CN102983011A - Graphene nitrogen atom displacement mixing method and application of prepared graphene and method for improving graphene mass specific capacitance - Google Patents
Graphene nitrogen atom displacement mixing method and application of prepared graphene and method for improving graphene mass specific capacitance Download PDFInfo
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- CN102983011A CN102983011A CN2012103744495A CN201210374449A CN102983011A CN 102983011 A CN102983011 A CN 102983011A CN 2012103744495 A CN2012103744495 A CN 2012103744495A CN 201210374449 A CN201210374449 A CN 201210374449A CN 102983011 A CN102983011 A CN 102983011A
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Abstract
The invention discloses a method for improving graphene material mass specific capacitance. On the condition that the high specific surface area and the single layer structure of graphene are kept, the electron energy band structure of the graphene is changed by the fact that nitrogen atom displacement mixing happens inside a graphene body, density of electronic states and carrier concentration are increased. The method includes that the graphene is subjected to activating treatment, and meanwhile a high-temperature reduction reaction is carried out, nitrogen atom displacement mixing of the graphene is completed in a one-shot mode. According to the method, the graphene mixed with nitrogen is high in nitrogen content, large in specific surface area, high in specific capacitance, simple in process, stable in nitrogen content, environment-friendly and high in production rate.
Description
Technical field
The present invention relates to method and application thereof that a kind of Graphene nitrogen mixes.
Background technology
Graphene, English name Graphene is that carbon atom is arranged the Colloidal particles that forms according to hexagonal.After 2004 are found by the scientist of University of Manchester, just become the focus that scientific circles and industrial quarters are paid close attention to.Because Graphene weird atom structure, wherein the behavior of charge carrier (electronics and hole) must just can be described with relativistic quantum mechanics.Simultaneously, as the monolayer carbon atomic structure, the theoretical specific area of Graphene is up to 2630m
2/ g.So high specific area and its special atomic structure characteristic are so that Graphene becomes the optimal electrode material of ultracapacitor.
At present, nitrogen-doped graphene is in order to improve the reducing degree of Graphene, to increase the electric conductivity of grapheme material, being mainly used in biology sensor, a ballistic transistor field.How develop in the field of a kind of energy Effective Raise Graphene than electric capacity, the method that scientists often adopts nitrogen to mix is regulated the electronic structure of Graphene.This mainly is because nitrogen-atoms has the atom similar to carbon atom size, and the N carrier density that provides electronics can improve grapheme material, and then increases it and compare electric capacity.Traditional method for preparing nitrogen-doped graphene mainly contains the method for chemical vapour deposition (CVD) and arc discharge, chemical vapour deposition technique is in the process of preparation Graphene, pass into simultaneously ammonia and carry out the nitrogen doping, high nitrogen content is 5%, but can't accomplish SP2 hydridization, can not be in same plane with Graphene, the gained nitrogen-doped graphene has lost planar structure, and doping nitrogen is unstable, very easily loses; Arc discharge method passes into the nitrogen-containing compounds such as pyridine or ammonia in the process of preparation Graphene, preparation nitrogen-doped graphene material, and high nitrogen content is 1%, and very easily loses.Nitrogen content is wayward in the nitrogen-doped graphene of this two kinds of methods preparation, course of reaction is complicated, severe reaction conditions, productive rate are low.
Therefore, in order to satisfy the demand of different field, it is little to develop a kind of environmental pollution, and process is simple, and the doping techniques that specific area is large, nitrogen content is stable, productive rate is higher is the problem that this area need to solve.
Summary of the invention
The technical problem to be solved in the present invention is to overcome existing defective, and the grapheme material that a kind of nitrogen content is high, specific area is large, the nitrogen-atoms displacement higher than electric capacity mixed is provided;
It is simple that another object of the present invention provides a kind of process, the graphene preparation method that nitrogen content is stable, environmental protection and the high nitrogen-atoms displacement of productive rate are mixed.
Purpose of the present invention is come specific implementation by the following technical programs:
The method that a kind of Graphene nitrogen-atoms displacement is mixed is carried out the high temperature reduction reaction in to the Graphene activation processing, a step finishes the nitrogen-atoms displacement of Graphene and mixes, and concrete operations are as follows:
A. pre-treatment: with graphene oxide and activator mix, fully stir drying;
B. simultaneously reduction of activation: the mixture of graphene oxide and activator is put into high temperature reaction stove, after taking out furnace air, in high temperature reaction stove, pass into inert gas protection, be warming up to 500-1500 ℃, then pass into nitrogenous reacting gas, more than the isothermal reaction 1min;
C. reprocessing: after the high temperature reduction reaction finishes, drop to room temperature in inert gas shielding, washing, drying obtain the Graphene that the nitrogen-atoms displacement is mixed.
Described graphene oxide is the product that graphite is peeled off after oxidation.Described mode of oxidizing adopts any one in Hummers method, Staudenmaier method or the Brodie method; Describedly peel off that mode adopts microwave to peel off, pyrolysis expansion is peeled off, in the ultrasonic dispersion any one.
Described activator is one or more the combination in potassium hydroxide, NaOH, phosphoric acid, the zinc chloride, is preferably potassium hydroxide, and optimum is the potassium hydroxide solution of 0.6-1.4g/l.
Described inert gas is selected from one or more the combination in nitrogen, helium, neon, argon gas, Krypton, xenon, the radon gas, is preferably nitrogen or argon gas, optimum for purity be that 99.999% nitrogen or purity are 99.99% argon gas; The flow that passes into inert gas is 80-200m
3/ min, preferred 150cm
3/ min.
Described nitrogenous reacting gas is ammonia, and the flow that passes into nitrogenous reacting gas is 20-100cm
3/ min, preferred 50cm
3/ min.
The temperature of high temperature reduction reaction is 700-1000 ℃ in the described activation while reduction process, preferred 800 ℃; Reaction time is 5-20min, preferred 10min.
Described high temperature reaction stove adopts vacuum tube furnace or calciner.
The grapheme material that a kind of nitrogen-atoms displacement is mixed is the individual layer planar structure, and its nitrogen content is 0.1wt%-21.5wt%, and nitrogen content is stable, and its specific area 〉=2000m2/g is with 1M TEABF
4/ PC as its quality of electrolyte than electric capacity 200F/g-300 F/g, take 6M KOH as its quality of electrolyte than electric capacity as 200F/g-400 F/g.
The grapheme material that above-mentioned nitrogen-atoms displacement is mixed is preferably, and its nitrogen content is 6wt%-9wt%, and nitrogen content is stable, and its specific area is 2100-3000m
2/ g.
The preferred version of the grapheme material that mixes as above-mentioned nitrogen-atoms displacement, the method for utilizing above-mentioned Graphene nitrogen-atoms displacement to mix makes.
A kind of grapheme material quality that improves is than the method for electric capacity, in the situation that keeps Graphene high-specific surface area and single layer structure, in the Graphene body, carry out displacement by nitrogen-atoms and mix, change the electronic band structure of Graphene, increase density of electronic states and carrier concentration, concrete steps are:
Carry out the high temperature reduction reaction in to the Graphene activation processing, a step finishes the nitrogen-atoms displacement of Graphene and mixes, and concrete operations are as follows:
A. pre-treatment: with graphene oxide and activator mix, fully stir drying;
B. simultaneously reduction of activation: the mixture of graphene oxide and activator is put into high temperature reaction stove, after taking out furnace air, in high temperature reaction stove, pass into inert gas protection, be warming up to 500-1500 ℃, then pass into nitrogenous reacting gas, more than the isothermal reaction 1min;
C. reprocessing: after the high temperature reduction reaction finishes, drop to room temperature in inert gas shielding, washing, drying obtain the Graphene that the nitrogen-atoms displacement is mixed.
The Graphene that nitrogen-atoms displacement of the present invention is mixed can be used for super capacitor, lithium ion battery or fuel cell.
The performance of the Graphene that gained nitrogen-atoms displacement of the present invention is mixed can referring to the collection of illustrative plates in the accompanying drawing and photo, be analyzed as follows:
1, Fig. 1,2 be respectively C and N can spectrogram, the C peak is narrower and be near the common 284.5eV of sp2 as can be seen from Figure 1, illustrate that wherein other forms of carbon (for example carbon of sp3 hydridization) content is less, the Graphene after nitrogen mixes still is the single layer structure existence.There are two peaks at the N peak of Fig. 2 near 398.2eV and 399.3 eV, the form that N is described mainly is pyridine type (N-6) and pyrroles's type (N-5).
Can be found out by accompanying drawing 3 that 2, the prepared Graphene of the present invention has obvious fold and hole, guarantee that prepared grapheme material has larger specific area and high porosity, and do not changed the basic structure of Graphene.
3, can find out that by Fig. 4,5 the prepared Graphene of the present invention is used for electrode material for super capacitor, keep preferably rectangle in water system and organic system electrolyte, all the non-oxidation reduction peak illustrates and does not introduce other functional groups in the preparation process.
Principle of the present invention:
Graphene is zero gap semiconductor, possesses unique charge carrier characteristic and excellent electricity quality.The interaction of its electronics and cellular periodic latlice of crystal structure gesture has produced a kind of quasi particle, and namely zero mass dirac-fermion has the characteristic that is similar to photon.The characteristic electron of Graphene can be described with traditional tight binding model, and in this model, electron energy and wave number can be used
Expression,
r 0 =2.8eV is for being close to most transition energy,
aBe lattice constant.The carrier concentration of single-layer graphene is not high, at room temperature has high mobility, and this is so that it can regulate its chemical potential and carrier concentration easily by field effect and gate voltage.For single-layer graphene, its charge carrier shows as the dirac fermion without quality, and Landau damping is
,
, this shows the electronics storage capacity that can improve Graphene by changing energy level.
For ultracapacitor, the relation between the total capacitance of ultracapacitor, quantum capacitance, the electric double layer capacitance three meets
Relation.
C EDL Depend on electrode material for super capacitor, and for some porousness and Carbon Materials with high specific surface area, quantum capacitance
C Q That the restriction ultracapacitor is than the key factor of electric capacity.
Quantum capacitance refers to the capacitance that produced by electronics, hole in the Graphene,
Carrier concentration is the charge carrier number of unit volume, and the carrier concentration of Graphene is from its intrinsic electrostatic potential,
, wherein
V Ch The electromotive force of Graphene,
v F Dirac-fermion speed,
hIt is Planck's constant.Therefore, quantum capacitance
C Q With carrier concentration
n Q Relation meet
And for specific area at 2000m
2Graphene more than the/g is substantially near single layer structure, so the increase of carrier concentration, can significantly improve quantum capacitance, and then increases the ratio electric capacity of grapheme material.
Thinking of the present invention is that Graphene mix is changed its electronic band structure by nitrogen, improves its intrinsic carrier concentration, thus the enhancer quantum capacitance, and then in individual layer has the material with carbon element of high-specific surface area, increase it and compare electric capacity.
The present invention is under inert environments, graphene oxide is fully mixed with activator, then mixture is carried out high-temperature process to remove its oxygen functional group in containing, research is found, Graphene is in activation, and its carbon-carbon bond is opened, and the displacement that more is conducive to nitrogen-atoms is mixed, be conducive to carry out SP2 nitrogen and mix, prepare the Graphene that structure is still mixed for the nitrogen-atoms displacement of individual layer.In this two-dimentional graphene platelet, single nitrogen-atoms has replaced the position of carbon atom, and the extra electron that each nitrogen-atoms provides has increased the carrier concentration of Graphene; Nitrogen mixes and has changed the characteristic electron of graphene platelet, but can not disturb its basic structure.The adding of activator can guarantee that the gained Graphene has larger specific area, does not introduce simultaneously other functional groups, has avoided the existence of fake capacitance, has guaranteed simultaneously the stability of nitrogen.
Beneficial effect of the present invention:
(1) gained grapheme material of the present invention not only can keep large specific area, and nitrogen be doped on the single-layer graphene can the Effective Raise Graphene carrier concentration, increase its quantum capacitance amount, thereby increase specific capacitance; And introducing does not add functional group, has avoided the existence of fake capacitance;
(2) technique of the present invention does not adopt poisonous and hazardous chemical reagent, has avoided a large amount of use chemical reagent, and environmental pollution is little, is applicable to the reduction doping based on the various powders of graphene oxide of the whole bag of tricks preparation;
(3) the present invention reduces doping time short (the shortest 5min), and simple to operate, activation was finished with one step of nitrating reduction reaction, and condition is easily controlled, and output is high, is suitable for industrialized mass;
(4) the present invention can realize the high-quality reduction of graphene oxide material, the Graphene that gained nitrogen mixes still is single layer structure, and itrogen content of getter with nitrogen doped is stable, itrogen content of getter with nitrogen doped is between 0.1%-21.5%, oxygen-containing functional group can be removed fully and is kept stable itrogen content of getter with nitrogen doped, stable itrogen content of getter with nitrogen doped is conducive to the repetition of material and the control of required nitrogen content, satisfies different requirements.
Description of drawings
Accompanying drawing is used to provide a further understanding of the present invention, and consists of the part of specification, is used for together with embodiments of the present invention explaining the present invention, is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is that itrogen content of getter with nitrogen doped of the present invention is the power spectrum collection of illustrative plates of the Graphene C 284.5 eV of 8wt% among the embodiment 1 near;
Fig. 2 is that itrogen content of getter with nitrogen doped of the present invention is the power spectrum collection of illustrative plates of the Graphene N 399.1 eV of 8wt% among the embodiment 1 near;
Fig. 3 is that itrogen content of getter with nitrogen doped of the present invention is the SEM collection of illustrative plates of the Graphene of 8wt% among the embodiment 1;
Fig. 4 is that itrogen content of getter with nitrogen doped of the present invention is that the Graphene of 8wt% among the embodiment 1 is when preparing ultracapacitor as electrode material, with the cyclic voltammetry curve of 1M TEABF4/PC as electrolyte;
Fig. 5 is that itrogen content of getter with nitrogen doped of the present invention is that the Graphene of 8wt% among the embodiment 1 is when preparing ultracapacitor as electrode material, with the cyclic voltammetry curve of 6M KOH as electrolyte.
Fig. 6 is that itrogen content of getter with nitrogen doped of the present invention is the power spectrum collection of illustrative plates of the Graphene C 284.5 eV of 6wt% among the embodiment 2 near;
Fig. 7 is that itrogen content of getter with nitrogen doped of the present invention is the power spectrum collection of illustrative plates of the Graphene N 399.1 eV of 6wt% among the embodiment 2 near;
Fig. 8 is that itrogen content of getter with nitrogen doped of the present invention is the SEM collection of illustrative plates of the Graphene of 6wt% among the embodiment 2;
Fig. 9 is that itrogen content of getter with nitrogen doped of the present invention is that the Graphene of 6wt% among the embodiment 2 is when preparing ultracapacitor as electrode material, with the cyclic voltammetry curve of 1M TEABF4/PC as electrolyte;
Figure 10 is that itrogen content of getter with nitrogen doped of the present invention is that the Graphene of 6wt% among the embodiment 2 is when preparing ultracapacitor as electrode material, with the cyclic voltammetry curve of 6M KOH as electrolyte.
Figure 11 is that itrogen content of getter with nitrogen doped of the present invention is the power spectrum collection of illustrative plates of the Graphene C 284.5 eV of 9wt% among the embodiment 3 near;
Figure 12 is that itrogen content of getter with nitrogen doped of the present invention is the power spectrum collection of illustrative plates of the Graphene N 399.1 eV of 9wt% among the embodiment 3 near;
Figure 13 is that itrogen content of getter with nitrogen doped of the present invention is the SEM collection of illustrative plates of the Graphene of 9wt% among the embodiment 3;
Figure 14 is that itrogen content of getter with nitrogen doped of the present invention is that the Graphene of 9wt% among the embodiment 3 is when preparing ultracapacitor as electrode material, with the cyclic voltammetry curve of 1M TEABF4/PC as electrolyte;
Figure 15 is that itrogen content of getter with nitrogen doped of the present invention is that the Graphene of 9wt% among the embodiment 3 is when preparing ultracapacitor as electrode material, with the cyclic voltammetry curve of 6M KOH as electrolyte.
Embodiment
Below in conjunction with accompanying drawing the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only is used for description and interpretation the present invention, is not intended to limit the present invention.
Embodiment 1:
The Graphene that a kind of nitrogen-atoms displacement is mixed, nitrogen content 8%, specific surface is 2970.8m
2/ g.
Its preparation method is to advance with nitrogen doping reduction reaction in to the Graphene activation, and concrete operations are as follows::
1, gets the standby graphite oxide of Hummers legal system, after microwave is peeled off, obtain the graphene oxide powder;
2, then weighing 500mg graphene oxide powder is dissolved in the KOH solution of 25ml 0.1g/mL, fully stirring, drying;
3, graphene oxide-KOH mixture is placed in the vacuum tube furnace, take out furnace air after, with 150cm
3It is 99.99% argon gas that the flow of/min passes into purity in the vacuum tube furnace, in the environment of inert atmosphere, is warming up to first 800 ℃, keeps temperature-resistant, again with 50cm
3The flow of/min passes into ammonia, and reaction is 10 minutes under 800 ℃ of high temperature;
4, naturally be cooled to room temperature after reaction is finished, washing, drying obtain the Graphene that the nitrogen-atoms displacement is mixed.
The application of gained grapheme material in ultracapacitor is with 1M TEABF
4/ PC is 261.0F/g as its specific capacitance of electrolyte, take 6M KOH as the electrolyte specific capacitance as 368.3F/g.
The XPS collection of illustrative plates of the Graphene that the displacement of gained nitrogen-atoms is mixed is seen Fig. 1, Fig. 2; The SEM collection of illustrative plates is seen Fig. 3; Its performance as electrode is seen Fig. 4, Fig. 5.
Embodiment 2:
The Graphene that a kind of nitrogen-atoms displacement is mixed, nitrogen content 6%, specific surface is 2110.6m
2/ g.
Its preparation method is to advance with nitrogen doping reduction reaction in to the Graphene activation, and concrete operations are as follows:
1, gets the standby graphite oxide of Hummers legal system, after microwave is peeled off, obtain the graphene oxide powder;
2, then weighing 300mg graphene oxide powder is dissolved in the KOH solution of 20ml 0.6g/mL, fully stirring, drying;
3, graphene oxide-KOH mixture is placed in the vacuum tube furnace, take out furnace air after, with 80cm
3It is 99.99% argon gas that the flow of/min passes into purity in the vacuum tube furnace, is warming up to first 1000 ℃, keeps temperature-resistant, again with 20cm
3The flow of/min passes into ammonia, and reaction is 5 minutes under 1000 ℃ of high temperature;
4, naturally be cooled to room temperature after reaction is finished, washing, drying obtain the Graphene that the nitrogen-atoms displacement is mixed.
The application of gained grapheme material in ultracapacitor, take 1M TEABF4/PC as its specific capacitance in the electrolyte as 200.7F/g, take 6M KOH as specific capacitance in the electrolyte as 241.2F/g.
The XPS collection of illustrative plates of the Graphene that the displacement of gained nitrogen-atoms is mixed is seen Fig. 6, Fig. 7; The SEM collection of illustrative plates is seen Fig. 8; Its performance as electrode is seen Fig. 9, Figure 10.
Embodiment 3:
The Graphene that a kind of nitrogen-atoms displacement is mixed, nitrogen content 9%, specific surface is 2300.3m
2/ g.
Its preparation method is to advance with nitrogen doping reduction reaction in to the Graphene activation, and concrete operations are as follows:
1, gets the standby graphite oxide of Hummers legal system, after microwave is peeled off, obtain the graphene oxide powder;
2, then weighing 350mg graphene oxide powder is dissolved in the KOH solution of 20ml 1.4g/mL, fully stirring, drying;
3, graphene oxide-KOH mixture is placed in the vacuum tube furnace, with 180cm
3It is 99.999% nitrogen that the flow of/min passes into purity in the vacuum tube furnace, is warming up to first 900 ℃, keeps temperature-resistant, again with 100cm
3The flow of/min passes into ammonia, and calcining is 10 minutes under 900 ℃ of high temperature;
4, naturally be cooled to room temperature after reaction is finished, washing, drying obtain the Graphene that the nitrogen-atoms displacement is mixed.
The application of gained grapheme material in ultracapacitor is with 1M TEABF
4/ PC is 240.5F/g as the electrolyte specific capacitance, take 6M KOH as specific capacitance in the electrolyte as 298.3F/g.
The XPS collection of illustrative plates of the Graphene that the displacement of gained nitrogen-atoms is mixed is seen Figure 11, Figure 12; The SEM collection of illustrative plates is seen Figure 13; Its performance as electrode is seen Figure 14, Figure 15.
Embodiment 4:
The Graphene that a kind of nitrogen-atoms displacement is mixed, nitrogen content 10%, specific surface is 2300.3m
2/ g.
Its preparation method is to advance with nitrogen doping reduction reaction in to the Graphene activation, and concrete operations are as follows::
1, gets the standby graphite oxide of Staudenmaier legal system, after microwave is peeled off, obtain the graphene oxide powder;
2, then weighing 350mg graphene oxide powder is dissolved in the KOH solution of 20ml 1.4g/mL, fully stirring, drying;
3, graphene oxide-KOH mixture is placed in the vacuum tube furnace, pass into purity in the vacuum tube furnace and be 99.99% argon gas, be warming up to first 700 ℃, keep temperature-resistant, again with 10m
3The flow of/h passes into ammonia, and calcining is 20 minutes under 700 ℃ of high temperature;
4, naturally be cooled to room temperature after reaction is finished, washing, drying obtain the Graphene that the nitrogen-atoms displacement is mixed.
The application of gained grapheme material in ultracapacitor is with 1M TEABF
4/ PC is 240.5F/g as the electrolyte specific capacitance, take 6M KOH as specific capacitance in the electrolyte as 298.3F/g.
The above only is the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment the present invention is had been described in detail, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment puts down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the Graphene nitrogen-atoms displacement method of mixing, it is characterized in that: carry out the high temperature reduction reaction in to the Graphene activation processing, a step finishes the nitrogen-atoms displacement of Graphene and mixes, and concrete operations are as follows:
A. pre-treatment: with graphene oxide and activator mix, fully stir drying;
B. simultaneously reduction of activation: the mixture of graphene oxide and activator is put into high temperature reaction stove, after taking out furnace air, in high temperature reaction stove, pass into inert gas protection, be warming up to 500-1500 ℃, then pass into nitrogenous reacting gas, more than the isothermal reaction 1min;
C. reprocessing: after the high temperature reduction reaction finishes, drop to room temperature in inert gas shielding, washing, drying obtain the Graphene that the nitrogen-atoms displacement is mixed.
2. the Graphene nitrogen-atoms displacement according to claim 1 method of mixing, it is characterized in that: described graphene oxide is the product that graphite is peeled off after oxidation.
3. the method for Graphene nitrogen-atoms displacement doping according to claim 2 is characterized in that: any one in described mode of oxidizing employing Hummers method, Staudenmaier method or the Brodie method; Describedly peel off that mode adopts microwave to peel off, pyrolysis expansion is peeled off, in the ultrasonic dispersion any one.
4. the described Graphene nitrogen-atoms displacement method of mixing according to claim 1, it is characterized in that: described activator is one or more the combination in potassium hydroxide, NaOH, phosphoric acid, the zinc chloride, be preferably potassium hydroxide, optimum is the potassium hydroxide solution of 0.6-1.4g/l.
5. the described Graphene nitrogen-atoms displacement method of mixing according to claim 1, it is characterized in that: described inert gas is nitrogen or argon gas, the flow that passes into inert gas is 80-200m
3/ min, preferred 150cm
3/ min.
6. the described Graphene nitrogen-atoms displacement method of mixing according to claim 1, it is characterized in that: described nitrogenous reacting gas is ammonia, the flow that passes into nitrogenous reacting gas is 20-100cm
3/ min, preferred 50cm
3/ min.
7. the described Graphene nitrogen-atoms displacement method of mixing according to claim 1 is characterized in that: described activation simultaneously in the reduction process temperature of high temperature reduction reaction be 700-1000 ℃, preferred 800 ℃; Reaction time is 5-20min, preferred 10min.
8. the Graphene that mixes of a nitrogen-atoms displacement, it is characterized in that: the Graphene that this nitrogen-atoms displacement is mixed is the individual layer planar structure, and its nitrogen content is 0.1wt%-21.5wt%, and nitrogen content is stable, its specific area 〉=2000m
2/ g is with 1M TEABF
4/ PC as its quality of electrolyte than electric capacity 200F/g-300 F/g, take 6M KOH as its quality of electrolyte than electric capacity as 200F/g-400 F/g.
9. the Graphene that mixes of nitrogen-atoms displacement according to claim 8, it is characterized in that: its nitrogen content is 6wt%-9wt%, and nitrogen content is stable, its specific area is 2100-3000m
2/ g.
10. one kind is improved the grapheme material quality than the method for electric capacity, it is characterized in that: in the situation that keeps Graphene high-specific surface area and single layer structure, nitrogen-atoms is carried out the SP2 displacement in the Graphene body mix, change the electronic band structure of Graphene, increase density of electronic states and carrier concentration, concrete steps are:
Carry out the high temperature reduction reaction in the time of to the Graphene activation processing, a step finishes the nitrogen-atoms displacement of Graphene and mixes, and concrete operations are as follows:
A. pre-treatment: with graphene oxide and activator mix, fully stir drying;
B. simultaneously reduction of activation: the mixture of graphene oxide and activator is put into high temperature reaction stove, after taking out furnace air, in high temperature reaction stove, pass into inert gas protection, be warming up to 500-1500 ℃, then pass into nitrogenous reacting gas, more than the isothermal reaction 1min;
C. reprocessing: after the high temperature reduction reaction finishes, drop to room temperature in inert gas shielding, washing, drying obtain the Graphene that the nitrogen-atoms displacement is mixed.
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| CN108242277A (en) * | 2018-01-10 | 2018-07-03 | 济南大学 | The graphene of a kind 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 |
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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 |
| CN105185605A (en) * | 2015-08-27 | 2015-12-23 | 长春工业大学 | Loaded graphene/metallic compound-contained electrode preparation method based on hollow cathode plasma reduction and nitridation |
| CN105185605B (en) * | 2015-08-27 | 2017-11-10 | 长春工业大学 | Load the electrode preparation method of graphene/metallic compound |
| CN108242277A (en) * | 2018-01-10 | 2018-07-03 | 济南大学 | The graphene of a kind of N doping/conductive metal composite cable and preparation method thereof |
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| 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 |
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