CN105621402A - Method for preparing three dimensional graphene by adopting sol gel method - Google Patents
Method for preparing three dimensional graphene by adopting sol gel method Download PDFInfo
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- CN105621402A CN105621402A CN201511024526.4A CN201511024526A CN105621402A CN 105621402 A CN105621402 A CN 105621402A CN 201511024526 A CN201511024526 A CN 201511024526A CN 105621402 A CN105621402 A CN 105621402A
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a method for preparing three dimensional graphene by adopting sol gel method, which comprises: dissolving analysis pure ethylcellulose and NaOH into alcohol in a molar ratio of 1:(0 to 3) to form sol, ageing the sol for 12h to obtain gel, and drying the gel for 6h at 60 DEG C to obtain dry gel; carbonizing the dry gem at 700-900 DEG C in argon gas to obtain a product A; processing a mixture of the carbonized product A and KOH in a tube furnace in a mass ratio of 1: (1 to 3), taking the argon gas as protection gas, preserving heat for 2-3h at 600-800 DEG C, washing the obtained product with deionized water till a solution pH is 6.8-7.2, performing vacuum filtration, and drying for 5h in an oven to obtain the three dimensional graphene. The ethylcellulose is taken as the raw material, the sol gel method is adopted to prepare the three dimensional graphene, and the raw materials are easy to obtain and low in cost, simple in process device and low in energy consumption.
Description
Technical field
The present invention relates to technical field of graphene, in particular to the preparation method of a kind of three-dimensional grapheme.
Background technology
Graphene is that carbon atom is with sp2The chip architecture that hydridization is formed, because it has big specific surface area, good conductivity, good physical and chemical stability, high light transmission rate and high physical strength, since being found just to attract attention.
But having stronger Van der Waals force between graphene film, make between sheet easily superimposed, its specific surface area declines, thus causes its performance to be restricted. Three-dimensional grapheme is caused by Graphene self-assembly, not only has the specific surface area that Graphene is big, has the specific conductivity compared favourably with Graphene simultaneously so that it is have bigger application prospect at energy storage technology and catalytic field.
Method primary template-CVD [the ZongpingChen preparing three-dimensional grapheme reported at present, WencaiRen, LiboGao, BiluLiu, SongfengPeiandHui-MingCheng, Three-dimensionalflexibleandconductiveinterconnectedgrap henenetworksgrownbychemicalvapourdeposition [J], NatureMaterials, 10, 424 428 (2011)], graphene oxide self-assembly method [YuxiXu, ZhaoyangLin, FlexibleSolid-StateSupercapacitorsBasedonThreeDimensiona lGrapheneHydrogelFilms [J] .ACSNANO, 5, 4042-4049 (2013)], biological carbon synthesis method [Xiang-FenJiang, Xue-BinWang, High-throughputfabricationofstruttedgraphenebyammonium-a ssistedchemicalblowingforhigh-performancesupercapacitors [J], Nanoenergy, 2015, 16:81-90] wherein template-CVD need to sacrifice template, the Nonrenewable resources such as methane are adopted to be raw materials for production, cause production cost height, product rate is low. it is precursor that graphene oxide self-assembly method need to prepare graphene oxide, complex process, and production cost height, is unfavorable for scale operation.
Summary of the invention
It is an object of the invention to provide a kind of method adopting sol-gel method to prepare three-dimensional grapheme, the method is solvent taking ethanol, and reaction raw materials is easy to get, and feasibility is strong, and processing unit is simple. Prepare the three-dimensional grapheme and there is good charge storage performance, greatly reduce production cost simultaneously, there is bigger industrial prospect.
In order to achieve the above object, the present invention adopts following technical scheme:
Adopt sol-gel method to prepare a method for three-dimensional grapheme, comprise the following steps:
1) it is dissolved in ethanol with the mol ratio of 1:0��3 to obtain colloidal sol by analytical pure ethyl cellulose and NaOH;
2) the at room temperature ageing of prepared colloidal sol is obtained gel;
3) gained gel drying is obtained xerogel;
4) by xerogel in inert protective atmosphere, 700��900 DEG C of insulation 3h carry out carbonizing treatment, obtain carbonized product A;
5) mixture that mass ratio is carbonized product A:KOH=1:1��3 is placed in the tube furnace that argon gas is protection gas; 2��3h it is incubated at 600��800 DEG C; by products therefrom deionized water wash until solution PH=6.8��7.2, after then product being carried out vacuum filtration, drying obtains three-dimensional grapheme in an oven.
Further, step 2) in digestion time be 12h.
Further, step 3) in specifically by gained gel at 60 DEG C of dry 6h, obtain xerogel.
Further, step 4) described in inert protective atmosphere be argon gas.
Further, step 5) in product is carried out vacuum filtration after in an oven 60 DEG C of dry 5h obtain three-dimensional grapheme.
Further, step 1) in ethanol: the mass ratio of the mixture of ethyl cellulose and NaOH is 15��30:1.
Further, step 1) in the mol ratio of ethyl cellulose and NaOH be 1:1��3.
Sol-gel method prepares a method for three-dimensional grapheme, specifically comprises the following steps:
1) it is dissolved in ethanol with the mol ratio of 1:2 to obtain colloidal sol by analytical pure ethyl cellulose and NaOH;
2) by prepared colloidal sol at room temperature ageing 12h, gel is obtained;
3) by gained gel at 60 DEG C of dry 6h, xerogel is obtained;
4) by xerogel taking argon gas as protection gas, 800 DEG C of insulation 3h carry out carbonizing treatment, obtain carbonized product A;
5) by mass ratio be the mixture process of carbonized product A:KOH=1:3 in tube furnace taking argon gas as protection gas; it is incubated 2h, by products therefrom deionized water wash until solution PH=7.0, with vacuum filtration at 700 DEG C; and 60 DEG C of dry 5h in an oven, obtain three-dimensional grapheme.
Relative to prior art, the present invention has following useful effect:
The present invention take ethyl cellulose as raw material, sol-gel method is adopted to prepare three-dimensional grapheme, the raw material of this reaction be easy to get and cost low, processing unit is simple, and energy consumption is low, and this reaction carries out at ambient pressure, using water as reaction solvent, security is good, and feasibility is strong, so very economical, practical, there is good industrial prospect. Step 5 of the present invention) in potassium hydroxide can play, with the decolorizing carbon reaction in carbonization after product, the object removing decolorizing carbon, simultaneously introduce pore structure in the product, improve the pore structure of product, it is to increase the specific surface area of product.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of three-dimensional grapheme prepared by the present invention;
Fig. 2 is the SEM figure of three-dimensional grapheme prepared by the present invention.
Embodiment
Embodiment 1
Adopt sol-gel method to prepare a method for three-dimensional grapheme, comprise the following steps:
1) analytical pure ethyl cellulose and NaOH are dissolved in right amount obtained colloidal sol in (ethanol: the mixture quality of ethyl cellulose and NaOH is than as 15:1) ethanol taking the mol ratio of 1:1;
2) by prepared colloidal sol at room temperature ageing 12h, gel is obtained;
3) by gained gel at 60 DEG C of dry 6h, xerogel is obtained;
4) by xerogel argon gas for protection gas, 700 DEG C insulation 3h carry out carbonizing treatment, obtain carbonized product A;
5) by mass ratio be the mixture process of carbonized product A:KOH=1:1 in tube furnace taking argon gas as protection gas; it is incubated 2h, by products therefrom deionized water wash until solution PH=6.8, with vacuum filtration at 600 DEG C; and 60 DEG C of dry 5h in an oven, obtain three-dimensional grapheme.
Embodiment 2
Adopt sol-gel method to prepare a method for three-dimensional grapheme, comprise the following steps:
1) analytical pure ethyl cellulose and NaOH are dissolved in right amount obtained colloidal sol in (ethanol: the mixture quality of ethyl cellulose and NaOH is than as 25:1) ethanol taking the mol ratio of 1:2;
2) by prepared colloidal sol at room temperature ageing 12h, gel is obtained;
3) by gained gel at 60 DEG C of dry 6h, xerogel is obtained;
4) by xerogel argon gas for protection gas, 800 DEG C insulation 3h carry out carbonizing treatment, obtain carbonized product A;
5) by mass ratio be the mixture process of carbonized product A:KOH=1:3 in tube furnace taking argon gas as protection gas; it is incubated 2h, by products therefrom deionized water wash until solution PH=7.0, with vacuum filtration at 700 DEG C; and 60 DEG C of dry 5h in an oven, obtain three-dimensional grapheme.
Embodiment 3
1) analytical pure ethyl cellulose and NaOH are dissolved in right amount obtained colloidal sol in (ethanol: the mixture quality of ethyl cellulose and NaOH is than as 30:1) ethanol taking the mol ratio of 1:3;
2) by prepared colloidal sol at room temperature ageing 12h, gel is obtained;
3) by gained gel at 60 DEG C of dry 6h, xerogel is obtained;
4) by xerogel argon gas for protection gas, 900 DEG C insulation 3h carry out carbonizing treatment, obtain carbonized product A;
5) by mass ratio be the mixture process of carbonized product A:KOH=1:3 in tube furnace taking argon gas as protection gas; it is incubated 3h, by products therefrom deionized water wash until solution PH=7.2, with vacuum filtration at 800 DEG C; and 60 DEG C of dry 5h in an oven, obtain three-dimensional grapheme.
Embodiment 4
1) analytical pure ethyl cellulose is dissolved in right amount in (ethanol: the mass ratio of ethyl cellulose is 20:1) ethanol and obtains colloidal sol;
2) by prepared colloidal sol at room temperature ageing 12h, gel is obtained;
3) by gained gel at 60 DEG C of dry 6h, xerogel is obtained;
4) by xerogel argon gas for protection gas, 800 DEG C insulation 3h carry out carbonizing treatment, obtain carbonized product A;
5) by mass ratio be the mixture process of carbonized product A:KOH=1:3 in tube furnace taking argon gas as protection gas; it is incubated 3h, by products therefrom deionized water wash until solution PH=7, with vacuum filtration at 600 DEG C; and 60 DEG C of dry 5h in an oven, obtain three-dimensional grapheme. (when NaOH gets 0, the chip architecture in three-dimensional net structure can be caused to diminish, but still be three-dimensional grapheme).
Referring to shown in Fig. 1, the Raman spectrogram of three-dimensional grapheme prepared by the embodiment of the present invention 2, Fig. 2 is the SEM figure of prepared three-dimensional grapheme, and composition graphs 1,2 can be found out for product is the Graphene with three-dimensional structure.
Claims (8)
1. one kind adopts the method that sol-gel method prepares three-dimensional grapheme, it is characterised in that, comprise the following steps:
1) it is dissolved in ethanol with the mol ratio of 1:0��3 to obtain colloidal sol by analytical pure ethyl cellulose and NaOH;
2) the at room temperature ageing of prepared colloidal sol is obtained gel;
3) gained gel drying is obtained xerogel;
4) by xerogel in inert protective atmosphere, 700��900 DEG C of insulation 3h carry out carbonizing treatment, obtain carbonized product A;
5) mixture that mass ratio is carbonized product A:KOH=1:1��3 is placed in the tube furnace that argon gas is protection gas; 2��3h it is incubated at 600��800 DEG C; by products therefrom deionized water wash until solution PH=6.8��7.2, after then product being carried out vacuum filtration, drying obtains three-dimensional grapheme in an oven.
2. sol-gel method according to claim 1 prepares the method for three-dimensional grapheme, it is characterised in that: step 2) in digestion time be 12h.
3. sol-gel method according to claim 1 prepares the method for three-dimensional grapheme, it is characterised in that: step 3) in specifically by gained gel at 60 DEG C of dry 6h, obtain xerogel.
4. sol-gel method according to claim 1 prepares the method for three-dimensional grapheme, it is characterised in that: step 4) described in inert protective atmosphere be argon gas.
5. sol-gel method according to claim 1 prepares the method for three-dimensional grapheme, it is characterised in that: step 5) in product is carried out vacuum filtration after in an oven 60 DEG C of dry 5h obtain three-dimensional grapheme.
6. sol-gel method according to claim 1 prepares the method for three-dimensional grapheme, it is characterised in that, step 1) in ethanol: the mass ratio of the mixture of ethyl cellulose and NaOH is 15��30:1.
7. sol-gel method according to claim 1 prepares the method for three-dimensional grapheme, it is characterised in that, step 1) in the mol ratio of ethyl cellulose and NaOH be 1:1��3.
8. sol-gel method according to claim 1 prepares the method for three-dimensional grapheme, it is characterised in that, specifically comprise the following steps:
1) it is dissolved in ethanol with the mol ratio of 1:2 to obtain colloidal sol by analytical pure ethyl cellulose and NaOH;
2) by prepared colloidal sol at room temperature ageing 12h, gel is obtained;
3) by gained gel at 60 DEG C of dry 6h, xerogel is obtained;
4) by xerogel taking argon gas as protection gas, 800 DEG C of insulation 3h carry out carbonizing treatment, obtain carbonized product A;
5) by mass ratio be the mixture process of carbonized product A:KOH=1:3 in tube furnace taking argon gas as protection gas; it is incubated 2h, by products therefrom deionized water wash until solution PH=7.0, with vacuum filtration at 700 DEG C; and 60 DEG C of dry 5h in an oven, obtain three-dimensional grapheme.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104692368A (en) * | 2015-02-11 | 2015-06-10 | 武汉科技大学 | Graphene prepared by taking cellulose as raw material and preparation method thereof |
| CN105060289A (en) * | 2015-09-21 | 2015-11-18 | 中南大学 | Method for preparing fewer-layer graphene on basis of biomass waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104692368A (en) * | 2015-02-11 | 2015-06-10 | 武汉科技大学 | Graphene prepared by taking cellulose as raw material and preparation method thereof |
| CN105060289A (en) * | 2015-09-21 | 2015-11-18 | 中南大学 | Method for preparing fewer-layer graphene on basis of biomass waste |
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