CN103935994A - Self-supported reduced graphene oxide paper and preparation method thereof - Google Patents
Self-supported reduced graphene oxide paper and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a piece of self-supported reduced graphene oxide paper and a preparation method thereof. The preparation method comprises the following steps: reducing a graphene oxide solution, performing carboxylation treatment on the reduced graphene oxide, preparing carboxylated reduced graphene oxide solid powder, and making the self-supported reduced graphene oxide paper. The preparation method is simple and feasible, and can be used for on-scale preparation. The self-supported reduced graphene oxide paper prepared by using the preparation method is relatively good in mechanical property, high in purity, uniform, flat, controllable in thickness and shape, and good in development prospect in fields such as functional composite materials and super capacitors.
Description
Technical field
The present invention relates to a kind of Graphene paper and preparation method thereof, relate in particular 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 being made up of carbon atom, since 2004 are found, has become at present the thinnest the hardest in the world nano material, and its intensity is 200 times of steel.Except intensity is high, Graphene has surprising flexibility, can not occur damaged in the situation that stretching 20%.This makes it aspect functional composite material, such as there is very large potential application foreground the aspects such as ultra-thin and ultra-light aircraft material, ultralight super tough flak jackets.The electroconductibility of Graphene excellence, thermal conductivity and and mechanical property, make it at matrix material, novel electron device, 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 dispersion, thereby becomes a popular method preparing redox graphene.
The method that adopts graphene dispersing solution to prepare graphene film has conventionally: filter deposition method, electrophoretic deposition, hot spray process, LB method, self-assembly method, spin-coating method, chemical vapour deposition etc. layer by layer.But the graphene film preparing by these methods is all difficult to peel off from base materials such as sheet glass, quartz plate, sheet micas, this has just hindered the transfer of graphene film and further application.
Through the retrieval of prior art is found, the Chen Xiaodong of Nanyang Technological University professor writes articles proposition 2972～2978 pages of Advanced Functional Materials the 23rd volumes, utilize the technology of sprawling waterborne to obtain self-supporting Graphene honeycomb film, have and can transfer to any suprabasil ability, the gate of self-supporting Graphene standby feasibility made of paper has been opened in their research, but this preparation method length consuming time, yield rate is low, dimensional thickness Modulatory character is poor.
Therefore, those skilled in the art is devoted to develop a kind of more simple, more extensive, more effective preparation method and realizes 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 and realizes 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) reduction of graphene oxide solution: at room temperature, graphite oxide is scattered in water, then adds tensio-active agent, obtaining concentration after supersound process is the graphite oxide dispersion liquid of 0.5～5mg/mL; Then in described graphite oxide dispersion liquid, add 1～5mL hydrazine hydrate, oil bath is heated to 90～120 DEG C, after reaction 5～24h, obtains redox graphene suspension;
(b) the hydroxylation processing of redox graphene: oil bath temperature of reaction is down to 80～90 DEG C, in described redox graphene suspension, add successively benzaminic acid and Isopentyl nitrite, the redox graphene dispersion liquid that obtains hydroxyl modified after 10h is at least reacted in oil bath;
(c) preparation of hydroxylation redox graphene pressed powder: the redox graphene dispersion liquid of described hydroxyl modified is carried out to suction filtration, and then washing, finally by crossing lyophilize processing, obtains described hydroxylation redox graphene pressed powder;
(d) generation of self-supporting redox graphene paper: described hydroxylation redox graphene pressed powder is scattered in solvent, after supersound process, obtaining concentration is the redox graphene dispersion liquid of 0.1～5mg/mL, after decompress filter is processed, described redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, described filter membrane comes off, and obtains described self-supporting redox graphene paper.
Further, the described graphite oxide adopting in described step (a) is prepared from by Hummers method, Brodie method or Staudenmaier method.
Further, the described tensio-active agent adopting 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 be carbon molar equivalent in described graphite oxide 2-6 doubly, the amount of described Isopentyl nitrite is 1～3 times of carbon molar equivalent in described graphite oxide.
Further, in described step (c), till described washing refers to, with deionized water, filtrate is washed till to colourless and 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 filter membrane, cellulose filter membrane or anodised aluminium filter membrane.
The invention also discloses a kind of self-supporting redox graphene paper that utilizes above-mentioned preparation method to make, described self-supporting redox graphene paper purity is high, evenly smooth, has good mechanical property.
Compared with existing Graphene Preparation Method made of paper, that the preparation method of self-supporting redox graphene paper of the present invention has advantages of is simple, can prepare on a large scale, can prepare as required the self-supporting reduction peroxidation Graphene paper of different thickness, size and dimension simultaneously, and very easily realize peeling off of self-supporting reduction peroxidation Graphene paper and base material, prepared self-supporting reduction peroxidation Graphene paper purity is high, evenly smooth, and has good mechanical property.
Brief description of the drawings
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 that Fig. 1 is the stress-strain curve of the self-supporting redox graphene paper of the embodiment of the present invention 1.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are elaborated, the present embodiment is implemented under taking technical solution of the present invention as prerequisite, provided detailed embodiment and concrete operating process, but protection domain of the present invention 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) at room temperature, 600mg graphite oxide is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate, after supersound process 1～3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL; Then in above-mentioned graphite oxide dispersion liquid, 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, in the redox graphene suspension obtaining in step (a), add successively 7.31g benzaminic acid and 3.15g Isopentyl nitrite, the redox graphene dispersion liquid that obtains hydroxyl modified after 10h is at least reacted in oil bath;
(c) the redox graphene dispersion liquid of hydroxyl modified step (b) being obtained carries out suction filtration, then filtrate is washed till to colourless and non-foam with deionized water, 24～36h is processed in last lyophilize, obtains hydroxylation redox graphene pressed powder;
(d) get the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 150mL deionized water, after supersound process 1～3h, obtaining concentration is the redox graphene dispersion liquid of 0.33mg/mL, utilizing aperture is that the cellulose filter membrane of 0.22 μ m carries out after decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, filter membrane comes off, and obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk of approximately 20 microns of the diameter 4cm, the thickness that exist with self-supporting form, smooth surface and smooth.In addition, as shown in Figure 1, the self-supporting redox graphene of the present embodiment is piled up and is formed by many single-layer graphenes, connects between layers closely.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) at room temperature, 300mg graphite oxide is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate, after supersound process 1～3h, obtaining concentration is the graphite oxide dispersion liquid of 0.5mg/mL; Then in above-mentioned graphite oxide dispersion liquid, 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, in the redox graphene suspension obtaining in step (a), add successively 7.31g benzaminic acid and 3.15g Isopentyl nitrite, the redox graphene dispersion liquid that obtains hydroxyl modified after 10h is at least reacted in oil bath;
(c) the redox graphene dispersion liquid of hydroxyl modified step (b) being obtained carries out suction filtration, then filtrate is washed till to colourless and non-foam with deionized water, 24～36h is processed in last lyophilize, obtains hydroxylation redox graphene pressed powder;
(d) get the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 150mL deionized water, after supersound process 1～3h, obtaining concentration is the redox graphene dispersion liquid of 0.33mg/mL, utilizing aperture is that the cellulose filter membrane of 0.22 μ m carries out after decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, filter membrane comes off, and obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk of approximately 20 microns of diameter 4cm, thickness, 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) at room temperature, 600mg graphite oxide is scattered in 600mL water, then adds 6g Sodium dodecylbenzene sulfonate, after supersound process 1～3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL; Then in above-mentioned graphite oxide dispersion liquid, 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, in the redox graphene suspension obtaining in step (a), add successively 7.31g benzaminic acid and 3.15g Isopentyl nitrite, the redox graphene dispersion liquid that obtains hydroxyl modified after 10h is at least reacted in oil bath;
(c) the redox graphene dispersion liquid of hydroxyl modified step (b) being obtained carries out suction filtration, then filtrate is washed till to colourless and non-foam with deionized water, 24～36h is processed in last lyophilize, obtains hydroxylation redox graphene pressed powder;
(d) get the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 150mL deionized water, after supersound process 1～3h, obtaining concentration is the redox graphene dispersion liquid of 0.33mg/mL, utilizing aperture is that the cellulose filter membrane of 0.22 μ m carries out after decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, filter membrane comes off, and obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk of approximately 80 microns of diameter 2cm, thickness, 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) at room temperature, 600mg graphite oxide is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate, after supersound process 1～3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL; Then in above-mentioned graphite oxide dispersion liquid, 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, in the redox graphene suspension obtaining in step (a), add successively 7.31g benzaminic acid and 3.15g Isopentyl nitrite, the redox graphene dispersion liquid that obtains hydroxyl modified after 10h is at least reacted in oil bath;
(c) the redox graphene dispersion liquid of hydroxyl modified step (b) being obtained carries out suction filtration, then filtrate is washed till to colourless and non-foam with deionized water, 24～36h is processed in last lyophilize, obtains hydroxylation redox graphene pressed powder;
(d) get the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 150mL deionized water, after supersound process 1～3h, obtaining concentration is the redox graphene dispersion liquid of 0.33mg/mL, utilizing aperture is that the cellulose filter membrane of 0.22 μ m carries out after decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, filter membrane comes off, and obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk of approximately 5 microns of diameter 8cm, thickness, 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) at room temperature, 600mg graphite oxide is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate, after supersound process 1～3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL; Then in above-mentioned graphite oxide dispersion liquid, 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, in the redox graphene suspension obtaining in step (a), add successively 7.31g benzaminic acid and 3.15g Isopentyl nitrite, the redox graphene dispersion liquid that obtains hydroxyl modified after 10h is at least reacted in oil bath;
(c) the redox graphene dispersion liquid of hydroxyl modified step (b) being obtained carries out suction filtration, then filtrate is washed till to colourless and non-foam with deionized water, 24～36h is processed in last lyophilize, obtains hydroxylation redox graphene pressed powder;
(d) get the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 150mL deionized water, after supersound process 1～3h, obtaining concentration is the redox graphene dispersion liquid of 0.33mg/mL, utilizing aperture is that the cellulose filter membrane of 0.22 μ m carries out after decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, filter membrane comes off, and obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk of approximately 20 microns of diameter 4cm, thickness, 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) at room temperature, 3000mg graphite oxide is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate, after supersound process 1～3h, obtaining concentration is the graphite oxide dispersion liquid of 5mg/mL; Then in above-mentioned graphite oxide dispersion liquid, 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, in the redox graphene suspension obtaining in step (a), add successively 21.93g benzaminic acid and 9.45g Isopentyl nitrite, the redox graphene dispersion liquid that obtains hydroxyl modified after 10h is at least reacted in oil bath;
(c) the redox graphene dispersion liquid of hydroxyl modified step (b) being obtained carries out suction filtration, then filtrate is washed till to colourless and non-foam with deionized water, 24～36h is processed in last lyophilize, obtains hydroxylation redox graphene pressed powder;
(d) get the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 150mL deionized water, after supersound process 1～3h, obtaining concentration is the redox graphene dispersion liquid of 0.33mg/mL, utilizing aperture is that the cellulose filter membrane of 0.22 μ m carries out after decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, filter membrane comes off, and obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk of approximately 20 microns of diameter 4cm, thickness, 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) at room temperature, 600mg graphite oxide is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate, after supersound process 1～3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL; Then in above-mentioned graphite oxide dispersion liquid, 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, in the redox graphene suspension obtaining in step (a), add successively 14.62g benzaminic acid and 6.3g Isopentyl nitrite, the redox graphene dispersion liquid that obtains hydroxyl modified after 10h is at least reacted in oil bath;
(c) the redox graphene dispersion liquid of hydroxyl modified step (b) being obtained carries out suction filtration, then filtrate is washed till to colourless and non-foam with deionized water, 24～36h is processed in last lyophilize, obtains hydroxylation redox graphene pressed powder;
(d) get the hydroxylation redox graphene pressed powder that 50mg is obtained by step (c), and be scattered in 500mL deionized water, after supersound process 1～3h, obtaining concentration is the redox graphene dispersion liquid of 0.1mg/mL, utilizing aperture is that the cellulose filter membrane of 0.22 μ m carries out after decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, filter membrane comes off, and obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk of approximately 20 microns of diameter 4cm, thickness, 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) at room temperature, 3000mg graphite oxide is scattered in 600mL water, then adds 1.5g Sodium dodecylbenzene sulfonate, after supersound process 1～3h, obtaining concentration is the graphite oxide dispersion liquid of 5mg/mL; Then in above-mentioned graphite oxide dispersion liquid, 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, in the redox graphene suspension obtaining in step (a), add successively 10.965g benzaminic acid and 4.725g Isopentyl nitrite, the redox graphene dispersion liquid that obtains hydroxyl modified after 10h is at least reacted in oil bath;
(c) the redox graphene dispersion liquid of hydroxyl modified step (b) being obtained carries out suction filtration, then filtrate is washed till to colourless and non-foam with deionized water, 24～36h is processed in last lyophilize, obtains hydroxylation redox graphene pressed powder;
(d) get the hydroxylation redox graphene pressed powder that 2500mg is obtained by step (c), and be scattered in 500mL deionized water, after supersound process 1～3h, obtaining concentration is the redox graphene dispersion liquid of 5mg/mL, utilizing aperture is that the cellulose filter membrane of 0.22 μ m carries out after decompress filter, redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, filter membrane comes off, and obtains self-supporting redox graphene paper.
The self-supporting redox graphene that the preparation method of the present embodiment obtains is the disk of approximately 20 microns of diameter 4cm, thickness, 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.The ordinary skill that should be appreciated that this area just can design according to the present invention be made many modifications and variations without creative work.Therefore, all technician in the art, all should be in 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 (10)
1. a self-supporting redox graphene Preparation Method made of paper, is characterized in that, comprises the following steps:
(a) reduction of graphene oxide solution: at room temperature, graphite oxide is scattered in water, then adds tensio-active agent, obtaining concentration after supersound process is the graphite oxide dispersion liquid of 0.5～5mg/mL; Then in described graphite oxide dispersion liquid, add 1～5mL hydrazine hydrate, oil bath is heated to 90～120 DEG C, after reaction 5～24h, obtains redox graphene suspension;
(b) the hydroxylation processing of redox graphene: oil bath temperature of reaction is down to 80～90 DEG C, in described redox graphene suspension, add successively benzaminic acid and Isopentyl nitrite, the redox graphene dispersion liquid that obtains hydroxyl modified after 10h is at least reacted in oil bath;
(c) preparation of hydroxylation redox graphene pressed powder: the redox graphene dispersion liquid of described hydroxyl modified is carried out to suction filtration, and then washing, finally by crossing lyophilize processing, obtains described hydroxylation redox graphene pressed powder;
(d) generation of self-supporting redox graphene paper: described hydroxylation redox graphene pressed powder is scattered in solvent, after supersound process, obtaining concentration is the redox graphene dispersion liquid of 0.1～5mg/mL, after decompress filter is processed, described redox graphene dispersion liquid forms oxidation graphene film on filter membrane, after seasoning, described filter membrane comes off, and obtains described self-supporting redox graphene paper.
2. self-supporting redox graphene as claimed in claim 1 Preparation Method made of paper, is characterized in that, the described graphite oxide adopting in described step (a) is prepared from by Hummers method, Brodie method or Staudenmaier method.
3. self-supporting redox graphene as claimed in claim 1 Preparation Method made of paper, is characterized in that, the described tensio-active agent adopting in described step (a) is cats product or anion surfactant.
4. self-supporting redox graphene as claimed in claim 3 Preparation Method made of paper, is characterized in that, described cats product is polyacrylamide.
5. self-supporting redox graphene as claimed in claim 3 Preparation Method made of paper, is characterized in that, described anion surfactant is sodium laurylsulfonate, Sodium dodecylbenzene sulfonate.
6. self-supporting redox graphene as claimed in claim 1 Preparation Method made of paper, 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 as claimed in claim 1 Preparation Method made of paper, it is characterized in that, in described step (b), the amount of described para-amino benzoic acid be carbon molar equivalent in described graphite oxide 2-6 doubly, the amount of described Isopentyl nitrite is 1～3 times of carbon molar equivalent in described graphite oxide.
8. self-supporting redox graphene as claimed in claim 1 Preparation Method made of paper, it is characterized in that, in described step (c), till described washing refers to, with deionized water, filtrate is washed till to colourless and 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 as claimed in claim 1 Preparation Method made of paper, 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 acetate filter membrane, cellulose filter membrane or anodised aluminium filter membrane.
10. the self-supporting redox graphene paper that the self-supporting redox graphene Preparation Method made of paper as described in any one in claim 1～9 makes.
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