CN105384164B - High-specific surface area hierarchical porous structure fold graphene and preparation method thereof - Google Patents
High-specific surface area hierarchical porous structure fold graphene and preparation method thereof Download PDFInfo
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- CN105384164B CN105384164B CN201510957934.9A CN201510957934A CN105384164B CN 105384164 B CN105384164 B CN 105384164B CN 201510957934 A CN201510957934 A CN 201510957934A CN 105384164 B CN105384164 B CN 105384164B
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- C01—INORGANIC CHEMISTRY
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/16—Pore diameter
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Abstract
High-specific surface area hierarchical porous structure fold graphene and preparation method thereof.This method includes：Graphene oxide and pore creating material are configured to uniform mixed liquor, wherein graphene oxide concentration is 0.1g/l 10g/l, and the mass ratio of pore creating material and graphene oxide is 0.2 20；Mixed liquor is atomized and heated so that the solvent in mixed liquor volatilizees and obtains the fold graphene oxide powder containing pore creating material；And collect graphene oxide powder of the gained containing pore creating material and activation heat treatment carried out under inert gas shielding to obtain high-specific surface area hierarchical porous structure fold graphene product, wherein the temperature control of activation heat treatment between 500 DEG C to 1100 DEG C and time control at 0.2 10 hours so that products obtained therefrom specific surface area is in 300m2/ g to 3000m2Between/g.The present invention can also optimize graphene pore structure while realization effectively improves fold graphene specific surface area, fold graphene is provided simultaneously with micropore, mesopore and macropore, preparation method is simple and cost is low.
Description
Technical field
The present invention relates to high-specific surface area hierarchical porous structure fold graphene and preparation method thereof.
Background technology
Graphene with two-dimensional structure with excellent performance due to attracting wide attention.In theory, two-dimentional graphite
Alkene has very high specific surface area, high conductivity, high carrier mobility etc., it is enjoyed pass in two-dimensional material application aspect
Note.An obstacle of the commercial application of grapheme material is van der waals force be present between graphene sheet layer at present so that
It is easy to stack between layers, this is greatly lowered its specific surface area, limits its performance and plays and apply.It is a kind of
Feasible method is exactly that two-dimensional nano lamellar structure is converted into the fold bulk structure of three-dimensional.Different from smooth lamella, tool
There is height fold bulk structure graphite alkene that there is very high free volume, and excellent compressive property.With common graphite alkene phase
Than the spitball shape graphene of fold still has preferably dispersiveness, pleat can just be made by shaking with hands under 55MPa compression
Wrinkle ball is dispersed in various solvents, and compression does not have too much influence to the pattern of fold.Utilize probe test fold
The electric conductivity of particle understands that its electric conductivity is similar to stratiform redox graphene, after applying certain pressure, its electric conductivity dimension
Hold constant.
Although can solve the problem that the agglomeration traits of graphene by the method for fold, the fold graphene for preparing at present
Still than relatively low, the specific surface area of the fold graphene prepared by common atomization-drying means is usually less than specific surface area
250m2/g.And improve catalytic site in the effective ratio area that photocatalysis field needs to improve material.Similar, in the energy
Field, the specific surface area of material are still to influence the principal element of graphene chemical property.
Inventor, which studies, to be found, using common activation method, i.e. finished product fold graphene oxide and pore creating material are mixed
Closing, the specific surface area and optimization pore structure of fold grapheme material can not be effectively improved by then carrying out the method for high-temperature activation, because
This traditional direct fold graphene that carbonaceous material and pore creating material Hybrid Heating are not suitable for preparing to high-specific surface area.With stone
The propulsion of black alkene research boom, the purposes of grapheme material are also constantly being widened, and fold graphene is expected to turn into energy field,
The brand-new material in the fields such as catalysis.How easily and effectively to improve the specific surface area of fold graphene and realize fold graphite
The multistage pore size distribution of alkene becomes particularly critical to the performance impact of fold graphene.
The content of the invention
An object of the present invention is to provide a kind of preparation method of fold graphene, and it can obtain high-specific surface area
And hierarchical porous structure.
According to the first aspect of the invention, there is provided a kind of preparation side of high-specific surface area hierarchical porous structure fold graphene
Method, including：
Graphene oxide and pore creating material are configured to uniform mixed liquor, wherein graphene oxide concentration is 0.1g/l-10g/
L, and the mass ratio of pore creating material and graphene oxide is 0.2-20；
Mixed liquor is atomized and heated so that the solvent in mixed liquor volatilizees and obtains the fold containing pore creating material and aoxidize stone
Black alkene powder (particle)；And collect graphene oxide powder of the gained containing pore creating material and lived under inert gas shielding
Change heat treatment to obtain high-specific surface area hierarchical porous structure fold graphene product, the temperature control of wherein activation heat treatment exists
Between 500 DEG C to 1100 DEG C and time control in 0.2-10 hours so that products obtained therefrom specific surface area is in 300m2/ g is extremely
3000m2Between/g.
In a preferred embodiment of the invention, inert protective gas can use argon gas, helium and nitrogen.
The activation heat treatment stage of the present invention makes the fold graphite oxide containing pore creating material (or being also referred to as " activator ")
The gases such as oxygen-containing functional group and pore creating material reaction generation carbon dioxide, water, carbon monoxide in alkene, the graphite oxide of such fold
Alkene is reduced and generates loose structure.Product is washed with water to neutrality again afterwards, washes away pore creating material and its accessory substance, after drying
Finally give the fold graphene product with high-specific surface area hierarchical porous structure.
In an embodiment of the present invention, pore creating material can be selected from sodium hydroxide, potassium carbonate, saleratus, potassium oxalate, chlorination
Calcium and phosphoric acid, preferably sodium hydroxide or potassium hydroxide.
Uniform mixed liquor is made by the way that pore creating material and graphene oxide press into certain proportioning in the present invention, by be atomized-
The fold graphene oxide containing pore creating material is prepared in drying, can be easily and effectively with reference to certain activation heat treatment technique
Improve fold graphene specific surface area and optimize the pore structure of fold graphene.
So, the method according to the invention can be easily by regulating and controlling graphene oxide concentration, pore creating material and oxygen
The mass ratio of graphite alkene and rational activation heat treatment technique, you can prepare high-specific surface area classification pore size distribution fold stone
Black alkene, method is simple and cost is low.
According to the second aspect of the invention, there is provided a kind of high-specific surface area hierarchical porous structure fold graphene, it is by upper
Method preparation is stated, and simultaneously comprising micropore (aperture is less than 2nm), mesopore (aperture：2nm-50nm) (aperture is more than with macropore
50nm) structure.
The present invention is realized while fold graphene microcosmic fold pattern is not changed, and also achieves increasing specific surface area
And pore volume, widen pore size distribution range.
Brief description of the drawings
Fig. 1-3 is the shape appearance figure of the fold graphene according to prepared by different embodiments of the invention.
Embodiment
The present invention is further illustrated below by embodiment, but it is not intended to limit the invention.
Embodiment 1
1g/l graphene oxide solution 100ml, 500mg potassium hydroxide is taken, is well mixed, atomization process, droplet passes through
200 DEG C -300 DEG C of tube furnace is dried, and collection device can collect the fold graphene oxide containing pore creating material, by what is be collected into
The graphene oxide of fold containing pore creating material encloses lower 800 DEG C in nitrogen protective atmosphere and is heat-treated 1.5 hours.Finally obtaining specific surface area is
548m2/ g spitball shape fold graphene, fold graphene pattern are as shown in Figure 1.
Embodiment 2
5g/l graphene oxide solution 100ml, 1500mg sodium hydroxide is taken, is well mixed, atomization process, droplet passes through
200-300 DEG C of tube furnace is dried, and collection device can collect the fold graphene oxide containing pore creating material, contain what is be collected into
Pore creating material fold graphene oxide is heat-treated 1 hour for 600 DEG C under inert gas shielding atmosphere.Finally obtaining specific surface area is
488m2/ g spitball shape fold graphene, fold graphene pattern are as shown in Figure 2.
Embodiment 3
0.5g/l graphene oxide solution 1000ml, 15g potassium hydroxide is taken, uniform mixed liquor is configured to, by mixed liquor
Atomization process, droplet are dried by 200-300 DEG C of tube furnace, and collection device collects the fold oxidation stone containing pore creating material
Black alkene, the fold containing pore creating material being collected into graphene oxide is heat-treated 1 hour for 1000 DEG C under inert gas shielding atmosphere.Most
After to obtain specific surface area be 1543m2/ g spitball shape fold graphene, fold graphene pattern are as shown in Figure 3.
The present invention can also optimize graphene pore structure while realization effectively improves fold graphene specific surface area, make
Fold graphene is provided simultaneously with micropore, mesopore and macropore, and preparation method is simple and cost is low.
Claims (1)
1. the preparation method of high-specific surface area hierarchical porous structure fold graphene, including：
Graphene oxide and pore creating material are configured to uniform mixed liquor, wherein graphene oxide concentration is 0.1g/l-10g/l, and
And the mass ratio of pore creating material and graphene oxide is 3-20；
Mixed liquor is atomized and is heated to 200 DEG C -300 DEG C so that the solvent in mixed liquor volatilizees and obtains the pleat containing pore creating material
Wrinkle graphene oxide powder；And collect graphene oxide powder of the gained containing pore creating material and carried out under inert gas shielding
To obtain high-specific surface area hierarchical porous structure fold graphene product, the temperature control of wherein activation heat treatment exists activation heat treatment
Between 600 DEG C to 1000 DEG C and time control in 1-1.5 hours so that products obtained therefrom specific surface area is in 300m2/ g to 3000m2/
While being more than 50nm macropore knot comprising micropore of the aperture less than 2nm, the mesopore that aperture is 2nm-50nm and aperture between g
Structure；
Carrying out washing treatment is carried out to the product after activation heat treatment to remove pore creating material,
Wherein pore creating material is selected from potassium hydroxide and sodium hydroxide.
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| CN106185904B (en) * | 2016-07-15 | 2018-02-09 | 浙江大学 | A kind of high fold graphene paper |
| CN106784694A (en) * | 2016-12-26 | 2017-05-31 | 四川科能锂电有限公司 | A kind of preparation method of lithium ferric phosphate/grapheme composite positive electrode material and lithium ion battery |
| CN107022121B (en) * | 2017-05-03 | 2018-09-21 | 杭州高烯科技有限公司 | A kind of compounded rubber and preparation method thereof microsphere modified based on spitball shape graphene |
| CN107200992B (en) * | 2017-06-21 | 2019-10-15 | 长兴德烯科技有限公司 | A kind of ABS composite material and preparation method thereof of graphene toughening |
| CN107324324A (en) * | 2017-07-18 | 2017-11-07 | 天津工业大学 | A kind of preparation method of fold porous graphene |
| CN107655226A (en) * | 2017-10-13 | 2018-02-02 | 杭州高烯科技有限公司 | A kind of graphene microballoon for solar absorption agent and preparation method thereof |
| CN108275681A (en) * | 2018-01-16 | 2018-07-13 | 上海理工大学 | A kind of preparation method of cellular porous carbon ball |
| CN108033440B (en) * | 2018-01-16 | 2021-07-13 | 上海理工大学 | Preparation method of porous folded graphene with high specific surface area |
| CN108117064B (en) * | 2018-03-01 | 2021-07-09 | 上海理工大学 | Preparation method of folded graphene |
| CN109802115A (en) * | 2019-01-15 | 2019-05-24 | 江西星盈科技有限公司 | Lithium ion battery and negative electrode material and preparation method thereof |
| CN113809336B (en) * | 2021-08-23 | 2023-10-24 | 安徽大学 | High-strength porous material compounded by carbon fibers and graphene and gas diffusion layer and preparation method thereof |
| CN114497513A (en) * | 2022-03-05 | 2022-05-13 | 青岛泰达华润新能源科技有限公司 | Graphene negative electrode material for lithium ion battery and preparation method thereof |
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| CN101993065B (en) * | 2010-12-17 | 2012-09-05 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene powder |
| CN102515145A (en) * | 2011-12-27 | 2012-06-27 | 常州第六元素材料科技股份有限公司 | Preparation process for high specific surface porous carbon material |
| US20140183415A1 (en) * | 2012-12-31 | 2014-07-03 | Cheil Industries Inc. | Graphene-Based Composite and Method of Preparing the Same |
| CN104860312B (en) * | 2015-05-27 | 2017-01-11 | 上海理工大学 | Preparation method for corrugated nitrogen-doped graphene |
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