CN104891483A - Preparation method of three-dimensional graphene - Google Patents
Preparation method of three-dimensional graphene Download PDFInfo
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- CN104891483A CN104891483A CN201510297350.3A CN201510297350A CN104891483A CN 104891483 A CN104891483 A CN 104891483A CN 201510297350 A CN201510297350 A CN 201510297350A CN 104891483 A CN104891483 A CN 104891483A
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Abstract
The invention belongs to the field of preparation of graphene, and in particular relates to a preparation method of a three-dimensional graphene material. The preparation method comprises the following steps: uniformly mixing polysaccharide alcohol, a metal salt and ammonium chloride, putting the mixture into a tubular furnace, performing high-temperature calcination on the mixture by taking high-purity nitrogen as a protective atmosphere, washing the product after calcination with acid at first, then washing with deionized water, and drying to obtain the three-dimensional graphene material. According to the preparation method provided by the invention, the graphene material is prepared in situ by virtue of a one-step calcination method, the process is simple and convenient to operate, and the prepared three-dimensional graphene material has a special porous structure.
Description
Technical field
The invention belongs to field of preparation of graphene, be specifically related to a kind of preparation method of three-dimensional grapheme material.
Background technology
Graphene is the two-dimentional monoatomic layer carbon material received much concern in recent years, has a lot of excellent specific property, as the mechanical property of high conductivity, high-specific surface area, high thermal conductivity and excellence, therefore has good application prospect in a lot of field.But due to magnetism strong between graphene sheet layer, the excellent properties such as high-specific surface area that single dispersing Graphene has that cause solid-state Graphene to lose due to gathering.For solving this puzzlement, each sheet Graphene is joined together to form three-dimensional honeycomb shape skeleton structure by researchers, then solid-state Graphene can be made to represent the excellent properties similar to monolithic graphite alkene.
Three-dimensional grapheme is because having the advantages such as the specific surface area of super large, high electric conductivity and good chemical stability, obtain investigation and application widely, in absorption, catalysis, sensing, Conversion of energy and the field such as storage and biological medicine, all there is good application prospect.
There is the multiple method preparing Graphene at present, if Chen etc. is with CH
4and H
2for raw material, chemical Vapor deposition process is adopted to obtain homogeneity good three-dimensional network shape Graphene (Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition.Nature Materials, 2011,424-428); Sheng etc. are with graphene oxide raw material, Graphene (the Ultrahigh-rate supercapacitors based on eletrochemically reduced graphene oxide for ac line-filtering.Scientific Reports with high specific capacitance cycle life has been obtained by electrochemical reducing, 2012,2,1-5); Hernandez etc. take Graphite Powder 99 as raw material, more large-tonnage Graphene (High-yield production of graphene by liquid-phase exfoliation of graphite.Nature Nanotechnology is obtained by ultrasonic stripping in organic solvent, 2008,3,563-568).But the above-mentioned method preparing Graphene is still comparatively complicated and difficult, and is not suitable for suitability for industrialized production.
Summary of the invention
Instant invention overcomes the deficiency in background technology, the method that have employed relative ease prepares three-dimensional grapheme material, and the concrete steps of aforesaid method are:
(1) multi-sugar alcohol, metal-salt and ammonium chloride are mixed,
Wherein, multi-sugar alcohol is glucose, sucrose, Sorbitol Powder, mannitol, erythritol, maltose alcohol, Saccharum lactis, Xylitol,
Metal-salt is muriate, nitrate, the water-soluble salt such as vitriol or acetate of iron, nickel, cobalt, copper, tin etc.,
The mass ratio of metal-salt and multi-sugar alcohol is 0.5 ~ 5:1, and as preferably, mass ratio is 1.12 ~ 1.35:1,
Ammonium chloride not only plays pore-creating effect, and also in preparation process, the Graphene played generating carries out moulding effect;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3), in the tube furnace in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, high-temperature calcination carried out to mixture,
The concrete operations of high-temperature calcination are: with the temperature rise rate of 1 ~ 10 DEG C/min, are warming up to 600 ~ 1200 DEG C, and maintain 1 ~ 5h, as preferably, with the temperature rise rate of 2 ~ 5 DEG C/min, are warming up to 900 ~ 1050 DEG C, and maintain 1 ~ 3h,
In calcination process, ionizable metal salt can change, and finally can be reduced to metal simple-substance, thus realizes its catalytic capability;
(4) product after high-temperature calcination in step (3) is first used pickling, then uses deionized water wash, after dry, obtain three-dimensional grapheme material,
The acid wherein adopted in pickling operation is hydrochloric acid, the nitric acid of 3mol/L, the sulfuric acid of 3mol/L of 3mol/L.
Beneficial effect of the present invention is: the present invention adopts one-step calcination method original position to prepare grapheme material, technological operation is easy, prepared three-dimensional grapheme material has special vesicular structure, raw materials metal-salt and multi-sugar alcohol cheap and easy to get, saved production cost.
Accompanying drawing explanation
The XRD figure of Fig. 1 three-dimensional grapheme material obtained by embodiment 1.
Fig. 2 obtained by embodiment 1 three-dimensional grapheme (a), do not add metal-salt obtain carbon material (b) and do not add ammonium chloride calcining obtain carbon material (c) UV-Vis absorb spectrogram.
The FESEM figure of Fig. 3 three-dimensional grapheme material obtained by embodiment 1.
Embodiment
Embodiment 1
(1) by 2g glucose, 2g NH
4cl and 1.30g nickelous chloride mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3), in the tube furnace in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 1000 DEG C with the heat-up rate of 5 DEG C/min, and maintain this temperature 1.5h, high-temperature calcination is carried out to mixture;
(4) product after high-temperature calcination in step (3) is used 3mol/L hydrochloric acid, deionized water wash successively, after dry, obtain three-dimensional grapheme material 0.51g.
Fig. 1 is the XRD figure of above-mentioned obtained three-dimensional grapheme material, and characterize through X-ray powder diffraction (XRD), obtained three-dimensional grapheme is high-graphitized product;
Fig. 2 does not add the UV-Vis not adding the carbon material (c) that ammonium chloride calcining obtains under metal-salt calcines the carbon material (b) and equal conditions obtained to scheme under above-mentioned obtained three-dimensional grapheme material (a), equal conditions, characterize known through its ultraviolet-visible spectrum (UV-Vis), only with the addition of the carbon material that metal-salt and ammonium chloride carry out calcining, wavelength be 270nm place occur obvious graphene-structured characteristic peak, show that products therefrom is Graphene.
Fig. 3 is the FESEM figure of above-mentioned obtained three-dimensional grapheme material, and characterize through field emission scanning electron microscope (FESEM), obtained Graphene product has obvious complex three-dimensional vesicular structure.
Embodiment 2
(1) by 2g sucrose, 2g NH
4cl and 1.63g iron trichloride mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3), in the tube furnace in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 1200 DEG C with the heat-up rate of 10 DEG C/min, and maintain this temperature 0.5h, high-temperature calcination is carried out to mixture;
(4) product after high-temperature calcination in step (3) is used 3mol/L sulfuric acid, deionized water wash successively, after dry, obtain three-dimensional grapheme material.
Embodiment 3
(1) by 2g glucose, 2g NH
4cl and 1.30g cobalt chloride mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3), in the tube furnace in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 1100 DEG C with the heat-up rate of 9 DEG C/min, and maintain this temperature 2h, high-temperature calcination is carried out to mixture;
(4) product after high-temperature calcination in step (3) is used 3mol/L hydrochloric acid, deionized water wash successively, after dry, obtain three-dimensional grapheme material.
Embodiment 4
(1) by 2g sucrose, 2g NH
4cl and 1.35g cupric chloride mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3), in the tube furnace in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 900 DEG C with the heat-up rate of 8 DEG C/min, and maintain this temperature 2.5h, high-temperature calcination is carried out to mixture;
(4) product after high-temperature calcination in step (3) is used 3mol/L nitric acid, deionized water wash successively, after dry, obtain three-dimensional grapheme material.
Embodiment 5
(1) by 2g glucose, 2g NH
4cl, 0.650g nickelous chloride and 0.815g iron trichloride mix;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3), in the tube furnace in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 850 DEG C with the heat-up rate of 7 DEG C/min, and maintain this temperature 1.5h, high-temperature calcination is carried out to mixture;
(4) product after high-temperature calcination in step (3) is used 3mol/L hydrochloric acid, deionized water wash successively, after dry, obtain three-dimensional grapheme material.
Embodiment 6
(1) by 2g sucrose, 2g NH
4cl, 0.650g nickelous chloride and 0.650g cobalt chloride mix;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3), in the tube furnace in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 800 DEG C with the heat-up rate of 6 DEG C/min, and maintain this temperature 3h, high-temperature calcination is carried out to mixture;
(4) product after high-temperature calcination in step (3) is used 3mol/L hydrochloric acid, deionized water wash successively, after dry, obtain three-dimensional grapheme material.
Embodiment 7
(1) by 2g glucose, 2g NH
4cl, 0.650g nickelous chloride and 0.675g cupric chloride mix;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3), in the tube furnace in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 900 DEG C with the heat-up rate of 4 DEG C/min, and maintain this temperature 3h, high-temperature calcination is carried out to mixture;
(4) product after high-temperature calcination in step (3) is used 3mol/L nitric acid, deionized water wash successively, after dry, obtain three-dimensional grapheme material.
Embodiment 8
(1) by 2g sucrose, 2g NH
4cl, 0.815g iron trichloride and 0.650g cobalt chloride mix;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3), in the tube furnace in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 700 DEG C with the heat-up rate of 2 DEG C/min, and maintain this temperature 6h, high-temperature calcination is carried out to mixture;
(4) product after high-temperature calcination in step (3) is used 3mol/L sulfuric acid, deionized water wash successively, after dry, obtain three-dimensional grapheme material.
Embodiment 9
(1) by 2g glucose, 2g NH
4cl, 0.815g iron trichloride and 0.675g cupric chloride mix;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3), in the tube furnace in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 600 DEG C with the heat-up rate of 1 DEG C/min, and maintain this temperature 8h, high-temperature calcination is carried out to mixture;
(4) product after high-temperature calcination in step (3) is used 3mol/L nitric acid, deionized water wash successively, after dry, obtain three-dimensional grapheme material.
Embodiment 10
(1) by 2g sucrose, 2g NH
4cl, 0.650g cobalt chloride and 0.675g cupric chloride mix;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3), in the tube furnace in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 800 DEG C with the heat-up rate of 3 DEG C/min, and maintain this temperature 3h, high-temperature calcination is carried out to mixture;
(4) product after high-temperature calcination in step (3) is used 3mol/L nitric acid, deionized water wash successively, after dry, obtain three-dimensional grapheme material.
According to the method for embodiment 1, the three-dimensional grapheme prepared by embodiment 2-10 carries out UV-Vis test and output weighs, and experimental result is as following table 1:
The three-dimensional grapheme that table 1 embodiment 2-10 prepares carries out UV-Vis test and output
| UV-Vis goes out peak position | Weight | |
| Example 2 | 266nm | 0.40g |
| Example 3 | 268nm | 0.42g |
| Example 4 | 271nm | 0.36g |
| Example 5 | 265nm | 0.34g |
| Example 6 | 272nm | 0.30g |
| Example 7 | 270nm | 0.38g |
| Example 8 | 267nm | 0.32g |
| Example 9 | 271nm | 0.46g |
| Example 10 | 270nm | 0.44g |
Claims (7)
1. a preparation method for three-dimensional grapheme material, is characterized in that: the concrete steps of described preparation method are,
(1) multi-sugar alcohol, metal-salt and ammonium chloride are mixed;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), using high pure nitrogen as protective atmosphere, high-temperature calcination is carried out to described mixture;
(4) product after high-temperature calcination in step (3) is first used pickling, then use deionized water wash, after dry, obtain three-dimensional grapheme material.
2. the preparation method of three-dimensional grapheme material as claimed in claim 1, is characterized in that: the multi-sugar alcohol described in step (1) is glucose, sucrose, Sorbitol Powder, mannitol, erythritol, maltose alcohol, Saccharum lactis, Xylitol.
3. the preparation method of three-dimensional grapheme material as claimed in claim 1, is characterized in that: the metal-salt described in step (1) is iron, nickel, cobalt, copper, the muriate of tin, nitrate, vitriol or acetate.
4. the preparation method of three-dimensional grapheme material as claimed in claim 1, is characterized in that: the mass ratio of the metal-salt described in step (1) and described multi-sugar alcohol is 0.5 ~ 5:1.
5. the preparation method of three-dimensional grapheme material as claimed in claim 1, is characterized in that: the high pure nitrogen described in step (3) is the nitrogen that purity is greater than 99.999%.
6. the preparation method of three-dimensional grapheme material as claimed in claim 1, is characterized in that: the concrete operations of the high-temperature calcination described in step (3) are, with the temperature rise rate of 1 ~ 10 DEG C/min, is warming up to 600 ~ 1200 DEG C, and maintains 1 ~ 5h.
7. the preparation method of three-dimensional grapheme material as claimed in claim 1, is characterized in that: the acid adopted in the pickling operation described in step (4) is the sulfuric acid of the hydrochloric acid of 3mol/L, the nitric acid of 3mol/L or 3mol/L.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329883A (en) * | 2015-10-14 | 2016-02-17 | 南京邮电大学 | Porous graphene preparation method |
| CN105632782A (en) * | 2016-03-22 | 2016-06-01 | 苏州捷德瑞精密机械有限公司 | Capacitor element composite material and preparation method therefor |
| CN107804836A (en) * | 2017-11-07 | 2018-03-16 | 桂林电子科技大学 | It is prepared by a kind of three-dimensional grapheme and its one-step method based on biopolymer |
| CN108975315A (en) * | 2018-07-28 | 2018-12-11 | 嘉兴学院 | The preparation method of the grapheme material of three-dimensional manometer lamellar structure |
| CN111825078A (en) * | 2019-04-22 | 2020-10-27 | 南京大学 | Method for preparing three-dimensional graphene foam material |
| CN112299768A (en) * | 2020-11-13 | 2021-02-02 | 西安建筑科技大学 | Graphene functionalized cement-based material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009062241A (en) * | 2007-09-07 | 2009-03-26 | Hokkaido Univ | Method for producing graphene sheet |
| US20130197256A1 (en) * | 2012-01-26 | 2013-08-01 | Yi-Shuen Wu | Method for the preparation of graphene |
| CN103449411A (en) * | 2012-05-30 | 2013-12-18 | 海洋王照明科技股份有限公司 | Preparation method for nitrogen-doped graphene |
| CN104495825A (en) * | 2014-12-17 | 2015-04-08 | 北京科技大学 | Method for preparing porous nanometer graphite |
-
2015
- 2015-06-03 CN CN201510297350.3A patent/CN104891483A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009062241A (en) * | 2007-09-07 | 2009-03-26 | Hokkaido Univ | Method for producing graphene sheet |
| US20130197256A1 (en) * | 2012-01-26 | 2013-08-01 | Yi-Shuen Wu | Method for the preparation of graphene |
| CN103449411A (en) * | 2012-05-30 | 2013-12-18 | 海洋王照明科技股份有限公司 | Preparation method for nitrogen-doped graphene |
| CN104495825A (en) * | 2014-12-17 | 2015-04-08 | 北京科技大学 | Method for preparing porous nanometer graphite |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329883A (en) * | 2015-10-14 | 2016-02-17 | 南京邮电大学 | Porous graphene preparation method |
| CN105632782A (en) * | 2016-03-22 | 2016-06-01 | 苏州捷德瑞精密机械有限公司 | Capacitor element composite material and preparation method therefor |
| CN107804836A (en) * | 2017-11-07 | 2018-03-16 | 桂林电子科技大学 | It is prepared by a kind of three-dimensional grapheme and its one-step method based on biopolymer |
| CN107804836B (en) * | 2017-11-07 | 2020-06-05 | 桂林电子科技大学 | Three-dimensional graphene based on biopolymer and one-step preparation method thereof |
| CN108975315A (en) * | 2018-07-28 | 2018-12-11 | 嘉兴学院 | The preparation method of the grapheme material of three-dimensional manometer lamellar structure |
| CN111825078A (en) * | 2019-04-22 | 2020-10-27 | 南京大学 | Method for preparing three-dimensional graphene foam material |
| CN111825078B (en) * | 2019-04-22 | 2021-12-10 | 南京大学 | Method for preparing three-dimensional graphene foam material |
| CN112299768A (en) * | 2020-11-13 | 2021-02-02 | 西安建筑科技大学 | Graphene functionalized cement-based material and preparation method thereof |
| CN112299768B (en) * | 2020-11-13 | 2022-05-03 | 西安建筑科技大学 | Graphene functionalized cement-based material and preparation method thereof |
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