CN104030280A - Preparation method of graphene paper - Google Patents
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- CN104030280A CN104030280A CN201410266889.8A CN201410266889A CN104030280A CN 104030280 A CN104030280 A CN 104030280A CN 201410266889 A CN201410266889 A CN 201410266889A CN 104030280 A CN104030280 A CN 104030280A
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Abstract
The invention discloses a preparation method of graphene paper. The preparation method specifically comprises the following steps: preparing a graphene oxide solid and dispersing the solid in a solvent; curtain-casting the dispersion liquid on a substrate, drying to form a film so as to form graphene oxide paper and soaking the graphene oxide paper in an ascorbic acid solution, and preparing the graphene paper by an in-situ reduction method; and soaking the graphene oxide paper in a mixed solution of ascorbic acid and silver nitrate to obtain the graphene paper with enhanced electrical properties. The graphene paper prepared by the method is regular in structure, uniform in height, high in purity and controllable in shape, dimension, thickness and square resistance of products. The preparation method disclosed by the invention is simple in process, strong in practicality and suitable for preparation on a large scale, and has a wide application prospect in the fields such as nanofiltration membranes, supercapacitors and lithium batteries.
Description
Technical field
The invention belongs to Graphene paper preparing technical field, relate to a kind of preparation method of Graphene paper.
Background technology
Graphene is a kind of two dimensional crystal material being made up of monolayer carbon atom close-packed arrays, there is unique quantum effect and excellent electricity, calorifics and mechanical property, be with a wide range of applications at aspects such as following novel nano electron device, matrix material, solar cell, super capacitors.With respect to traditional physical method, Graphene prepared by chemical local reduction way has that productive rate is high, preparation method is simple and lower-cost advantage, and therefore it has become an ordinary method prepared by Graphene.
Adopt chemical process by the oxidation of flakey natural graphite, the graphene oxide obtaining can be dispersed in water, further prepares Graphene by the method for chemical reduction.Utilize the method for filtration under diminished pressure to obtain having graphene oxide and the Graphene paper of considerable intensity.In order further to improve the electric property of Graphene paper, the people such as Lu Zheng 376～381 pages of the 201st volumes on Journal of Power Sources are write articles, and adopt metallic silver particles to modify to realize the electric property of Graphene paper is strengthened.
But the graphene oxide paper that filtration under diminished pressure method obtains is unsuitable for suitability for industrialized production, and existing in-situ reducing method also has certain infringement to the mechanical property of Graphene paper.Therefore prepare on a large scale Graphene paper and be necessary to find the method for simple possible.Although the people such as Titelman GI 641～649 pages of the 43rd volumes on Carbon are write articles, graphene oxide dispersion liquid can become graphene oxide film by dried coating film, has no report but big area self-supporting that can be complete has the preparation of the Graphene paper of considerable electric property simultaneously.
Therefore, those skilled in the art be devoted to develop a kind of can be complete big area self-supporting and the preparation method of the controlled Graphene paper of electric property.
Summary of the invention
The object of the invention is to overcome the defect that above-mentioned prior art exists, and then realize the extensive preparation of the Graphene paper of big area self-supporting that can be complete, and can be according to the electric property of preparation method's control Graphene paper.
For achieving the above object, the invention provides a kind of preparation method of Graphene paper, adopt specific base material, by graphene oxide dispersion liquid casting film-forming, can realize the extensive preparation of graphene oxide paper, adopt local reduction way can realize the transformation of graphene oxide principal direction Graphene paper, in reduction process, add Silver Nitrate and can realize the electric property enhancing of Graphene paper and control.
Specific embodiments of the present invention comprise the following steps:
A. under room temperature, graphite is joined in the vitriol oil and stirred, after adding again SODIUMNITRATE fully to stir, carry out cooling process, then add potassium permanganate in batches, be finally heated to 35 ± 3 DEG C with water-bath, fully after reaction, add mixture of ice and water cancellation reaction, obtain brown graphite suspension;
B. keeping, under the condition stirring, adding hydrogen peroxide in graphite suspension, obtain glassy yellow graphene oxide suspension;
C. will after glassy yellow graphene oxide suspension filtered, obtain filemot filter cake, by filter cake with after cleanup acid treatment, further with deionized water wash to filtrate without Cl
-, final drying processing, obtains graphene oxide solid;
D. graphene oxide solid is scattered in solvent, supersound process, obtains homodisperse graphene oxide suspension;
E. by homodisperse graphene oxide suspension curtain coating in substrate, drying and forming-film, thus obtain graphene oxide paper;
F. graphene oxide paper step e being obtained, together with soaking substrate in certain density ascorbic acid solution, after reaction for some time, will complete the film drying of reduction, thereby obtains Graphene paper.
Preferably, step f of the present invention replaces by step g: the graphene oxide paper that step e is obtained is immersed in certain density xitix and Silver Nitrate mixing solutions together with substrate, after reaction for some time, will complete the film drying of reduction, obtain the Graphene paper that electric property strengthens.
Preferably, in above-mentioned steps a: described graphite is the natural flaky graphite of 200～500 object or expanded graphite; The concentration of the described vitriol oil is by mass percentage 98%; Add the described well-beaten time after SODIUMNITRATE to be greater than 1h; Described cooling process is reaction vessel to be placed in to ice bath or cryosel bathe and be cooled to below 0 DEG C or 0 DEG C; The described potassium permanganate amount that in batches adds potassium permanganate to refer at every turn to add is 2～3g, and the timed interval is 20min, so that the temperature of reaction system remains on below 15 DEG C; Described sufficient reaction time after heating in water bath is greater than 2h.
Preferably, the concentration of the described hydrogen peroxide in above-mentioned steps b is by mass percentage 30%.
Preferably, the dilute hydrochloric acid repetitive scrubbing that is that to adopt mass percent be 3% of the cleanup acid treatment in above-mentioned steps c to filtrate without SO
4 2-; Above-mentioned drying treatment refers to 40 DEG C of vacuum in vacuum drying oven, dry 24h.
Preferably, the solvent in above-mentioned steps d is the mixture that is selected from water, second alcohol and water, N, the mixture of dinethylformamide and water, the mixture of N,N-dimethylacetamide and water, the mixture of N-Methyl pyrrolidone and water, the one in the mixture of dimethyl sulfoxide (DMSO) and water; Above-mentioned supersound process is 40～200kHz for adopting operating frequency, and ultrasonic power is 50～200W, and ultrasonic time is 1～5h; The concentration of above-mentioned graphene oxide suspension is 0.1～5mg/ml.
Preferably, in above-mentioned steps e: substrate is to comprise a kind of material being selected from tetrafluoroethylene, polycarbonate, polyethylene, polypropylene, polyimide, steel plate, PET, polyaryletherketone, polyvinyl chloride, polyvinylidene difluoride (PVDF), urethane, poly(lactic acid), polystyrene, ABS resin, polyacrylonitrile, poly (arylene ether nitrile), polyethersulfone, polysiloxane, Mierocrystalline cellulose, rubber, Polyvinyl carbazole, mica, epoxy resin, resol, maleic resin, fluoro-resin; Drying and forming-film is to place 6～24h in temperature is the baking oven of 20～80 DEG C.
Preferably, in above-mentioned steps f: substrate is to comprise a kind of material being selected from tetrafluoroethylene, polycarbonate, polyethylene, polypropylene, polyimide, steel plate, PET, polyaryletherketone, polyvinyl chloride, polyvinylidene difluoride (PVDF), urethane, poly(lactic acid), polystyrene, ABS resin, polyacrylonitrile, poly (arylene ether nitrile), polyethersulfone, polysiloxane, Mierocrystalline cellulose, rubber, Polyvinyl carbazole, mica, epoxy resin, resol, maleic resin, fluoro-resin; The concentration of ascorbic acid solution is 0.1～5mg/ml, and the quality percentage composition of described xitix is 0.1%～5%; The time of reaction is 10min～24h; Dry is to be dry 6～24h in the baking oven of 20～80 DEG C in temperature.
Preferably, in above-mentioned steps g: substrate is to comprise a kind of material being selected from tetrafluoroethylene, polycarbonate, polyethylene, polypropylene, polyimide, steel plate, PET, polyaryletherketone, polyvinyl chloride, polyvinylidene difluoride (PVDF), urethane, poly(lactic acid), polystyrene, ABS resin, polyacrylonitrile, poly (arylene ether nitrile), polyethersulfone, polysiloxane, Mierocrystalline cellulose, rubber, Polyvinyl carbazole, mica, epoxy resin, resol, maleic resin, fluoro-resin; The total concn of xitix and Silver Nitrate mixing solutions is 0.1～5mg/ml, and the quality percentage composition of described xitix and Silver Nitrate is 0.1%～5%; The time of described reaction is 10min～24h; Described dry be to be dry 6～24h in the baking oven of 20～80 DEG C in temperature.
The present invention realizes the extensive preparation of graphene oxide paper by casting filming therapy in substrate and local reduction way; In reductive agent, add Silver Nitrate, realize Graphene paper electric property strengthen and controlled.
Than prior art, the present invention is simple, be suitable for extensive preparation, and can design as required the Graphene paper of different thickness, size and dimension, the Graphene paper structure that the electric property obtaining strengthens is regular, highly even, has enough physical strengths and lower square resistance resistance.
Below with reference to accompanying drawing, the technique effect of design of the present invention, concrete structure and generation is described further, to understand fully object of the present invention, feature and effect.
Brief description of the drawings
Fig. 1 is schematic diagram of the present invention;
Fig. 2 is the surface scan electron micrograph of the Graphene paper prepared of the embodiment of the present invention 1;
Fig. 3 is the surface scan electron micrograph of the Graphene paper prepared of the embodiment of the present invention 6.
Embodiment
Embodiment 1
As shown in Fig. 1 step (1), the large-scale producing method of the Graphene paper described in the present embodiment, comprises the following steps:
A. at room temperature, natural 10g500 object flaky graphite is joined in 1000ml flask, after mechanical stirring is even, add 5g SODIUMNITRATE, continue to stir 1h, ice bath is cooled to 0 DEG C, then, in 5h, add 30g potassium permanganate in batches, keep temperature of reaction system not higher than 15 DEG C, remove ice bath, temperature of reaction system is risen to 35 ± 3 DEG C with heating in water bath, fully stirring reaction 2h, obtains brown graphite suspension;
B. 500ml frozen water is added in flask to quencher reaction, slowly adding subsequently mass percent concentration is 30% aqueous hydrogen peroxide solution 35ml, obtains glassy yellow graphene oxide suspension;
C. by graphene oxide suspension filtered, obtain tawny filter cake, the dilute hydrochloric acid solution that is 3% by mass percentage concentration washing until filtrate without SO
4 2-, continue to wash with water, until filtrate is without Cl
-, the filter cake obtaining is placed in 40 DEG C of vacuum-drying 24h of vacuum drying oven, obtains graphene oxide solid;
D. graphene oxide is scattered in water to supersound process 5h under 200Hz frequency, 50W power, the dispersion liquid of formation 0.5mg/ml;
E. dispersion liquid is prolonged to film forming at tetrafluoroethylene substrate upper reaches, 60 DEG C of heat treated 24h;
F. graphene oxide paper is immersed in the ascorbic acid solution that concentration is 0.5mg/ml together with substrate, after 5h, takes out, after 80 DEG C of heat treated 6h, peel off and obtain Graphene paper.
The surface scan electron micrograph of Graphene paper prepared by embodiment 1 as shown in Figure 2.
Embodiment 2
As shown in Fig. 1 step (1), the large-scale producing method of the Graphene paper described in the present embodiment, comprises the following steps:
A. at room temperature, natural 10g200 object flaky graphite is joined in 1000ml flask, after mechanical stirring is even, add 5g SODIUMNITRATE, continue to stir 1h, ice bath is cooled to 0 DEG C, then, in 5h, add 30g potassium permanganate in batches, keep temperature of reaction system not higher than 15 DEG C, remove ice bath, temperature of reaction system is risen to 35 ± 3 DEG C with heating in water bath, fully stirring reaction 2h, obtains brown graphite suspension;
B. 500ml frozen water is added in flask to quencher reaction, slowly adding subsequently mass percent concentration is 30% aqueous hydrogen peroxide solution 35ml, obtains glassy yellow graphene oxide suspension;
C. by graphene oxide suspension filtered, obtain tawny filter cake, the dilute hydrochloric acid solution that is 3% by mass percentage concentration washing until filtrate without SO
4 2-, continue to wash with water, until filtrate is without Cl
-, the filter cake obtaining is placed in 40 DEG C of vacuum-drying 24h of vacuum drying oven, obtains graphene oxide solid;
D. graphene oxide is scattered in water to supersound process 1h under 40Hz frequency, 200W power, the dispersion liquid of formation 0.1mg/ml;
E. dispersion liquid is prolonged to film forming at tetrafluoroethylene substrate upper reaches, tetrafluoroethylene substrate can use polycarbonate, polyethylene, polypropylene, polyimide, steel plate, PET, polyaryletherketone, polyvinyl chloride, polyvinylidene difluoride (PVDF), urethane, poly(lactic acid), polystyrene, ABS resin, polyacrylonitrile, poly (arylene ether nitrile), polyethersulfone, polysiloxane, Mierocrystalline cellulose, rubber, Polyvinyl carbazole, mica, epoxy resin, resol, maleic resin or fluoro-resin to substitute, 20 DEG C of heat treated 20h;
F. graphene oxide paper is immersed in after reacting 10min in the ascorbic acid solution that concentration is 5mg/ml and is taken out together with substrate, after 20 DEG C of heat treated 24h, peel off and obtain Graphene paper.
Embodiment 3
As shown in Fig. 1 step (2), the large-scale producing method of the Graphene paper described in the present embodiment, comprises the following steps:
A. at room temperature, the natural flaky graphite of 10g 300 object is joined in 1000ml flask, after mechanical stirring is even, add 5g SODIUMNITRATE, continue to stir 1h, ice bath is cooled to 0 DEG C, then, in 5h, add 30g potassium permanganate in batches, keep temperature of reaction system not higher than 15 DEG C, remove ice bath, temperature of reaction system is risen to 35 ± 3 DEG C with heating in water bath, fully stirring reaction 2h, obtains brown graphite suspension;
B. 500ml frozen water is added in flask to quencher reaction, slowly adding subsequently mass percent concentration is 30% aqueous hydrogen peroxide solution 35ml, obtains glassy yellow graphene oxide suspension;
C. by graphene oxide suspension filtered, obtain tawny filter cake, the dilute hydrochloric acid solution that is 3% by mass percentage concentration washing until filtrate without SO
4 2-, continue to wash with water, until filtrate is without Cl
-, the filter cake obtaining is placed in 40 DEG C of vacuum-drying 24h of vacuum drying oven, obtains graphene oxide solid;
D. graphene oxide is scattered in water, the water solvent used water here, the mixture of second alcohol and water, N, the mixture of dinethylformamide and water, N, the mixture of N-N,N-DIMETHYLACETAMIDE and water, the mixture replacing of the mixture of N-Methyl pyrrolidone and water or dimethyl sulfoxide (DMSO) and water, the dispersion liquid of formation 0.5mg/ml;
E. dispersion liquid is prolonged to film forming at tetrafluoroethylene substrate upper reaches, tetrafluoroethylene substrate can use polycarbonate, polyethylene, polypropylene, polyimide, steel plate, PET, polyaryletherketone, polyvinyl chloride, polyvinylidene difluoride (PVDF), urethane, poly(lactic acid), polystyrene, ABS resin, polyacrylonitrile, poly (arylene ether nitrile), polyethersulfone, polysiloxane, Mierocrystalline cellulose, rubber, Polyvinyl carbazole, mica, epoxy resin, resol, maleic resin or fluoro-resin to substitute, 80 DEG C of heat treated 6h;
F. graphene oxide paper is soaked and is immersed in xitix and Silver Nitrate mixing solutions together with substrate, wherein the concentration of xitix is 0.5mg/ml, the concentration of Silver Nitrate is 0.0667mg/ml, after 5h, take out, after 60 DEG C of heat treated 24h, peel off and can obtain the electricity enhancing Graphene paper that square resistance is about 6500 Ω.
Embodiment 4
A. at room temperature, natural 10g500 object flaky graphite is joined in 1000ml flask, after mechanical stirring is even, add 5g SODIUMNITRATE, continue to stir 1h, ice bath is cooled to 0 DEG C, then, in 5h, add 30g potassium permanganate in batches, keep temperature of reaction system not higher than 15 DEG C, remove ice bath, temperature of reaction system is risen to 35 ± 3 DEG C with heating in water bath, fully stirring reaction 2h, obtains brown graphite suspension;
B. the frozen water of 500ml is added in flask to quencher reaction, slowly adding subsequently mass percent concentration is 30% aqueous hydrogen peroxide solution 35ml, obtains glassy yellow graphene oxide suspension;
C. by graphene oxide suspension filtered, obtain tawny filter cake, the dilute hydrochloric acid solution that is 3% by mass percentage concentration washing until filtrate without SO
4 2-till existence, continue to wash with water, until filtrate is without Cl
-exist, the filter cake obtaining is placed in 40 DEG C of vacuum-drying 24h of vacuum drying oven, obtains graphene oxide solid;
D. graphene oxide is scattered in water, the water solvent used water here, the mixture of second alcohol and water, N, the mixture of dinethylformamide and water, the mixture of N,N-dimethylacetamide and water, the mixture replacing of the mixture of N-Methyl pyrrolidone and water or dimethyl sulfoxide (DMSO) and water, supersound process 3h under 200Hz, 200W power, the dispersion liquid of formation 1mg/ml;
E. prolong film forming at tetrafluoroethylene substrate upper reaches, 60 DEG C of heat treated 24h;
F. graphene oxide paper is immersed in xitix and Silver Nitrate mixing solutions together with substrate, wherein the concentration of xitix is 0.5mg/ml, the concentration of Silver Nitrate is 0.1667mg/ml, after 5h, take out, after 60 DEG C of heat treated 24h, peel off and can obtain the electricity enhancing Graphene paper that square resistance is about 1500 Ω.
Embodiment 5
A. at room temperature, natural 10g500 object flaky graphite is joined in 1000ml flask, after mechanical stirring is even, add 5g SODIUMNITRATE, continue to stir 1h, ice bath is cooled to 0 DEG C, then, in 5h, add 30g potassium permanganate in batches, keep temperature of reaction system not higher than 15 DEG C, remove ice bath, temperature of reaction system is risen to 35 ± 3 DEG C with heating in water bath, fully stirring reaction 2h, obtains brown graphite suspension;
B. the frozen water of 500ml is added in flask to quencher reaction, slowly adding subsequently mass percent concentration is 30% aqueous hydrogen peroxide solution 35ml, obtains glassy yellow graphene oxide suspension;
C. by graphene oxide suspension filtered, obtain tawny filter cake, the dilute hydrochloric acid solution that is 3% by mass percentage concentration washing until filtrate without SO
4 2-till existence, continue to wash with water, until filtrate is without Cl
-exist, the filter cake obtaining is placed in 40 DEG C of vacuum-drying 24h of vacuum drying oven, obtains graphene oxide solid;
D. graphene oxide is scattered in water, the water solvent used water here, the mixture of second alcohol and water, N, the mixture of dinethylformamide and water, the mixture of N,N-dimethylacetamide and water, the mixture replacing of the mixture of N-Methyl pyrrolidone and water or dimethyl sulfoxide (DMSO) and water, supersound process 3h under 200Hz, 200W power, the dispersion liquid of formation 2mg/ml;
E. dispersion liquid is prolonged to film forming at tetrafluoroethylene substrate upper reaches, tetrafluoroethylene substrate can use polycarbonate, polyethylene, polypropylene, polyimide, steel plate, PET, polyaryletherketone, polyvinyl chloride, polyvinylidene difluoride (PVDF), urethane, poly(lactic acid), polystyrene, ABS resin, polyacrylonitrile, poly (arylene ether nitrile), polyethersulfone, polysiloxane, Mierocrystalline cellulose, rubber, Polyvinyl carbazole, mica, epoxy resin, resol, maleic resin or fluoro-resin to substitute, 60 DEG C of heat treated 24h;
F. graphene oxide paper is immersed in xitix and Silver Nitrate mixing solutions together with substrate, wherein the concentration of xitix is 0.5mg/ml, the concentration of Silver Nitrate is 0.3333mg/ml, after 5h, take out, after 60 DEG C of heat treated 24h, peel off and can obtain the electricity enhancing Graphene paper that square resistance is about 1500 Ω.
Embodiment 6
A. at room temperature, natural 10g500 object flaky graphite is joined in 1000ml flask, after mechanical stirring is even, add 5g SODIUMNITRATE, continue to stir 1h, ice bath is cooled to 0 DEG C, then, in 5h, add 30g potassium permanganate in batches, keep temperature of reaction system not higher than 15 DEG C, remove ice bath, temperature of reaction system is risen to 35 ± 3 DEG C with heating in water bath, fully stirring reaction 2h, obtains brown graphite suspension;
B. the frozen water of 500ml is added in flask to quencher reaction, slowly adding subsequently mass percent concentration is 30% aqueous hydrogen peroxide solution 35ml, obtains glassy yellow graphene oxide suspension;
C. by graphene oxide suspension filtered, obtain tawny filter cake, the dilute hydrochloric acid solution that is 3% by mass percentage concentration washing until filtrate without SO
4 2-till existence, continue to wash with water, until filtrate is without Cl
-exist, the filter cake obtaining is placed in 40 DEG C of vacuum-drying 24h of vacuum drying oven, obtains graphene oxide solid;
D. graphene oxide is scattered in water to supersound process 3h under 200Hz, 200W power, the dispersion liquid of formation 3mg/ml;
E. prolong film forming at tetrafluoroethylene substrate upper reaches, 60 DEG C of heat treated 24h;
F. graphene oxide paper is immersed in bad hematic acid and Silver Nitrate mixing solutions together with substrate, wherein the concentration of xitix is 0.5mg/ml, the concentration of Silver Nitrate is 0.0667mg/ml, after 5h, take out, after 60 DEG C of heat treated 24h, peel off and can obtain the electricity enhancing Graphene paper that square resistance is about 1500 Ω.
In the preparation process at graphene oxide of embodiment 6, by adopting the method for potassium permanganate/vitriol oil intercalation oxidation, obtain can be in organic solvent the graphene oxide sheet of Monolayer Dispersion, this is beneficial to and in reduction process, further obtains the Graphene that disperses in organic solvent.The scanning electronic microscope morphology characterization of the Graphene paper shown in Fig. 3 shows, the size of Graphene and metallic silver particles is micron level.
Can find out from embodiment 1 to embodiment 6, in the preparation process of Graphene paper, by controlling concentration and the volume of graphene oxide suspension, can control the thickness of graphene oxide paper.By controlling quality percentage composition and the reaction times of Silver Nitrate, the electric property that can control Graphene paper strengthens degree.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just can design according to the present invention make 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 preparation method for Graphene paper, is characterized in that, comprises the following steps:
A. under room temperature, graphite is joined in the vitriol oil and stirred, add wherein again SODIUMNITRATE, after fully stirring, carry out cooling process, then add wherein potassium permanganate in batches, finally be heated to 35 ± 3 DEG C with water-bath, fully after reaction, add mixture of ice and water cancellation reaction, obtain brown graphite suspension;
B. keeping, under the condition stirring, adding hydrogen peroxide in brown graphite suspension, obtain glassy yellow graphene oxide suspension;
C. will after glassy yellow graphene oxide suspension filtered, obtain filemot filter cake, by filter cake with after cleanup acid treatment, further with deionized water wash to filtrate without Cl
-, final drying processing, obtains graphene oxide solid;
D. graphene oxide solid is scattered in solvent, supersound process, obtains homodisperse graphene oxide suspension;
E. by homodisperse graphene oxide suspension curtain coating in substrate, drying and forming-film, obtains graphene oxide paper;
F. graphene oxide paper step e being obtained is immersed in ascorbic acid solution together with substrate, after reaction for some time, will complete the film drying of reduction, thereby obtains Graphene paper.
2. the preparation method of a Graphene paper according to claim 1, it is characterized in that, described step f substitutes by step g: the graphene oxide paper that step e is obtained is immersed in xitix and Silver Nitrate mixing solutions together with substrate, after reaction for some time, to complete the film drying of reduction, obtain the Graphene paper that electric property strengthens.
3. a preparation method for Graphene paper according to claim 1, is characterized in that, in described step a: described graphite is the natural flaky graphite of 200～500 object or expanded graphite; The concentration of the described vitriol oil is by mass percentage 98%; Add the described well-beaten time after SODIUMNITRATE to be greater than 1h; Described cooling process is reaction vessel to be placed in to ice bath or cryosel bathe and be cooled to below 0 DEG C or 0 DEG C; The described potassium permanganate amount that in batches adds potassium permanganate to refer at every turn to add is 2～3g, and the timed interval is 20min, so that the temperature of reaction system remains on below 15 DEG C; Described sufficient reaction time after heating in water bath is greater than 2h.
4. a preparation method for Graphene paper according to claim 1, is characterized in that, the concentration of the described hydrogen peroxide in described step b is by mass percentage 30%.
5. a preparation method for Graphene paper according to claim 1, is characterized in that, in described step c: described cleanup acid treatment refers to that to adopt mass percent be 3% dilute hydrochloric acid repetitive scrubbing to filtrate without SO
4 2-; Described drying treatment refers to 40 DEG C of vacuum-drying 24h in vacuum drying oven.
6. the preparation method of a Graphene paper according to claim 1, it is characterized in that, in described steps d: described solvent is the mixture that is selected from water, second alcohol and water, N, the mixture of dinethylformamide and water, the mixture of N,N-dimethylacetamide and water, the mixture of N-Methyl pyrrolidone and water, the one in the mixture of dimethyl sulfoxide (DMSO) and water; Described supersound process is 40～200kHz for adopting operating frequency, and ultrasonic power is 50～200W, and ultrasonic time is 1～5h; The concentration of described graphene oxide suspension is 0.1～5mg/ml.
7. the preparation method of a Graphene paper according to claim 1, it is characterized in that, in described step e: described substrate is to comprise a kind of material being selected from tetrafluoroethylene, polycarbonate, polyethylene, polypropylene, polyimide, steel plate, PET, polyaryletherketone, polyvinyl chloride, polyvinylidene difluoride (PVDF), urethane, poly(lactic acid), polystyrene, ABS resin, polyacrylonitrile, poly (arylene ether nitrile), polyethersulfone, polysiloxane, Mierocrystalline cellulose, rubber, Polyvinyl carbazole, mica, epoxy resin, resol, maleic resin, fluoro-resin; Described drying and forming-film refers in temperature is the baking oven of 20～80 DEG C places 6～24h.
8. the preparation method of a Graphene paper according to claim 1, it is characterized in that, in described step f: described substrate is to comprise a kind of material being selected from tetrafluoroethylene, polycarbonate, polyethylene, polypropylene, polyimide, steel plate, PET, polyaryletherketone, polyvinyl chloride, polyvinylidene difluoride (PVDF), urethane, poly(lactic acid), polystyrene, ABS resin, polyacrylonitrile, poly (arylene ether nitrile), polyethersulfone, polysiloxane, Mierocrystalline cellulose, rubber, Polyvinyl carbazole, mica, epoxy resin, resol, maleic resin, fluoro-resin; The concentration of described ascorbic acid solution is 0.1～5mg/ml; The time of described reaction is 10min～24h; Described dry referring in temperature is the baking oven of 20～80 DEG C placed 6～24h.
9. the preparation method of a Graphene paper according to claim 2, it is characterized in that, in described step g: described substrate is and comprises a kind of material being selected from tetrafluoroethylene, polycarbonate, polyethylene, polypropylene, polyimide, steel plate, PET, polyaryletherketone, polyvinyl chloride, polyvinylidene difluoride (PVDF), urethane, poly(lactic acid), polystyrene, ABS resin, polyacrylonitrile, poly (arylene ether nitrile), polyethersulfone, polysiloxane, Mierocrystalline cellulose, rubber, Polyvinyl carbazole, mica, epoxy resin, resol, maleic resin, fluoro-resin; The total concn of described xitix and Silver Nitrate mixing solutions is 0.1～5mg/ml; The time of described reaction is 10min～24h; Described dry referring in temperature is the baking oven of 20～80 DEG C placed 6～24h.
10. a Graphene paper of preparing according to the method described in arbitrary claim in claim 1 to 9.
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| CN105788874A (en) * | 2014-12-24 | 2016-07-20 | 中国科学院宁波材料技术与工程研究所 | Composite graphene paper and preparation method thereof |
| CN105776185A (en) * | 2014-12-25 | 2016-07-20 | 江南石墨烯研究院 | Preparation method of graphene paper with high thermal conductivity and electrical conductivity |
| CN107324321A (en) * | 2017-07-24 | 2017-11-07 | 济南大学 | Load the preparation method of golden flower three-dimensional redox graphene |
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| CN109071234A (en) * | 2016-02-26 | 2018-12-21 | 纳米技术能源公司 | For handling the methods, devices and systems of carbonaceous composition |
| CN109091676A (en) * | 2018-08-23 | 2018-12-28 | 浙江理工大学 | A kind of preparation method of pharmaceutical carrier of the modified with folic acid fluorinated graphene with target function |
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| CN109071234A (en) * | 2016-02-26 | 2018-12-21 | 纳米技术能源公司 | For handling the methods, devices and systems of carbonaceous composition |
| CN107324321A (en) * | 2017-07-24 | 2017-11-07 | 济南大学 | Load the preparation method of golden flower three-dimensional redox graphene |
| CN107814390A (en) * | 2017-11-01 | 2018-03-20 | 山东圣泉新材料股份有限公司 | A kind of grapheme material combined mica, preparation method and purposes |
| CN109091676A (en) * | 2018-08-23 | 2018-12-28 | 浙江理工大学 | A kind of preparation method of pharmaceutical carrier of the modified with folic acid fluorinated graphene with target function |
| CN112938957A (en) * | 2021-04-14 | 2021-06-11 | 新乡医学院 | Graphene oxide paper and preparation method thereof |
| CN113643867A (en) * | 2021-10-13 | 2021-11-12 | 浙江荣泰电工器材股份有限公司 | Mica piece with high surface tear strength and forming method thereof |
| CN113643867B (en) * | 2021-10-13 | 2021-12-31 | 浙江荣泰电工器材股份有限公司 | Mica piece with high surface tear strength and forming method thereof |
| CN114005678A (en) * | 2021-11-03 | 2022-02-01 | 安徽赛福电子有限公司 | Metallized film capacitor, method for manufacturing same, and metallized film laminate |
| CN114975878A (en) * | 2022-05-09 | 2022-08-30 | 上海交通大学 | Method for preparing large-area thickness-controllable ordered porous electrode by tape casting method |
| CN114975878B (en) * | 2022-05-09 | 2024-03-19 | 上海交通大学 | Method for preparing large-area thickness controllable ordered porous electrode by tape casting method |
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