CN105502355A - High-electrochemical-property nitrogen-doped folded graphene and preparation method thereof - Google Patents
High-electrochemical-property nitrogen-doped folded graphene and preparation method thereof Download PDFInfo
- Publication number
- CN105502355A CN105502355A CN201510957985.1A CN201510957985A CN105502355A CN 105502355 A CN105502355 A CN 105502355A CN 201510957985 A CN201510957985 A CN 201510957985A CN 105502355 A CN105502355 A CN 105502355A
- Authority
- CN
- China
- Prior art keywords
- graphene
- fold
- nitrogen
- graphene oxide
- doping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention provides high-electrochemical-property nitrogen-doped folded graphene and a preparation method thereof. The method comprises the steps that graphene oxide and a nitrogen-containing compound are prepared into uniform mixed liquid; the mixed liquid is atomized and heated to enable solvent in the mixed liquid to be volatilized to obtain nitrogen compound-folded graphene oxide powder; heat treatment is performed on the obtained nitrogen compound-folded graphene oxide powder to obtain the high-electrochemical-property nitrogen-doped folded graphene powder product, wherein the heat treatment temperature ranges from 400 DEG C to 1500 DEG C, the temperature increasing speed is 5-100 DEG C/s, and the heat treatment time is 5 seconds to 0.5 hour. According to the high-electrochemical-property nitrogen-doped folded graphene and the preparation method thereof, by performing quick heat treatment on the folded graphene oxide, the preparation cycle of the nitrogen-doped folded graphene product can be greatly shortened, the folded graphene product with the high electrochemical property can be obtained, and the cost is reduced.
Description
Technical field
The present invention relates to high electrochemical performance N doping fold Graphene and preparation method thereof.
Background technology
The Graphene with two-dirnentional structure attracts wide attention owing to having excellent performance.In theory, two-dimensional graphene has very high specific surface area, high conductivity, high carrier mobility etc., makes it receive much concern in two-dimensional material application aspect.An obstacle of the commercial application of current grapheme material there is van der waals forces between graphene sheet layer, and make to be easy between layers stacking, this specific surface area just greatly reducing it, limits its performance and application.A kind of feasible method is exactly two-dimensional nano laminated structure is converted into three-dimensional fold bulk structure.Be different from smooth lamella, there is height fold bulk structure graphite alkene there is very high free volume, and the compressive property of excellence.Compared with common graphite alkene, the spitball shape Graphene of fold, under the stress of 55MPa, still has good dispersiveness, fold ball just can be made to be dispersed in all kinds of SOLVENTS, and the pattern of stress to fold does not have too much influence with hand moving
Chemical modification is carried out to Graphene, as generated derivative, surface functionalization, chemically modified, chemical doping etc., can its stuctures and properties of modulation effectively, and then realize the more function of horn of plenty and the wide application of Graphene and associated materials thereof.For chemical doping, the equiatomic doping of N, P, S, F, B, has important impact to the performance of Graphene, and Heteroatom doping Graphene shows the performance of the more excellences of purer Graphene.
Contriver studies discovery, and the performance of thermal treatment process on fold Graphene has obvious impact, and the fold Graphene that rapid heating obtains shows excellent chemical property.
Summary of the invention
An object of the present invention is the preparation method providing a kind of N doping fold Graphene, and it effectively can improve the chemical property of fold Graphene.
According to a first aspect of the invention, a kind of high electrochemical performance N doping fold graphene preparation method is provided.The method comprises:
Graphene oxide and nitrogenous compound are mixed with Homogeneous phase mixing liquid;
Mixed solution is atomized and heats (drying) and obtain nitrogen compound/fold graphene oxide powder (particle) to make the solvent evaporates in mixed solution; And
Heat-treat to obtain high electrochemical performance N doping fold graphene powder product to gained nitrogen compound/fold graphene oxide powder,
Wherein thermal treatment temp is 400 DEG C to 1500 DEG C, and heat-up rate is 5-100 DEG C/s, and heat treatment time was 5 seconds to 0.5 hour.
In a particular embodiment of the present invention, atomization drying temperature can be 50 DEG C to 400 DEG C, is preferably 100 DEG C to 200 DEG C.
In a preferred embodiment of the invention, thermal treatment temp can between 500 DEG C to 1100 DEG C.
In different embodiments of the invention, thermal treatment can be carried out under atmosphere of inert gases (such as nitrogen, argon atmosphere), also can carry out under air atmosphere.
In different embodiments of the invention, nitrogenous compound can also comprise be selected from sulphur, phosphorus, fluorine, boron one or more.In other words, in fold Graphene of the present invention, except nitrating, can also adulterate in sulphur, phosphorus, fluorine, boron one or more.
In a preferred embodiment of the invention, nitrogenous compound can be selected from urea, trimeric cyanamide, tricyanic acid, thiocarbamide, ammonium salt and prussiate.
In a particular embodiment of the present invention, also need after the heat treatment immediately product (nature) to be cooled to room temperature.
In different embodiments of the invention, graphene oxide (preferably) provides with the form of the graphene oxide water solution improveing Hummer ' s method and prepare, or directly provides with pure zirconia Graphene form.
According to a second aspect of the invention, provide a kind of high electrochemical performance N doping fold Graphene, it is prepared by aforesaid method, and (as capacitor electrode material) ratio capacitance is 130F/g-200F/g under current density is 0.5-30A/g condition.
According to fold Graphene of the present invention, wherein doped element (always) content is preferably between 1% to 15%.
The present invention is by carrying out above-mentioned rapid thermal process by the fold graphene oxide including nitrogenous compound, not only greatly can shorten the cycle of preparation containing N doping fold graphene product, can obtain that there is high electrochemical performance fold graphene product simultaneously, and cost-saving.
Accompanying drawing explanation
The microscopic appearance figure of the N doping fold Graphene of Fig. 1 (a) prepared by method according to a first embodiment of the present invention, the direct current graphic representation of the electrode of super capacitor that Fig. 1 (b) is prepared by N doping fold Graphene;
The microscopic appearance figure of the nitrogenous fold Graphene of Fig. 2 (a) prepared by method according to a second embodiment of the present invention, the CD graphic representation of the electrode of super capacitor that Fig. 2 (b) is prepared by nitrogenous fold Graphene;
The microscopic appearance figure of the N doping fold Graphene of Fig. 3 (a) prepared by method according to a third embodiment of the present invention, the CD graphic representation of the electrode of super capacitor that Fig. 3 (b) is prepared by N doping fold Graphene.
Embodiment
Below by embodiment, the present invention is set forth further, but it is not limited to the present invention.
Embodiment 1
Get the graphene oxide of 100mg, 300mg urea, be mixed with 100ml solution, mixed solution is through atomization process, collect the fold graphene oxide containing nitrogen compound, by the fold graphene oxide of nitrogenous compound collected with the heating rate of 50 DEG C/s to 800 DEG C, thermal treatment 30 seconds, then shift out fast, cooling.Finally obtain the fold Graphene of N doping, fold Graphene pattern is as shown in Fig. 1 (a), and under current density is 20A/g condition, quality is 150F/g than electric capacity, as shown in Fig. 1 (b).
Embodiment 2
Get the graphene oxide solution 100ml of 0.5g/l, 100mg trimeric cyanamide, mix, atomization process, 300 DEG C of dryings, collection device can obtain the fold graphene oxide containing nitrogen, sulphur compound, has the nitrogen fold Graphene of nitrogen, sulphur compound rapid thermal process 600 seconds in the body of heater being preheating to 600 DEG C by what collect, then shift out fast, cooling.Finally obtain the fold Graphene of N doping, fold Graphene pattern is as shown in Fig. 2 (a), and under current density is 1A/g condition, quality is about 140F/g (monolithic quality is 21 milligrams), as shown in Fig. 2 (b) than electric capacity.
Embodiment 3
Get the graphene oxide solution 100ml of 2g/l, 1500mg urea, mix, atomization process, 200 DEG C of dryings, the fold graphene oxide containing nitrogenous compound can be collected by collection device, by the 1000 DEG C of thermal treatment 25 seconds under air atmosphere of the nitrogenous fold Graphene collected, then shift out fast, cooling.Fold Graphene pattern is as shown in Fig. 3 (a), and under current density is 1A/g condition, ratio capacitance is 189F/g, as shown in Fig. 3 (b).
The present invention can also maintain the peculiar pattern of fold Graphene while realizing fold Graphene Effective Doping, compares traditional slow heating process, significantly can improve the performance of fold Graphene, as having the excellent electrochemical performances such as the volumetric capacitance of superelevation.This energy saving technology, cost are low and method is simple.
Claims (5)
1. high electrochemical performance N doping fold graphene preparation method, comprising:
Graphene oxide and nitrogenous compound are mixed with Homogeneous phase mixing liquid;
Mixed solution is atomized and heats make the solvent evaporates in mixed solution and obtain nitrogen compound/fold graphene oxide powder; And
Heat-treat to obtain high electrochemical performance N doping fold graphene powder product to gained nitrogen compound/fold graphene oxide powder,
Wherein thermal treatment temp is 400 DEG C to 1500 DEG C, and heat-up rate is 5-100 DEG C/s, and heat treatment time was 5 seconds to 0.5 hour.
2. method according to claim 1, wherein nitrogenous compound also comprise be selected from sulphur, phosphorus, fluorine, boron one or more.
3. method according to claim 1, wherein nitrogenous compound is selected from urea, trimeric cyanamide, tricyanic acid, thiocarbamide, ammonium salt and prussiate.
4. method according to claim 1, wherein thermal treatment is carried out under atmosphere of inert gases.
5. high electrochemical performance N doping fold Graphene, prepared by the method for one of claim 1-4, under current density is 0.5-30A/g condition, its ratio capacitance is 130F/g-200F/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510957985.1A CN105502355B (en) | 2015-12-18 | 2015-12-18 | High electrochemical performance N doping fold graphene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510957985.1A CN105502355B (en) | 2015-12-18 | 2015-12-18 | High electrochemical performance N doping fold graphene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105502355A true CN105502355A (en) | 2016-04-20 |
| CN105502355B CN105502355B (en) | 2018-01-09 |
Family
ID=55710742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510957985.1A Expired - Fee Related CN105502355B (en) | 2015-12-18 | 2015-12-18 | High electrochemical performance N doping fold graphene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105502355B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517174A (en) * | 2016-11-25 | 2017-03-22 | 西安交通大学 | Quick heating method for graphene and deep processing method based on same |
| CN106517162A (en) * | 2016-12-15 | 2017-03-22 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of nitrogen/ sulphur co-doping three-dimensional graphene sponge |
| CN106542522A (en) * | 2017-01-16 | 2017-03-29 | 哈尔滨工业大学 | The method that template prepares three-dimensional grapheme |
| CN108033440A (en) * | 2018-01-16 | 2018-05-15 | 上海理工大学 | A kind of preparation method of high specific surface area porous fold graphene |
| CN113912051A (en) * | 2021-11-22 | 2022-01-11 | 北京石墨烯技术研究院有限公司 | Preparation method of doped graphene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979532A (en) * | 2014-06-04 | 2014-08-13 | 福州大学 | Nitrogen-doped graphene sheet and preparation method and application thereof |
| CN104108705A (en) * | 2014-07-11 | 2014-10-22 | 同济大学 | Preparation method of nitrogen-doped directional graphene |
| CN104860312A (en) * | 2015-05-27 | 2015-08-26 | 上海理工大学 | Preparation method for corrugated nitrogen-doped graphene |
-
2015
- 2015-12-18 CN CN201510957985.1A patent/CN105502355B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979532A (en) * | 2014-06-04 | 2014-08-13 | 福州大学 | Nitrogen-doped graphene sheet and preparation method and application thereof |
| CN104108705A (en) * | 2014-07-11 | 2014-10-22 | 同济大学 | Preparation method of nitrogen-doped directional graphene |
| CN104860312A (en) * | 2015-05-27 | 2015-08-26 | 上海理工大学 | Preparation method for corrugated nitrogen-doped graphene |
Non-Patent Citations (2)
| Title |
|---|
| DONG UN LEE ET AL.，: "Highly Active Graphene Nanosheets Prepared via Extremely rapid Heating as Efficient Zinc-Air Battery Electrode Material", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
| XUSHENG DU ET AL.，: "Facile chemical synthesis of nitrogen-doped graphene sheets and their electrochemical capacitance", 《JOURNAL OF POWER SOURCES》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517174A (en) * | 2016-11-25 | 2017-03-22 | 西安交通大学 | Quick heating method for graphene and deep processing method based on same |
| CN106517174B (en) * | 2016-11-25 | 2019-04-12 | 西安交通大学 | A kind of quick heating means of graphene and the deep working method based on it |
| CN106517162A (en) * | 2016-12-15 | 2017-03-22 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of nitrogen/ sulphur co-doping three-dimensional graphene sponge |
| CN106542522A (en) * | 2017-01-16 | 2017-03-29 | 哈尔滨工业大学 | The method that template prepares three-dimensional grapheme |
| CN108033440A (en) * | 2018-01-16 | 2018-05-15 | 上海理工大学 | A kind of preparation method of high specific surface area porous fold graphene |
| CN113912051A (en) * | 2021-11-22 | 2022-01-11 | 北京石墨烯技术研究院有限公司 | Preparation method of doped graphene |
| CN113912051B (en) * | 2021-11-22 | 2022-11-29 | 北京石墨烯技术研究院有限公司 | Preparation method of doped graphene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105502355B (en) | 2018-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105502355A (en) | High-electrochemical-property nitrogen-doped folded graphene and preparation method thereof | |
| Deng et al. | Review on recent advances in nitrogen-doped carbons: preparations and applications in supercapacitors | |
| Dong et al. | Biomass-derived carbon and polypyrrole addition on SiC whiskers for enhancement of electromagnetic wave absorption | |
| White et al. | A sustainable synthesis of nitrogen-doped carbon aerogels | |
| CN105384164B (en) | High-specific surface area hierarchical porous structure fold graphene and preparation method thereof | |
| JP6378059B2 (en) | Method for producing graphene oxide foam, graphene oxide / carbon nanotube composite foam, graphene aerogel or graphene / carbon nanotube composite aerogel | |
| CN104045077A (en) | Graphene three-dimensional hierarchical porous carbon material and preparation method thereof | |
| CN103466607A (en) | Graphene-metallic oxide nano-particle three-dimensional porous composite material | |
| CN104860312A (en) | Preparation method for corrugated nitrogen-doped graphene | |
| CN103991864B (en) | A kind of preparation method of graphene aerogel | |
| CN103449427B (en) | A kind of preparation method of porous graphene-ferric oxide composite material | |
| CN105197917A (en) | Preparation method of nitrogen-doped graphene quantum dot dispersion liquid | |
| CN108264037B (en) | Three-dimensional porous nitrogen-doped graphene answers the preparation method of material and nitrogen-doped graphene | |
| CN104966817A (en) | Molybdenum disulfide-carbon three-dimensional porous network composite and preparation method thereof | |
| CN104609404A (en) | Method for preparing graphene and composite material through sunlight reduction or laser reduction | |
| CN105084345A (en) | Graphene material powder and preparation method | |
| CN108530073A (en) | A kind of preparation method of the three-dimensional porous graphene film of flexible self-supporting | |
| Qian et al. | Sol-gel assisted chemical activation for nitrogen doped porous carbon | |
| CN104925796A (en) | Preparation method of porous graphene | |
| Yu et al. | Enhancement of structural stability of graphene aerogel for thermal energy harvesting | |
| He et al. | Molecular‐Based Design of Microporous Carbon Nanosheets | |
| Li et al. | Assembling carbon fiber–graphene–carbon fiber hetero-structures into 1D–2D–1D junction fillers and patterned structures for improved microwave absorption | |
| CN106082194A (en) | A kind of method preparing bigger serface and the less Graphene of the number of plies | |
| Yang et al. | A facile and versatile post-treatment method to efficiently functionalize 3D-printed carbon aerogels via introducing tailored metal elements | |
| Sun et al. | Ultrafast and cost-effective fabrication of high-performance carbon-based flexible thermoelectric hybrid films and their devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180109 Termination date: 20211218 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |