CN105384164A - Crumpled graphene with characteristics of high specific surface area and graded pore structure, and preparation method thereof - Google Patents
Crumpled graphene with characteristics of high specific surface area and graded pore structure, and preparation method thereof Download PDFInfo
- Publication number
- CN105384164A CN105384164A CN201510957934.9A CN201510957934A CN105384164A CN 105384164 A CN105384164 A CN 105384164A CN 201510957934 A CN201510957934 A CN 201510957934A CN 105384164 A CN105384164 A CN 105384164A
- Authority
- CN
- China
- Prior art keywords
- pore
- surface area
- specific surface
- graphene
- graphene oxide
- 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
- C01B2204/32—Size or surface area
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The invention relates to crumpled graphene with characteristics of high specific surface area and graded pore structure, and a preparation method thereof. The method comprises: preparing a uniform mixing liquid from graphene oxide and a pore forming agent, wherein the concentration of the graphene oxide is 0.1-10 g/l, and a mass ratio of the pore forming agent to the graphene oxide is 0.2-20; atomizing the mixing liquid and heating to make the solvent in the mixing liquid be volatilized so as to obtain crumpled graphene oxide powder containing the pore filming agent; and collecting the obtained crumpled graphene oxide powder containing the pore filming agent, and carrying out an activation heat treatment under the protection of an inert gas so as to obtain the crumpled graphene product with characteristics of high specific surface area and graded pore structure, wherein the temperature of the activation heat treatment is controlled at 500-1100 DEG C and the time of the activation heat treatment is controlled to 0.2-10 h so as to make the specific surface area of the product be 300-3000 m<2>/g. According to the present invention, the specific surface area of the crumpled graphene is effectively achieved while the pore structure of graphene is optimized, such that the crumpled graphene concurrently has micro-pores, mesopores and macropores; and the preparation method is simple, and the 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
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.Utilize the electroconductibility of probe test fold particle known, its electroconductibility is similar to stratiform redox graphene, and after applying certain pressure, its electroconductibility remains unchanged.
Although can be solved the agglomeration traits of Graphene by the way of fold, the specific surface area of the fold Graphene of preparation is at present still lower, and the specific surface area of the fold Graphene prepared by common atomization-drying means is usually less than 250m
2/ g.And need the effective ratio area improving material to improve catalytic site in photocatalysis field.Similar, at energy field, the specific surface area of material remains the principal element affecting Graphene chemical property.
Contriver studies discovery, adopt common activation method, namely, by finished product fold graphene oxide and pore-forming material mixing, the method of then carrying out high-temperature activation effectively can not improve the specific surface area of fold grapheme material and optimize pore structure, therefore traditionally direct carbonaceous material and pore-forming material Hybrid Heating is not suitable for the fold Graphene preparing high-specific surface area.Along with the propelling of Graphene research boom, the purposes of grapheme material is also constantly being widened, and fold Graphene is expected to become energy field, the brand-new material in the fields such as catalysis.How easily and effectively improve fold Graphene specific surface area and the multi-stage porous distribution that realizes fold Graphene the performance impact of fold Graphene is become particularly crucial.
Summary of the invention
An object of the present invention is the preparation method providing a kind of fold Graphene, and it can obtain high-ratio surface sum hierarchical porous structure.
According to a first aspect of the invention, provide a kind of preparation method of high-specific surface area hierarchical porous structure fold Graphene, comprising:
Graphene oxide and pore-forming material are mixed with Homogeneous phase mixing liquid, and wherein graphene oxide concentration is 0.1g/l-10g/l, and the mass ratio of pore-forming material and graphene oxide is 0.2-20;
Mixed solution is atomized and the fold graphene oxide powder (particle) heating to make the solvent evaporates in mixed solution and obtain containing pore-forming material; And collect gained and contain the graphene oxide powder of pore-forming material and under protection of inert gas, carry out activation heat treatment to obtain high-specific surface area hierarchical porous structure fold graphene product, wherein the temperature of activation heat treatment to control between 500 DEG C to 1100 DEG C and time controling at 0.2-10 hour to make products obtained therefrom specific surface area at 300m
2/ g to 3000m
2between/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 oxygen-containing functional group in the fold graphene oxide containing pore-forming material (or also can be described as " activator ") and pore-forming material reaction generate the gases such as carbonic acid gas, water, carbon monoxide, and the graphene oxide of such fold is reduced and generates vesicular structure.Again that products in water washing is extremely neutral afterwards, wash away pore-forming material and by product thereof, after drying, finally obtain the fold graphene product with high-specific surface area hierarchical porous structure.
In an embodiment of the present invention, pore-forming material can be selected from sodium hydroxide, salt of wormwood, saleratus, potassium oxalate, calcium chloride and phosphoric acid, is preferably sodium hydroxide or potassium hydroxide.
The present invention is by pressing certain proportioning by pore-forming material and graphene oxide, make Homogeneous phase mixing liquid, the fold graphene oxide containing pore-forming material is prepared by atomization-drying, in conjunction with certain activation heat treatment technique, easily and effectively can improve fold Graphene specific surface area and optimize the pore structure of fold Graphene.
Like this, can easily by mass ratio and the rational activation heat treatment technique of regulation and control graphene oxide concentration, pore-forming material and graphene oxide according to method of the present invention, can prepare high-specific surface area grading-hole distribution fold Graphene, method is simple and cost is low.
According to a second aspect of the invention, provide a kind of high-specific surface area hierarchical porous structure fold Graphene, it is prepared by aforesaid method, and comprises micropore (aperture is less than 2nm), mesopore (aperture: 2nm-50nm) and macropore (aperture is greater than 50nm) structure simultaneously.
Present invention achieves while not changing fold Graphene microcosmic fold pattern, also achieve increasing specific surface area and pore volume, widen pore size distribution range.
Accompanying drawing explanation
Fig. 1-3 is shape appearance figures of the fold Graphene prepared by different embodiments of the invention.
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 solution 100ml of 1g/l; 500mg potassium hydroxide; mix; atomization process; droplet is dry by the tube furnace of 200 DEG C-300 DEG C; fold graphene oxide containing pore-forming material can be collected by collection device, by collect containing the 800 DEG C of thermal treatment 1.5 hours under nitrogen protection atmosphere of pore-forming material fold graphene oxide.Finally obtaining specific surface area is 548m
2the spitball shape fold Graphene of/g, fold Graphene pattern as shown in Figure 1.
Embodiment 2
Get the graphene oxide solution 100ml of 5g/l; 1500mg sodium hydroxide; mix; atomization process; droplet is dry by the tube furnace of 200-300 DEG C; fold graphene oxide containing pore-forming material can be collected by collection device, by collect containing the 600 DEG C of thermal treatment 1 hour under protection of inert gas atmosphere of pore-forming material fold graphene oxide.Finally obtaining specific surface area is 488m
2the spitball shape fold Graphene of/g, fold Graphene pattern as shown in Figure 2.
Embodiment 3
Get the graphene oxide solution 1000ml of 0.5g/l; 15g potassium hydroxide; be mixed with Homogeneous phase mixing liquid; by mixed solution atomization process; droplet is dry by the tube furnace of 200-300 DEG C; collection device can collect the fold graphene oxide containing pore-forming material, by collect containing the 1000 DEG C of thermal treatment 1 hour under protection of inert gas atmosphere of pore-forming material fold graphene oxide.Finally obtaining specific surface area is 1543m
2the spitball shape fold Graphene of/g, fold Graphene pattern as shown in Figure 3.
The present invention can also optimize Graphene pore structure while realization effectively improves fold Graphene specific surface area, makes fold Graphene possess micropore, mesopore and macropore simultaneously, and preparation method is simple and cost is low.
Claims (4)
1. the preparation method of high-specific surface area hierarchical porous structure fold Graphene, comprising:
Graphene oxide and pore-forming material are mixed with Homogeneous phase mixing liquid, and wherein graphene oxide concentration is 0.1g/l-10g/l, and the mass ratio of pore-forming material and graphene oxide is 0.2-20;
Mixed solution is atomized and the fold graphene oxide powder heating to make the solvent evaporates in mixed solution and obtain containing pore-forming material; And collect gained and contain the graphene oxide powder of pore-forming material and under protection of inert gas, carry out activation heat treatment to obtain high-specific surface area hierarchical porous structure fold graphene product, wherein the temperature of activation heat treatment to control between 500 DEG C to 1100 DEG C and time controling at 0.2-10 hour to make products obtained therefrom specific surface area at 300m
2/ g to 3000m
2between/g.
2. method according to claim 1, also comprises: carry out carrying out washing treatment to remove pore-forming material to the product after activation heat treatment.
3. method according to claim 1, wherein pore-forming material is selected from potassium hydroxide, sodium hydroxide, salt of wormwood, saleratus, potassium oxalate, calcium chloride and phosphoric acid.
4. high-specific surface area hierarchical porous structure fold Graphene, prepared by the method according to one of claim 1-3, it comprises micropore, mesopore and macroporous structure simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510957934.9A CN105384164B (en) | 2015-12-18 | 2015-12-18 | High-specific surface area hierarchical porous structure fold graphene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510957934.9A CN105384164B (en) | 2015-12-18 | 2015-12-18 | High-specific surface area hierarchical porous structure fold graphene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105384164A true CN105384164A (en) | 2016-03-09 |
| CN105384164B CN105384164B (en) | 2018-01-09 |
Family
ID=55417006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510957934.9A Expired - Fee Related CN105384164B (en) | 2015-12-18 | 2015-12-18 | High-specific surface area hierarchical porous structure fold graphene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105384164B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106185904A (en) * | 2016-07-15 | 2016-12-07 | 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 |
| CN107022121A (en) * | 2017-05-03 | 2017-08-08 | 杭州高烯科技有限公司 | A kind of compounded rubber microsphere modified based on spitball shape graphene and preparation method thereof |
| CN107200992A (en) * | 2017-06-21 | 2017-09-26 | 长兴德烯科技有限公司 | A kind of ABS composite material of graphene toughness reinforcing and preparation method thereof |
| 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 |
| 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 |
| CN108117064A (en) * | 2018-03-01 | 2018-06-05 | 上海理工大学 | A kind of preparation method of fold graphene |
| CN108275681A (en) * | 2018-01-16 | 2018-07-13 | 上海理工大学 | A kind of preparation method of cellular porous carbon ball |
| 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 |
| CN113809336A (en) * | 2021-08-23 | 2021-12-17 | 安徽大学 | Carbon fiber and graphene compounded high-strength porous material 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993065A (en) * | 2010-12-17 | 2011-03-30 | 中国科学院上海微***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 |
| 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 CN201510957934.9A patent/CN105384164B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993065A (en) * | 2010-12-17 | 2011-03-30 | 中国科学院上海微***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 |
| CN104860312A (en) * | 2015-05-27 | 2015-08-26 | 上海理工大学 | Preparation method for corrugated nitrogen-doped graphene |
Non-Patent Citations (1)
| Title |
|---|
| HONGWEI QIU ET AL,: "Evaporative assembly of graphene oxide for electric double-layer capacitor electrode application", 《POWDER TECHNOLOGY》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106185904A (en) * | 2016-07-15 | 2016-12-07 | 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 |
| CN107022121A (en) * | 2017-05-03 | 2017-08-08 | 杭州高烯科技有限公司 | A kind of compounded rubber microsphere modified based on spitball shape graphene and preparation method thereof |
| 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 |
| CN107200992A (en) * | 2017-06-21 | 2017-09-26 | 长兴德烯科技有限公司 | A kind of ABS composite material of graphene toughness reinforcing and preparation method thereof |
| 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 |
| 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 |
| CN108117064A (en) * | 2018-03-01 | 2018-06-05 | 上海理工大学 | A kind of preparation method of fold graphene |
| 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 |
| CN113809336A (en) * | 2021-08-23 | 2021-12-17 | 安徽大学 | Carbon fiber and graphene compounded high-strength porous material and gas diffusion layer 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105384164B (en) | 2018-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105384164A (en) | Crumpled graphene with characteristics of high specific surface area and graded pore structure, and preparation method thereof | |
| Yu et al. | One-pot synthesis of highly ordered nitrogen-containing mesoporous carbon with resorcinol–urea–formaldehyde resin for CO2 capture | |
| Wang et al. | Solution-based carbohydrate synthesis of individual solid, hollow, and porous carbon nanospheres using spray pyrolysis | |
| Bano et al. | Hierarchical synthesis of silver monoliths and their efficient catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol | |
| CN107249730A (en) | Compound, its preparation method and its purposes of carbon structure and covalent organic framework | |
| Qiu et al. | Low-temperature selective catalytic reduction of NO with NH3 over ordered mesoporous MnxCo3− xO4 catalyst | |
| US20130230709A1 (en) | Porous graphene material and preparation method and uses as electrode material thereof | |
| Liu et al. | Versatile bifunctional nitrogen-doped porous carbon derived from biomass in catalytic reduction of 4-nitrophenol and oxidation of styrene | |
| Zhao et al. | Hierarchical porous carbon with graphitic structure synthesized by a water soluble template method | |
| CN104722276B (en) | A kind of melon ring/graphene oxide magnetic composite and preparation method thereof | |
| Huang et al. | Nitrogen-containing mesoporous carbons prepared from melamine formaldehyde resins with CaCl2 as a template | |
| CN104045077A (en) | Graphene three-dimensional hierarchical porous carbon material and preparation method thereof | |
| Shen et al. | Construction of hierarchically porous 3D graphene-like carbon material by B, N co-doping for enhanced CO2 capture | |
| CN108530073A (en) | A kind of preparation method of the three-dimensional porous graphene film of flexible self-supporting | |
| CN106006620A (en) | Graphene oxide aerogel and graphene aerogel, as well as preparation methods and environmental application of graphene oxide aerogel and graphene aerogel | |
| Zhang et al. | One-pot solvent-free synthesis of nitrogen and magnesium codoped mesoporous carbon composites for CO2 capture | |
| Hampsey et al. | Templating synthesis of ordered mesoporous carbon particles | |
| Pan et al. | P-modified microporous carbon nanospheres for direct propane dehydrogenation reactions | |
| Wiśniewski et al. | New phosphorus-containing spherical carbon adsorbents as promising materials in drug adsorption and release | |
| Luan et al. | Synthesis of ordered hierarchically mesoporous/microporous carbon materials via compressed CO2 for fructose-to-HMF transformation | |
| CN110498400A (en) | A kind of preparation method and its H of the porous BCN of two-dimensional layer2S selective oxidation application | |
| CN106927451B (en) | Three-dimensional structure graphene and its carbon source self-template catalytic pyrolysis preparation method | |
| Hua et al. | Porous Ag3PO4 microtubes with improved photocatalytic properties | |
| Xie et al. | Kinetics-controlled synthesis of hierarchically porous materials with tunable properties from diverse building blocks | |
| Shen et al. | A trimodal porous carbon as an effective catalyst for hydrogen production by methane decomposition |
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 |