time 12h,
Obtain three-dimensional grapheme hydrogel.The microstructure of three-dimensional grapheme is shown in Fig. 1
Step S3：Three-dimensional grapheme-polyaniline composite material is prepared using three-dimensional grapheme hydrogel；By three-dimensional grapheme
Hydrogel adds in the sulfuric acid solution of 1mol/L, according still further to three-dimensional grapheme and aniline mass ratio 1:10, it is acid toward three-dimensional grapheme
Quantitative aniline is added in solution, 1h is stirred, according still further to aniline and ammonium persulfate mass ratio 5:5 add in ammonium persulfate, continue to stir
10min is mixed, is transferred in the container of polytetrafluoroethylene (PTFE), is placed on hydro-thermal reaction in reaction kettle, reaction temperature is 140 DEG C, and the time is
Polymerisation occurs under these conditions for 12h, aniline monomer, is grown in inside three-dimensional grapheme, filters product after cooling, according to
It is secondary that extra impurity is cleaned with ethyl alcohol and deionized water, using the method for freeze-drying, it is multiple to obtain dry three-dimensional grapheme-polyaniline
Condensation material, the microstructure of three-dimensional grapheme-polyaniline manufactured in the present embodiment are shown in Fig. 2, Fig. 3.
Step S4：N doping three-dimensional grapheme is prepared using three-dimensional grapheme-polyaniline composite material.By three-dimensional graphite
Alkene-polyaniline mixture is placed in argon gas (being passed through rate as 200ml/min) atmosphere, is first vacuumized removing air and is being passed through argon
Gas, is then heated to 800 DEG C of insulation reaction 2h with the heating rate of 5 DEG C/min, and cooled to room temperature obtains N doping three-dimensional
Graphene.
The mass percentage of each element of N doping three-dimensional grapheme manufactured in the present embodiment is shown in Table 1.The present embodiment system
The chemical property of standby N doping three-dimensional grapheme is shown in Table 2, the microcosmic knot of N doping three-dimensional grapheme manufactured in the present embodiment
Structure is shown in Fig. 4.
The each element mass percentage of the nitrogen-doped graphene of the preparation of 1 1~embodiment of embodiment 3 of table
| Carbon (%) | Nitrogen (%) | Oxygen element (%) | |
| Embodiment 1 | 90.8 | 5.8 | 3.4 |
| Embodiment 2 | 89.4 | 7.7 | 2.9 |
| Embodiment 3 | 86.5 | 10.8 | 2.7 |
From table 1 it follows that N doping three-dimensional grapheme prepared by 1~embodiment of embodiment 3 is respectively provided with higher contain
Nitrogen quantity, the mass percentage of nitrogen are at least 5.8%, reach as high as 10.8%.
The chemical property of the nitrogen-doped graphene of the preparation of 2 1~embodiment of embodiment 3 of table.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Capacitance (C) | 145 | 196 | 228 |
From Table 2, it can be seen that nitrogen-doped graphene prepared by 1~embodiment of embodiment 3 is respectively provided with compared with high electrochemical
Can, usual 100C of capacitance data of general N doping or so, and currently on the market, with the N doping stone of Nanjing Xian Feng nanometers of sale
For black alkene, capacitance only has 66 or so.It can be seen that it is proposed that a kind of N doping three-dimensional grapheme chemical property it is more traditional
Nitrogen-doped graphene tool is significantly improved, N doping three-dimensional grapheme the capacitance at least 145C, up to 256C that we prepare.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of N doping three-dimensional grapheme, which is characterized in that be as follows：
Step S1：Graphene oxide is prepared using graphite；
Step S2：Three-dimensional grapheme hydrogel is prepared using graphene oxide：It is 1~2mg according to mass volume ratio:1ml, by oxygen
Graphite alkene is added in deionized water, by being ultrasonically treated, graphene oxide water solution is configured to, then by graphene oxide
Aqueous solution is transferred in the container of polytetrafluoroethylene (PTFE), is put and is carried out hydro-thermal reaction in a kettle, three-dimensional grapheme is obtained after cooling
Hydrogel；
Step S3：Three-dimensional grapheme-polyaniline composite material is prepared using three-dimensional grapheme hydrogel：According to three-dimensional grapheme with
Acid solution mass volume ratio 1mg：The three-dimensional grapheme hydrogel is immersed in an acidic solution by the amount of 20~50ml,
It is 1 according to three-dimensional grapheme and aniline mass ratio:5~10 amount, oxytropism solution instill quantitative aniline and stirring, allow aniline
It is then 5 by aniline and ammonium persulfate mass ratio well into the microcellular structure to three-dimensional grapheme:3~5 amount, it is quantitative
Ammonium persulfate is added in, and is stirred, mixed liquor is transferred to polytetrafluoroethylcontainer container again, it is anti-to be put into continuation hydro-thermal in reaction kettle
Should, product is filtered and is cleaned, dry three-dimensional grapheme-polyaniline composite material is obtained by freeze-drying；
Step S4：N doping three-dimensional grapheme is prepared using three-dimensional grapheme-polyaniline composite material：In inert gas shielding
Under, gained three-dimensional grapheme-Polyaniline is heated to 750~1000 DEG C, keeps the temperature 1~2h, high-performance is obtained through cooling
N doping three-dimensional grapheme.
2. N doping three-dimensional grapheme preparation method according to claim 1, which is characterized in that prepared using the graphite
The method of graphene oxide is included using Hummers methods, specific step is improved：
(1) it is 5g according to mass volume ratio：200ml, it is 3 that expansible graphite, which is added to by volume ratio,:1 concentrated sulfuric acid and dense nitre
In the mixed liquor of acid composition, and pre-expansion is stirred at room temperature, with deionized water dilute reaction solution, collected by suction product simultaneously dries in the air
It is dry, it is heated with microwave 1800W, the microwave time, 40~60s made graphite expand completely；
(2) it is 5g by expanded graphite and concentrated sulfuric acid mass volume ratio：300ml adds in expanded graphite in the concentrated sulfuric acid, then by expansion
Graphite：Potassium peroxydisulfate：Phosphorus pentoxide mass ratio is 5:4.2:6.2 amount is separately added into potassium peroxydisulfate and phosphorus pentoxide,
3~5h is stirred at 60~80 DEG C, has reacted and has used deionized water dilute reaction solution, then is washed with deionized and is filtered and dry, is obtained
To pre-oxidation graphite；
(3) it is 5g according to the mass volume ratio of pre-oxidation graphite and the concentrated sulfuric acid:200ml, by the pre-oxidation stone obtained by step (2)
Ink is added in the concentrated sulfuric acid, is then heated to 35~40 DEG C, and 1~2h of stirring is removed and intercalation, then dilute with deionized water
Release, the hydrogen peroxide that 10ml volume fractions are 3% instilled into dilution, be stirred continuously to solution occur it is golden yellow, after standing,
Solution supernatant is removed, golden yellow mixed liquor is left, then distinguish centrifugal treating with hydrochloric acid, deionized water, obtains graphene oxide point
Dispersion liquid is finally lyophilized, and obtains golden yellow solid oxide graphene.
3. the preparation method of N doping three-dimensional grapheme according to claim 1, which is characterized in that in above-mentioned steps S2,
When carrying out the hydro-thermal reaction, reaction temperature is 140~180 DEG C, and the time is 8~12h.
4. the preparation method of N doping three-dimensional grapheme according to claim 1, which is characterized in that in above-mentioned steps S3,
When carrying out hydro-thermal reaction again, reaction temperature is 120~160 DEG C, and the time is 10~12h.
5. the preparation method of N doping three-dimensional grapheme according to claim 1, it is characterised in that in above-mentioned steps S3, institute
The pH value for stating acid flux material is 1~5, is hydrochloric acid, sulfuric acid or perchloric acid；Aniline solution should be slowly added to and magnetic force is needed to stir
Mix 1-2h；When adding in ammonium persulfate, need first to be dissolved in above-mentioned acid solution the ammonium persulfate of solid, and stirring 10~
30min。
6. N doping three-dimensional grapheme preparation method according to claim 1, which is characterized in that in above-mentioned steps S3, institute
The filtered cleaning of three-dimensional grapheme-Polyaniline after, under freeze drier be lyophilized 12~for 24 hours, keep graphite
Moisture is extracted out under the three-dimensional structure of alkene.
7. the preparation method of N doping three-dimensional grapheme according to claim 1, which is characterized in that in above-mentioned steps S4,
The heating condition of the graphene oxide-polyaniline mixture is：750 are risen to the heating rate of 5~10 DEG C/min~
1000℃。
8. the preparation method of N doping three-dimensional grapheme according to claim 1, which is characterized in that in above-mentioned steps S4,
The condition of inert gas shielding is that three-dimensional grapheme-polyaniline mixture is placed in high temperature resistant tube furnace, first takes out tube furnace
Vacuum removes air, then is passed through inert gas with the rate of 100~300ml/min, forms oxygen-free environment.
9. N doping three-dimensional grapheme preparation method according to claim 1, which is characterized in that N doping three-dimensional grapheme
In nitrogen content mass percent be 5.3~10.8%.
10. N doping three-dimensional grapheme preparation method according to claim 1, which is characterized in that N doping three-dimensional graphite
The specific surface area of alkene is 580m2/ g, BJH desorption accumulation internal surface of hole product 474.86m2Porous structure is presented in/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610184640.1A CN105645403B (en) | 2016-03-28 | 2016-03-28 | A kind of preparation method of high-performance N doping three-dimensional grapheme |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610184640.1A CN105645403B (en) | 2016-03-28 | 2016-03-28 | A kind of preparation method of high-performance N doping three-dimensional grapheme |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105645403A CN105645403A (en) | 2016-06-08 |
| CN105645403B true CN105645403B (en) | 2018-06-22 |
Family
ID=56495713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610184640.1A Active CN105645403B (en) | 2016-03-28 | 2016-03-28 | A kind of preparation method of high-performance N doping three-dimensional grapheme |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105645403B (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105938908B (en) * | 2016-06-12 | 2019-05-31 | 江苏大学 | A kind of N doping three-dimensional grapheme catalyst and preparation method thereof |
| CN105836742B (en) * | 2016-06-17 | 2018-01-19 | 西北师范大学 | A kind of preparation method with three-dimensional network-like structure graphene |
| CN106024426B (en) * | 2016-07-07 | 2017-12-05 | 常州大学 | A kind of preparation and its capacitive property research using amidated graphene oxide as the nitrogen-doped graphene of presoma |
| CN108123112B (en) * | 2016-11-30 | 2020-10-23 | 比亚迪股份有限公司 | Nitrogen-doped porous graphene aggregate and preparation method and application thereof |
| CN108439371A (en) * | 2016-12-13 | 2018-08-24 | 无锡格致新材料研发科技有限公司 | A kind of preparation method of three-dimensional (3D) graphene |
| CN110800077B (en) * | 2017-05-05 | 2022-09-13 | 西格马-奥尔德里奇有限责任公司 | Method for manufacturing graphene oxide gel |
| CN107583664A (en) * | 2017-10-13 | 2018-01-16 | 上海交通大学 | A kind of sulphur/nitrogen co-doped graphene and preparation method thereof |
| CN109678139A (en) * | 2017-10-18 | 2019-04-26 | 天津大学 | Fluorine nitrogen codope porous graphene hydrogel and preparation method thereof for electrode of super capacitor |
| CN108285139B (en) * | 2017-12-11 | 2021-06-18 | 昆明理工大学 | Preparation method and application of nitrogen-doped graphene carbon material |
| CN109911887A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of N doping porous graphene |
| CN108359092A (en) * | 2018-01-10 | 2018-08-03 | 沈阳大学 | A kind of preparation method of three-dimensional meso-hole grapheme/polyaniline composite material |
| CN108219453B (en) * | 2018-01-10 | 2019-06-25 | 沈阳大学 | A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material |
| CN108147397A (en) * | 2018-02-13 | 2018-06-12 | 成都理工大学 | A kind of preparation method of N doping three-dimensional grapheme |
| CN108962432B (en) * | 2018-06-01 | 2020-05-12 | 湖南国盛石墨科技有限公司 | Graphene conductive film |
| CN109021798B (en) * | 2018-06-01 | 2020-05-08 | 湖南国盛石墨科技有限公司 | Graphene conductive coating for protecting thin film |
| CN110606480A (en) * | 2018-06-16 | 2019-12-24 | 浙江晨阳新材料有限公司 | Nitrogen-doped porous graphene and preparation method thereof |
| CN108922792B (en) * | 2018-07-13 | 2020-01-07 | 黑龙江省科学院高技术研究院 | Preparation method of graphene/ZnO/NiO composite material |
| CN109085221A (en) * | 2018-07-27 | 2018-12-25 | 华南理工大学 | A kind of enzyme biologic sensor of doped graphene and its preparation and the application in detection phenol |
| CN108872343A (en) * | 2018-08-30 | 2018-11-23 | 华南理工大学 | A kind of Dopamine Sensor and its preparation and application based on nitrogen-doped graphene |
| CN109060918B (en) * | 2018-08-30 | 2020-08-18 | 华南理工大学 | Hydroquinone biosensor based on nitrogen-doped graphene composite horseradish peroxidase and preparation and application thereof |
| CN109444250B (en) * | 2018-09-30 | 2021-04-02 | 中国科学院山西煤炭化学研究所 | Preparation and mass spectrometry application of double-heteroatom-doped graphene/porous carbon composite |
| KR20200075353A (en) * | 2018-12-18 | 2020-06-26 | 대주전자재료 주식회사 | Reduced grafhene oxides, and manufacturing method of the same |
| CN110078058A (en) * | 2019-04-08 | 2019-08-02 | 南京工业大学 | A kind of three-dimensional porous graphene-polymer presoma conversion ceramic composite and preparation method thereof |
| CN111591981B (en) * | 2020-04-21 | 2022-09-30 | 东北大学 | Preparation method of low-layer gauze-shaped nitrogen-doped graphene |
| CN111943269B (en) * | 2020-08-06 | 2022-09-06 | 华侨大学 | Preparation method of molybdenum disulfide/graphene composite material |
| CN112768901B (en) * | 2020-12-31 | 2022-08-19 | 西安工业大学 | Three-dimensional graphene antenna and preparation method thereof |
| CN113270623A (en) * | 2021-06-10 | 2021-08-17 | 中国科学技术大学 | Microbial electrochemical system |
| CN113559913B (en) * | 2021-08-23 | 2023-07-21 | 湖南文理学院 | Sandwich-structured coated nitrogen-doped graphene composite material and preparation method and application thereof |
| CN115845805A (en) * | 2022-11-18 | 2023-03-28 | 哈尔滨工业大学（深圳） | Preparation method of nitrogen-doped Fe-BTC derived carbon-based material for activating peroxymonosulfate |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145888A (en) * | 2011-04-12 | 2011-08-10 | 东南大学 | Preparation method of grapheme three-dimensional entity |
| CN102432720A (en) * | 2011-08-10 | 2012-05-02 | 东华大学 | Preparation method for graphene based compound hydrogel modified with poly (N-isopropylacrylamide) |
| CN102718210A (en) * | 2012-07-03 | 2012-10-10 | 新疆大学 | Method for preparing graphene oxide three-dimensional self-assembled aerogel and application of graphene oxide three-dimensional self-assembled aerogel |
| CN103738944A (en) * | 2013-11-14 | 2014-04-23 | 盐城增材科技有限公司 | Method for preparing three-dimensional graphene through doping of nanoparticles |
| CN104353480A (en) * | 2014-09-26 | 2015-02-18 | 广西师范大学 | Three-dimensional nitrogen-doped graphene platinoid-loaded composite electro-catalyst and preparation method thereof |
| CN104409724A (en) * | 2014-12-09 | 2015-03-11 | 孚派特环境科技（苏州）有限公司 | Nitrogen-doped grapheme-cobalt oxide composite material and glassy carbon electrode modifying method |
| CN104559176A (en) * | 2015-01-27 | 2015-04-29 | 西南科技大学 | Preparation method of three-dimensional reduced graphene oxide/polyaniline composite material |
| CN104558998A (en) * | 2015-01-28 | 2015-04-29 | 云南中烟工业有限责任公司 | Graphene-polymer composite aerogel filter tip high-efficient adsorption stick and preparation method thereof |
| CN104828807A (en) * | 2015-04-10 | 2015-08-12 | 中国科学院重庆绿色智能技术研究院 | Preparation method of three-dimensional graphene oxide aerogel with high specific surface area |
| CN104934237A (en) * | 2015-05-26 | 2015-09-23 | 中国石油大学(华东) | Preparation method for nitrogen-doped porous carbon/graphene two-dimensional composite electrode material |
| CN105000548A (en) * | 2014-04-22 | 2015-10-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of novel three-dimensional nitrogen doped graphene composite material system |
-
2016
- 2016-03-28 CN CN201610184640.1A patent/CN105645403B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145888A (en) * | 2011-04-12 | 2011-08-10 | 东南大学 | Preparation method of grapheme three-dimensional entity |
| CN102432720A (en) * | 2011-08-10 | 2012-05-02 | 东华大学 | Preparation method for graphene based compound hydrogel modified with poly (N-isopropylacrylamide) |
| CN102718210A (en) * | 2012-07-03 | 2012-10-10 | 新疆大学 | Method for preparing graphene oxide three-dimensional self-assembled aerogel and application of graphene oxide three-dimensional self-assembled aerogel |
| CN103738944A (en) * | 2013-11-14 | 2014-04-23 | 盐城增材科技有限公司 | Method for preparing three-dimensional graphene through doping of nanoparticles |
| CN105000548A (en) * | 2014-04-22 | 2015-10-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of novel three-dimensional nitrogen doped graphene composite material system |
| CN104353480A (en) * | 2014-09-26 | 2015-02-18 | 广西师范大学 | Three-dimensional nitrogen-doped graphene platinoid-loaded composite electro-catalyst and preparation method thereof |
| CN104409724A (en) * | 2014-12-09 | 2015-03-11 | 孚派特环境科技（苏州）有限公司 | Nitrogen-doped grapheme-cobalt oxide composite material and glassy carbon electrode modifying method |
| CN104559176A (en) * | 2015-01-27 | 2015-04-29 | 西南科技大学 | Preparation method of three-dimensional reduced graphene oxide/polyaniline composite material |
| CN104558998A (en) * | 2015-01-28 | 2015-04-29 | 云南中烟工业有限责任公司 | Graphene-polymer composite aerogel filter tip high-efficient adsorption stick and preparation method thereof |
| CN104828807A (en) * | 2015-04-10 | 2015-08-12 | 中国科学院重庆绿色智能技术研究院 | Preparation method of three-dimensional graphene oxide aerogel with high specific surface area |
| CN104934237A (en) * | 2015-05-26 | 2015-09-23 | 中国石油大学(华东) | Preparation method for nitrogen-doped porous carbon/graphene two-dimensional composite electrode material |
Non-Patent Citations (2)
| Title |
|---|
| Simple preparation of nanoporous few-layer nitrogen-doped graphene for use as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions;Ziyin Lin等;《CARBON》;20121026;第53卷;第131页第2部分 * |
| 三维氮掺杂多孔炭/石墨烯的合成及应用;赵彦华;《万方期刊数据库》;20151231;第16-17页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105645403A (en) | 2016-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105645403B (en) | A kind of preparation method of high-performance N doping three-dimensional grapheme | |
| CN105552371B (en) | The preparation and application of nitrogen-doped graphene carbon nanohorn composite | |
| CN104386680B (en) | The method of large stretch of Graphene is prepared in scale | |
| CN103420352B (en) | A kind of high Oil repellent fluorinated graphene and preparation method thereof | |
| CN103991860A (en) | Nitrogen-doped graphene and preparation method thereof | |
| CN101993056B (en) | Graphene-based porous macroscopic carbon material and preparation method thereof | |
| CN102464313B (en) | Preparation method of graphene | |
| CN101948108B (en) | Preparation method of oxidized graphite paper | |
| JP2018511554A (en) | Method for preparing biomass graphene from cellulose | |
| CN107180706A (en) | The preparation method and application of dyefunctionalized grapheme/polyaniline composite material | |
| CN104817075B (en) | Preparation method of highly dispersed graphene oxide nanobelt solution | |
| CN107585758A (en) | A kind of graphene aerogel and its preparation method and application | |
| CN104787751B (en) | A kind of graphene powder and preparation method thereof | |
| CN106732589A (en) | A kind of preparation method of cupric oxide/cuprous oxide/graphene nanocomposite material | |
| CN106395803A (en) | Biomass auxiliary preparation method and application of nitrogen doped graphene | |
| CN105858642A (en) | Porous graphene material, and preparation method and application thereof | |
| CN105668552A (en) | Preparation method of easy-to-disperse nitrogen-doped graphene powder | |
| CN105836742B (en) | A kind of preparation method with three-dimensional network-like structure graphene | |
| CN105449210A (en) | Preparation method for porous graphene micro-sheet | |
| KR101670260B1 (en) | Method of manufacturing for graphene/carbon nanotube composite membrane | |
| CN103359708A (en) | Preparation method of nitrogen-doped graphene | |
| CN103253661A (en) | Method for preparing graphene powder at large scale | |
| CN104045080A (en) | Activated graphene sheet and preparation method thereof | |
| CN103896240A (en) | Preparation method for graphene/carbon nanotube composite material | |
| CN103951916A (en) | RGO (Reduced Graphene oxide)/ferric oxide-filled polyvinylidene fluoride composite wave-absorbing material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Min Yonggang Inventor after: Xiao Zhuangqing Inventor after: Shen Jiaxin Inventor after: Feng Yafei Inventor before: Min Yonggang Inventor before: Xiao Zhuangqing Inventor before: Shen Jiaxin Inventor before: Feng Yafei |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |