CN103935994B - A kind of self-supporting redox graphene paper and preparation method thereof - Google Patents
A kind of self-supporting redox graphene paper and preparation method thereof Download PDFInfo
- Publication number
- CN103935994B CN103935994B CN201410174812.8A CN201410174812A CN103935994B CN 103935994 B CN103935994 B CN 103935994B CN 201410174812 A CN201410174812 A CN 201410174812A CN 103935994 B CN103935994 B CN 103935994B
- Authority
- CN
- China
- Prior art keywords
- redox graphene
- self
- paper
- preparation
- supporting
- 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
Abstract
The invention discloses a kind of self-supporting redox graphene paper and preparation method thereof, step comprises: the reduction of graphene oxide solution; The carboxylated process of redox graphene; The preparation of carboxylated redox graphene pressed powder; The preparation of self-supporting redox graphene paper, this preparation method is simple, can be used for extensive preparation.The self-supporting redox graphene paper adopting this preparation method to obtain has good mechanical property, and purity is high, uniform ground, thickness and controlled shape, has good development prospect in the field such as functional composite material, ultracapacitor.
Description
Technical field
The present invention relates to a kind of graphene paper and preparation method thereof, particularly relate to a kind of self-supporting redox graphene paper and preparation method thereof.
Background technology
Graphene, as a kind of novel material of the individual layer sheet structure be made up of carbon atom, since being found from 2004, become at present the hardest the thinnest nano material in the world, its intensity is 200 times of steel.Except intensity is high, Graphene has surprising flexibility, can stretch 20% when there is not breakage.This makes it in functional composite material, and there is very large potential application foreground the aspects such as such as ultra-thin and ultra-light aircraft materials, ultralight super tough flak jackets.The electroconductibility of Graphene excellence, thermal conductivity and and mechanical property, make it at matrix material, Novel electronic devices, solar cell, ultracapacitor, the new energy fields such as hydrogen storage material are with a wide range of applications.
The preparation method of redox graphene has a variety of, and wherein, it is high that chemical reduction method has productive rate, preparation method is simple, lower-cost advantage, and the redox graphene of preparation has good solvent-dispersible, thus becomes the popular method preparing redox graphene.
The method adopting graphene dispersing solution to prepare graphene film has usually: filter deposition method, electrophoretic deposition, hot spray process, LB method, LBL self-assembly method, spin-coating method, chemical vapour deposition etc.But the graphene film prepared by these methods is all difficult to peel off from base materials such as sheet glass, quartz plate, sheet micas, and this just hinders the transfer of graphene film and further applies.
Through finding the retrieval of prior art, Nanyang Technological University Chen Xiaodong professor writes articles proposition Advanced Functional Materials the 23rd volume 2972 ~ 2978 pages, technology of sprawling waterborne is utilized to obtain self-supporting Graphene honeycomb film, have and can transfer to any suprabasil ability, their research opens the gate that self-supporting graphene paper prepares feasibility, but this preparation method length consuming time, yield rate are low, dimensional thickness Modulatory character is poor.
Therefore, those skilled in the art is devoted to a kind of more simple, more extensive, more effective preparation method of exploitation to realize the preparation of self-supporting graphene paper.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem to be solved by this invention is to provide a kind of more simple, more extensive, more effective preparation method to realize the preparation of self-supporting graphene paper.
For achieving the above object, the invention provides a kind of preparation method of self-supporting redox graphene paper, comprise the following steps:
A the reduction of () graphene oxide solution: at room temperature, is scattered in graphite oxide in water, then adds tensio-active agent, obtain the graphite oxide dispersion that concentration is 0.5 ~ 5mg/mL after supersound process; Then in described graphite oxide dispersion, add 1 ~ 5mL hydrazine hydrate, oil bath is heated to 90 ~ 120 DEG C, obtains redox graphene suspension after reaction 5 ~ 24h;
The hydroxylation process of (b) redox graphene: oil bath temperature of reaction is down to 80 ~ 90 DEG C, in described redox graphene suspension, add benzaminic acid and Isopentyl nitrite successively, oil bath obtains the redox graphene dispersion liquid of hydroxyl modified after reacting at least 10h;
C the preparation of () hydroxylation redox graphene pressed powder: the redox graphene dispersion liquid of described hydroxyl modified is carried out suction filtration, then washes, eventually pass lyophilize process, obtains described hydroxylation redox graphene pressed powder;
The generation of (d) self-supporting redox graphene paper: described hydroxylation redox graphene pressed powder is scattered in solvent, the redox graphene dispersion liquid that concentration is 0.1 ~ 5mg/mL is obtained after supersound process, after decompress filter process, described redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, described floatation of filter film, obtains described self-supporting redox graphene paper.
Further, the described graphite oxide adopted in described step (a) is prepared from by Hummers method, Brodie method or Staudenmaier method.
Further, the described tensio-active agent adopted in described step (a) is cats product or anion surfactant.
Further, described cats product is polyacrylamide.
Further, described anion surfactant is sodium laurylsulfonate, Sodium dodecylbenzene sulfonate.
Further, in described step (a) or described step (d), described supersound process is the ultrasonication under operating frequency 40 ~ 200kHz, ultrasonic power 50 ~ 200W, and ultrasonic time is 1 ~ 3h.
Further, in described step (b), the amount of described para-amino benzoic acid is 2-6 times of carbon molar equivalent in described graphite oxide, and the amount of described Isopentyl nitrite is 1 ~ 3 times of carbon molar equivalent in described graphite oxide.
Further, in described step (c), described washing refers to and is washed till colourless with deionized water by filtrate and till non-foam, the described lyophilize treatment time is 24 ~ 36h; In described step (d), described seasoning refers at room temperature, naturally dry through 8 ~ 24h in air.
Further, in described step (d), described solvent is deionized water, ethanol, DMF, the mixing of one or more in N,N-dimethylacetamide; Described filter membrane is polyvinylidene difluoride (PVDF) filter membrane, cellulose acetate sheets, cellulose filter membrane or anodised aluminium filter membrane.
The invention also discloses a kind of self-supporting redox graphene paper utilizing above-mentioned preparation method to obtain, described self-supporting redox graphene paper purity be high, uniform ground, there is good mechanical property.
Compared with existing graphene paper preparation method, the preparation method of self-supporting redox graphene paper of the present invention has advantage that is simple, that can prepare on a large scale, the self-supporting redox graphene paper of different thickness, size and dimension can be prepared as required simultaneously, and very easily realize the stripping of self-supporting redox graphene paper and base material, prepared self-supporting redox graphene paper purity is high, uniform ground, and has good mechanical property.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the self-supporting redox graphene paper cross section of the embodiment of the present invention 1;
Fig. 2 is the stress-strain curve of the self-supporting redox graphene paper of the embodiment of the present invention 1.
Embodiment
Elaborate to embodiments of the invention below in conjunction with accompanying drawing, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but scope is not limited to following embodiment.
Embodiment 1:
The self-supporting redox graphene Preparation Method made of paper of the embodiment of the present invention 1 comprises the following steps:
A 600mg graphite oxide at room temperature, is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate by (), obtain the graphite oxide dispersion that concentration is 1mg/mL after supersound process 1 ~ 3h; Then in above-mentioned graphite oxide dispersion, add 3mL hydrazine hydrate, oil bath is heated to 100 DEG C, obtains the redox graphene suspension of black after reaction 14h;
B oil bath temperature of reaction is down to 80 DEG C by (), in the redox graphene suspension that step (a) obtains, add 7.31g benzaminic acid and 3.15g Isopentyl nitrite successively, oil bath obtains the redox graphene dispersion liquid of hydroxyl modified after reacting at least 10h;
The redox graphene dispersion liquid of c hydroxyl modified that step (b) obtains by () carries out suction filtration, then filtrate is washed till colourless and non-foam with deionized water, last lyophilize process 24 ~ 36h, obtains hydroxylation redox graphene pressed powder;
D () gets the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 150mL deionized water, the redox graphene dispersion liquid that concentration is 0.33mg/mL is obtained after supersound process 1 ~ 3h, aperture is utilized to be after the cellulose filter membrane of 0.22 μm carries out decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, floatation of filter film, obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk that the diameter existed with self-supporting form is about 4cm, thickness about 20 microns, smooth surface and smooth.In addition, as shown in Figure 1, the self-supporting redox graphene of the present embodiment is piled up by many single-layer graphenes and is formed, and connection closely between layers.As shown in Figure 2, the mechanical moduli of the self-supporting redox graphene of the present embodiment is 7.5Gpa, illustrates that it has good mechanical property.
Embodiment 2:
The self-supporting redox graphene Preparation Method made of paper of the embodiment of the present invention 2 comprises the following steps:
A 300mg graphite oxide at room temperature, is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate by (), obtain the graphite oxide dispersion that concentration is 0.5mg/mL after supersound process 1 ~ 3h; Then in above-mentioned graphite oxide dispersion, add 3mL hydrazine hydrate, oil bath is heated to 100 DEG C, obtains the redox graphene suspension of black after reaction 14h;
B oil bath temperature of reaction is down to 80 DEG C by (), in the redox graphene suspension that step (a) obtains, add 7.31g benzaminic acid and 3.15g Isopentyl nitrite successively, oil bath obtains the redox graphene dispersion liquid of hydroxyl modified after reacting at least 10h;
The redox graphene dispersion liquid of c hydroxyl modified that step (b) obtains by () carries out suction filtration, then filtrate is washed till colourless and non-foam with deionized water, last lyophilize process 24 ~ 36h, obtains hydroxylation redox graphene pressed powder;
D () gets the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 150mL deionized water, the redox graphene dispersion liquid that concentration is 0.33mg/mL is obtained after supersound process 1 ~ 3h, aperture is utilized to be after the cellulose filter membrane of 0.22 μm carries out decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, floatation of filter film, obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk that diameter is about 4cm, thickness about 20 microns, smooth surface and smooth.The mechanical moduli of the self-supporting redox graphene of the present embodiment is 9Gpa, illustrates that it has good mechanical property.
Embodiment 3:
The self-supporting redox graphene Preparation Method made of paper of the embodiment of the present invention 3 comprises the following steps:
A 600mg graphite oxide at room temperature, is scattered in 600mL water, then adds 6g Sodium dodecylbenzene sulfonate by (), obtain the graphite oxide dispersion that concentration is 1mg/mL after supersound process 1 ~ 3h; Then in above-mentioned graphite oxide dispersion, add 3mL hydrazine hydrate, oil bath is heated to 100 DEG C, obtains the redox graphene suspension of black after reaction 14h;
B oil bath temperature of reaction is down to 80 DEG C by (), in the redox graphene suspension that step (a) obtains, add 7.31g benzaminic acid and 3.15g Isopentyl nitrite successively, oil bath obtains the redox graphene dispersion liquid of hydroxyl modified after reacting at least 10h;
The redox graphene dispersion liquid of c hydroxyl modified that step (b) obtains by () carries out suction filtration, then filtrate is washed till colourless and non-foam with deionized water, last lyophilize process 24 ~ 36h, obtains hydroxylation redox graphene pressed powder;
D () gets the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 150mL deionized water, the redox graphene dispersion liquid that concentration is 0.33mg/mL is obtained after supersound process 1 ~ 3h, aperture is utilized to be after the cellulose filter membrane of 0.22 μm carries out decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, floatation of filter film, obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk that diameter is about 2cm, thickness about 80 microns, smooth surface and smooth.The mechanical moduli of the self-supporting redox graphene of the present embodiment is 8.25Gpa, illustrates that it has good mechanical property.
Embodiment 4:
The self-supporting redox graphene Preparation Method made of paper of the embodiment of the present invention 4 comprises the following steps:
A 600mg graphite oxide at room temperature, is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate by (), obtain the graphite oxide dispersion that concentration is 1mg/mL after supersound process 1 ~ 3h; Then in above-mentioned graphite oxide dispersion, add 3mL hydrazine hydrate, oil bath is heated to 100 DEG C, obtains the redox graphene suspension of black after reaction 5h;
B oil bath temperature of reaction is down to 80 DEG C by (), in the redox graphene suspension that step (a) obtains, add 7.31g benzaminic acid and 3.15g Isopentyl nitrite successively, oil bath obtains the redox graphene dispersion liquid of hydroxyl modified after reacting at least 10h;
The redox graphene dispersion liquid of c hydroxyl modified that step (b) obtains by () carries out suction filtration, then filtrate is washed till colourless and non-foam with deionized water, last lyophilize process 24 ~ 36h, obtains hydroxylation redox graphene pressed powder;
D () gets the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 150mL deionized water, the redox graphene dispersion liquid that concentration is 0.33mg/mL is obtained after supersound process 1 ~ 3h, aperture is utilized to be after the cellulose filter membrane of 0.22 μm carries out decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, floatation of filter film, obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk that diameter is about 8cm, thickness about 5 microns, smooth surface and smooth.The mechanical moduli of the self-supporting redox graphene of the present embodiment is 7.65Gpa, illustrates that it has good mechanical property.
Embodiment 5:
The self-supporting redox graphene Preparation Method made of paper of the embodiment of the present invention 5 comprises the following steps:
A 600mg graphite oxide at room temperature, is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate by (), obtain the graphite oxide dispersion that concentration is 1mg/mL after supersound process 1 ~ 3h; Then in above-mentioned graphite oxide dispersion, add 3mL hydrazine hydrate, oil bath is heated to 100 DEG C, obtains the redox graphene suspension of black after reaction 24h;
B oil bath temperature of reaction is down to 80 DEG C by (), in the redox graphene suspension that step (a) obtains, add 7.31g benzaminic acid and 3.15g Isopentyl nitrite successively, oil bath obtains the redox graphene dispersion liquid of hydroxyl modified after reacting at least 10h;
The redox graphene dispersion liquid of c hydroxyl modified that step (b) obtains by () carries out suction filtration, then filtrate is washed till colourless and non-foam with deionized water, last lyophilize process 24 ~ 36h, obtains hydroxylation redox graphene pressed powder;
D () gets the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 150mL deionized water, the redox graphene dispersion liquid that concentration is 0.33mg/mL is obtained after supersound process 1 ~ 3h, aperture is utilized to be after the cellulose filter membrane of 0.22 μm carries out decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, floatation of filter film, obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk that diameter is about 4cm, thickness about 20 microns, smooth surface and smooth.The mechanical moduli of the self-supporting redox graphene of the present embodiment is 6Gpa, illustrates that it has good mechanical property.
Embodiment 6:
The self-supporting redox graphene Preparation Method made of paper of the embodiment of the present invention 6 comprises the following steps:
A 3000mg graphite oxide at room temperature, is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate by (), obtain the graphite oxide dispersion that concentration is 5mg/mL after supersound process 1 ~ 3h; Then in above-mentioned graphite oxide dispersion, add 5mL hydrazine hydrate, oil bath is heated to 120 DEG C, obtains the redox graphene suspension of black after reaction 5h;
B oil bath temperature of reaction is down to 90 DEG C by (), in the redox graphene suspension that step (a) obtains, add 21.93g benzaminic acid and 9.45g Isopentyl nitrite successively, oil bath obtains the redox graphene dispersion liquid of hydroxyl modified after reacting at least 10h;
The redox graphene dispersion liquid of c hydroxyl modified that step (b) obtains by () carries out suction filtration, then filtrate is washed till colourless and non-foam with deionized water, last lyophilize process 24 ~ 36h, obtains hydroxylation redox graphene pressed powder;
D () gets the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 150mL deionized water, the redox graphene dispersion liquid that concentration is 0.33mg/mL is obtained after supersound process 1 ~ 3h, aperture is utilized to be after the cellulose filter membrane of 0.22 μm carries out decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, floatation of filter film, obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk that diameter is about 4cm, thickness about 20 microns, smooth surface and smooth.The mechanical moduli of the self-supporting redox graphene of the present embodiment is 9Gpa, illustrates that it has good mechanical property.
Embodiment 7:
The self-supporting redox graphene Preparation Method made of paper of the embodiment of the present invention 7 comprises the following steps:
A 600mg graphite oxide at room temperature, is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate by (), obtain the graphite oxide dispersion that concentration is 1mg/mL after supersound process 1 ~ 3h; Then in above-mentioned graphite oxide dispersion, add 3mL hydrazine hydrate, oil bath is heated to 90 DEG C, obtains the redox graphene suspension of black after reaction 24h;
B oil bath temperature of reaction is down to 80 DEG C by (), in the redox graphene suspension that step (a) obtains, add 14.62g benzaminic acid and 6.3g Isopentyl nitrite successively, oil bath obtains the redox graphene dispersion liquid of hydroxyl modified after reacting at least 10h;
The redox graphene dispersion liquid of c hydroxyl modified that step (b) obtains by () carries out suction filtration, then filtrate is washed till colourless and non-foam with deionized water, last lyophilize process 24 ~ 36h, obtains hydroxylation redox graphene pressed powder;
D () gets the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 500mL deionized water, the redox graphene dispersion liquid that concentration is 0.1mg/mL is obtained after supersound process 1 ~ 3h, aperture is utilized to be after the cellulose filter membrane of 0.22 μm carries out decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, floatation of filter film, obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk that diameter is about 4cm, thickness about 20 microns, smooth surface and smooth.The mechanical moduli of the self-supporting redox graphene of the present embodiment is 8Gpa, illustrates that it has good mechanical property.
Embodiment 8:
The self-supporting redox graphene Preparation Method made of paper of the embodiment of the present invention 8 comprises the following steps:
A 3000mg graphite oxide at room temperature, is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate by (), obtain the graphite oxide dispersion that concentration is 5mg/mL after supersound process 1 ~ 3h; Then in above-mentioned graphite oxide dispersion, add 1mL hydrazine hydrate, oil bath is heated to 120 DEG C, obtains the redox graphene suspension of black after reaction 24h;
B oil bath temperature of reaction is down to 85 DEG C by (), in the redox graphene suspension that step (a) obtains, add 10.965g benzaminic acid and 4.725g Isopentyl nitrite successively, oil bath obtains the redox graphene dispersion liquid of hydroxyl modified after reacting at least 10h;
The redox graphene dispersion liquid of c hydroxyl modified that step (b) obtains by () carries out suction filtration, then filtrate is washed till colourless and non-foam with deionized water, last lyophilize process 24 ~ 36h, obtains hydroxylation redox graphene pressed powder;
D () gets the hydroxylation redox graphene pressed powder that 2500mg is obtained by step (c), and be scattered in 500mL deionized water, the redox graphene dispersion liquid that concentration is 5mg/mL is obtained after supersound process 1 ~ 3h, aperture is utilized to be after the cellulose filter membrane of 0.22 μm carries out decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, floatation of filter film, obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk that diameter is about 4cm, thickness about 20 microns, smooth surface and smooth.The mechanical moduli of the self-supporting redox graphene of the present embodiment is 7.8Gpa, illustrates that it has good mechanical property.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that the ordinary skill of this area just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technician in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (9)
1. a self-supporting redox graphene Preparation Method made of paper, is characterized in that, comprise the following steps:
A the reduction of () graphene oxide solution: at room temperature, is scattered in graphite oxide in water, then adds tensio-active agent, obtain the graphite oxide dispersion that concentration is 0.5 ~ 5mg/mL after supersound process; Then in described graphite oxide dispersion, add 1 ~ 5mL hydrazine hydrate, oil bath is heated to 90 ~ 120 DEG C, obtains redox graphene suspension after reaction 5 ~ 24h;
The hydroxylation process of (b) redox graphene: oil bath temperature of reaction is down to 80 ~ 90 DEG C, in described redox graphene suspension, add benzaminic acid and Isopentyl nitrite successively, oil bath obtains the redox graphene dispersion liquid of hydroxyl modified after reacting at least 10h;
C the preparation of () hydroxylation redox graphene pressed powder: the redox graphene dispersion liquid of described hydroxyl modified is carried out suction filtration, then washes, eventually pass lyophilize process, obtains described hydroxylation redox graphene pressed powder;
The generation of (d) self-supporting redox graphene paper: described hydroxylation redox graphene pressed powder is scattered in solvent, the redox graphene dispersion liquid that concentration is 0.1 ~ 5mg/mL is obtained after supersound process, after decompress filter process, described redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, described floatation of filter film, obtains described self-supporting redox graphene paper.
2. self-supporting redox graphene Preparation Method made of paper as claimed in claim 1, is characterized in that, the described graphite oxide adopted in described step (a) is prepared from by Hummers method, Brodie method or Staudenmaier method.
3. self-supporting redox graphene Preparation Method made of paper as claimed in claim 1, is characterized in that, the described tensio-active agent adopted in described step (a) is cats product or anion surfactant.
4. self-supporting redox graphene Preparation Method made of paper as claimed in claim 3, it is characterized in that, described cats product is polyacrylamide.
5. self-supporting redox graphene Preparation Method made of paper as claimed in claim 3, it is characterized in that, described anion surfactant is sodium laurylsulfonate, Sodium dodecylbenzene sulfonate.
6. self-supporting redox graphene Preparation Method made of paper as claimed in claim 1, it is characterized in that, in described step (a) or described step (d), described supersound process is the ultrasonication under operating frequency 40 ~ 200kHz, ultrasonic power 50 ~ 200W, and ultrasonic time is 1 ~ 3h.
7. self-supporting redox graphene Preparation Method made of paper as claimed in claim 1, it is characterized in that, in described step (b), the amount of described benzaminic acid is 2-6 times of carbon molar equivalent in described graphite oxide, and the amount of described Isopentyl nitrite is 1 ~ 3 times of carbon molar equivalent in described graphite oxide.
8. self-supporting redox graphene Preparation Method made of paper as claimed in claim 1, it is characterized in that, in described step (c), described washing refers to and is washed till colourless with deionized water by filtrate and till non-foam, the described lyophilize treatment time is 24 ~ 36h; In described step (d), described seasoning refers at room temperature, naturally dry through 8 ~ 24h in air.
9. self-supporting redox graphene Preparation Method made of paper as claimed in claim 1, is characterized in that, in described step (d), described solvent is deionized water, ethanol, N, dinethylformamide, the mixing of one or more in N,N-dimethylacetamide; Described filter membrane is polyvinylidene difluoride (PVDF) filter membrane, cellulose filter membrane or anodised aluminium filter membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410174812.8A CN103935994B (en) | 2014-04-28 | 2014-04-28 | A kind of self-supporting redox graphene paper and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410174812.8A CN103935994B (en) | 2014-04-28 | 2014-04-28 | A kind of self-supporting redox graphene paper and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103935994A CN103935994A (en) | 2014-07-23 |
| CN103935994B true CN103935994B (en) | 2015-09-09 |
Family
ID=51183923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410174812.8A Active CN103935994B (en) | 2014-04-28 | 2014-04-28 | A kind of self-supporting redox graphene paper and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103935994B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211053A (en) * | 2014-09-04 | 2014-12-17 | 济宁利特纳米技术有限责任公司 | Preparation method of modified graphene aqueous dispersion |
| CN104310384A (en) * | 2014-10-08 | 2015-01-28 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of hydroxylated graphene powder with controllable conductive performance |
| CN104448704B (en) * | 2014-11-14 | 2016-08-24 | 中国航空工业集团公司北京航空材料研究院 | The preparation method of high tenacity carboxylated graphene-epoxy resin composite material |
| CN104445163B (en) * | 2014-11-14 | 2016-08-24 | 中国航空工业集团公司北京航空材料研究院 | A kind of preparation method of carboxylated Graphene |
| CN104891477B (en) * | 2015-05-15 | 2016-11-09 | 北京交通大学 | A kind of simple and environmentally-friendly graphene paper preparation method |
| CN106128788B (en) * | 2016-06-02 | 2019-01-18 | 华南理工大学 | A kind of supercapacitor and preparation method thereof |
| CN107324321B (en) * | 2017-07-24 | 2019-07-19 | 济南大学 | Load the preparation method of the three-dimensional redox graphene of golden flower |
| JP2020531387A (en) * | 2017-10-13 | 2020-11-05 | ヂェァジァン ユニバーシティＺｈｅｊｉａｎｇ Ｕｎｉｖｅｒｓｉｔｙ | Self-supporting graphene film and its manufacturing method |
| CN108845007A (en) * | 2018-04-25 | 2018-11-20 | 上海第二工业大学 | A kind of platinum/graphen paper nanometer combined electrode material and preparation method thereof for detecting hydrogen peroxide |
| CN108862262B (en) * | 2018-07-10 | 2020-05-12 | 杭州高烯科技有限公司 | Preparation method of graphene-based ultrathin composite film |
| CN108840329B (en) * | 2018-07-10 | 2020-07-07 | 杭州高烯科技有限公司 | Preparation method of independent self-supporting graphene-based ultrathin film |
| CN109148863B (en) * | 2018-09-03 | 2021-11-19 | 新奥石墨烯技术有限公司 | Lithium titanate-graphene composite material and preparation method and application thereof |
| WO2021146810A1 (en) * | 2020-01-23 | 2021-07-29 | The Royal Institution For The Advancement Of Learning / Mcgill University | Electronic circuit having graphene oxide paper substrate and method of recovering parts of an electronic circuit |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103427088A (en) * | 2012-05-25 | 2013-12-04 | 海洋王照明科技股份有限公司 | Making method of graphene paper collector |
| CN103700513A (en) * | 2013-12-30 | 2014-04-02 | 中山大学 | Graphene paper and preparation method and application thereof |
| CN103723717A (en) * | 2014-01-03 | 2014-04-16 | 中国科学院山西煤炭化学研究所 | Preparation method of nitrogen-doped graphene thin film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011041663A2 (en) * | 2009-10-02 | 2011-04-07 | Board Of Regents, The University Of Texas System | Exfoliation of graphite oxide in propylene carbonate and thermal reduction of resulting graphene oxide platelets |
-
2014
- 2014-04-28 CN CN201410174812.8A patent/CN103935994B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103427088A (en) * | 2012-05-25 | 2013-12-04 | 海洋王照明科技股份有限公司 | Making method of graphene paper collector |
| CN103700513A (en) * | 2013-12-30 | 2014-04-02 | 中山大学 | Graphene paper and preparation method and application thereof |
| CN103723717A (en) * | 2014-01-03 | 2014-04-16 | 中国科学院山西煤炭化学研究所 | Preparation method of nitrogen-doped graphene thin film |
Non-Patent Citations (1)
| Title |
|---|
| Mechanically Strong,Electrically Conductive,and Biocompatible Graphene Paper;Haiqun Chen et al.;《Advanced Materials》;20080723;第20卷;第3557页右侧栏第2段，第3560页"实验"部分，图1和3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103935994A (en) | 2014-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103935994B (en) | A kind of self-supporting redox graphene paper and preparation method thereof | |
| Wang et al. | Low-temperature carbonized carbon nanotube/cellulose aerogel for efficient microwave absorption | |
| Yao et al. | Boosting gravimetric and volumetric energy density via engineering macroporous MXene films for supercapacitors | |
| CN103466603B (en) | The preparation method of graphene dispersing solution and graphene film | |
| US10472243B2 (en) | Industrial method for preparing large-sized graphene | |
| CN104556018B (en) | A kind of preparation method of high-quality graphene conductive film | |
| Ye et al. | Producing large-area, foldable graphene paper from graphite oxide suspensions by in-situ chemical reduction process | |
| CN104925788B (en) | A kind of method that utilization discharge-induced explosion prepares grapheme material | |
| CN105000542A (en) | Preparation method for graphene-carbon nano tube three-dimensional structure composite material | |
| Luo et al. | MnO2-decorated 3D porous carbon skeleton derived from mollusc shell for high-performance supercapacitor | |
| US20210354990A1 (en) | Porous graphene film, its manufacturing method and electronic product | |
| CN102205959A (en) | Graphite alkene nanotube and preparation method thereof | |
| Mehrabi-Matin et al. | Silver fiber fabric as the current collector for preparation of graphene-based supercapacitors | |
| El Ghazaly et al. | Ultrafast, one-step, salt-solution-based acoustic synthesis of Ti3C2 MXene | |
| CN107954420A (en) | A kind of Anodic peels off the method that graphite prepares three-dimensional grapheme | |
| Wang et al. | Laser induced self-propagating reduction and exfoliation of graphite oxide as an electrode material for supercapacitors | |
| Lin et al. | Highly flexible, foldable carbon cloth/MXene/polyaniline/CoNi layered double hydroxide electrode for high-performance all solid-state supercapacitors | |
| Zhu et al. | Free-standing graphene films prepared via foam film method for great capacitive flexible supercapacitors | |
| Li et al. | 3D nanostructured CuxO modified copper foam as a binder-free electrode for all-solid-state supercapacitor | |
| Wang et al. | MnO2@ polypyrrole composite with hollow microsphere structure for electrode material of supercapacitors | |
| Sridhar et al. | Microwave synthesis of three dimensional graphene-based shell-plate hybrid nanostructures | |
| Liang et al. | Synthesis of ultra-thin graphene-like nanosheets from lignin based on evaporation induced self-assembly for supercapacitors | |
| Zhao et al. | Facile synthesis of graphene nanosheets via barium ferrite assisted intercalation and secondary expansion of graphite | |
| Shen et al. | Preparation of high quality graphene using high gravity technology | |
| Zhu et al. | Similar “relay race” capacitance behaviors of folded graphene films based high-performance supercapacitors |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170817 Address after: 200444 block A, building 4, building 511, Baoshan District Road, Shanghai, No. 2 Patentee after: Shanghai Co., Ltd of Li Wusheng enterprise group Address before: 200240 Dongchuan Road, Shanghai, No. 800, No. Patentee before: Shanghai Jiao Tong University |
|
| TR01 | Transfer of patent right | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20140723 Assignee: Shanghai Li Sheng Nano Technology Co., Ltd. Assignor: Shanghai Co., Ltd of Li Wusheng enterprise group Contract record no.: X2019310000016 Denomination of invention: Self-supported reduced graphene oxide paper and preparation method thereof Granted publication date: 20150909 License type: Exclusive License Record date: 20191015 |
|
| EE01 | Entry into force of recordation of patent licensing contract |