CN102983011B - Graphene nitrogen-atoms displacement doping method and the Graphene of preparation and the method are improving Graphene quality than the application in electric capacity - Google Patents
Graphene nitrogen-atoms displacement doping method and the Graphene of preparation and the method are improving Graphene quality than the application in electric capacity Download PDFInfo
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Abstract
The present invention discloses and a kind of improves the grapheme material quality method than electric capacity, in the case of keeping Graphene high-specific surface area and single layer structure, in Graphene body, displacement doping is carried out by nitrogen-atoms, change the electronic band structure of Graphene, increase density of electronic states and carrier concentration, concretely comprising the following steps: carry out high temperature reduction reaction while to Graphene activation processing, a step completes the nitrogen-atoms displacement doping of Graphene.Use that gained nitrogen-doped graphene nitrogen content of the present invention is high, specific surface area big, higher than electric capacity, the procedure that the present invention provides is simple, nitrogen content is stable, environmental protection and productivity high.
Description
Technical field
The present invention relates to method and the application thereof of a kind of Graphene N doping.
Background technology
Graphene, English name Graphene, is the Colloidal particles that arranges according to hexagonal of carbon atom.From 2004
After being found by the scientist of University of Manchester, just become scientific circles and industrial quarters focus of attention.Owing to Graphene is special
Atomic structure, wherein the behavior of carrier (electronics and hole) could must be described by relativistic quantum mechanics.Meanwhile, as list
Layer atomic structure of carbon, the theoretical specific surface area of Graphene is up to 2630m2/g.The highest specific surface area and its special atom
Architectural characteristic makes Graphene become the optimal electrode material of ultracapacitor.
At present, nitrogen-doped graphene is the reducing degree in order to improve Graphene, increases the electric conductivity of grapheme material,
It is mainly used in biosensor, Flied emission field of transistors.How to develop a kind of Graphene that can be effectively improved than electric capacity
In field, scientists regulates the electronic structure of Graphene frequently with the method for N doping.This is primarily due to nitrogen-atoms tool
There is the atom size similar to carbon atom, and N provides electronics can improve the carrier density of grapheme material, and then increase
It compares electric capacity.Traditional method preparing nitrogen-doped graphene mainly has chemical gaseous phase deposition and the method for arc discharge, chemistry
Vapour deposition process, during preparing Graphene, is passed through ammonia simultaneously and carries out N doping, and high nitrogen content is 5%, but cannot
Accomplishing SP2 hydridization, can not be in same plane with Graphene, gained nitrogen-doped graphene loses planar structure, and doping nitrogen
Instability, easily loses；Arc discharge method, during preparing Graphene, is passed through the nitrogen-containing compound such as pyridine or ammonia,
Preparing nitrogen-doped graphene material, high nitrogen content is 1%, and easily loses.In nitrogen-doped graphene prepared by both approaches
Nitrogen content is wayward, course of reaction is complicated, severe reaction conditions, productivity are low.
Therefore, in order to meet the demand of different field, developing a kind of environmental pollution little, process is simple, specific surface area
Greatly, the doping techniques that nitrogen content is stable, productivity is higher is the problem that this area needs to solve.
Summary of the invention
The technical problem to be solved in the present invention is to overcome existing defect, it is provided that a kind of nitrogen content is high, specific surface area is big,
The grapheme material of the nitrogen-atoms displacement doping higher than electric capacity；
It is a further object of the present invention to provide a kind of process simple, nitrogen content is stable, environmental protection and the high nitrogen-atoms of productivity replace
The graphene preparation method of position doping.
The purpose of the present invention implements by the following technical programs:
The method of a kind of Graphene nitrogen-atoms displacement doping, carries out high temperature reduction anti-while to Graphene activation processing
Should, a step completes the nitrogen-atoms displacement doping of Graphene, and concrete operations are as follows:
A. pre-treatment: mixed with activator by graphene oxide, is sufficiently stirred for, and is dried；
B. reduction simultaneously is activated: put in high temperature reaction stove by the mixture of graphene oxide Yu activator, pump in stove
After air, in high temperature reaction stove, it is passed through noble gas protects, be warming up to 500-1500 DEG C, then pass to nitrogenous reaction gas
Body, more than isothermal reaction 1min；
C. post processing: after high temperature reduction reaction terminates, drop to room temperature in inert gas shielding, washs, is dried, obtain nitrogen
The Graphene of atom displacement doping.
Described graphene oxide be graphite oxidized after carry out the product peeled off.Described mode of oxidizing employing Hummers method,
Any one in Staudenmaier method or Brodie method；Described stripping mode uses microwave stripping, pyrolysis expansion to peel off, surpass
Sound dispersion in any one.
Described activator is the combination of one or more in potassium hydroxide, sodium hydroxide, phosphoric acid, zinc chloride, is preferably
Potassium hydroxide, optimum is the potassium hydroxide solution of 0.6-1.4g/l.
The described noble gas group of one or more in nitrogen, helium, neon, argon, Krypton, xenon, radon gas
Close, preferably nitrogen or argon, optimum for purity be 99.999% nitrogen or purity be 99.99% argon；It is passed through indifferent gas
The flow of body is 80-200m3/ min, preferably 150cm3/min。
Described nitrogenous reacting gas is ammonia, and the flow being passed through nitrogenous reacting gas is 20-100cm3/ min, preferably
50cm3/min。
In described activation reduction process simultaneously, the temperature of high temperature reduction reaction is 700-1000 DEG C, preferably 800 DEG C；During reaction
Between be 5-20min, preferably 10min.
Described high temperature reaction stove uses vacuum tube furnace or calcining furnace.
The grapheme material of a kind of nitrogen-atoms displacement doping, for single layer planar structure, its nitrogen content is 0.1wt%-
21.5wt%, and nitrogen content is stable, its specific surface area >=2000m2/g, with 1M TEABF4/ PC is as its mass ratio electricity of electrolyte
Hold 200F/g-300 F/g, using 6M KOH as its quality of electrolyte than electric capacity for 200F/g-400 F/g.
The grapheme material of above-mentioned nitrogen-atoms displacement doping, is preferably, and its nitrogen content is 6wt%-9wt%, and nitrogen content is steady
Fixed, its specific surface area is 2100-3000m2/g。
As the preferred version of the grapheme material of above-mentioned nitrogen-atoms displacement doping, utilize above-mentioned Graphene nitrogen-atoms displacement
The method of doping prepares.
A kind of improve the grapheme material quality method than electric capacity, keep Graphene high-specific surface area and single layer structure
In the case of, in Graphene body, carry out displacement doping by nitrogen-atoms, change the electronic band structure of Graphene, increase electronic state
Density and carrier concentration, concretely comprise the following steps:
Carrying out high temperature reduction reaction while to Graphene activation processing, a step completes the nitrogen-atoms displacement of Graphene and mixes
Miscellaneous, concrete operations are as follows:
A. pre-treatment: mixed with activator by graphene oxide, is sufficiently stirred for, and is dried；
B. reduction simultaneously is activated: put in high temperature reaction stove by the mixture of graphene oxide Yu activator, pump in stove
After air, in high temperature reaction stove, it is passed through noble gas protects, be warming up to 500-1500 DEG C, then pass to nitrogenous reaction gas
Body, more than isothermal reaction 1min；
C. post processing: after high temperature reduction reaction terminates, drop to room temperature in inert gas shielding, washs, is dried, obtain nitrogen
The Graphene of atom displacement doping.
The Graphene of nitrogen-atoms displacement of the present invention doping can be used for super capacitor, lithium ion battery or fuel electricity
Pond.
The performance of the Graphene of gained nitrogen-atoms displacement of the present invention doping can be found in the collection of illustrative plates in accompanying drawing and photo, analyzes such as
Under:
1, Fig. 1,2 be respectively C and N can spectrogram, C peak is narrower as can be seen from Figure 1 and is in the common 284.5eV of sp2
Near, illustrating that carbon (carbon of the such as sp3 hydridization) content of wherein other forms is less, the Graphene after N doping is still tied for monolayer
Structure exists.The N peak of Fig. 2 has two peaks near 398.2eV and 399.3 eV, illustrates that the form of N is mainly pyridine type (N-6)
With pyrroles's type (N-5).
2, by accompanying drawing 3 it can be seen that the Graphene prepared by the present invention has obvious fold and hole, it is ensured that made
Standby grapheme material has bigger specific surface area and high porosity, and does not change the basic structure of Graphene.
3, by Fig. 4,5 can be seen that Graphene prepared by the present invention for electrode material for super capacitor, in water system with have
Machine system electrolyte keeps preferable rectangle, equal non-oxidation reduction peak, illustrates preparation process does not introduce other functional groups.
The principle of the present invention:
Graphene is zero gap semiconductor, possesses the carrier properties of uniqueness and excellent electricity quality.Its electronics and honeybee
The interaction of nest shape periodic latlice of crystal structure gesture creates a kind of quasi particle, the most zero mass dirac-fermion, has similar
Characteristic in photon.The characteristic electron of Graphene can describe by traditional tight binding model, in this model, and electronic energy
Amount can be used with wave numberRepresent,r 0 =2.8eV is for being most close to transition
Energy,aFor lattice paprmeter.The carrier concentration of single-layer graphene is the highest, at room temperature has high mobility, and this makes it
Its chemical potential and carrier concentration can be regulated easily by field effect and gate voltage.Single-layer graphene is come
Saying, its carrier shows as the dirac fermion without quality, and Landau damping is,, thus
The visible electronics storage capacity that can improve Graphene by changing energy level.
Pass for ultracapacitor, between the total capacitance of ultracapacitor, quantum capacitance, electric double layer capacitance three
System meetsRelation.C EDL Depend on electrode material for super capacitor, and for some porous and have
For the Carbon Materials of high specific surface area, quantum capacitanceC Q It it is the restriction ultracapacitor key factor than electric capacity.
Quantum capacitance refers to by capacitance produced by electronics, hole in Graphene,.Carrier is dense
Degree is the carrier number of unit volume, the carrier concentration of Graphene from its intrinsic electrostatic potential,, whereinV ch It is the electromotive force of Graphene,v F It is dirac-fermion speed,hIt is that Planck is normal
Number.Therefore, quantum capacitanceC Q With carrier concentrationn Q Relation meet.And for than
Surface area is at 2000m2Substantially close to single layer structure for the Graphene of/more than g, the therefore increase of carrier concentration, it is possible to aobvious
Write and improve quantum capacitance, and then increase the ratio electric capacity of grapheme material.
The thinking of the present invention is that by N doping, Graphene is changed its electronic band structure, improves its intrinsic carrier dense
Degree, thus enhancer quantum capacitance, and then in monolayer has the material with carbon element of high-specific surface area, increase it compare electric capacity.
Graphene oxide in an inert atmosphere, is sufficiently mixed by the present invention with activator, then mixture is carried out high temperature
Processing to remove the oxygen functional group during it contains, research finds, Graphene is while activation, and its carbon-carbon bond is opened, and is more beneficial for
The displacement doping of nitrogen-atoms, is conducive to carrying out SP2 N doping, prepares the graphite that structure is still adulterated for the nitrogen-atoms displacement of monolayer
Alkene.In this two-dimensional graphene thin slice, single nitrogen-atoms instead of the position of carbon atom, the additional electric that each nitrogen-atoms provides
Son, increases the carrier concentration of Graphene；N doping changes the characteristic electron of graphene platelet, but without interference with its base
This structure.The addition of activator ensure that gained Graphene has bigger specific surface area, does not the most introduce other officials
Can group, it is to avoid the existence of fake capacitance, ensure that the stability of nitrogen simultaneously.
Beneficial effects of the present invention:
(1) gained grapheme material of the present invention can not only keep big specific surface area, and N doping is to mono-layer graphite
The carrier concentration of Graphene can be effectively improved on alkene, increase its quantum capacitance amount, thus increase specific capacitance；And do not have
Introduce additional functional group, it is to avoid the existence of fake capacitance；
(2) present invention process is provided without poisonous and hazardous chemical reagent, it is to avoid a large amount of use chemical reagent, dirty to environment
Contaminate little, it is adaptable to reduction doping based on the various powder body of graphene oxide prepared by various methods；
(3) present invention reduces doping time short (the shortest 5min), simple to operate, activates complete with nitrating reduction reaction one step
Becoming, condition is easily-controllable, and yield is high, is suitable to industrialized mass；
(4) present invention is capable of the high-quality reduction of graphene oxide composite material, and the Graphene of gained N doping is still single
Rotating fields, and itrogen content of getter with nitrogen doped is stable, oxygen-containing functional group, between 0.1%-21.5%, can be removed and keep stable by itrogen content of getter with nitrogen doped completely
Itrogen content of getter with nitrogen doped, stable itrogen content of getter with nitrogen doped is conducive to repeating and the control of required nitrogen content of material, meets different requirements.
Accompanying drawing explanation
Accompanying drawing is for providing a further understanding of the present invention, and constitutes a part for description, with the reality of the present invention
Execute example together for explaining the present invention, be not intended that limitation of the present invention.In the accompanying drawings:
Fig. 1 be itrogen content of getter with nitrogen doped of the present invention be the Graphene of 8wt% power spectrum collection of illustrative plates of C near 284.5 eV in embodiment 1；
Fig. 2 be itrogen content of getter with nitrogen doped of the present invention be the Graphene of 8wt% power spectrum collection of illustrative plates of N near 399.1 eV in embodiment 1；
Fig. 3 be itrogen content of getter with nitrogen doped of the present invention be the SEM collection of illustrative plates of the Graphene of 8wt% in embodiment 1；
Fig. 4 is itrogen content of getter with nitrogen doped of the present invention when being that in embodiment 1, the Graphene of 8wt% prepares ultracapacitor as electrode material,
Using 1M TEABF4/PC as the cyclic voltammetry curve of electrolyte；
Fig. 5 is itrogen content of getter with nitrogen doped of the present invention when being that in embodiment 1, the Graphene of 8wt% prepares ultracapacitor as electrode material,
Using 6M KOH as the cyclic voltammetry curve of electrolyte.
Fig. 6 be itrogen content of getter with nitrogen doped of the present invention be the Graphene of 6wt% power spectrum collection of illustrative plates of C near 284.5 eV in embodiment 2；
Fig. 7 be itrogen content of getter with nitrogen doped of the present invention be the Graphene of 6wt% power spectrum collection of illustrative plates of N near 399.1 eV in embodiment 2；
Fig. 8 be itrogen content of getter with nitrogen doped of the present invention be the SEM collection of illustrative plates of the Graphene of 6wt% in embodiment 2；
Fig. 9 is itrogen content of getter with nitrogen doped of the present invention when being that in embodiment 2, the Graphene of 6wt% prepares ultracapacitor as electrode material,
Using 1M TEABF4/PC as the cyclic voltammetry curve of electrolyte；
Figure 10 be itrogen content of getter with nitrogen doped of the present invention be that in embodiment 2, the Graphene of 6wt% prepares ultracapacitor as electrode material
Time, using 6M KOH as the cyclic voltammetry curve of electrolyte.
Figure 11 be itrogen content of getter with nitrogen doped of the present invention be the Graphene of 9wt% power spectrum collection of illustrative plates of C near 284.5 eV in embodiment 3；
Figure 12 be itrogen content of getter with nitrogen doped of the present invention be the Graphene of 9wt% power spectrum collection of illustrative plates of N near 399.1 eV in embodiment 3；
Figure 13 be itrogen content of getter with nitrogen doped of the present invention be the SEM collection of illustrative plates of the Graphene of 9wt% in embodiment 3；
Figure 14 be itrogen content of getter with nitrogen doped of the present invention be that in embodiment 3, the Graphene of 9wt% prepares ultracapacitor as electrode material
Time, using 1M TEABF4/PC as the cyclic voltammetry curve of electrolyte；
Figure 15 be itrogen content of getter with nitrogen doped of the present invention be that in embodiment 3, the Graphene of 9wt% prepares ultracapacitor as electrode material
Time, using 6M KOH as the cyclic voltammetry curve of electrolyte.
Detailed description of the invention
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are illustrated, it will be appreciated that preferred reality described herein
Execute example be merely to illustrate and explain the present invention, be not intended to limit the present invention.
Embodiment 1:
The Graphene of a kind of nitrogen-atoms displacement doping, nitrogen content 8%, specific surface is 2970.8m2/g。
Its preparation method is to enter same N doping reduction reaction while activating Graphene, and concrete operations are as follows::
1, take graphite oxide prepared by Hummers method, after microwave is peeled off, obtain graphene oxide powder；
2, then weigh 500mg graphene oxide powder to be dissolved in the KOH solution of 25ml 0.1g/mL, be sufficiently stirred for, do
Dry；
3, graphene oxide-KOH mixture is placed in vacuum tube furnace, after pumping furnace air, with 150cm3/min
Flow to be passed through purity in vacuum tube furnace be the argon of 99.99%, in the environment of inert atmosphere, be first warming up to 800 DEG C,
Keep temperature-resistant, then with 50cm3The flow of/min is passed through ammonia, reacts 10 minutes under 800 DEG C of high temperature；
4, it is naturally cooling to room temperature after having reacted, washs, be dried, obtain the Graphene of nitrogen-atoms displacement doping.
The application in ultracapacitor of the gained grapheme material, with 1M TEABF4/ PC is as its specific capacitance of electrolyte
For 261.0F/g, with 6M KOH as electrolyte specific capacitance as 368.3F/g.
The XPS collection of illustrative plates of the Graphene of gained nitrogen-atoms displacement doping is shown in Fig. 1, Fig. 2；Fig. 3 is shown in by SEM collection of illustrative plates；It is as electrode
Performance see Fig. 4, Fig. 5.
Embodiment 2:
The Graphene of a kind of nitrogen-atoms displacement doping, nitrogen content 6%, specific surface is 2110.6m2/g。
Its preparation method is to enter same N doping reduction reaction while activating Graphene, and concrete operations are as follows:
1, take graphite oxide prepared by Hummers method, after microwave is peeled off, obtain graphene oxide powder；
2, then weigh 300mg graphene oxide powder to be dissolved in the KOH solution of 20ml 0.6g/mL, be sufficiently stirred for, do
Dry；
3, graphene oxide-KOH mixture is placed in vacuum tube furnace, after pumping furnace air, with 80cm3/ min's
It is the argon of 99.99% that flow is passed through purity in vacuum tube furnace, is first warming up to 1000 DEG C, keeps temperature-resistant, then with
20cm3The flow of/min is passed through ammonia, reacts 5 minutes under 1000 DEG C of high temperature；
4, it is naturally cooling to room temperature after having reacted, washs, be dried, obtain the Graphene of nitrogen-atoms displacement doping.
The application in ultracapacitor of the gained grapheme material, using 1M TEABF4/PC as electrolyte in its than electricity
Capacity is 200.7F/g, with 6M KOH as specific capacitance in electrolyte as 241.2F/g.
The XPS collection of illustrative plates of the Graphene of gained nitrogen-atoms displacement doping is shown in Fig. 6, Fig. 7；Fig. 8 is shown in by SEM collection of illustrative plates；It is as electrode
Performance see Fig. 9, Figure 10.
Embodiment 3:
The Graphene of a kind of nitrogen-atoms displacement doping, nitrogen content 9%, specific surface is 2300.3m2/g。
Its preparation method is to enter same N doping reduction reaction while activating Graphene, and concrete operations are as follows:
1, take graphite oxide prepared by Hummers method, after microwave is peeled off, obtain graphene oxide powder；
2, then weigh 350mg graphene oxide powder to be dissolved in the KOH solution of 20ml 1.4g/mL, be sufficiently stirred for, do
Dry；
3, graphene oxide-KOH mixture is placed in vacuum tube furnace, with 180cm3The flow of/min is to electron tubes type
Being passed through purity in stove is the nitrogen of 99.999%, is first warming up to 900 DEG C, keeps temperature-resistant, then with 100cm3The flow of/min leads to
Enter ammonia, calcine 10 minutes under 900 DEG C of high temperature；
4, it is naturally cooling to room temperature after having reacted, washs, be dried, obtain the Graphene of nitrogen-atoms displacement doping.
The application in ultracapacitor of the gained grapheme material, with 1M TEABF4/ PC is as electrolyte specific capacitance
For 240.5F/g, with 6M KOH as specific capacitance in electrolyte as 298.3F/g.
The XPS collection of illustrative plates of the Graphene of gained nitrogen-atoms displacement doping is shown in Figure 11, Figure 12；Figure 13 is shown in by SEM collection of illustrative plates；It is as electricity
The performance of pole is shown in Figure 14, Figure 15.
Embodiment 4:
The Graphene of a kind of nitrogen-atoms displacement doping, nitrogen content 10%, specific surface is 2300.3m2/g。
Its preparation method is to enter same N doping reduction reaction while activating Graphene, and concrete operations are as follows::
1, take graphite oxide prepared by Staudenmaier method, after microwave is peeled off, obtain graphene oxide powder；
2, then weigh 350mg graphene oxide powder to be dissolved in the KOH solution of 20ml 1.4g/mL, be sufficiently stirred for, do
Dry；
3, being placed in vacuum tube furnace by graphene oxide-KOH mixture, being passed through purity in vacuum tube furnace is
The argon of 99.99%, is first warming up to 700 DEG C, keeps temperature-resistant, then with 10m3The flow of/h is passed through ammonia, at 700 DEG C of high temperature
Lower calcining 20 minutes；
4, it is naturally cooling to room temperature after having reacted, washs, be dried, obtain the Graphene of nitrogen-atoms displacement doping.
The application in ultracapacitor of the gained grapheme material, with 1M TEABF4/ PC is as electrolyte specific capacitance
For 240.5F/g, with 6M KOH as specific capacitance in electrolyte as 298.3F/g.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to aforementioned reality
Executing example to be described in detail the present invention, for a person skilled in the art, it still can be to aforementioned each enforcement
Technical scheme described in example is modified, or wherein portion of techniques feature is carried out equivalent.All essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (14)
1. the method for a Graphene nitrogen-atoms displacement doping, it is characterised in that: carry out while to Graphene activation processing
High temperature
Reduction reaction, a step completes the nitrogen-atoms displacement doping of Graphene, and concrete operations are as follows:
A. pre-treatment: mixed with activator by graphene oxide, is sufficiently stirred for, and is dried；
B. reduction simultaneously is activated: put in high temperature reaction stove by the mixture of graphene oxide Yu activator, pump furnace air
After, in high temperature reaction stove, it is passed through noble gas protects, be warming up to 500-1500 DEG C, then pass to nitrogenous reacting gas,
Described nitrogenous reacting gas is ammonia, and the flow being passed through nitrogenous reacting gas is 20-100cm3/ min, isothermal reaction 5min with
On, described high temperature reaction stove uses vacuum tube furnace；
C. post processing: after high temperature reduction reaction terminates, drop to room temperature in inert gas shielding, washs, is dried, obtain nitrogen-atoms
The Graphene of displacement doping.
The method of Graphene nitrogen-atoms displacement the most according to claim 1 doping, it is characterised in that: described graphene oxide
The product peeled off is carried out after oxidized for graphite.
The method of Graphene nitrogen-atoms displacement the most according to claim 2 doping, it is characterised in that: described mode of oxidizing is adopted
With any one in Hummers method, Staudenmaier method or Brodie method；Described stripping mode uses microwave to peel off, heat
Solution expands any one in stripping, ultrasonic disperse.
The method of Graphene nitrogen-atoms displacement doping the most according to claim 1, it is characterised in that: described activator is hydrogen-oxygen
Change the combination of one or more in potassium, sodium hydroxide, phosphoric acid, zinc chloride.
The method of Graphene nitrogen-atoms displacement doping the most according to claim 4, it is characterised in that: described activator is hydrogen-oxygen
Change potassium.
The method of Graphene nitrogen-atoms displacement doping the most according to claim 5, it is characterised in that: described activator is 0.6-
The potassium hydroxide solution of 1.4g/l.
The method of Graphene nitrogen-atoms displacement doping the most according to claim 1, it is characterised in that: described noble gas is argon
Gas, the flow being passed through noble gas is 80-200cm3/min。
The method of Graphene nitrogen-atoms displacement doping the most according to claim 7, it is characterised in that: the stream of described noble gas
Amount is 150cm3/min。
The method of Graphene nitrogen-atoms displacement doping the most according to claim 1, it is characterised in that: it is passed through nitrogenous reacting gas
Flow be 50cm3/min。
The method of Graphene nitrogen-atoms displacement doping the most according to claim 1, it is characterised in that: described activation also simultaneously
During former, the temperature of high temperature reduction reaction is 700-1000 DEG C；Response time is 5-20min.
11. methods that the displacement of Graphene nitrogen-atoms is adulterated according to claim 10, it is characterised in that: described activation also simultaneously
During former, the temperature of high temperature reduction reaction is 800 DEG C；Response time is 10min.
The Graphene of 12. 1 kinds of nitrogen-atoms displacement doping prepared according to method described in claim 1, it is characterised in that: should
The Graphene of nitrogen-atoms displacement doping is single layer planar structure, and its nitrogen content is 0.1wt%-21.5wt%, and nitrogen content is stable, its
Specific surface area >=2000m2/ g, with 1M TEABF4/ PC as its quality of electrolyte than electric capacity 200F/g-300 F/g, with 6M KOH
It is 200F/g-400 F/g as its quality of electrolyte than electric capacity.
The Graphene of 13. nitrogen-atoms displacement according to claim 12 doping, it is characterised in that: its nitrogen content is 6wt%-
9wt%, and nitrogen content is stable, its specific surface area is 2100-3000m2/g。
14. 1 kinds are improved the grapheme material quality method than electric capacity, it is characterised in that: keep Graphene high-specific surface area and
In the case of single layer structure, nitrogen-atoms is carried out in Graphene body SP2 displacement doping, change the electron energy band knot of Graphene
Structure, increases density of electronic states and carrier concentration, concretely comprises the following steps:
To carrying out high temperature reduction reaction while Graphene activation processing, a step completes the nitrogen-atoms displacement doping of Graphene, tool
Gymnastics is made as follows:
A. pre-treatment: mixed with activator by graphene oxide, is sufficiently stirred for, and is dried；
B. reduction simultaneously is activated: put in high temperature reaction stove by the mixture of graphene oxide Yu activator, pump furnace air
After, in high temperature reaction stove, it is passed through noble gas protects, be warming up to 500-1500 DEG C, then pass to nitrogenous reacting gas,
Described nitrogenous reacting gas is ammonia, and the flow being passed through nitrogenous reacting gas is 20-100cm3/ min, isothermal reaction 5min with
On；
C. post processing: after high temperature reduction reaction terminates, drop to room temperature in inert gas shielding, washs, is dried, obtain nitrogen-atoms
The Graphene of displacement doping.
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| CN104409739A (en) * | 2014-11-14 | 2015-03-11 | 天津大学 | Preparation method of nitrogen doped graphite felt used for direct flow methanol fuel cell cathode |
| CN105185605B (en) * | 2015-08-27 | 2017-11-10 | 长春工业大学 | Load the electrode preparation method of graphene/metallic compound |
| CN108242277B (en) * | 2018-01-10 | 2019-10-29 | 济南大学 | A kind of graphene of N doping/conductive metal composite cable and preparation method thereof |
| CN109607524A (en) * | 2019-01-31 | 2019-04-12 | 清华大学深圳研究生院 | Porous nitrogen-doped graphene material, preparation method and lithium ion battery |
| CN111986832A (en) * | 2020-07-08 | 2020-11-24 | 大同新成新材料股份有限公司 | Nitrogen-containing semiconductor graphite and preparation method thereof |
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| CN102180462A (en) * | 2011-02-17 | 2011-09-14 | 无锡第六元素高科技发展有限公司 | Method for preparing modified graphene material in controlled atmosphere environment by microwave irradiation |
| CN102515145A (en) * | 2011-12-27 | 2012-06-27 | 常州第六元素材料科技股份有限公司 | Preparation process for high specific surface porous carbon material |
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| CN102180462A (en) * | 2011-02-17 | 2011-09-14 | 无锡第六元素高科技发展有限公司 | Method for preparing modified graphene material in controlled atmosphere environment by microwave irradiation |
| CN102070140A (en) * | 2011-02-28 | 2011-05-25 | 无锡第六元素高科技发展有限公司 | Method for preparing high-specific surface area graphene material by utilizing strong base chemical treatment |
| CN102515145A (en) * | 2011-12-27 | 2012-06-27 | 常州第六元素材料科技股份有限公司 | Preparation process for high specific surface porous carbon material |
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