CN101831622A - Grapheme foam and preparation method thereof - Google Patents
Grapheme foam and preparation method thereof Download PDFInfo
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- CN101831622A CN101831622A CN 201010183833 CN201010183833A CN101831622A CN 101831622 A CN101831622 A CN 101831622A CN 201010183833 CN201010183833 CN 201010183833 CN 201010183833 A CN201010183833 A CN 201010183833A CN 101831622 A CN101831622 A CN 101831622A
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Abstract
The invention discloses grapheme foam and a preparation method thereof. The grapheme foam provided by the invention is prepared by the method comprising the following steps: 1) putting a metal foam material into a vacuum tube type furnace, and calcining the metal foam material under non-oxidizing atmosphere; 2) depositing grapheme on the calcined metal foam material by adopting a chemical vapor deposition method; and 3) removing foam metal from the obtained grapheme modified metal foam material, cleaning the obtained foam material by using deionized water, ethanol and ether in turn, taking the foam material out and drying the foam material to obtain grapheme foam. The grapheme foam material has a three-dimensional hollow porous netlike structure, the grapheme is on the netlike wall, and the structural characteristic effectively prevents the agglomeration of the grapheme; and the grapheme foam material integrates the characteristics of a foam material and a conductive material, and has the advantages of ultra-low density, ultra-high surface area, high heat conduction, high temperature resistance, corrosion resistance and the like.
Description
Technical field
The present invention relates to a kind of type material grapheme foam and preparation method thereof.
Background technology
Carbon material is being played the part of vital role in current science and technology field.Carbon extensively exists at nature, can form diamond and the crystal structure of graphite.Along with the discovery of soccerballene, carbon nanotube, people have had new understanding to carbon material.The Graphene of two dimension is another existence form of the carbon of recent findings.This material has excellent machinery, physics, chemistry and optical property.At present people have utilized mechanically peel, silicon carbide epitaxial growth, graphite oxide reduction, ultra-sonic dispersion and chemical vapour deposition prepared high performance Graphene sample (Science 2004,306 for K.S.Novoselov, A.K.Geim, 666.; C.Berger, Z.Song, X.Li, Science 2006,312, and 1191.; V.C.Tung, M.J.Allen, Nat.Nanotechnol.2009,4,25.; Y.Hemandez, V.Nicolosi, Nat.Nanotechnol.2008,3,563.; K.S.Kim, Y.Zhao, Nature 2009,457, and 706.; X.Li, W.Cai, Science 2009,324, and 1312.).This material is in molectronics, micro-nano device, and the high conversion efficiency battery, the invented solid gas dependent sensor, storing hydrogen and prepare composite have important application prospects (K.Geim, K.S.Novoselov, Nat.Mater.2007,6,183.; D.Pan, S.Wang, Chem.Mater.2009,21,3136.; X.Lu, Y.X Nat.Nanotechnol.2006,1,163.; S.Stankovich, D.A.Dikin, Nature 2006,442, and 282.).The two-dirnentional structure characteristics of Graphene make its easy reunion, and difficult the dispersion, the high surface area that the liquid phase dispersion method obtains is difficult to keep in the following process process, and it is being restricted again aspect high efficiency energy storage.Therefore how the novel graphite alkene material of dried preparation high surface area is an important directions of Graphene research.This will make Graphene at lithium ion battery, fuel cell, and ultracapacitor homenergic storage art is with a wide range of applications.
Summary of the invention
The purpose of this invention is to provide a kind of grapheme foam and preparation method thereof.
Grapheme foam provided by the present invention prepares according to following method: remove the foamed metal in the metal foaming material that Graphene modifies; Then the foam materials that obtains is cleaned with deionized water, ethanol, ether successively, take out oven dry, promptly obtain described grapheme foam.
Can adopt the method for conventional dissolution of metals to remove foamed metal in the metal foaming material that Graphene modifies.As adopting dissolving with hydrochloric acid foam iron, foam cobalt, nickel foam, but for nickel foam, dissolving with hydrochloric acid is slower, and concentrated nitric acid (massfraction is the salpeter solution of 65%-68%) dissolving is very fast, generally removes with iron(ic) chloride or iron nitrate (concentration is 0.05-0.1g/ml) for foam copper.
Grapheme foam provided by the present invention is three-dimensional hollow porous reticulated structure, the aperture, outer hole of described grapheme foam is by the hole decision of foamed metal, pore size can be 200-500 μ m, and the endoporus aperture is by the size decision of foamed metal, and pore size can be 30-200 μ m.
The metal foaming material that Graphene described in the present invention is modified can prepare according to the method that comprises the steps:
1) metal foaming material is put in the vacuum tube furnace, and under non-oxidizing atmosphere, calcined;
2) adopt chemical Vapor deposition process, on the metal foaming material after the calcining, deposit Graphene, obtain the metal foaming material that Graphene is modified.
Wherein, the made foam materials of alloy that metal foaming material described in the step 1) can be selected from the made foam materials of following any one metal or be made up of following at least two kinds of metals: nickel, copper, iron and cobalt specifically can be nickel foam, foam copper, foam iron, foam cobalt etc.Non-oxidizing atmosphere described in the step 1) specifically can be provided by hydrogen, nitrogen or rare gas element.The temperature of incinerating described in the step 1) can be 800-1100 ℃, and the incinerating time can be 0.5-1 hour.
Step 2) method that deposits Graphene on the metal foaming material after the calcining is specific as follows: keep described calcining temperature, in described vacuum tube furnace, feed carbon-source gas and feed hydrogen simultaneously, carry out the growth of Graphene, behind the growth 15-30min, close carbon source, under hydrogen gas stream, after furnace cooling 50-100 ℃, be cooled fast to room temperature.
Wherein, described carbon-source gas is carbonaceous organic molecule, specifically can be methane, methyl alcohol or ethanol; When adopting methane to do carbon source, gas flow is 30-50sccm; When adopting methyl alcohol or ethanol to do carbon source, with the argon gas bubbling of 30-50sccm.In the described Graphene process of growth, the volume ratio of carbon-source gas and hydrogen is 1: 1-1: 2.
Step 2) on the metal foaming material after the calcining number of plies of sedimentary Graphene can be the 1-20 layer.The number of plies of Graphene is relevant with growth time and speed of cooling, and preferred number of plies scope is the 2-10 layer.
Metal foaming material described in the step 1) also needs to clean according to following method before use: metal foaming material is cleaned and oven dry with deionized water, ethanol, acetone successively.
The above-mentioned metal foaming material of modifying through Graphene also belongs to protection content of the present invention.
Foamed metal and hollow porous grapheme foam that Graphene provided by the present invention is modified both can be used as electrode materials, can be used as energy storage material again and were used for energy storage.
Grapheme foam material provided by the present invention is a kind of novel porous material.Structurally it both had been different from soccerballene, the carbon ball of zero dimension, the unidimensional carbon nanotube, and the Graphene of two dimension also is different from carbon black, the diamond of tetrahedral structure, the graphite of laminate structure and the porous graphitic carbon foam of three-dimensional, amorphous structure.It has three-dimensional hollow porous reticulated structure, and the net wall is a Graphene, and this constructional feature has effectively stoped the reunion of Graphene; Gathered foam materials, the characteristics of electro-conductive material; Have extremely-low density, ultra-high surface area, high heat conduction, advantage such as high temperature resistant, corrosion-resistant.It also has porous, damping, damping, sound-absorbing, heat radiation, energy storage as functional materials, multiple physicals such as electromagnetic shielding.Therefore can extensively be used to industry, space flight and high-technology field.For example replace polymeric matrix foam, metal foam, acetylene charcoal, fibrous ceramic insulation, glass fibre etc.
The present invention has and has following beneficial effect:
1, the present invention discloses the hollow porous foam materials of a kind of novel Graphene first, and preparation technology is simple, can scale operation;
2, the prepared hollow porous grapheme foam of the present invention has high specific surface area (30-50m
2/ g), with metal foam (0.08-0.12m
2/ g) compare, improved 3～4 orders of magnitude; The specific surface area of superelevation has strengthened storage capacity, thereby further reduces the cost of energy storage device;
3, the used foamed metal of the present invention can be removed fully, can not pollute the grapheme foam material;
4, the resulting porous foam grapheme material of the present invention Stability Analysis of Structures, convenient transportation;
5, the resulting hollow porous grapheme foam material of the present invention, both can replace graphene oxide, directly be pressed into Graphene paper, also can replace crystalline flake graphite, expanded graphite, under ultrasound condition, be distributed to N-Methyl pyrrolidone, N, in the multiple solvent such as dinethylformamide and ethanol, obtain high-quality Graphene sample solution.
Description of drawings
Fig. 1 is the stereoscan photograph that is used for the nickel foam of hollow porous grapheme foam material growth among the embodiment 1;
The experimental installation structural representation of Fig. 2 for using in the present invention the prepares hollow porous grapheme foam material;
Fig. 3 is the optical photograph of the porous graphite alkene foam materials of embodiment 1 preparation;
Fig. 4 is the stereoscan photograph of the hollow porous grapheme foam of the present invention's preparation, (a) photo of low power amplification; (b) photo of high power amplification;
Fig. 5 is the transmission electron microscope photo of the hollow porous grapheme foam material of the present invention's preparation;
Fig. 6 is the Raman spectrum of the hollow porous grapheme foam material of the present invention's preparation, and the line 1 expression Graphene number of plies is two-layer, and the line 2 expression Graphene numbers of plies are the 3-5 layer, and the line 3 expression Graphene numbers of plies are multilayer (greater than 5 layers).；
Fig. 7 is the stereoscan photograph (nickel foam is a template, and methane is carbon source) of the Graphene modifying foam nickel of embodiment 1 preparation;
Fig. 8 is the stereoscan photograph (nickel foam is a template, and ethanol is carbon source) of the Graphene modifying foam nickel of embodiment 2 preparations;
Fig. 9 is the stereoscan photograph (foam copper is a template, and methane is carbon source) of the Graphene modifying foam copper of embodiment 3 preparations;
Figure 10 is the stereoscan photograph (foam copper is a template, and ethanol is carbon source) of the Graphene modifying foam copper of embodiment 4 preparations;
Figure 11 is the thermogravimetric curve of the hollow porous grapheme foam material of embodiment 1 preparation; Straight line is the thermal weight loss under the nitrogen atmosphere, and curve is the thermal weight loss under the air atmosphere.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments, but the present invention is not limited thereto.
Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
The first step is cleaned the nickel foam template
Nickel foam (Fig. 1) was dried with deionized water, acetone, each ultrasonic cleaning of ethanol successively in 30 minutes;
Second step, calcining nickel foam template
Used experimental installation is put into the tube furnace silica tube with nickel foam as shown in Figure 2, vacuumizes air pressure in the pipe is reduced to below the 10Pa, feeds hydrogen to normal pressure, gets rid of inner air tube three times repeatedly.The control hydrogen flowing quantity is 50sccm, and heat temperature raising when temperature rises to 1000 ℃, continued constant temperature 0.5-1 hour;
The 3rd step, growth Graphene (promptly preparing the nickel foam that Graphene is modified)
1000 ℃ of holding temperatures feed methane and hydrogen, and gas flow is methane 30sccm, hydrogen 50sccm, growth 30min closes carbon source, behind furnace cooling to 900 under the 50sccm hydrogen gas stream ℃, be cooled fast to room temperature, promptly obtain the Graphene number of plies and be the nickel foam that the Graphene of 2-10 layer is modified;
The 4th step, scumming nickel template
(2cm * 4cm) put into 50ml concentrated nitric acid (massfraction is 65%-68%) soaked 24 hours with the nickel foam that is loaded with Graphene; It is neutral spending ion-cleaning to solution, is using ethanol successively, and ether embathes, and takes out back 50 ℃ of vacuum-dryings 8 hours, promptly obtains porous graphite alkene foam materials, and its optical photograph as shown in Figure 3;
In the 4th step, material characterizes
The 3rd nickel foam (Fig. 7) and the 4th that goes on foot the Graphene modification that obtains is gone on foot the hollow porous grapheme foam (Fig. 4) that obtains carry out the scanning electron microscope sign, scanning electron microscope is field emission scanning electron microscope S-4300, acceleration voltage is 15kV, grapheme foam is a three-dimensional porous structure as seen from the figure, the outer hole of grapheme foam is by the hole decision of foamed metal, aperture, outer hole is 200-500 μ m, and the endoporus of grapheme foam has the size decision of foamed metal, and pore size is 30-200 μ m.Fig. 4 b be grapheme foam than the high-amplification-factor photo, from photo as can be seen grapheme foam constitute by thin Graphene.The Graphene modifying foam nickel that the 3rd step was obtained carries out Raman spectrum sign (Fig. 6), Raman spectrometer is a HR800 type confocal microscopy Raman spectrometer, excitation wavelength is 514nm, by Raman spectrum as can be known grapheme foam have very high crystalline structure, promptly there is minority layer (＜5 layers), also has most layers.The hollow porous grapheme foam ultra-sonic dispersion that the 4th step was obtained carries out transmission electron microscope sign (Fig. 5) in ethanol, transmission electron microscope is transmission electron microscope JEM-2011, acceleration voltage 200kV, magnification is 500,000 times, by transmission electron microscope photo as can be known grapheme foam be the crystalline form laminate structure.Figure 11 is the thermogravimetric curve of grapheme foam, and thermogravimetric analyzer is differential thermal/thermogravimetric synthesis analyzer Diamond Tg/DTA, under nitrogen atmosphere, when temperature rises to 1000 ℃, weight loss is 4.3%, can be heat-resisting under the air atmosphere to 600 degree, and the thermogravimetric loss is 3.7%.
Embodiment 2, preparation grapheme foam
Press the preparation method among the embodiment 1,1000 ℃ the calcining 0.5-1 hour after, cool to 850 ℃, the 30sccm argon gas fed to hold carry out bubbling in the alcoholic acid jar, ethanol is carbon source, carry out the Graphene growth, the scanning electronic microscope of the nickel foam that prepared graphene is modified characterizes, as shown in Figure 8.On the surface of Graphene attached to nickel foam, because the shrinkage coefficient of Graphene and nickel foam is different, there is gauffer in Graphene.
Press the preparation method among the embodiment 1, different is with foam copper as growth templates, is 0.05-0.1g/ml iron(ic) chloride or iron nitrate scumming copper with concentration, and the scanning electronic microscope of the foam copper that prepared graphene is modified characterizes, as shown in Figure 9.On the surface of Graphene attached to foam copper, because the shrinkage coefficient of Graphene and foam copper is different, there is gauffer in Graphene.
Embodiment 4, preparation grapheme foam
Press the preparation method among the embodiment 2, different is with foam copper as growth templates, and with 0.05-0.1g/ml iron(ic) chloride or iron nitrate scumming copper, the scanning electronic microscope of the foam copper that prepared graphene is modified characterizes, as shown in figure 10.On the surface of Graphene attached to foam copper, the shrinkage coefficient difference causes the Graphene gauffer.
Claims (11)
1. method for preparing the metal foaming material that Graphene modifies may further comprise the steps:
1) metal foaming material is put in the vacuum tube furnace, and under non-oxidizing atmosphere, calcined;
2) adopt chemical Vapor deposition process, on the metal foaming material after the calcining, deposit Graphene, obtain the metal foaming material that Graphene is modified.
2. method according to claim 1 is characterized in that: the made foam materials of alloy that metal foaming material described in the step 1) is selected from the made foam materials of following any one metal or is made up of following at least two kinds of metals: nickel, copper, iron and cobalt; Described non-oxidizing atmosphere is provided by hydrogen, nitrogen or rare gas element; Described incinerating temperature is 800-1100 ℃, and the incinerating time is 0.5-1 hour.
3. method according to claim 1 and 2, it is characterized in that: step 2) on the metal foaming material after the calcining deposition Graphene method be: keep described calcining temperature, in described vacuum tube furnace, feed carbon-source gas and feed hydrogen simultaneously, carry out the growth of Graphene, behind the growth 15-30min, close carbon source, under hydrogen gas stream, after furnace cooling 50-100 ℃, be cooled fast to room temperature.
4. method according to claim 3 is characterized in that: described carbon-source gas is carbonaceous organic molecule, is preferably methane, methyl alcohol or ethanol; In the process of described Graphene growth, the volume ratio of carbon-source gas and hydrogen is 1: 1-1: 2.
5. method according to claim 4 is characterized in that: described carbon source is a methane, and the gas flow of methane is 30-50sccm; Or described carbon source is methyl alcohol or ethanol, and adopting gas flow is the argon gas bubbling of 30-50sccm.
6. according to arbitrary described method among the claim 1-5, it is characterized in that: step 2) described in the number of plies of Graphene be the 1-20 layer, the preferred number of plies is the 2-10 layer.
7. according to arbitrary described method among the claim 1-6, it is characterized in that: described method also is included in the preceding step that described metal foaming material is cleaned according to following method of step 1): metal foaming material is cleaned and oven dry with deionized water, ethanol, acetone successively.
8. the metal foaming material that the Graphene that arbitrary described method prepares among the claim 1-7 is modified.
9. a method for preparing grapheme foam is that the foamed metal in the metal foaming material of the described Graphene modification of claim 8 is removed; Then the foam materials that obtains is cleaned with deionized water, ethanol, ether successively, take out oven dry, obtain described grapheme foam.
10. the grapheme foam for preparing of the described method of claim 9.
11. grapheme foam according to claim 10 is characterized in that: described grapheme foam is three-dimensional hollow porous reticulated structure, and the aperture, outer hole of described grapheme foam is 200-500 μ m, and the endoporus aperture is 30-200 μ m.
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