CN104229784B - A kind of preparation method of ion-enhanced graphene film - Google Patents
A kind of preparation method of ion-enhanced graphene film Download PDFInfo
- Publication number
- CN104229784B CN104229784B CN201410457039.6A CN201410457039A CN104229784B CN 104229784 B CN104229784 B CN 104229784B CN 201410457039 A CN201410457039 A CN 201410457039A CN 104229784 B CN104229784 B CN 104229784B
- Authority
- CN
- China
- Prior art keywords
- massfraction
- graphene
- solution
- ion
- preparation
- 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.)
- Active
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of ion-enhanced graphene film, the method is: by the Graphene of 1 weight part or graphene oxide, after the solvent of 10 ~ 1000 weight parts, mixed solution is extruded from continuously and smoothly the preparation facilities with in-line outlet, enter the solidification liquid containing coordination ion, be frozen into Graphene or graphene oxide gel film, the Graphene that the ion obtaining macroscopic view continuously after dry strengthens or graphene oxide membrane.The inventive method is easy, technique is simple, energy consumption is low, environmental protection, and the graphene film thickness obtained, size all can regulate, and the graphene film intensity after ion strengthens is high, can be applied to many different fields.
Description
Technical field
The present invention relates to the preparation method of graphene film, particularly relate to a kind of preparation method of ion-enhanced graphene film.
Background technology
2010, two professor AndreGeim and KonstantinNovoselov of Univ Manchester UK obtained Nobel Prize in physics because successfully isolate stable Graphene first, have started the upsurge that the whole world is studied Graphene.Graphene (Graphene) is a kind of unimolecular layer two dimensional crystal, have the highest intensity of known materials (Science, 2008,
321, 385-388) and the electroconductibility of excellence and thermal conductivity, be current optimal two-dimension nano materials.The graphene film of macroscopic view assembling is the main application form of nanoscale graphite alkene, and conventional preparation method is suction method, scrapes embrane method, spin-coating method, spraying method and dip coating etc.But these preparation methods are difficult to the large-scale continuous preparation of the regular graphene film of implementation structure.Meanwhile, easily there is the slippage between sheet in the Graphene of one-component nanoscale graphite alkene sheet composition or graphene oxide membrane, greatly can affect use performance and the mechanical property of film under external force.Therefore, continuous production compound with regular structure, high performance graphene film remain a challenge, and the film preparing high-strength high-performance is challenged especially.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of ion to strengthen the preparation method of macroscopical graphene film.
The object of the invention is to be achieved through the following technical solutions: a kind of preparation method of ion-enhanced graphene film, its step is as follows:
(1) by the Graphene of 1 weight part, the solvent of 5 ~ 150 weight parts, obtains graphene solution after ultrasonic disperse;
(2) by graphene solution, extrude in the preparation facilities of in-line die orifice with the extruded velocity of 10 ~ 1000mL/h, stop 1 ~ 100 second freezing film in 10 ~ 80 DEG C contain in the solidification liquid of coordination ion, after drying, obtain ion-enhanced graphene film.
The preparation facilities of the in-line die orifice in described step (2) is rectangular structure, and centre has an in-line die orifice narrowed gradually.
The solvent of described step (1) is primarily of water, methyl alcohol, ethanol, N-Methyl pyrrolidone, acetone, methyl-sulphoxide, pyridine, dioxane, N, one or more mixed solutions be mixed to get according to any proportioning in dinethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), butanone, ethylene glycol, glycol ether.
Solidification liquid containing coordination ion in described step (2) primarily of massfraction be the calcium chloride water of 5-20%, the massfraction zinc sulfate solution that is 5-20%, the massfraction magnesium sulfate solution that is 5-20%, massfraction be the ferric chloride aqueous solutions of 5-20%, massfraction is that one or more in the copper sulfate solution of 5-20% are according to any proportioning mixing composition.
The method also can be made up of following steps:
(1) by the graphene oxide of 1 weight part, the solvent of 5 ~ 150 weight parts, obtains graphene oxide solution after supersound process.
(2) by graphene oxide solution, extrude in the preparation facilities of in-line die orifice with the extruded velocity of 10 ~ 1000mL/h, stop 1 ~ 100 second freezing film in 10 ~ 80 DEG C contain in the solidification liquid of coordination ion, after drying, obtain graphene oxide membrane.
(3) graphene oxide membrane that step (2) obtains is placed in reductive agent to reduce, washing drying obtains ion-enhanced graphene film.
The preparation facilities of the in-line die orifice in described step (2) is rectangular structure, and centre has an in-line die orifice narrowed gradually.
The solvent of described step (1) is primarily of water, methyl alcohol, ethanol, N-Methyl pyrrolidone, acetone, methyl-sulphoxide, pyridine, dioxane, N, one or more mixed solutions be mixed to get according to any proportioning in dinethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), butanone, ethylene glycol, glycol ether.
Solidification liquid containing coordination ion in described step (2) primarily of massfraction be the calcium chloride water of 5-20%, the massfraction zinc sulfate solution that is 5-20%, the massfraction magnesium sulfate solution that is 5-20%, massfraction be the ferric chloride aqueous solutions of 5-20%, massfraction is that one or more in the copper sulfate solution of 5-20% are according to any proportioning mixing composition.
Further, described reductive agent is selected from the hydrazine hydrate that massfraction is 1%-40%, massfraction is the sodium borohydride aqueous solution of 1%-40%, massfraction is the phenylhydrazine aqueous solution of 1%-40%, massfraction is the hydrobromic acid aqueous solution of 1%-40%, massfraction is the tea-polyphenol aqueous solution of 1%-40%, massfraction is the aqueous solution of urea of 1%-40%, massfraction is the sodium thiosulfate solution of 1%-20%, massfraction is the aqueous sodium hydroxide solution of 1%-5%, massfraction is the potassium hydroxide aqueous solution of 1%-40%, massfraction is the vitamins C aqueous solution of 5%-50%, massfraction is the D/W of 1%-40%, massfraction is the hydriodic acid aqueous solution of 1%-40%, massfraction is the aqueous acetic acid of 1%-40%, massfraction is the phenol solution of 1%-40%.
The beneficial effect that the present invention compared with prior art has: the Macro film of the Graphene that the present invention prepares arranges accumulation by Graphene along in-plane and forms, tensile strength is 100 ~ 300MPa, elongation at break is 0.3-20%, and electric conductivity is greater than 10000S/m, and thermal conductivity is 10-2000W/mK.Tensile strength is 100 ~ 300MPa, and elongation at break is 0.3-15%.The method has the following advantages: 1) primary raw materials of Graphene or graphene oxide is graphite, raw material sources extensively, be easy to get, with low cost; 2) method adopting solution to spin has prepared graphene film, operates fast and convenient, environmental protection, can prepare on a large scale; 3) thickness and the width of graphene film can be controlled; 4) obtained graphene film has good intensity and toughness, has excellent heat conductance and electroconductibility simultaneously.
Accompanying drawing explanation
Fig. 1 is the sectional view of the preparation facilities of in-line die orifice;
Fig. 2 is the front view of the preparation facilities of in-line die orifice;
Fig. 3 is the rear view of the preparation facilities of in-line die orifice;
Fig. 4 is the electron scanning micrograph of the graphene film doubling that embodiment 1 prepares;
Fig. 5 is the electron scanning micrograph of graphene film Tensile fracture.
Embodiment
As Figure 1-3, the preparation facilities of in-line die orifice is rectangular structure, and centre has in-line die orifice, and described in-line die orifice is a runner narrowed gradually.The runner narrowed gradually effectively can increase the reactive force of flow field to graphene film, is conducive to the formation of the regular oriented structure of graphene dispersion system.
Below in conjunction with embodiment, the present invention is described specifically; the present embodiment is only for the present invention is described further; limiting the scope of the invention can not be interpreted as; those skilled in the art makes some nonessential change and adjustment according to the content of foregoing invention, all belongs to protection scope of the present invention.
embodiment 1:
1) by 1g graphene oxide and 5g deionized water, in 20 ~ 80 DEG C with the supersound process 10 hours of 5 ~ 50KHz, graphene oxide solution is obtained.
2) by graphene oxide solution, extrude in the preparation facilities of in-line die orifice with the extruded velocity of 1000mL/h, in the calcium chloride waters of 80 DEG C (massfraction is 5%), stop 100 seconds freezing films, after drying, obtain graphene oxide membrane.
3) graphene oxide membrane that step (2) obtains is placed in massfraction be 40% hydrazine hydrate reduction 10 minutes, washing drying obtain ion-enhanced graphene film.
Through above step, as shown in Figure 4, the graphene film thickness of preparation is 1 micron, and has good toughness, and through Mechanics Performance Testing, its tensile strength is 300MPa, and elongation at break is 1.4%.
embodiment 2:
1) by the graphene oxide of 1 weight part, the N-Methyl pyrrolidone of 10 weight parts, in 80 DEG C with the supersound process 5 hours of 50KHz, obtains graphene oxide solution.
2) by graphene oxide solution, with the extruded velocity of 50mL/h, continuously and smoothly in the preparation facilities with in-line die orifice extrudes, and stops 1 second freezing film, obtain graphene oxide membrane after drying in the magnesium sulfate solutions of 60 DEG C (massfraction is 20%).
3) graphene oxide membrane that step (2) obtains is placed in massfraction be 20% sodium thiosulfate solution reduction 1 hour, washing drying obtain ion-enhanced graphene film.
The graphene film thickness of preparation is 1 millimeter, and as shown in Figure 5, graphene film has good stratiform orientation arrangement structure, and through Mechanics Performance Testing, its tensile strength is 290MPa, and elongation at break is 2%.
embodiment 3:
1) by the Graphene of 1 weight part, the DMF of 5 weight parts, in 50 DEG C with the supersound process 1 hour of 50KHz, obtains graphene solution.
2) by graphene solution, with the extruded velocity of 400mL/h, continuously and smoothly in the preparation facilities with in-line die orifice extrudes, and stops 16 seconds freezing films, obtain graphene film after drying in the zinc sulfate solutions of 25 DEG C (massfraction is 10%).
Through above step, the graphene film thickness of preparation is 30 microns, and tensile strength is 270MPa, and elongation at break is 1.2%, and electric conductivity is greater than 10000S/m, and thermal conductivity is 1200W/mK, has good toughness simultaneously.
embodiment 4:
1) by the Graphene of 1 weight part, 20 weight parts glycol ether, 20 weight parts N-Methyl pyrrolidone, 20 weight parts pyridine in 60 DEG C with the supersound process 2 hours of 40KHz, obtain graphene solution.
2) by graphene solution, with the extruded velocity of 500mL/h, continuously and smoothly in the preparation facilities with in-line die orifice extrudes, and stops 20 seconds freezing films, obtain graphene film after drying in the ferric chloride aqueous solutionses of 25 DEG C (massfraction is 8%).
Through above step, the graphene film thickness of preparation is 8 microns, and tensile strength is 300MPa, and elongation at break is 1.5%, and electric conductivity is greater than 10000S/m, and thermal conductivity is 1500W/mK, has good toughness simultaneously.
embodiment 5:
1) N,N-dimethylacetamide of the graphene oxide of 1 weight part, 5 weight parts, the methyl-sulphoxide of 20 weight parts with the supersound process 2 hours of 30KHz, are obtained graphene oxide solution in 25 DEG C.
2) by graphene oxide solution, with the extruded velocity of 10mL/h, continuously and smoothly in the preparation facilities with in-line die orifice extrudes, in the copper sulfate of 25 DEG C and calcium chloride mixed aqueous solution (massfraction of copper sulfate and calcium chloride is 10%), stop 1 second freezing film, after drying, obtain graphene oxide membrane.
3) graphene oxide membrane that step (2) obtains is placed in massfraction be 20% hydriodic acid aqueous solution reduction 0.1 ~ 100 hour, washing drying obtain ion-enhanced graphene film.
Through above step, the graphene film thickness of preparation is 3 microns, and tensile strength is 220MPa, and elongation at break is 1.6%.
embodiment 6:
1) by the graphene oxide of 1 weight part, the N-Methyl pyrrolidone of 40 weight parts and the ethylene glycol of 20 weight parts with the supersound process 2 hours of 40KHz, obtain graphene oxide solution in 30 DEG C.
2) by graphene oxide solution, with the extruded velocity of 500mL/h, continuously and smoothly in the preparation facilities with in-line die orifice extrudes, in the magnesium sulfate of 10 DEG C and zinc sulfate mixed aqueous solution, (massfraction of magnesium sulfate is 5%, the massfraction of zinc sulfate is 10%) middle stop 16 seconds freezing films, obtain graphene oxide membrane after drying.
3) graphene oxide membrane that step (2) obtains is placed in the sodium borohydride reductase 12 hour that massfraction is 20%, washing drying obtains ion-enhanced graphene film.
Through above step, the graphene film thickness of preparation is 1 micron, and tensile strength is 290MPa, and elongation at break is 1.8%.
Claims (3)
1. a preparation method for ion-enhanced graphene film, is characterized in that, its step is as follows:
(1) by the Graphene of 1 weight part, the solvent of 5 ~ 150 weight parts, obtains graphene solution after ultrasonic disperse;
(2) by graphene solution, extrude in the preparation facilities of in-line die orifice with the extruded velocity of 10 ~ 1000mL/h, stop 1 ~ 100 second freezing film in 10 ~ 80 DEG C contain in the solidification liquid of coordination ion, after drying, obtain ion-enhanced graphene film;
The preparation facilities of the in-line die orifice in described step (2) is rectangular structure, and centre has an in-line die orifice narrowed gradually;
The solvent of described step (1) is primarily of water, methyl alcohol, ethanol, N-Methyl pyrrolidone, acetone, methyl-sulphoxide, pyridine, dioxane, N, one or more mixed solutions be mixed to get according to any proportioning in dinethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), butanone, ethylene glycol, glycol ether;
Solidification liquid containing coordination ion in described step (2) primarily of massfraction be the calcium chloride water of 5-20%, the massfraction zinc sulfate solution that is 5-20%, the massfraction magnesium sulfate solution that is 5-20%, massfraction be the ferric chloride aqueous solutions of 5-20%, massfraction is that one or more in the copper sulfate solution of 5-20% are according to any proportioning mixing composition.
2. a preparation method for ion-enhanced graphene film, is characterized in that, its step is as follows:
(1) by the graphene oxide of 1 weight part, the solvent of 5 ~ 150 weight parts, obtains graphene oxide solution after supersound process;
(2) by graphene oxide solution, extrude in the preparation facilities of in-line die orifice with the extruded velocity of 10 ~ 1000mL/h, stop 1 ~ 100 second freezing film in 10 ~ 80 DEG C contain in the solidification liquid of coordination ion, after drying, obtain graphene oxide membrane;
(3) graphene oxide membrane that step (2) obtains is placed in reductive agent to reduce, washing drying obtains ion-enhanced graphene film;
The preparation facilities of the in-line die orifice in described step (2) is rectangular structure, and centre has an in-line die orifice narrowed gradually;
The solvent of described step (1) is primarily of water, methyl alcohol, ethanol, N-Methyl pyrrolidone, acetone, methyl-sulphoxide, pyridine, dioxane, N, one or more mixed solutions be mixed to get according to any proportioning in dinethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), butanone, ethylene glycol, glycol ether;
Solidification liquid containing coordination ion in described step (2) primarily of massfraction be the calcium chloride water of 5-20%, the massfraction zinc sulfate solution that is 5-20%, the massfraction magnesium sulfate solution that is 5-20%, massfraction be the ferric chloride aqueous solutions of 5-20%, massfraction is that one or more in the copper sulfate solution of 5-20% are according to any proportioning mixing composition.
3. the preparation method of a kind of ion-enhanced graphene film according to claim 2, it is characterized in that, described reductive agent is selected from the hydrazine hydrate solution that massfraction is 1%-40%, massfraction is the sodium borohydride aqueous solution of 1%-40%, massfraction is the phenylhydrazine aqueous solution of 1%-40%, massfraction is the hydrobromic acid aqueous solution of 1%-40%, massfraction is the tea-polyphenol aqueous solution of 1%-40%, massfraction is the aqueous solution of urea of 1%-40%, massfraction is the sodium thiosulfate solution of 1%-20%, massfraction is the aqueous sodium hydroxide solution of 1%-5%, massfraction is the potassium hydroxide aqueous solution of 1%-40%, massfraction is the vitamins C aqueous solution of 5%-50%, massfraction is the D/W of 1%-40%, massfraction is the hydriodic acid aqueous solution of 1%-40%, massfraction is the aqueous acetic acid of 1%-40%, massfraction is the phenol solution of 1%-40%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410457039.6A CN104229784B (en) | 2014-09-10 | 2014-09-10 | A kind of preparation method of ion-enhanced graphene film |
| PCT/CN2015/070510 WO2016037456A1 (en) | 2014-09-10 | 2015-01-12 | Method for preparing graphene and composite film thereof based on i-shaped die |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410457039.6A CN104229784B (en) | 2014-09-10 | 2014-09-10 | A kind of preparation method of ion-enhanced graphene film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104229784A CN104229784A (en) | 2014-12-24 |
| CN104229784B true CN104229784B (en) | 2016-04-13 |
Family
ID=52218808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410457039.6A Active CN104229784B (en) | 2014-09-10 | 2014-09-10 | A kind of preparation method of ion-enhanced graphene film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104229784B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823830A (en) * | 2017-02-27 | 2017-06-13 | 中南大学 | A kind of preparation method of the self-supporting graphene oxide film with water phase stability high |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016037456A1 (en) * | 2014-09-10 | 2016-03-17 | 浙江碳谷上希材料科技有限公司 | Method for preparing graphene and composite film thereof based on i-shaped die |
| CN104609410A (en) * | 2015-01-30 | 2015-05-13 | 浙江碳谷上希材料科技有限公司 | Preparation method of high-performance graphene porous membrane |
| CN114180558B (en) * | 2021-12-27 | 2023-09-08 | 广东墨睿科技有限公司 | Preparation method of graphene micro-nano cavity superconducting film, related product and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102438944A (en) * | 2009-03-27 | 2012-05-02 | 独立行政法人科学技术振兴机构 | Method for producing graphene film, method for manufacturing electronic element, and method for transferring graphene film to substrate |
| CN102557728A (en) * | 2012-02-17 | 2012-07-11 | 上海大学 | Method for preparing graphene film and graphene composite carbon film |
| CN102794945A (en) * | 2011-05-27 | 2012-11-28 | 清华大学 | Method for preparing graphene carbon nano tube composite membrane structure |
| CN103253653A (en) * | 2012-02-15 | 2013-08-21 | 国家纳米科学中心 | Oxidized graphene film, graphene film, preparation method and application thereof |
-
2014
- 2014-09-10 CN CN201410457039.6A patent/CN104229784B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102438944A (en) * | 2009-03-27 | 2012-05-02 | 独立行政法人科学技术振兴机构 | Method for producing graphene film, method for manufacturing electronic element, and method for transferring graphene film to substrate |
| CN102794945A (en) * | 2011-05-27 | 2012-11-28 | 清华大学 | Method for preparing graphene carbon nano tube composite membrane structure |
| CN103253653A (en) * | 2012-02-15 | 2013-08-21 | 国家纳米科学中心 | Oxidized graphene film, graphene film, preparation method and application thereof |
| CN102557728A (en) * | 2012-02-17 | 2012-07-11 | 上海大学 | Method for preparing graphene film and graphene composite carbon film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823830A (en) * | 2017-02-27 | 2017-06-13 | 中南大学 | A kind of preparation method of the self-supporting graphene oxide film with water phase stability high |
| CN106823830B (en) * | 2017-02-27 | 2019-03-29 | 中南大学 | A kind of preparation method of the self-supporting graphene oxide film with high water phase stability |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104229784A (en) | 2014-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104229783B (en) | A kind of preparation method of high thermal conductivity graphene film | |
| CN104211056B (en) | A kind of preparation method of high strength graphite alkene film | |
| CN104229784B (en) | A kind of preparation method of ion-enhanced graphene film | |
| CN104229782B (en) | A kind of preparation method of Graphene ordered porous membrane | |
| CN104211977A (en) | Preparation method of graphene-based composite membrane | |
| Xie et al. | Cost‐effective fabrication of micro‐nanostructured superhydrophobic polyethylene/graphene foam with self‐floating, optical trapping, acid‐/alkali resistance for efficient photothermal deicing and interfacial evaporation | |
| CN104210168B (en) | A kind of preparation method of Graphene metal composite electromagnetic shielding film | |
| Wei et al. | Conductive herringbone structure carbon nanotube/thermoplastic polyurethane porous foam tuned by epoxy for high performance flexible piezoresistive sensor | |
| CN103603088B (en) | Conductive fiber with scabbard type structure and preparation method thereof | |
| CN104232108B (en) | A kind of preparation method of the pure inorganic substances compound membrane based on Graphene | |
| CN104219797A (en) | Graphene electrothermal film | |
| CN104211055B (en) | A kind of preparation method of Graphene metallic nanoparticle composite membrane | |
| CN104609410A (en) | Preparation method of high-performance graphene porous membrane | |
| CN104451959B (en) | A kind of graphene fiber of porous surface high-specific surface area and preparation method thereof | |
| CN106044753B (en) | Preparation method of high-orientation graphene film | |
| CN103772902A (en) | Polyformaldehyde nanopore film with micro-nano bicontinuous porous structure and preparation method of polyformaldehyde nanopore film | |
| CN104261391A (en) | Self-supported graphene hydrogel membrane and preparation method thereof | |
| CN105778257B (en) | Linear low density polyethylene/carbon nanotube hole-opening foaming material and preparation method thereof | |
| CN104877277B (en) | Method for preparing bismuth tungstate/ polyvinylidene fluoride composite material | |
| CN108912350B (en) | Spherical aramid fiber nano material and preparation method thereof | |
| Liu et al. | Low-cost, scalable, and durable coal-based composite aerogel beads solar evaporator for efficient seawater desalination and wastewater purification | |
| Wu et al. | Fabrication of corrosion-resistant and heat-resistant multi-walled carbon nanotubes/poly ether ether ketone/thermoplastic polyimide electromagnetic shielding foams based on double percolation structure | |
| WO2016037456A1 (en) | Method for preparing graphene and composite film thereof based on i-shaped die | |
| CN104692366B (en) | A kind of method of the concentration and purification of Graphene and graphene-based composite dispersion liquid | |
| CN104403121A (en) | Method for preparing graphene-based biodegradable composite film used in parks |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |