CN102557022B - Preparation method of graphene conductive foam - Google Patents
Preparation method of graphene conductive foam Download PDFInfo
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- CN102557022B CN102557022B CN2012100529285A CN201210052928A CN102557022B CN 102557022 B CN102557022 B CN 102557022B CN 2012100529285 A CN2012100529285 A CN 2012100529285A CN 201210052928 A CN201210052928 A CN 201210052928A CN 102557022 B CN102557022 B CN 102557022B
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Abstract
The invention relates to a preparation method of graphene conductive foam. The method comprises the following steps: adding a graphite sheet into concentrated sulfuric acid containing sodium nitrate, adding potassium permanganate and preserving heat at the temperature of between 35 and 40 DEG C for 60 to 90 minutes; adding water under magnetic stirring and preserving heat at the temperature of between 85 and 95 DEG C for 60 to 90 minutes; adding hydrogen peroxide with the mass content of 30 percent, stirring, filtering, dispersing for twice, centrifugally separating and ultrasonically separating to obtain oxidized graphene; and dispersing foam into water containing the oxidized graphene, coating the oxidized graphene on the surface of the foam, taking out the foam, soaking into aqueous solution containing a reducing agent and performing reducing reaction to obtain the conductive foam with the surface coated with a graphene conductive layer. By the method, the conductive foam is obtained by adsorbing the graphene conductive film to the surface of the foam. The prepared conductive foam has the advantages of low density, high conductivity, large specific surface area and low cost.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of preparation method of graphene conductive foam.
Background technology
Conductive foam is the conductive solid material that a kind of inside is uniform-distribution with a large amount of connections or disconnected bubble, for antistatic, electromagnetic shielding, air-sensitive or the fields such as voltage sensitive sensor, sewage purification.The preparation method that conductive foam is commonly used is that in polymkeric substance prepared by foam process by filled conductive material carbon black.
Graphene is plane bidimensional monoatomic layer carbon material, is to find at present the hardest nano material, and under room temperature, the electronic mobility of Graphene reaches 10
6cm
2v
-1s
-1, resistivity approximately 10
-6Ω cm is also the material of resistivity minimum.These performance guarantees of Graphene the foam that prepared by Graphene there is lower density and the conductivity of Geng Gao than regular foam material.Chemical Vapor deposition process can prepare the small size grapheme foam, but is subject to preparation method's restriction, and grapheme foam can't volume production.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of graphene conductive foam, the method is utilized Graphene and the common insulating foams Material cladding of high conductivity, realizes the preparation of low density, high conductivity graphene conductive foam.
The inventive method be take flake graphite as starting material employing chemical oxidization method, be prepared into the graphene oxide material, graphene oxide is coated in to the foam surfaces such as urethane, polystyrene or polyethylene by padding technique, then the graphene oxide on polyethylene surface is reduced into to Graphene, obtains the graphene coated conductive foams of foam surface such as urethane.
The concrete steps of the inventive method are:
Step (1). SODIUMNITRATE is added in the vitriol oil as reaction solution, and in reaction solution, the mass content of SODIUMNITRATE is 1～2 ﹪; Then graphite flake is added in reaction solution, the mass ratio of graphite flake and reaction solution is 1:80～100;
Step (2). add potassium permanganate in reaction solution, temperature is incubated 60～90 minutes after rising to 35～40 ℃; To add potassium permanganate be 6～10:1 with the mass ratio of the graphite flake that adds;
Step (3). the magnetic agitation limit is carried out in the reaction solution limit and add water, temperature is incubated 60～90 minutes after rising to 85～95 ℃; To add water be 350～400:1 with the mass ratio of the graphite flake that adds;
Step (4). add the hydrogen peroxide of mass content 30%, stir after 5～10 minutes and filter; To add hydrogen peroxide be 5～6:1 with the mass ratio of the graphite flake that adds;
Step (5). water disperses filtration product, then with whizzer, with the speed of 1000～2000 rev/mins, carries out a centrifugation;
Step (6). the product that a centrifugation is gone out is used water-dispersion again, then with whizzer, with the speed of 8000～10000 rev/mins, carries out the secondary centrifuging separation;
Step (7). add water in the isolated product of secondary centrifuging, and separate with ultrasonic echography, obtain graphene oxide;
Step (8). foam is immersed in the water that is dispersed with graphene oxide of step (7) acquisition, with padding technique, graphene oxide is coated in to foam surface; Add foam and graphite flake mass ratio be 1～20:1;
Described foam is polyurethane foam, polystyrene foam, polyethylene, polyvinyl chloride foam or polypropylene foam;
Step (9). there is the foam of graphene oxide to pull out in the aqueous solution that rear immersion contains reductive agent surface-coated and carry out reduction reaction, obtain the conductive foam of surface-coated graphene conductive layer; Wherein in the aqueous solution, the mass ratio of contained reductive agent and graphite flake is 2～10:1.
Described reductive agent is hydrazine, dimethylhydrazine, sodium borohydride, lithium aluminium hydride, hydroiodic acid HI or Hydrogen bromide.
The inventive method is adsorbed graphene conductive film by foam surface and is obtained conductive foam, and the conductive foam of preparation has advantages of that density is low, specific conductivity is high, specific surface area is large, cost is low.The conductive layer Graphene of foam surface does not come off through the water repetitive scrubbing, after the material for core filtered as the environmental protection equipment pollutent is used, through cleaning, can recirculation use.That tradition gas sensor complex manufacturing technology, difficulty require is high, surrounding environment is required harshly with existing sensor, to compare, and the Novel air dependent sensor prepared with the grapheme foam material can overcome above-mentioned shortcoming and plays a significant role in gas detection and environment detection.Graphene conductive foam physical strength and good springiness prepared by the inventive method, under the external force such as extruding, bending, resistance will produce considerable change, can be for the preparation of novel vibrating sensor etc.
Embodiment
Embodiment 1.
Step (1). 10 gram SODIUMNITRATE are added in the vitriol oil of 990 gram 98 ﹪ as reaction solution, then 10 gram graphite flakes are added in reaction solution;
Step (2). slowly add 60 gram potassium permanganate in reaction solution, after temperature rises to 35 ℃, insulation is 90 minutes;
Step (3). the magnetic agitation limit is carried out in the reaction solution limit and add 4 premium on currency, after temperature rises to 85 ℃, insulation is 90 minutes;
Step (4). add the hydrogen peroxide of 50 gram mass content 30%, stir after 10 minutes and filter;
Step (5). water disperses filtration product, then with whizzer, with the speed of 1000 rev/mins, carries out a centrifugation;
Step (6). the product that a centrifugation is gone out is used water-dispersion again, then with whizzer, with the speed of 10000 rev/mins, carries out the secondary centrifuging separation;
Step (7). add water in the isolated product of secondary centrifuging, and separate with ultrasonic echography, obtain graphene oxide;
Step (8). 200 gram polyurethane foams are immersed and are dispersed with in the water of graphene oxide, with padding technique, graphene oxide is coated in to foam surface;
Step (9). after having the polyurethane foam of graphene oxide to pull out surface-coated, immerse in the aqueous solution that contains 20 gram dimethylhydrazines and carry out reduction reaction, obtain the conductive foam of surface-coated graphene conductive layer.
Embodiment 2.
Step (1). 15 gram SODIUMNITRATE are added in the vitriol oil of 785 gram 98 ﹪ as reaction solution, then 10 gram graphite flakes are added in reaction solution;
Step (2). slowly add 70 gram potassium permanganate in reaction solution, after temperature rises to 37 ℃, insulation is 70 minutes;
Step (3). the magnetic agitation limit is carried out in the reaction solution limit and add 3.5 premium on currency, after temperature rises to 90 ℃, insulation is 75 minutes;
Step (4). add the hydrogen peroxide of 60 gram mass content 30%, stir after 5 minutes and filter;
Step (5). water disperses filtration product, then with whizzer, with the speed of 1500 rev/mins, carries out a centrifugation;
Step (6). the product that a centrifugation is gone out is used water-dispersion again, then with whizzer, with the speed of 5000 rev/mins, carries out the secondary centrifuging separation;
Step (7). add water in the isolated product of secondary centrifuging, and separate with ultrasonic echography, obtain graphene oxide;
Step (8). 100 gram polystyrene foams are immersed and are dispersed with in the water of graphene oxide, with padding technique, graphene oxide is coated in to foam surface;
Step (9). after having the polystyrene foam of graphene oxide to pull out surface-coated, immerse in the aqueous solution that contains 100 gram sodium borohydrides and carry out reduction reaction, obtain the conductive foam of surface-coated graphene conductive layer.
Embodiment 3.
Step (1). 18 gram SODIUMNITRATE are added in the vitriol oil of 882 gram 98 ﹪ as reaction solution, then 10 gram graphite flakes are added in reaction solution;
Step (2). slowly add 80 gram potassium permanganate in reaction solution, after temperature rises to 40 ℃, insulation is 60 minutes;
Step (3). the magnetic agitation limit is carried out in the reaction solution limit and add 3.8 premium on currency, after temperature rises to 95 ℃, insulation is 60 minutes;
Step (4). add the hydrogen peroxide of 55 gram mass content 30%, stir after 8 minutes and filter;
Step (5). water disperses filtration product, then with whizzer, with the speed of 2000 rev/mins, carries out a centrifugation;
Step (6). the product that a centrifugation is gone out is used water-dispersion again, then with whizzer, with the speed of 8000 rev/mins, carries out the secondary centrifuging separation;
Step (7). add water in the isolated product of secondary centrifuging, and separate with ultrasonic echography, obtain graphene oxide;
Step (8). 10 gram polyethylenes are immersed and are dispersed with in the water of graphene oxide, with padding technique, graphene oxide is coated in to foam surface;
Step (9). after having the polyethylene of graphene oxide to pull out surface-coated, immerse in the aqueous solution that contains 50 gram hydrazines and carry out reduction reaction, obtain the conductive foam of surface-coated graphene conductive layer.
Embodiment 4.
Step (1). 15 gram SODIUMNITRATE are added in the vitriol oil of 985 gram 98 ﹪ as reaction solution, then 10 gram graphite flakes are added in reaction solution;
Step (2). slowly add 90 gram potassium permanganate in reaction solution, after temperature rises to 35 ℃, insulation is 75 minutes;
Step (3). the magnetic agitation limit is carried out in the reaction solution limit and add 3.6 premium on currency, after temperature rises to 88 ℃, insulation is 75 minutes;
Step (4). add the hydrogen peroxide of 57 gram mass content 30%, stir after 6 minutes and filter;
Step (5). water disperses filtration product, then with whizzer, with the speed of 1200 rev/mins, carries out a centrifugation;
Step (6). the product that a centrifugation is gone out is used water-dispersion again, then with whizzer, with the speed of 10000 rev/mins, carries out the secondary centrifuging separation;
Step (7). add water in the isolated product of secondary centrifuging, and separate with ultrasonic echography, obtain graphene oxide;
Step (8). 50 gram polypropylene foams are immersed and are dispersed with in the water of graphene oxide, with padding technique, graphene oxide is coated in to foam surface;
Step (9). after having the polypropylene foam of graphene oxide to pull out surface-coated, immerse in the aqueous solution that contains 40 gram hydroiodic acid HIs and carry out reduction reaction, obtain the conductive foam of surface-coated graphene conductive layer.
Embodiment 5.
Step (1). 10 gram SODIUMNITRATE are added in the vitriol oil of 790 gram 98 ﹪ as reaction solution, then 10 gram graphite flakes are added in reaction solution;
Step (2). slowly add 70 gram potassium permanganate in reaction solution, after temperature rises to 40 ℃, insulation is 70 minutes;
Step (3). the magnetic agitation limit is carried out in the reaction solution limit and add 3.9 premium on currency, after temperature rises to 92 ℃, insulation is 70 minutes;
Step (4). add the hydrogen peroxide of 52 gram mass content 30%, stir after 9 minutes and filter;
Step (5). water disperses filtration product, then with whizzer, with the speed of 2000 rev/mins, carries out a centrifugation;
Step (6). the product that a centrifugation is gone out is used water-dispersion again, then with whizzer, with the speed of 5000 rev/mins, carries out the secondary centrifuging separation;
Step (7). add water in the isolated product of secondary centrifuging, and separate with ultrasonic echography, obtain graphene oxide;
Step (8). 150 gram polyvinyl chloride foams are immersed and are dispersed with in the water of graphene oxide, with padding technique, graphene oxide is coated in to foam surface;
Step (9). after having the polyvinyl chloride foam of graphene oxide to pull out surface-coated, immerse to contain in the hydrobromic aqueous solution of 80 gram and carry out reduction reaction, obtain the conductive foam of surface-coated graphene conductive layer.
Embodiment 6.
Step (1). 10 gram SODIUMNITRATE are added in the vitriol oil of 890 gram 98 ﹪ as reaction solution, then 10 gram graphite flakes are added in reaction solution;
Step (2). slowly add 100 gram potassium permanganate in reaction solution, after temperature rises to 35 ℃, insulation is 80 minutes;
Step (3). the magnetic agitation limit is carried out in the reaction solution limit and add 3.7 premium on currency, after temperature rises to 85 ℃, insulation is 80 minutes;
Step (4). add the hydrogen peroxide of 55 gram mass content 30%, stir after 7 minutes and filter;
Step (5). water disperses filtration product, then with whizzer, with the speed of 1800 rev/mins, carries out a centrifugation;
Step (6). the product that a centrifugation is gone out is used water-dispersion again, then with whizzer, with the speed of 3000 rev/mins, carries out the secondary centrifuging separation;
Step (7). add water in the isolated product of secondary centrifuging, and separate with ultrasonic echography, obtain graphene oxide;
Step (8). 20 gram polyurethane foams are immersed and are dispersed with in the water of graphene oxide, with padding technique, graphene oxide is coated in to foam surface;
Step (9). after having the polyurethane foam of graphene oxide to pull out surface-coated, immerse in the aqueous solution that contains 30 gram lithium aluminium hydride and carry out reduction reaction, obtain the conductive foam of surface-coated graphene conductive layer.
Claims (3)
1. the preparation method of graphene conductive foam is characterized in that the concrete steps of the method are:
Step (1). SODIUMNITRATE is added in the vitriol oil as reaction solution, and in reaction solution, the mass content of SODIUMNITRATE is 1～2 ﹪; Graphite flake is added in reaction solution, the mass ratio of graphite flake and reaction solution is 1:80～100 again;
Step (2). add potassium permanganate in reaction solution, temperature is incubated 60～90 minutes after rising to 35～40 ℃; To add potassium permanganate be 6～10:1 with the mass ratio of the graphite flake that adds;
Step (3). the magnetic agitation limit is carried out in the reaction solution limit and add water, temperature is incubated 60～90 minutes after rising to 85～95 ℃; To add water be 350～400:1 with the mass ratio of the graphite flake that adds;
Step (4). add the hydrogen peroxide of mass content 30%, stir after 5～10 minutes and filter; To add hydrogen peroxide be 5～6:1 with the mass ratio of the graphite flake that adds;
Step (5). water disperses filtration product, then with whizzer, with the speed of 1000～2000 rev/mins, carries out a centrifugation;
Step (6). the product that a centrifugation is gone out is used water-dispersion again, then with whizzer, with the speed of 8000～10000 rev/mins, carries out the secondary centrifuging separation;
Step (7). add water in the isolated product of secondary centrifuging, and separate with ultrasonic echography, obtain graphene oxide;
Step (8). foam is immersed and is dispersed with in the water of graphene oxide, with padding technique, graphene oxide is coated in to foam surface; Add foam and graphite flake mass ratio be 1～20:1;
Step (9). there is the foam of graphene oxide to pull out in the aqueous solution that rear immersion contains reductive agent surface-coated and carry out reduction reaction, obtain the conductive foam of surface-coated graphene conductive layer; Wherein in the aqueous solution, the mass ratio of contained reductive agent and graphite flake is 2～10:1.
2. the preparation method of graphene conductive foam as claimed in claim 1, it is characterized in that: the foam described in step (8) is polyurethane foam, polystyrene foam, polyethylene, polyvinyl chloride foam or polypropylene foam.
3. the preparation method of graphene conductive foam as claimed in claim 1, it is characterized in that: the reductive agent described in step (9) is hydrazine, dimethylhydrazine, sodium borohydride, lithium aluminium hydride, hydroiodic acid HI or Hydrogen bromide.
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| CN2012100529285A CN102557022B (en) | 2012-03-02 | 2012-03-02 | Preparation method of graphene conductive foam |
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| CN2012100529285A CN102557022B (en) | 2012-03-02 | 2012-03-02 | Preparation method of graphene conductive foam |
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| CN102557022B true CN102557022B (en) | 2013-12-18 |
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| WO2014028978A1 (en) * | 2012-08-23 | 2014-02-27 | Monash University | Graphene-based materials |
| CN103663414A (en) * | 2012-09-03 | 2014-03-26 | 国家纳米科学中心 | Preparation method of graphene sponge |
| CN103663433A (en) * | 2012-09-26 | 2014-03-26 | 海洋王照明科技股份有限公司 | Graphene as well as preparation method and application thereof |
| CN103342827B (en) * | 2013-06-28 | 2015-05-06 | 上海大学 | Preparation method of hydrophobic/lipophilic polyurethane sponge |
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| CN106243378A (en) * | 2016-07-14 | 2016-12-21 | 温州乐发教育科技有限公司 | A kind of graphene conductive foam and preparation method thereof |
| CN106432671A (en) * | 2016-09-21 | 2017-02-22 | 江苏盖姆纳米材料科技有限公司 | Preparation method of carbon-base sponge and foam material |
| CN107522895A (en) * | 2017-08-08 | 2017-12-29 | 东南大学 | A kind of gentle method for preparing graphene polyurethane sponge composite |
| US11760056B2 (en) * | 2018-12-05 | 2023-09-19 | Battelle Memorial Institute | Flexible foam resistive heaters and methods of making flexible resistive heaters |
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| CN101029456A (en) * | 2007-03-06 | 2007-09-05 | 天津工业大学 | Non-woven elastic substrate and its production |
| WO2009073324A2 (en) * | 2007-11-29 | 2009-06-11 | Invista Technologies S.A.R.L. | High-loft nonwoven including stabilizer or binder |
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