CN107879329A - Nitrogen-doped graphene and preparation method thereof - Google Patents
Nitrogen-doped graphene and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of nitrogen-doped graphene and preparation method thereof, belong to technical field of inorganic nonmetallic materials.The method of the present invention includes：A. graphite is sufficiently mixed with the concentrated sulfuric acid at 5~5 DEG C；B. 10~20 DEG C are warming up to, point 3~6 addition potassium permanganate, each 5~15min of interval time；C. 25~60 DEG C are warming up to, 1~2h is reacted, obtains mixed reaction solution；D. 98 DEG C~100 DEG C 20~60min of isothermal reaction are warming up to；E. hydrogen peroxide reaction is added after being cooled to room temperature；F. purifying obtains graphene oxide；G. graphene oxide is well mixed with water, nitrogen-containing compound and reducing agent, 50~180 DEG C of 3~8h of reaction；H. purify, be drying to obtain nitrogen-doped graphene.The yield of the present invention is high, and the graphene yield of N doping is 32~42%；Fault of construction is less.
Description
Technical field
The present invention relates to a kind of nitrogen-doped graphene and preparation method thereof, belong to technical field of inorganic nonmetallic materials.
Background technology
Graphene is a kind of inorganic non-metallic material emerging in recent years, has the big (2630m of specific surface area2/ g), intensity
High (young's modulus is up to 1TPa), carrier mobility height (200000cm2V-1s-1), thermal conductivity high (5000W/mK), thermostabilization
The excellent properties such as property height, have very extensive application prospect.Graphene size and edge shape can be changed by element doping
Looks, so as to regulate and control graphene physical property and expand the application of graphene.
The property of nitrogen-doping graphene and graphene are significantly different, such as the spin density and distribution of charges of carbon atom
Influenceed by neighboring atom, new avtive spot is created in graphenic surface.These avtive spots are also the work of catalytic reaction
Property site, metallic atom are easier to deposit on these avtive spots.Why the performance of nitrogen-doped graphene is than graphene
It is because introducing nitrogen-atoms well, surface defect and randomness increase is caused by nitrogen-atoms, add electrode and electrolyte solution
Wettability and improve chemical property.But the nitrogen-atoms contained by the nitrogen-doped graphene used in above-mentioned work mainly with
Pyridine nitrogen and the form of graphite nitrogen are present, and there are some researches show pyridine nitrogen and graphite nitrogen species can promote lithium ion in graphite layers
Insertion and disengaging, therefore the high nitrogen-doped graphene of graphite nitrogen content can be as the excellent performance electrode material of lithium ion battery
Material.
Generally, carrying out N doping to graphene often has two kinds, it is a kind of be on the adsorption of graphene gas,
Metal or organic molecule, another method are then that the carbon atom in lattice is replaced with hetero atoms such as N, B or P.Both approaches are equal
Can be with the chemical property of modulation graphene, but the latter is more stable.After N atoms are incorporated into graphene, nitrogen-atoms mainly with
Three kinds of forms are present：With two carbon atom bondings at edge or fault location, the P electronics of nitrogen-atoms contributes to the pi-conjugated of graphene
Three carbon atom bondings inside system, with graphene.Pyridine nitrogen or pyrroles's nitrogen can be then generated with two carbon atom bondings, with three
Individual carbon atom bonding then generates graphite nitrogen, position of intersecting point of the graphite nitrogen in three phenyl ring.In the synthetic method of nitrogen-doped graphene
Post-processing approach is only to carry out N doping to surface, theoretically, in the nitrogen-doped graphene that direct synthesis technique obtains
Nitrogen-atoms can be evenly distributed in graphene-structured.
With the development of graphene, the preparation of graphene is progressively ripe, because physical method prepares graphene yield institute
Limit, material supply section scholar more stress to attempt now chemically to look for it is a kind of can industrialized production high-quality graphene experiment side
Case.Wherein oxidation-reduction method synthesizing graphite alkene, because its finished product is stable, securely and reliably, cost is cheap extensively to be favored.Hummers methods
It is exactly the common method that forefathers prepare graphene oxide by long-felt, but Hummers methods prepare the process of graphene oxide
Fault of construction, composition regulation and control and environment on final product influence larger difficulty, and low yield be present, are prepared at present by graphite
Nitrogen-doped graphene method, by graphite feed intake with terms of output, yield 20% or so.
The content of the invention
The invention solves first technical problem be to provide a kind of preparation method of nitrogen-doped graphene, this method
Yield is high.
To solve first technical problem of the present invention, the preparation method of nitrogen-doped graphene of the invention includes following step
Suddenly：
A. graphite is sufficiently mixed with the concentrated sulfuric acid at -5~5 DEG C；
B. 10~20 DEG C are warming up to, point 3~6 addition potassium permanganate, each 5~15min of interval time；
C. 25~60 DEG C are warming up to, 1~2h is reacted, obtains mixed reaction solution；
D. 98 DEG C~100 DEG C 20~60min of isothermal reaction are warming up to；
E. hydrogen peroxide reaction is added after being cooled to room temperature；
F. purifying obtains graphene oxide；
G. graphene oxide and water, nitrogen-containing compound and reducing agent are mixed, 50~180 DEG C are reacted 3~8h or will aoxidized
Graphene is warming up to 400~600 DEG C of insulations with being incubated 20~40min at 200~400 DEG C after nitrogen-containing compound, reducing agent mixing
20~40min, then it is warming up to 700~900 DEG C of 20~40min of insulation；H. purify, be drying to obtain nitrogen-doped graphene；
Wherein, the mass volume ratio of the graphite and the concentrated sulfuric acid is 1:15~40g/mL；The quality of graphite and potassium permanganate
Than for：1：3~6；The mass volume ratio of the graphite and hydrogen peroxide is 1:10~25g/mL；The nitrogen-containing compound is dimethyl
At least one of formamide, urea or melamine.
Preferably, the reducing agent is at least one of L-AA, urea or melamine；The graphite oxide
The mass ratio of alkene and nitrogen-containing compound, reducing agent is 1:0.54:3~8.
Preferably, a steps also add sodium nitrate, and the mass ratio of the graphite and sodium nitrate is 1~3：1.
Preferably, the step c is additionally included in the mixed reaction solution plus water reacts 10~40min, adds Gao Meng
Sour 10~20min of nak response, potassium permanganate that water adds with step c, the mass ratio of graphite are：150:1:1.
Preferably, the technique purified described in f steps is：It is miscellaneous that 3000~5000r/min centrifuges 5~15min removing bulky grains
Matter, then it is adjusted to 3000~5000r/min and carries out 3~5 centrifugations, 5~15min, is carried out 3~5 times with distilled water afterwards every time
Centrifugation, until centrifugate is in neutral or with watery hydrochloric acid and each centrifuge washing of ethanol more than 5 times, until in solution without chlorion.
Preferably, the concentration of hydrogen peroxide described in step e is 20~40%.
Preferably, purifying described in h steps is absolute ethyl alcohol eccentric cleaning 3~5 times, 2000~5000r/min of rotating speed centrifugations 5
~15min, then centrifuged more than 6 times or with deionized water 4500r.m with distilled water-1Centrifuge washing 5~10 times, the drying process
Dried 12~36 hours for 20~40 DEG C.
Preferably, a steps and the method for the mixing described in g steps are at least one of ultrasound or stirring.
Preferably, the method for the mixing described in g steps is ultrasound after graphene oxide mixes 20~40min with water
1~4h is handled, after adding nitrogen-containing compound and reducing agent, is ultrasonically treated 0.5~2h.
The invention solves second technical problem be to provide a kind of few nitrogen-doped graphene of defect, the N doping
Graphene is adopted to be prepared with the aforedescribed process；The N doping rate of the nitrogen-doped graphene is preferably 6.2~8.1%, by oxygen
It is few that atom interts formation fault of construction in carbon-coating.
Beneficial effect：The present invention has synthesized graphene oxide by improving Hummers methods, specific such as feed change proportioning,
The measures such as reduction mode, realize the purpose of optimization graphene oxide institutional framework, there is provided the graphene material needed for battery can be met
The preparation method of material, and there is following significant advantage：
1st, yield is high, and the graphene yield of N doping is 32~42%；
2nd, the graphene-structured defect that the present invention obtains is less；
3rd, the present invention carries out carrying for N doping amount by different nitrogen sources, such as dimethylformamide, trimerization of nitriles ammonia, urea etc.
Height, while focus on the change of temperature in preparation method, reducing agent, dispersing mode, can so as to improve N doping amount in graphene
Control property；
4th, environment influence is small in reduction process, and reduces more abundant.
Brief description of the drawings
Fig. 1 is that the nitrogen-doped graphene SEM of embodiment 1 schemes；
Fig. 2 is that the nitrogen-doped graphene SEM of embodiment 2 schemes；
Fig. 3 is that the nitrogen-doped graphene SEM of embodiment 3 schemes；
Fig. 4 is the resistivity map of different samples；
Fig. 5 is the Raman spectrogram of inventive samples；
Fig. 6 is the XRD of inventive samples；
Wherein C is graphite, and GO is graphene oxide, and VC-RGO is the nitrogen-doped graphene of embodiment 1, and NH-RGO is implementation
The nitrogen-doped graphene of example 2.
Embodiment
To solve first technical problem of the present invention, the preparation method of nitrogen-doped graphene of the invention includes following step
Suddenly：
A. graphite is sufficiently mixed with the concentrated sulfuric acid at -5~5 DEG C；
B. 10~20 DEG C are warming up to, point 3~6 addition potassium permanganate, each 5~15min of interval time；
C. 25~60 DEG C are warming up to, 1~2h is reacted, obtains mixed reaction solution；
D. 98 DEG C~100 DEG C 20~60min of isothermal reaction are warming up to；
E. hydrogen peroxide reaction is added after being cooled to room temperature；
F. purifying obtains graphene oxide；
G. graphene oxide and water, nitrogen-containing compound and reducing agent are mixed, 50~180 DEG C are reacted 3~8h or will aoxidized
Graphene is warming up to 400~600 DEG C of insulations with being incubated 20~40min at 200~400 DEG C after nitrogen-containing compound, reducing agent mixing
20~40min, then it is warming up to 700~900 DEG C of 20~40min of insulation；
H. purify, be drying to obtain nitrogen-doped graphene；
Wherein, the mass volume ratio of the graphite and the concentrated sulfuric acid is 1:15~40g/mL；The quality of graphite and potassium permanganate
Than for：1：3~6；The mass volume ratio of the graphite and hydrogen peroxide is 1:10~25g/mL；The nitrogen-containing compound is dimethyl
At least one of formamide, urea or melamine.
Preferably, the reducing agent is at least one of L-AA, urea or melamine；The graphite oxide
The mass ratio of alkene and nitrogen-containing compound, reducing agent is 1:0.54:3~8.
Preferably, a steps also add sodium nitrate, and the mass ratio of the graphite and sodium nitrate is 1~3：1.
Preferably, the step c is additionally included in the mixed reaction solution plus water reacts 10~40min, adds Gao Meng
Sour 10~20min of nak response, potassium permanganate that water adds with step c, the mass ratio of graphite are：150:1:1.
Preferably, the technique purified described in f steps is：It is miscellaneous that 3000~5000r/min centrifuges 5~15min removing bulky grains
Matter, then it is adjusted to 3000~5000r/min and carries out 3~5 centrifugations, 5~15min, is carried out 3~5 times with distilled water afterwards every time
Centrifugation, until centrifugate is in neutral or with watery hydrochloric acid and each centrifuge washing of ethanol more than 5 times, until in solution without chlorion.
Preferably, the concentration of hydrogen peroxide described in step e is 20~40%.
Preferably, purifying described in h steps is absolute ethyl alcohol eccentric cleaning 3~5 times, 2000~5000r/min of rotating speed centrifugations 5
~15min, then centrifuged more than 6 times or with deionized water 4500r.m with distilled water-1Centrifuge washing 5~10 times, the drying process
Dried 12~36 hours for 20~40 DEG C.
Preferably, a steps and the method for the mixing described in g steps are at least one of ultrasound or stirring.
Preferably, the method for the mixing described in g steps is ultrasound after graphene oxide mixes 20~40min with water
1~4h is handled, after adding nitrogen-containing compound and reducing agent, is ultrasonically treated 0.5~2h.
The invention solves second technical problem be to provide a kind of few nitrogen-doped graphene of defect, the N doping
Graphene is adopted to be prepared with the aforedescribed process；The N doping rate of the nitrogen-doped graphene is preferably 6.2~8.1%, by oxygen
It is few that atom interts formation fault of construction in carbon-coating.
The embodiment of the present invention is further described with reference to embodiment, therefore not limited the present invention
System is among described scope of embodiments.
Embodiment 1
2g graphite powders and 1g sodium nitrate are taken, is put into 500mL beakers.The 50mL concentrated sulfuric acids are measured again to pour into beaker and put
In the electric-heated thermostatic water bath for being placed with a large amount of ice cubes, 0 DEG C is kept the temperature at, uses magnetic stirrer 30min；Afterwards
Add people's potassium permanganate, by 3 additions of 6g potassium permanganate point, each 2g, each interval time is 15min, and this process ensures
Reaction temperature is in 15 DEG C of progress.Electric hot water bath is then turned on, by temperature setting at 35 DEG C, isothermal reaction 2h, is slowly added to
300mL distilled water dilutes solution.30min is reacted after adding distilled water diluting, is slowly added to 2g potassium permanganate reaction 15min,
Water-bath is set to be warming up to 98 DEG C of isothermal reaction 30min again.
Beaker is taken out to be cooled to 50mL30% hydrogen peroxide is added after room temperature, observation solution colour change, solution by
Brownish black quickly becomes golden yellow and is put into ultrasonic 30min in ultrasonic cleaner afterwards with a large amount of bubbles, and what is obtained is scattered
Liquid pours into centrifuge tube and centrifuged in batches.Rotating speed is first adjusted to 4000r/min centrifugations 10min and removes large granular impurity, then
It is adjusted to 5000r/min repeatedly to be centrifuged, each 10min, until detecting the filtrate of centrifugation with powder, solution is still clear
Clearly.Repeatedly centrifuged with distilled water afterwards, until using pH test paper detection centrifugate medication will be precipitated in centrifuge tube in neutrality
Spoon takes out.Finally, mistake in baking oven is put the precipitate in, duration is dried and is more than 36h, obtained solid is graphene oxide sample
Product.
Take 1g graphene oxides sample to be mixed with 250ml distilled water, after stirring 30min at room temperature, be ultrasonically treated 2h.Its
Secondary, the L-AA powder for weighing 4g is added in graphene oxide solution, ultrasonic 0.5h.Then L-AA will be added
Graphene oxide solution be placed in 80 DEG C of water-bath and equally cover water-bath pot cover, avoid a large amount of evaporations of moisture, constant temperature
React 8h；Because in whole course of reaction, L-AA plays a part of reducing agent, and its oxidation product plays stabilizer
Effect, therefore whole reaction need not add stabilizer.Still use absolute ethyl alcohol eccentric cleaning 1 time, rotating speed 5000r/min centrifugations
10min, then centrifuged 6 times with distilled water, obtains centrifuge tube bottom sediment and is transferred to 60 DEG C of dryings in drying box and be more than 24h, obtains
To solid be nitrogen-doped graphene.
Nitrogen content in nitrogen-doped graphene is evaluated by xps, the graphene N doping rate for detecting acquisition is 8.1%.Nitrogen
The yield of doped graphene is that it is 42% to calculate graphene yield by the mass ratio of the product and input graphite powder of acquisition,
Resistivity refers to table 1 and Fig. 4.Its SEM figure refers to Fig. 1, and Raman spectrum and XRD refer to Fig. 5 and Fig. 6.
Embodiment 2
Take a large amount of ice cubes to be put into 1000mL beaker, add appropriate water, keep the temperature at 0 DEG C.Again by one
Individual 250mL beakers are placed in large beaker, are measured the 46mL concentrated sulfuric acids and are slowly added in small beaker.2g graphite powders are weighed to be added slowly to
In the 46mL concentrated sulfuric acids, side slowly stirs.Solution is changed into grey black from water white transparency, slightly metallic luster on face.Weigh 6g Gao Meng
Sour potassium, six parts are divided into, every five minutes plus once, and prolonged agitation.Liquid is become by grey black after adding potassium permanganate
Emerged with purple cyan, and with purple smoke, keeping temperature is no more than 20 DEG C.Beaker is taken out into ice bath bar after addition
Part, 1h is reacted in placement at room temperature, and is stirred continuously always.Magnetic stirring apparatus heat button is opened, beaker is put into 100 DEG C of perseverance
30Min is reacted in warm magnetic stirring apparatus, insulation reaction 30min is rearmounted to be cooled down at room temperature.Then it is double to be slowly added into 20mL30%
Oxygen water and 200mL deionized waters, the boiling of solution moment are changed into yellowish-brown.With watery hydrochloric acid and each centrifuge washing of ethanol 5 times after standing,
Until without chlorion, GO dispersion liquids are obtained after standing in solution.
The isabelline dispersion liquids of a 30mL are taken to be positioned in beaker；GO is pressed again：Urea is 1:5 be placed in ultrasonator surpass
30min is swung in acoustic shock, allows GO dispersion liquids to be sufficiently mixed with urea；Mixed liquor is put into magnetic stirring apparatus again, while opens heating
Switch, temperature setting stir 40min at 60 DEG C, allow both to be sufficiently mixed；Mixed solution is positioned in hydrothermal reaction kettle again, will
The reactor for tightening reaction kettle cover is put into 180 DEG C of drying box and reacts 3h；Reactor is taken out after 3h and places nature at room temperature
Cooling；Sample is taken out from reactor and obtains black solid, then with deionized water 4500r.m-1It is put in after centrifuge washing 10 times
Taken out after being dried 24 hours in 30 DEG C of thermostatic drying chamber and obtain nitrogen-doped graphene.
It is 6.2% to detect graphene N doping rate, and it is 32% to calculate graphene yield, and resistivity refers to table 1 and Fig. 4.Its
SEM figures refer to Fig. 2, and Raman spectrum and XRD refer to Fig. 5 and Fig. 6.
Embodiment 3
Graphene oxide dispersion is prepared with embodiment 2.
Take 1g graphene oxides to be mixed in 4g melamines in Yan Portland and grind 30min；It is to be ground into by taupe pasty state
Put after thing with square crucible, being put in tube furnace and calcining；Tube furnace is opened, after being passed through, releasing nitrogen three times, is passed through nitrogen.
The design temperature program on interface display plate, temperature rise to 200 DEG C of insulation 30min, and temperature rises to 500 DEG C of insulation 30min,
Temperature is risen into 800 DEG C of insulation 30min again.The release of nitrogen is paid attention in operating process, prevents suck-back phenomenon.Calcine
Cheng Hou, sample is taken out after tube furnace cooling, obtains black powder material.It is subsequently placed in Yan Portland plus little water is ground
20min, then centrifuge washing 5 times, finally it is put in drying box and dries i.e. acquisition nitrogen-doped graphene.
The graphene N doping rate of detection doping is 7.6%, and it is 39.5% to calculate graphene yield, and resistivity refers to table 1
And Fig. 4.Its SEM figure refers to Fig. 3.
The resistivity of the nitrogen-doped graphene of the graphite of table 1, graphite oxide and embodiment 1~3
| Sample | Resistivity | Deviation |
| Native graphite | 81 | +3.3 |
| Graphene oxide | 426 | +5.7 |
| Embodiment 1 | 16.8 | +1.5 |
| Embodiment 2 | 35.3 | +2.5 |
| Embodiment 3 | 20.5 | +2 |
As seen from Figure 5 the VC-RGO of embodiment 1 G peak broadening compare embodiment 2 NH-RGO it is smaller, ID/IG's
Value is also smaller.In addition, with respect to NH-RGO to high frequency field offset, these all illustrate VC-RGO's for VC-RGO G peaks and D peaks in figure
The smaller contained defect of crystal face is less, and performance is more excellent.
As seen from Figure 6, compared to graphite (C), the nitrogen-doped graphene diffraction maximum that Examples 1 and 2 are prepared is equal
It is contained therein because that cannot be removed completely in reduction process although being all 002 crystal face in graphite diffraction maximum angle direction less than normal
Oxygen-containing functional group.So although the interlayer spacing of graphene has reduced, but still it is bigger than graphite.
In addition, NH-RGO and VC-RGO is contrastingly, NH-RGO occurs diffraction maximum, but peak value unobvious in 2 θ=24.68 °
And slightly drift.VC-RGO then becomes apparent than NH-RGO diffraction maximum, and its 2 θ=24.38 ° is it can be seen that use L-AA
Oxygen-containing functional group contained by the graphene oxide of reduction is less, structure is more complete.
Claims (10)
1. the preparation method of nitrogen-doped graphene, it is characterised in that the preparation method of the nitrogen-doped graphene includes following step
Suddenly：
A. graphite is sufficiently mixed with the concentrated sulfuric acid at -5~5 DEG C；
B. 10~20 DEG C are warming up to, point 3~6 addition potassium permanganate, each 5~15min of interval time；
C. 25~60 DEG C are warming up to, 1~2h is reacted, obtains mixed reaction solution；
D. 98 DEG C~100 DEG C 20~60min of isothermal reaction are warming up to；
E. hydrogen peroxide reaction is added after being cooled to room temperature；
F. purifying obtains graphene oxide；
G. graphene oxide and water, nitrogen-containing compound and reducing agent are mixed, 50~180 DEG C of 3~8h of reaction or by graphite oxide
Alkene and nitrogen-containing compound, reducing agent at 200~400 DEG C are incubated 20~40min after mixing, be warming up to 400~600 DEG C of insulations 20~
40min, then it is warming up to 700~900 DEG C of 20~40min of insulation；
H. purify, be drying to obtain nitrogen-doped graphene；
Wherein, the mass volume ratio of the graphite and the concentrated sulfuric acid is 1:15~40g/mL；The mass ratio of graphite and potassium permanganate is：
1：3~6；The mass volume ratio of the graphite and hydrogen peroxide is 1:10~25g/mL；The nitrogen-containing compound is dimethyl formyl
At least one of amine, urea or melamine.
2. the preparation method of nitrogen-doped graphene according to claim 1, it is characterised in that the reducing agent is that L- is anti-bad
At least one of hematic acid, urea or melamine；The mass ratio of the graphene oxide and nitrogen-containing compound, reducing agent is 1:
0.54:3~8.
3. the preparation method of nitrogen-doped graphene according to claim 1 or 2, it is characterised in that a steps are also added
Sodium nitrate, the mass ratio of the graphite and sodium nitrate is 1~3：1.
4. the preparation method of the nitrogen-doped graphene according to any one of claims 1 to 3, it is characterised in that the step c
It is additionally included in the mixed reaction solution plus water reacts 10~40min, adds potassium permanganate and react 10~20min, water walks with c
Suddenly potassium permanganate, the mass ratio of graphite added be：150:1:1.
5. the preparation method of the nitrogen-doped graphene according to any one of Claims 1 to 4, it is characterised in that described in f steps
The technique of purifying is：3000~5000r/min centrifuges 5~15min and removes large granular impurity, is then adjusted to 3000~5000r/
Min carries out 3~5 centrifugations, 5~15min every time, carries out 3~5 centrifugations with distilled water afterwards, until centrifugate in neutrality or
With watery hydrochloric acid and each centrifuge washing of ethanol more than 5 times, until in solution without chlorion.
6. the preparation method of the nitrogen-doped graphene according to any one of Claims 1 to 5, it is characterised in that described in step e
The concentration of hydrogen peroxide is 20~40%.
7. the preparation method of the nitrogen-doped graphene according to any one of claim 1~6, it is characterised in that described in h steps
Purify as absolute ethyl alcohol eccentric cleaning 3~5 times, 2000~5000r/min of rotating speed centrifuges 5~15min, then centrifuges 6 with distilled water
More than secondary or with deionized water 4500rm-1Centrifuge washing 5~10 times, the drying process are that 20~40 DEG C of dryings 12~36 are small
When.
8. the preparation method of the nitrogen-doped graphene according to any one of claim 1~6, it is characterised in that a steps and g
The method of mixing described in step is at least one of ultrasound or stirring.
9. the preparation method of nitrogen-doped graphene according to claim 8, it is characterised in that mixing described in g steps
Method is after graphene oxide mixes 20~40min with water, to be ultrasonically treated 1~4h, adds nitrogen-containing compound and reducing agent
Afterwards, it is ultrasonically treated 0.5~2h.
10. nitrogen-doped graphene, it is characterised in that the nitrogen-doped graphene is using the side described in any one of claim 1~9
Method is prepared；The N doping rate of the nitrogen-doped graphene is preferably 6.2~8.1%, is interted by oxygen atom in carbon-coating and is formed
Fault of construction is few.
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| CN108706578A (en) * | 2018-07-05 | 2018-10-26 | 新奥石墨烯技术有限公司 | Nitrogen-doped graphene and preparation method thereof and capacitor |
| CN108963270A (en) * | 2018-07-12 | 2018-12-07 | 山东联星能源集团有限公司 | A kind of preparation method of nitrogen-doped graphene/di-iron trioxide combination electrode material |
| CN109264704A (en) * | 2018-12-10 | 2019-01-25 | 成都理工大学 | Improve redox graphene preparation method |
| CN111707720A (en) * | 2020-07-13 | 2020-09-25 | 重庆文理学院 | Preparation and application of nano-silver/pyridine functionalized graphene modified electrode |
| CN113402939A (en) * | 2021-06-24 | 2021-09-17 | 陈小花 | Graphene conductive coating and preparation method thereof |
| CN115318268A (en) * | 2021-09-30 | 2022-11-11 | 湘潭大学 | Preparation method and application of nonmetallic catalyst for liquid-phase hydrogenation of nitroarene |
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| CN106276885A (en) * | 2016-10-21 | 2017-01-04 | 兰州理工大学 | The fast preparation method of high conductivity nitrogen-doped graphene |
| US20170174522A1 (en) * | 2015-12-16 | 2017-06-22 | Agency For Defense Development | Nitrogen-doped graphene assembly and method of preparing the same |
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| CN102120572A (en) * | 2011-01-24 | 2011-07-13 | 南京大学 | Method for preparing nitrogen-doped graphene |
| CN102616775A (en) * | 2012-04-16 | 2012-08-01 | 南京大学 | Preparation method for water phase of nitrogen-doped graphene |
| US20170174522A1 (en) * | 2015-12-16 | 2017-06-22 | Agency For Defense Development | Nitrogen-doped graphene assembly and method of preparing the same |
| CN106276885A (en) * | 2016-10-21 | 2017-01-04 | 兰州理工大学 | The fast preparation method of high conductivity nitrogen-doped graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108706578A (en) * | 2018-07-05 | 2018-10-26 | 新奥石墨烯技术有限公司 | Nitrogen-doped graphene and preparation method thereof and capacitor |
| CN108706578B (en) * | 2018-07-05 | 2020-08-11 | 新奥石墨烯技术有限公司 | Nitrogen-doped graphene, preparation method thereof and capacitor |
| CN108963270A (en) * | 2018-07-12 | 2018-12-07 | 山东联星能源集团有限公司 | A kind of preparation method of nitrogen-doped graphene/di-iron trioxide combination electrode material |
| CN109264704A (en) * | 2018-12-10 | 2019-01-25 | 成都理工大学 | Improve redox graphene preparation method |
| CN111707720A (en) * | 2020-07-13 | 2020-09-25 | 重庆文理学院 | Preparation and application of nano-silver/pyridine functionalized graphene modified electrode |
| CN113402939A (en) * | 2021-06-24 | 2021-09-17 | 陈小花 | Graphene conductive coating and preparation method thereof |
| CN115318268A (en) * | 2021-09-30 | 2022-11-11 | 湘潭大学 | Preparation method and application of nonmetallic catalyst for liquid-phase hydrogenation of nitroarene |
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