CN109485031A - A kind of nitrogen-doped graphene and preparation method thereof - Google Patents
A kind of nitrogen-doped graphene and preparation method thereof Download PDFInfo
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- CN109485031A CN109485031A CN201811374952.4A CN201811374952A CN109485031A CN 109485031 A CN109485031 A CN 109485031A CN 201811374952 A CN201811374952 A CN 201811374952A CN 109485031 A CN109485031 A CN 109485031A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 29
- 239000006185 dispersion Substances 0.000 claims abstract description 26
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 5
- 239000011343 solid material Substances 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000010828 elution Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000002604 ultrasonography Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- -1 graphite Alkene Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of preparation methods of nitrogen-doped graphene, comprising the following steps: mixes melamine and graphene oxide dispersion, carries out hydro-thermal reaction, obtain N doping redox graphene；The N doping redox graphene is made annealing treatment, nitrogen-doped graphene is obtained.The present invention can also be effectively by N doping into redox graphene structure while redox graphene using hydro-thermal reaction；Unreduced oxygen-containing functional group in hydrothermal reaction process can further be restored by carrying out annealing, obtain nitrogen-doped graphene.There is good charge-discharge performance and higher charging and discharging capacity when electrode material of the graphene of the present invention as lithium ion battery.
Description
Technical field
The present invention relates to doped graphene technical field more particularly to a kind of preparation methods of nitrogen-doped graphene.
Background technique
Graphene is a kind of two-dimensional layered-structure material, since its unique property, such as fast ionic insertion and charge turn
Shifting ability and the factors such as additional chemical bond are formed with other materials, extensive concern has been obtained in lithium ion battery.So
And accumulating between graphene sheet layer structure again and its lower theoretical capacity limit it in electronic and hybrid-power electric vehicle
Further applying in.
And N doping then can effectively regulate and control the electronic structure of graphene, and then improve the chemical property of graphene.
In the prior art, the method for preparing nitrogen-doped graphene mainly includes chemical vapor deposition, electrothermal reaction, plasma-deposited
Method.But there is graphene surface high oxygen content, in electrochemical applications in the nitrogen-doped graphene that the above method is prepared
The few defect of active site.
Summary of the invention
The purpose of the present invention is to provide a kind of method for preparing nitrogen-doped graphene, the nitrogen that the method is prepared is mixed
Miscellaneous graphene surface oxygen content is low, and active site is more in electrochemical applications.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of nitrogen-doped graphene, comprising the following steps:
Melamine and graphene oxide dispersion are mixed, hydro-thermal reaction is carried out, obtains N doping reduction-oxidation graphite
Alkene；
The N doping redox graphene is made annealing treatment, nitrogen-doped graphene is obtained.
Preferably, the mass ratio of graphene oxide and melamine is 1:(1~5 in the graphene oxide dispersion).
Preferably, the concentration of the graphene oxide dispersion is 0.5~5mg/mL.
Preferably, the mixed temperature is 60~90 DEG C, and the mixed time is 0.5~3.5h.
Preferably, the temperature of the hydro-thermal reaction is 150~200 DEG C, and the time of the hydro-thermal reaction is 10~35h.
Preferably, after the hydro-thermal reaction further include: be separated by solid-liquid separation gained system, successively to obtained solid material
It is washed and is dried, obtain N doping redox graphene.
Preferably, the temperature of the annealing is 500~900 DEG C, and the time of the annealing is 0.5~2.5h.
Preferably, the annealing carries out in vacuum environment.
The present invention also provides the nitrogen-doped graphenes that the preparation method is prepared.
Preferably, the nitrogen content in the nitrogen-doped graphene is 3.0%~12.0%.
The present invention provides a kind of preparation methods of nitrogen-doped graphene, comprising the following steps: by melamine and oxidation
Graphene dispersing solution mixing, carries out hydro-thermal reaction, obtains N doping redox graphene；By the N doping oxygen reduction fossil
Black alkene is made annealing treatment, and nitrogen-doped graphene is obtained.The present invention is using the high melamine of nitrogen content as nitrogen source, with oxidation
Hydro-thermal reaction occurs for graphene mixing, can also be effectively by N doping to oxygen reduction fossil while redox graphene
In black alkene structure；Unreduced oxygen-containing functional group in hydrothermal reaction process can further be restored by carrying out annealing, into one
Step reduces the oxygen content in graphene, while annealing improves the content of pyridine nitrogen in nitrogen-doped graphene, and the nitrogen is mixed
It is miscellaneous enter graphene lattice in, generate vacancy defect, be the attached of lithium ion when enabling its electrode material as lithium ion battery
More active sites are provided, and then make the lithium ion battery that there is good charge-discharge performance and higher fill
Specific discharge capacity.
Detailed description of the invention
Fig. 1 is the SEM figure of nitrogen-doped graphene described in embodiment 1；
Fig. 2 is the TEM figure of nitrogen-doped graphene described in embodiment 1；
Fig. 3 is the XRD diagram of nitrogen-doped graphene described in embodiment 1；
Fig. 4 is the XPS C1s spectrogram of nitrogen-doped graphene described in embodiment 1；
Fig. 5 is the XPS N1s spectrogram of nitrogen-doped graphene described in embodiment 1；
Fig. 6 is nitrogen-doped graphene described in embodiment 1 in 200 charge and discharge cycles figures.
Specific embodiment
The present invention provides a kind of preparation methods of nitrogen-doped graphene, comprising the following steps:
Melamine and graphene oxide dispersion are mixed, hydro-thermal reaction is carried out, obtains N doping reduction-oxidation graphite
Alkene；
The N doping redox graphene is made annealing treatment, nitrogen-doped graphene is obtained.
In the present invention, if without specified otherwise, all raw material components are commercial product well known to those skilled in the art.
The present invention mixes melamine and graphene oxide dispersion, carries out hydro-thermal reaction, obtains N doping oxygen reduction
Graphite alkene.
In the present invention, the preparation method of the graphene oxide dispersion, preferably includes following steps: by graphite oxide
Alkene is mixed with water, obtains graphene oxide dispersion.In the present invention, the graphene uses preferably using graphite as raw material
Hummer method is prepared.The present invention does not have any special restriction to the detailed process of the Hummer method, using this field
Process known to technical staff carries out.In the present invention, the mixing preferably carries out under conditions of ultrasound.In the present invention
In, the time of the ultrasound is preferably 0.5~1.5h, more preferably 0.8~1.2h.The present invention does not have the rate of the ultrasound
Any special restriction, using ultrasonic rate well known to those skilled in the art.
In the present invention, the concentration of the graphene oxide dispersion is preferably 0.5~5mg/mL, more preferably 1~
4mg/mL, most preferably 2~3mg/mL.
In the present invention, the mass ratio of graphene oxide and melamine is preferably 1 in the graphene oxide dispersion:
(1~5), more preferably 1:(2~4)；In a specific embodiment of the present invention, graphite oxide in the graphene oxide dispersion
The mass ratio of alkene and melamine can be selected specifically to 1:1,1:3 or 1:5.
In the present invention, the melamine and the temperature of graphene oxide dispersion mixing are preferably 60~90 DEG C, more
Preferably 65~85 DEG C, most preferably 70~80 DEG C；The time of the melamine and graphene oxide dispersion mixing is preferred
For 0.5~3.5h, more preferably 1~3h, most preferably 1.5~2.5h.In the present invention, the mixing is preferably in the item of stirring
It is carried out under part.The present invention does not have any special restriction to the rate of the stirring, is stirred using well known to those skilled in the art
Mix rate.
In the present invention, the temperature of the hydro-thermal reaction is preferably 150~200 DEG C, more preferably 160~190 DEG C, optimal
It is selected as 170~180 DEG C；The time of the hydro-thermal reaction is preferably 10~35h, more preferably 15~30h, most preferably 20~
25h。
The present invention does not have any special restriction to the device that the hydro-thermal reaction occurs, ripe using those skilled in the art
The device for the generation hydro-thermal reaction known.It can be selected specifically to hydrothermal reaction kettle in a specific embodiment of the present invention.
After the completion of hydro-thermal reaction, the present invention is preferably separated by solid-liquid separation the product system obtained after hydro-thermal reaction, to institute
Solid material is obtained successively to be washed and dried.
In the present invention, preferably that the product system obtained after hydro-thermal reaction is cooling before being separated by solid-liquid separation；The cooling
Preferably cooled to room temperature.In the present invention, the separation of solid and liquid preferably filters；The present invention is to the filtering without appointing
What special restriction using filtering well known to those skilled in the art and obtains solid product.
In the present invention, the washing preferably includes the salt acid elution successively carried out and distillation water washing；In the present invention,
The number of the salt acid elution is preferably 4~5 times；The present invention does not have the concentration of the hydrochloric acid and the dosage of hydrochloric acid when washing every time
There is any special restriction, using concentration well known to those skilled in the art and dosage.The present invention is gone by salt acid elution
Except impurity such as the melamines and melamine derivative for having neither part nor lot in reaction.The present invention is to the number for distilling water washing and often
The dosage of distilled water is without any special restriction when secondary washing, using washing times well known to those skilled in the art and use
It measures and achievees the purpose that wash product to neutrality.
In the present invention, the drying is preferably freeze-dried, and the present invention is no any special to the freeze-drying
It limits, using freezing dry process well known to those skilled in the art.
After obtaining N doping redox graphene, the present invention carries out the N doping redox graphene at annealing
Reason, obtains nitrogen-doped graphene.
In the present invention, the temperature of the annealing is preferably 500~900 DEG C, more preferably 600~800 DEG C, optimal
It is selected as 650~750 DEG C；The time of the annealing is preferably 0.5~2.5h, more preferably 1.0~2.0h.In the present invention
In, the annealing preferably carries out under vacuum conditions；It is any special that the present invention does not have the vacuum degree of the vacuum environment
Restriction, using vacuum degree well known to those skilled in the art.
The present invention also provides the nitrogen-doped graphene that the preparation method is prepared, in the nitrogen-doped graphene
Nitrogen content is 3.0%~12.0%.
A kind of preparation method of nitrogen-doped graphene provided by the invention is described in detail below with reference to embodiment,
But they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
0.6g graphene oxide is mixed into 1h under ultrasound condition with 300mL distilled water, obtains the graphite oxide of 2mg/mL
Alkene dispersion liquid；
Under conditions of 80 DEG C, stirring, above-mentioned graphene oxide dispersion and 0.6g melamine mixing 1h move to anti-
Kettle is answered, under the conditions of 180 DEG C, for 24 hours, solid product is obtained by filtration in cooled to room temperature to hydro-thermal reaction, with salt acid elution 4 times,
It is washed with distilled water to neutrality again, is freeze-dried, obtains the redox graphene of N doping；
The N doping redox graphene is annealed 1h under the conditions of 700 DEG C, obtains nitrogen-doped graphene, nitrogen content
It is 4.68%.
Fig. 1 is that the SEM of the nitrogen-doped graphene schemes, and Fig. 2 is that the TEM of the nitrogen-doped graphene schemes；By Fig. 1 and Fig. 2
It is found that the nitrogen-doped graphene shows the transparent two-dimensional layered structure with fold, illustrate through the preparation method
The nitrogen-doped graphene being prepared maintains the microscopic appearance of graphene oxide；
Fig. 3 is the XRD diagram of the nitrogen-doped graphene, as seen from the figure, the nitrogen-doped graphene at 26.43 ° and
Peak at 43.27 ° corresponds respectively to (002) crystal face and (100) crystal face of graphene, it was demonstrated that graphene oxide is anti-by hydro-thermal
Should with after annealing, be successfully reduced to the preferable graphene of crystallization degree, and in nitrogen-atoms incorporation graphite lattice, do not change
Become the crystal phase structure of graphene；
Fig. 4 is the XPS C1s spectrogram of the nitrogen-doped graphene, and Fig. 5 is that the XPS N1s of the nitrogen-doped graphene is composed
Figure；As seen from the figure, nitrogen mainly exists in graphene with pyrroles's type nitrogen in the nitrogen-doped graphene, Zhan Suoyou N content
55.47%；Pyridine type nitrogen oxides accounts for the 17.6% of all N contents, and pyridine type nitrogen accounts for the 26.86% of all N contents, and stone
Pyridine type nitrogen present in black alkene lattice can make graphene have more vacancy；Pyrroles's type nitrogen, pyridine type nitrogen oxides
With pyridine type nitrogen in terms of nitrogen；
Lithium ion battery is prepared using the nitrogen-doped graphene as the negative electrode material of lithium ion battery, and tests institute
State the charging and discharging capacity and coulombic efficiency of lithium ion battery.It will be appreciated from fig. 6 that the first discharge specific capacity of the lithium ion battery
For 852mAh/g, after 200 charge and discharge cycles, specific discharge capacity 714mAh/g, it can be seen that, the lithium ion battery
Charge and discharge cycles stability is preferable；Meanwhile the lithium ion battery is due to solid electrolyte interface film during first charge-discharge
Formation, cause for the first time coulombic efficiency be 65%, but after 10 circulations, the coulombic efficiency that recycles every time is stablized on 98% left side
The right side, it follows that the lithium ion battery has preferable invertibity in charge and discharge process.
Embodiment 2
0.6g graphene oxide is mixed into 1h under ultrasound condition with 300mL distilled water, obtains the graphite oxide of 2mg/mL
Alkene dispersion liquid；
Under conditions of 80 DEG C, stirring, above-mentioned graphene oxide dispersion and 0.6g melamine mixing 1h move to anti-
Kettle is answered, under the conditions of 180 DEG C, for 24 hours, solid product is obtained by filtration in cooled to room temperature to hydro-thermal reaction, with salt acid elution 4 times,
It is washed with distilled water to neutrality again, is freeze-dried, obtains the redox graphene of N doping；
The N doping redox graphene is annealed 1h under the conditions of 500 DEG C, obtains nitrogen-doped graphene, nitrogen content
It is 4.82%.
The product structure that the present embodiment is prepared is tested, test result and embodiment 1 are almost the same.
Embodiment 3
0.6g graphene oxide is mixed into 1h under ultrasound condition with 300mL distilled water, obtains the graphite oxide of 2mg/mL
Alkene dispersion liquid；
Under conditions of 80 DEG C, stirring, above-mentioned graphene oxide dispersion and 0.6g melamine mixing 1h move to anti-
Kettle is answered, under the conditions of 180 DEG C, for 24 hours, solid product is obtained by filtration in cooled to room temperature to hydro-thermal reaction, with salt acid elution 4 times,
It is washed with distilled water to neutrality again, is freeze-dried, obtains the redox graphene of N doping；
The N doping redox graphene is annealed 1h under the conditions of 900 DEG C, obtains nitrogen-doped graphene, nitrogen content
It is 3.41%.
The product structure that the present embodiment is prepared is tested, test result and embodiment 1 are almost the same.
Embodiment 4
0.6g graphene oxide is mixed into 1h under ultrasound condition with 300mL distilled water, obtains the graphite oxide of 2mg/mL
Alkene dispersion liquid；
Under conditions of 80 DEG C, stirring, above-mentioned graphene oxide dispersion and 1.8g melamine mixing 1h move to anti-
Kettle is answered, under the conditions of 180 DEG C, for 24 hours, solid product is obtained by filtration in cooled to room temperature to hydro-thermal reaction, with salt acid elution 4 times,
It is washed with distilled water to neutrality again, is freeze-dried, obtains the redox graphene of N doping；
The N doping redox graphene is annealed 1h under the conditions of 700 DEG C, obtains nitrogen-doped graphene, nitrogen content
It is 4.34%.
The product structure that the present embodiment is prepared is tested, test result and embodiment 1 are almost the same.
Embodiment 5
0.6 graphene oxide is mixed into 1h under ultrasound condition with 300mL distilled water, obtains the graphene oxide of 2mg/mL
Dispersion liquid；
Under conditions of 80 DEG C, stirring, above-mentioned graphene oxide dispersion and 3.0g melamine mixing 1h move to anti-
Kettle is answered, under the conditions of 180 DEG C, for 24 hours, solid product is obtained by filtration in cooled to room temperature to hydro-thermal reaction, with salt acid elution 4 times,
It is washed with distilled water to neutrality again, is freeze-dried, obtains the redox graphene of N doping；
The N doping redox graphene is annealed 1h under the conditions of 700 DEG C, obtains nitrogen-doped graphene, nitrogen content
It is 4.42%.
The product structure that the present embodiment is prepared is tested, test result and embodiment 1 are almost the same.
As seen from the above embodiment, the nitrogen-doped graphene that preparation method of the present invention is prepared is as lithium ion
There is good charge-discharge performance and higher charging and discharging capacity when the electrode material of battery.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nitrogen-doped graphene, comprising the following steps:
Melamine and graphene oxide dispersion are mixed, hydro-thermal reaction is carried out, obtains N doping redox graphene；
The N doping redox graphene is made annealing treatment, nitrogen-doped graphene is obtained.
2. preparation method as described in claim 1, which is characterized in that in the graphene oxide dispersion graphene oxide with
The mass ratio of melamine is 1:(1~5).
3. preparation method as claimed in claim 1 or 2, which is characterized in that the concentration of the graphene oxide dispersion is 0.5
~5mg/mL.
4. preparation method as described in claim 1, which is characterized in that the mixed temperature is 60~90 DEG C, the mixing
Time be 0.5~3.5h.
5. preparation method as described in claim 1, which is characterized in that the temperature of the hydro-thermal reaction is 150~200 DEG C, institute
The time for stating hydro-thermal reaction is 10~35h.
6. preparation method as claimed in claim 1 or 5, which is characterized in that after the hydro-thermal reaction further include: by gained system
It is separated by solid-liquid separation, obtained solid material is successively washed and dried, N doping redox graphene is obtained.
7. preparation method as described in claim 1, which is characterized in that the temperature of the annealing is 500~900 DEG C, institute
The time for stating annealing is 0.5~2.5h.
8. preparation method as claimed in claim 1 or 7, which is characterized in that the annealing carries out in vacuum environment.
9. the nitrogen-doped graphene that preparation method according to any one of claims 1 to 8 is prepared.
10. nitrogen-doped graphene as claimed in claim 9, which is characterized in that the nitrogen content in the nitrogen-doped graphene is
3.0%~12.0%.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110127672A (en) * | 2019-06-10 | 2019-08-16 | 中国烟草总公司郑州烟草研究院 | A kind of preparation method of redox graphene film |
| CN110323443A (en) * | 2019-05-27 | 2019-10-11 | 北京理工大学 | A kind of spherical N doping redox graphene material and its application |
| CN111268642A (en) * | 2020-01-16 | 2020-06-12 | 长沙理工大学 | Sodium borohydride/nitrogen-doped graphene hydrogen storage composite material and preparation method thereof |
| 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 |
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| CN110790268B (en) * | 2019-10-29 | 2021-05-25 | 中国科学院宁波材料技术与工程研究所 | Boron and nitrogen co-doped graphene wave-absorbing material and preparation method and application thereof |
| CN111268642A (en) * | 2020-01-16 | 2020-06-12 | 长沙理工大学 | Sodium borohydride/nitrogen-doped graphene hydrogen storage composite material and preparation method thereof |
| CN111268642B (en) * | 2020-01-16 | 2022-12-06 | 长沙理工大学 | Sodium borohydride/nitrogen-doped graphene hydrogen storage composite material and preparation method thereof |
| 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 |
| WO2022062836A1 (en) * | 2020-09-27 | 2022-03-31 | 东莞理工学院 | Pyrrolic nitrogen-dominated nitrogen-doped graphene synthesis method and pyrrolic nitrogen-dominated nitrogen-doped graphene prepared by method |
| CN113066981A (en) * | 2021-03-22 | 2021-07-02 | 内蒙古杉杉科技有限公司 | N-doped graphene slurry and graphite material modified by using same |
| CN113387346A (en) * | 2021-06-29 | 2021-09-14 | 有研工程技术研究院有限公司 | Ultralow-oxygen-content three-dimensional nitrogen-doped graphene aerogel and preparation method thereof |
| CN113651320A (en) * | 2021-10-19 | 2021-11-16 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery negative electrode graphite material |
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