CN102659099B - Preparation method of anisotropic graphene foam - Google Patents
Preparation method of anisotropic graphene foam Download PDFInfo
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- CN102659099B CN102659099B CN201210171707.XA CN201210171707A CN102659099B CN 102659099 B CN102659099 B CN 102659099B CN 201210171707 A CN201210171707 A CN 201210171707A CN 102659099 B CN102659099 B CN 102659099B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 73
- 239000006260 foam Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 53
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 44
- 239000010439 graphite Substances 0.000 claims abstract description 44
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 230000000694 effects Effects 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- -1 graphite alkene Chemical class 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000013543 active substance Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000006872 improvement Effects 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 230000003019 stabilising effect Effects 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005189 flocculation Methods 0.000 claims description 4
- 230000016615 flocculation Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 2
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 2
- 229960005055 sodium ascorbate Drugs 0.000 claims description 2
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000011814 protection agent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000000725 suspension Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000003252 repetitive effect Effects 0.000 description 3
- 238000005201 scrubbing Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 229920003081 Povidone K 30 Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000006262 metallic foam Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 229940001516 sodium nitrate Drugs 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002238 carbon nanotube film Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 230000005520 electrodynamics Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of anisotropic graphene foam. The method comprises the following steps of: (1) preparing graphite oxide; (2) preparing a graphene oxide dispersion solution, namely dispersing the graphite oxide prepared in the step (1) into a solution to prepare the graphene oxide dispersion solution; (3) preparing a graphene dispersion solution, namely adding a surfactant or a reducing agent with certain surface activity into the dispersion solution of the step (2) to be used as a protection agent; and preparing the graphene dispersion solution through chemical liquid-phase reduction; and (4) preparing the anisotropic graphene foam: damaging a previous graphene stable system to self-assemble the graphene into the anisotropic graphene foam. The graphene foam prepared by the method is composed of at least one layer of graphene structure unit and has anisotropies of a structure and a property in a graphene growth direction and in a direction which is vertical to the growth direction; the specific surface area of the anisotropic graphene foam is 200-2000 m<2>/g; and the heat conductivity difference in the graphene growth direction and in the direction which is vertical to the growth direction reaches to two magnitudes.
Description
Technical field
The present invention relates to a kind of preparation method of anisotropic graphite alkene foam, belong to new material technology field.
Background technology
New material industry become enter 21 century since one of new high-tech industry with fastest developing speed, the technological highland that Ye Shi various countries competitively capture.Be that the research of the new carbon of representative obtains a series of important breakthrough with Graphene, on October 5th, 2010, physicist An Deliehaimu (Andre Geim) professor of Univ Manchester UK and Constantine Nuo Woxiaoluofu (Konstantin Novoselov) professor are because being engaged in the research of Graphene and disclosing its character and obtain Nobel Prize in physics in 2010.
Graphene is the carbon simple substance of neatly being arranged by hexagonal lattice by carbon atom, and structure is highly stable.Research shows, the electronic mobility of Graphene is higher, can electrode be done thinner, more transparent, and good electroconductibility and the high-permeability to light thereof make it in the unique advantage in the field such as liquid-crystal display and solar cell.Graphene film has the field emission characteristic comparable with carbon nano-tube film, has application prospect widely in semiconducter device and flat pannel display etc.; Due to two-dirnentional structure and the excellent crystallography quality of its uniqueness, the research for quantum electrodynamics phenomenon provides desirable platform, has important theoretical investigation and is worth.In addition, after Graphene and plastics compound, can conductor be become and improve its mechanical property and thermotolerance.Graphene and the compounded novel material of plastics, light and handy and firm, can be applicable to the vehicles such as man-made satellite of new generation, aircraft and automobile.Thus, Graphene is expected to obtain in fields such as high-performance nano electron device, matrix material, gas sensor and stored energies to apply widely.
Graphene and associated materials thereof, due to the electricity of its excellence, calorifics and mechanical property, cause the extensive concern of community of physicists, material educational circles.The preparation method of Graphene comprises: micromechanics partition method, epitaxy method-Epitaxial Growth, heating SiC method, chemical Vapor deposition process, chemical reduction method etc.Graphene is unit molecule planar materials, is a kind of two-dirnentional structure, adopt this two-dirnentional structure material to construct the document of said three-dimensional body material and patent still rarely found.2011, metal institute of Chinese Academy of Sciences Shenyang Materials science country (associating) laboratory Cheng Huiming, appoint literary talent Graphene said three-dimensional body material (the Chen ZP that led research team to prepare, Ren WC, GaoLB, Liu BL, Pei SF, Cheng HM, Three-dimensional flexible and conductiveinterconnected graphene networks grown by chemical vapour deposition.Nature Material, 2011,10,424 – 428).The method that they adopt is chemical vapour deposition: with the foamed metal such as copper or nickel for body material, monolayer carbon atom invests the surface of foamed metal, and like this, Graphene body material intactly replicates the structure of foamed metal; After the matrix metal such as copper or nickel material etches is fallen, just obtain this Graphene said three-dimensional body material.The method that the process employs a kind of similar hard template (taking metal foam as template) has prepared three-dimensional graphene foam, but the method for chemical vapour deposition, the more difficult control of processing condition, need personnel's accuracy controlling of very specialty, and need with the foamed metal such as copper or nickel as hard template, the preparation technology of this hard template is comparatively complicated, and price is more expensive, and in the process of etching removing hard template, the defect that some affect Graphene performance may be formed.Still seldom have at present and adopt the method for self-assembly to prepare grapheme foam, the method is for hard template method, self-assembly method preparation technology is simpler, the pressure of environmental pollution is not had yet, and the method can obtain the grapheme foam with anisotropic character, significant for the characteristic playing Graphene.
Summary of the invention
The object of the invention is to overcome the deficiency in existing graphene preparation method; and a kind of preparation method of anisotropic graphite alkene foam is provided; the method does not adopt the body materials such as foamed metal; do not need removing metal foam template, have with low cost, simple, the advantage such as be produced on a large scale.
For realizing object of the present invention, technical scheme of the present invention is:
A preparation method for anisotropic graphite alkene foam, the method comprises the following steps:
(1) graphite oxide is prepared;
(2) graphene oxide dispersion is prepared: by the dispersion of the graphite oxide of preparation in step (1) in the solution, preparation graphene oxide dispersion;
(3) prepare graphene dispersing solution: to step 2) in dispersion liquid in reductive agent itself that add tensio-active agent or there is certain surface activity as protective material, prepare graphene dispersing solution by chemical liquid phase reduction;
(4) anisotropic graphite alkene foam is prepared: destroy original Graphene stabilising system, make Graphene be self-assembled into anisotropic foam.
In the preferred embodiment of the present invention, preparation has the method for anisotropic graphite alkene foam, in step 1), the method preparing graphite oxide is Hummers method, the one improved in Hummers method, the Brodie method of improvement, the Staudenmaier method of improvement or Hofmann method.
In the preferred embodiment of the present invention, the described method preparing anisotropic graphite alkene foam, step 2) in, described solution is water or ethanol.
In the preferred embodiment of the present invention, the described method preparing anisotropic graphite alkene foam, step 2) in, what described graphite oxide dispersion adopted is ultrasonic, or mechanical stirring or both common implementings.
In the preferred embodiment of the present invention, the described method preparing anisotropic graphite alkene foam, in step 3), described tensio-active agent is one or more the mixture in polyoxyethylene glycol, polyvinylpyrrolidone or sodium polyacrylate.
In the preferred embodiment of the present invention, the described method preparing anisotropic graphite alkene foam, in step 3), described reductive agent is one or more the mixture in Cys, citric acid, Trisodium Citrate, xitix or sodium ascorbate.
In the preferred embodiment of the present invention, the described method preparing anisotropic graphite alkene foam, in step 4), destroy original Graphene stabilising system method adopt be heating, radiation or flocculation in one or both more than common implementing.
The present invention is compared with existing preparation method, its advantage and positively effect are: the method preparing anisotropic graphite alkene foam disclosed by the invention take graphene oxide dispersion as presoma, by the reduction to graphene oxide, prepare graphene dispersing solution, original Graphene stabilising system is destroyed again by methods such as heating, radiation or flocculations, Graphene is become non-hydrophilic from wetting ability, thus being self-assembled into grapheme foam, this grapheme foam has larger specific surface area (200-2000m
2/ g); Graphene is in the process of assembling, due to reasons such as migration resistance, there is anisotropic feature, it reaches two orders of magnitude along graphene growth direction with perpendicular to the thermal conductivity difference of production mode reform, this is that chemical Vapor deposition process not accomplished, thermal conductivity along graphene growth direction can reach 200W/m.k, and only has 0.5W/m.k perpendicular to the thermal conductivity of production mode reform.
Accompanying drawing explanation
The photo of sample in synthesis liquid that Fig. 1 (a) is prepared for adopting example 1, the photo after the sample taking-up that Fig. 1 (b) prepare for example 1.This grapheme foam is cylindric, and diameter is about 3cm, is highly 3.5cm, and its specific surface area is 2012m
2/ g, the thermal conductivity along graphene growth direction is 211W/m.k, and the thermal conductivity perpendicular to production mode reform is 0.5W/m.k.
The sample photo that Fig. 2 (a) is prepared for adopting example 2, this grapheme foam is cylindric, and there is depression at middle part, and diameter is about 2.8cm, highly about 4cm.The scanning electron microscope (SEM) photograph that Fig. 2 (b) is this sample, can find out, this grapheme foam is obvious anisotropy, and its specific surface area is 536m
2/ g, the thermal conductivity along graphene growth direction is 120W/m.k, and the thermal conductivity perpendicular to production mode reform is 0.3W/m.k.
Fig. 3 (a) is for adopting the scanning electron microscope (SEM) photograph of the sample of example 3 preparation, therefrom can find out, this grapheme foam is obvious laminate structure, this grapheme foam defines slight crack in the process of drying, Fig. 3 (b) is the photo after sample amplification, obviously can find out that this Graphene tiles to a direction, also present obvious anisotropy, its specific surface area is 365m
2/ g, the thermal conductivity along graphene growth direction is 63W/m.k, and the thermal conductivity perpendicular to production mode reform is 0.8W/m.k.
Fig. 4 (a) is for adopting the scanning electron microscope (SEM) photograph of the sample of example 4 preparation, and therefrom can find out, this sample is strip.Because the precursor concentration of this grapheme foam is lower, so the grapheme foam preparing gained is smaller.Fig. 4 (b) is the scanning electron microscope (SEM) photograph of this sample end face, can find out grapheme foam anisotropic character highly significant, and its specific surface area is 536m
2/ g, the thermal conductivity along graphene growth direction is 870W/m.k, and the thermal conductivity perpendicular to production mode reform is 0.7W/m.k.
Fig. 5 (a), (b) are the scanning electron microscope (SEM) photograph of the grapheme foam different angles adopting example 5 to prepare, therefrom can find out, a () is Graphene tiling direction, and (b) is the side elevational view in tiling direction, can find out that this grapheme foam has in obvious laminate structure, have anisotropic character, its specific surface area is 1036m
2/ g, the thermal conductivity along graphene growth direction is 96W/m.k, and the thermal conductivity perpendicular to production mode reform is 0.5W/m.k.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention.
Embodiment 1
Adopt Hummers legal system for graphite oxide: in ice bath, 10g Graphite Powder 99 and 5g SODIUMNITRATE to be mixed with the 230mL vitriol oil, in stirring, slowly add 30g KMnO
4; Transfer them in 35 ° of C water-baths and react 30 minutes, more progressively add 460mL deionized water, after temperature rises to 98 DEG C, continue reaction 40 minutes, mixture becomes glassy yellow by brown, further thin up, and is the H of 30% with massfraction
2o
2solution-treated, neutralizes unreacted permanganic acid, centrifuging repetitive scrubbing filter cake, finally namely its vacuum-drying is obtained graphite oxide; Graphite oxide is ground, in water, prepares 2mg/mL suspension 100mL, supersound process 30min, obtain the graphene oxide colloidal suspensions of isotropic stable; Add tensio-active agent polyvinylpyrrolidone (PVP-K30) 0.2g, ultrasonic dissolution, add 1g Cys, obtain stable graphene dispersing solution; This dispersion liquid is heated to 95 DEG C and continues reaction 2 hours, after cooling, can grapheme foam be obtained.
Embodiment 2
Adopt Staudenmaier legal system for graphite oxide: the mixed solution first preparing nitrosonitric acid (27ml) and the vitriol oil (87.5ml) in there-necked flask, then this there-necked flask is put and cool in ice bath, under agitation slowly being entered by 5g Graphite Powder 99 subsequently (is noted: need to be put in ice bath by this there-necked flask always, with slowed down reaction speed, avoid blast), 55g sodium chlorate is added in above-mentioned reaction system, continue stirring reaction 96 hours, after reaction terminates, reaction mixture filtration washing is obtained graphite oxide; Graphite oxide is ground, in water, prepares 2mg/mL suspension 100mL, supersound process 30min, obtain the graphene oxide colloidal suspensions of isotropic stable; Add tensio-active agent sodium polyacrylate 0.2g, ultrasonic dissolution, add 2g Trisodium Citrate; This dispersion liquid is heated to 95 DEG C of reactions after 4 hours, rapidly after cooling, can grapheme foam be obtained.
Embodiment 3
The Brodie method of improvement is adopted to prepare graphite oxide: in ice bath, 10g Graphite Powder 99 and 85g sodium chlorate to be mixed with 200mL nitrosonitric acid, stirred at ambient temperature 24 hours.After reaction terminates, centrifuging repetitive scrubbing filter cake, namely purifying, finally obtain graphite oxide by its vacuum-drying.Graphite oxide is ground, in water, prepares 2mg/mL suspension 100mL, supersound process 30min, obtain the graphene oxide colloidal suspensions of isotropic stable.Add xitix 2g, ultrasonic dissolution, obtain stable graphene dispersing solution.By this graphene dispersing solution microwave radiation reaction 15min, cool latter 12 hours and can obtain grapheme foam.
Embodiment 4
Adopt Hummers legal system for graphite oxide: in ice bath, 10g Graphite Powder 99 and 5g SODIUMNITRATE to be mixed with the 230mL vitriol oil, in stirring, slowly add 30g KMnO
4, transfer them in 35 ° of C water-baths and react 30 minutes, more progressively add 460mL deionized water, after temperature rises to 98 DEG C, continue reaction 40 minutes, mixture becomes glassy yellow by brown, further thin up, and is the H of 30% with massfraction
2o
2solution-treated, neutralizes unreacted permanganic acid, centrifuging repetitive scrubbing filter cake, finally namely its vacuum-drying is obtained graphite oxide; Ground by graphite oxide, prepare 0.5mg/mL suspension 100mL in ethanol, supersound process 30min, obtains the graphene oxide colloidal suspensions of isotropic stable; Add tensio-active agent polyvinylpyrrolidone (PVP-K30) 0.2g, ultrasonic dissolution, add 1g Cys, obtain stable graphene dispersing solution; This dispersion liquid is added flocculation agent aluminum chloride 0.1g, after 12 hours, can grapheme foam be obtained.
Embodiment 5
Adopt Staudenmaier legal system for graphite oxide: the mixed solution first preparing nitrosonitric acid (27ml) and the vitriol oil (87.5ml) in there-necked flask, then this there-necked flask is put and cool in ice bath, under agitation slowly being entered by 5g Graphite Powder 99 subsequently (is noted: need to be put in ice bath by this there-necked flask always, with slowed down reaction speed, avoid blast), 55g sodium chlorate is added in above-mentioned reaction system, continue stirring reaction 96 hours, after reaction terminates, reaction mixture filtration washing is obtained graphite oxide; Graphite oxide is ground, in water, prepares 2mg/mL suspension 100mL, ultrasonic double stir process 60min, obtain the graphene oxide colloidal suspensions of isotropic stable; Add surfactant polyethylene 0.2g, ultrasonic dissolution, add 2g Cys, obtain stable graphene dispersing solution; By this dispersion liquid microwave radiation reaction 30min, after Slow cooling, grapheme foam can be obtained.
Claims (4)
1. a preparation method for anisotropic graphite alkene foam, is characterized in that, the method comprises the following steps:
(1) graphite oxide is prepared;
(2) graphene oxide dispersion is prepared: by the dispersion of the graphite oxide of preparation in step (1) in the solution, preparation graphene oxide dispersion;
(3) graphene dispersing solution is prepared: the reductive agent adding tensio-active agent or itself have a certain surface activity in the dispersion liquid in step (2), as protective material, prepares graphene dispersing solution by chemical liquid phase reduction;
(4) anisotropic graphite alkene foam is prepared: destroy original Graphene stabilising system, Graphene is made to become non-hydrophilic from wetting ability, be self-assembled into anisotropic graphite alkene foam, this anisotropic graphite alkene foam reaches 200W/m.k along the thermal conductivity in graphene growth direction, and only has 0.5W/m.k perpendicular to the thermal conductivity of the direction of growth;
In step (3), described tensio-active agent is one or more the mixture in polyoxyethylene glycol, polyvinylpyrrolidone or sodium polyacrylate; Described reductive agent is one or more the mixture in Cys, citric acid, Trisodium Citrate, xitix or sodium ascorbate;
In step (4), destroy original Graphene stabilising system method adopt be heating, microwave radiation or flocculation in one or both more than common implementing.
2. preparation according to claim 1 has the method for anisotropic graphite alkene foam, it is characterized in that, step 1) in, the method preparing graphite oxide is Hummers method, the one improved in Hummers method, the Brodie method of improvement, the Staudenmaier method of improvement or Hofmann method.
3. the method preparing anisotropic graphite alkene foam according to claim 1, is characterized in that, step 2) in, described solution is water or ethanol.
4. the method preparing anisotropic graphite alkene foam according to claim 1, is characterized in that, step 2) in, what the dispersion of described graphite oxide adopted is ultrasonic, or mechanical stirring or both common implementings.
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| CN102826543B (en) * | 2012-09-19 | 2014-05-28 | 北京理工大学 | Preparation method of foamable three-dimensional graphene |
| 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 |
| CN103072981B (en) * | 2013-02-26 | 2014-12-17 | 武汉大学 | Preparation method for graphene |
| CN103342827B (en) * | 2013-06-28 | 2015-05-06 | 上海大学 | Preparation method of hydrophobic/lipophilic polyurethane sponge |
| CN103407994A (en) * | 2013-07-17 | 2013-11-27 | 苏州艾特斯环保材料有限公司 | Method for reducing graphene oxide |
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| CN101941693A (en) * | 2010-08-25 | 2011-01-12 | 北京理工大学 | Graphene aerogel and preparation method thereof |
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