CN106904601A - A kind of preparation method of arch Graphene three-dimensional network - Google Patents
A kind of preparation method of arch Graphene three-dimensional network Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of arch Graphene three-dimensional network, it is on the basis of conventional copper-based bottom chemical vapor deposition growth Graphene, the number of plies and continuity of Graphene are regulated and controled by introducing trace meter nickel steam, the Graphene three-dimensional network that it grows in three-dimensional copper catalysis template is set with optimal self-supporting and to be suitable to strain sensing and detect optimal electronic transport performance in transfer, and soft objectives substrate is transferred to using the method for coating of soft gel half when separating and shifting Graphene three-dimensional network, so as to prepare a kind of three-dimensional grapheme network with special domes.
Description
Technical field
The present invention relates to technical field of graphene, particularly a kind of preparation method of arch Graphene three-dimensional network.
Background technology
Graphene（graphene）It is a kind of bi-dimensional cellular shape crystal structure tightly packed by single layer of carbon atom, tool
There are the characteristics such as excellent electricity, mechanics, calorifics and optics.Graphene network structure refers to be shaped with Graphene as seamless connection
Into it is a kind of two dimension or three dimensions on keep interconnected network structure.Such as Chinese patent application 201210043497.6
Disclosed in one kind with copper networks as template, and with chemical meteorology deposition method prepare Graphene network.Due to based on chemical gas
Graphene network prepared by phase sedimentation its features such as there is transparent, intensity high, good conductivity, have in novel sensor design
Important application, such as based on Graphene network strain transducer medical diagnostics, Human Physiology monitoring, man-made electronic's skin,
By numerous studies, it is in some specific function devices for the application of the technical fields such as bio-robot, flexible touch screen, flexible display screen
Part（Such as strain transducer）It is considered as compared to graphene planes structure advantageously in design.
The Graphene network structure of existing report is generally planar structure, is mainly prepared in two class methods：One is based on chemistry
Vapour deposition process is shifted after preparing and obtained, and two in solution or other solvents, are borrowed by by redox graphene dispersion
Help follow-up patterning schemes or network structure template realize network structure based on graphene oxide sheet multi-layer film structure
Graphene network.
The Graphene prepared based on chemical vapour deposition technique has the advantages that ultra-thin, transparency is high, the regulation and control of its number of plies it is many with
Carbon source ratio or alloy substrates are realized.Such as, one kind is disclosed in Chinese patent application 201410364096.X to be splashed by magnetic control
The method penetrated forms a certain proportion of corronil in monocrystal silicon substrate, in this, as process for preparing graphenes by chemical vapour deposition
Catalytic substrate, then will grow graphene film with dissolved with polymethyl methacrylate（PMMA）Acetone soln be coated on
Graphenic surface, in this, as the medium of transfer Graphene, the graphene film that will be grown is transferred to target substrate.It is Chinese special
Profit application 201410214108.0 discloses a kind of similar method, i.e., first chosen target substrate, such as silica, sapphire
Etc. substrate, and plated in target substrate last layer copper, nickel or, the metal such as corronil or ferro-cobalt strengthens as plasma
The catalytic substrate of chemical vapor deposition growth Graphene, the method removal for then etching catalytic metal.
But these method substrates and technology controlling and process are complex, it is adapted to the control of the uniform Graphene number of plies, but be not suitable for
The control of the Graphene number of plies of Graphene three-dimensional net structure.
Meanwhile, it is both needed to be transferred to other substrates after Graphene network growth prepared by current chemical vapour deposition technique, it is such as soft
Property film etc..Transfer method mainly has：
（1）Substrate etching method, a kind of transfer method as disclosed in Chinese patent application 201110342036.4, its feature is
Spin coated last layer polymethyl methacrylate is used as supporting layer on the Graphene for first growing on the metals such as Copper Foil, then by copper
The corrosive solutions such as the growth substrates ammonium persulfate such as paper tinsel are removed, then will remove the poly-methyl methacrylate after metal catalytic substrate
Ester/graphene composite film is attached in target substrate, then removes polymethyl methacrylate using methyl phenyl ethers anisole.
（2）Dry transfer method, such as Chinese patent application 201410845702.X, are first substrate grown Graphene with Copper Foil, then
PPC solution is spun to graphenic surface, is then recycled flexible polymer to uncover and be transferred to target PPC from Copper Foil and is served as a contrast
On bottom and by heating removal PPC, finally remaining PPC is removed with chloroform again.
（3）One kind is disclosed in electrochemistry Bubbling method, such as Chinese patent 201310193868.3 direct on the metallic substrate
The method of the graphenic surface spin coating of growth prepares flexible substrate, then with electrochemistry Bubbling method by graphene film and its base
Peeled off from growth catalytic substrate in the lump at bottom.
（4）Volume to volume transfer method, as described in Chinese patent application 201510837047.8, first with metal as catalytic substrate
With process for preparing graphenes by chemical vapour deposition, then the metallic substrates that length has Graphene are heated under conditions of having oxygen, afterwards
Plastic bottom layer is prepared in the substrate of heating, makes the laminated film to form plastic bottom layer-Graphene-metallic substrates, then by institute
Laminated film is stated to be put into water and heat, finally by the laminated film in volume to volume device by plastics-Graphene THIN COMPOSITE
Film is separated from metallic substrates, so that it may by Graphene it is coiled be transferred to plastic-substrates.
Above-mentioned transfer method is all to develop design for the transfer of large-area planar Graphene, when Graphene network is shifted
Larger structural damage can be brought, the reservation of Graphene three-dimensional network space structure is also not suitable for.
Additionally, in order to widen application of the Graphene network structure in fields such as energy storage, sensors, having there is some
Report on three-dimensional grapheme network structure.It is as a kind of with three-dimensional bubble in disclosed in Chinese patent application 201110056973.3
Foam nickel or foamed iron, foam cobalt etc. are the catalytic substrate of process for preparing graphenes by chemical vapour deposition, then using substrate etching method
Transfer, has prepared the three-dimensional foam Graphene network structure of the three-dimensional full UNICOM network of cellular；Such as Chinese patent application
Using the preparation method and transfer method in Chinese patent application 201110056973.3 by this three in 201210351691.0
Dimension foamy graphite alkene is used in flexible lithium ion quick charging battery field；One is disclosed in Chinese patent application 201510818014.9
The growth templates with three-dimensional foam nickel as chemical vapour deposition technique are planted, be grown on three-dimensional foam nickel with chemical vapour deposition technique
Graphene, the three-dimensional graphene foam structure caved in, then penetrates into three-dimensional graphene foam by dimethyl silicone polymer again
In, it is prepared for the flexible pulse monitor of three-dimensional grapheme.
But the grapheme foam of above three-dimensional structure is prepared by template of random three-dimensional foam metal more, obtains
The three-dimensional grapheme for arriving is the unordered foaming structure in space, and transfer process is slowly complicated（Such as need long-time freeze-drying）Or turn
Cause big structural damage after shifting and cave in, be unfavorable for the reservation of graphene three-dimensional structure and the performance of intrinsic excellent properties.
The present invention is different from above technical method, and feature is：It is chemical gaseous phase by weaving copper networks with 100 mesh of rule
Sedimentation prepares the template of Graphene, and be aided with micro-nickel steam for catalysis regulation and control substance, obtained support performance it is good three
Dimension Graphene network, recycling partly solidifies soft gel half and wraps up the arch Graphene three-dimensional network that a step transfer method is prepared for rule
Structure.
The content of the invention
Regarding to the issue above, chemical vapor deposition growth Graphene method of the present invention in routine with metallic copper as template
On the basis of, introduce micro-nickel steam and growth course is regulated and controled, and improve existing Graphene shifting process, there is provided one kind tool
There is the preparation method of the three-dimensional grapheme network of domes, what the present invention was obtained by：
A kind of preparation method of arch Graphene three-dimensional network, its specific preparation process is as follows：
Step one, with three-dimensional copper mesh as template, is grown using micro-nickel steam auxiliary Graphene three-dimensional network chemical vapor deposition,
Lift the continuity and self-supporting of graphene-structured；The growth temperature of growth furnace is set as 990-1020 DEG C, methane flow 20-
50 sccm, hydrogen flowing quantity 5-15 sccm, growth time 30-60 minutes, are then cooled to room temperature, that is, obtain being grown on copper mesh mould
Graphene three-dimensional network on plate；
Step 2, the Graphene three-dimensional network that step one is obtained is placed in soft gel surface, natural subsidence 5-8 minutes, obtains glue
Body half wraps up the Graphene three-dimensional network containing copper core；Half clad structure is formed by the control to the sedimentation time,
Step 3, be continuously injected into the method removal step two of etching fluid acquisition Graphene three-dimensional network in copper core, with
Keep the connective and self-supporting of Graphene three-dimensional network；
Step 4, the Graphene three-dimensional network after the removal copper core of cleaning step three, dries, that is, obtain the arch Graphene three
Dimension network.
Further, in the preparation method step one of arch Graphene three-dimensional network of the present invention, the nickel steam adds
Dosage is that nickel vapour concentration is 0.05 ~ 2ppm in growth furnace chamber under reaction temperature.
Further, in the preparation method of arch Graphene three-dimensional network of the present invention, nickel steam is utilized described in step one
The chemical vapor deposition growth of auxiliary Graphene three-dimensional network refers to after three-dimensional copper mesh cleaning, growth to be put into together with nickel wire or nickel powder
Chemical vapor deposition growth is carried out in stove.
Further, in the preparation method of arch Graphene three-dimensional network of the present invention, cleaning described in step one refers to：Will
Three-dimensional copper mesh is put into alcohol and the isometric mixed solution of acetone, with ultrasonic cleaning 40-80 minutes of 200-400W, then is spent
Ionized water is rinsed well repeatedly.
Further, in the preparation method of arch Graphene three-dimensional network of the present invention, soft gel is this described in step 2
What sample was obtained：By dimethyl silicone polymer and its silane coupler in mass ratio 10:1 is well mixed, natural levelling 10 minutes, then
Vacuum outgas 10 minutes, then 50-60 DEG C stands 40-60 minutes, that is, obtain the soft gel；
Or, silicon rubber is placed in container natural levelling 2 minutes, stand 15 minutes then at 25 DEG C, that is, obtain the soft gel.
Further, in the preparation method of arch Graphene three-dimensional network of the present invention, etching fluid is described in step 3
Refer to that concentration is the liquor ferri trichloridi or ammonium persulfate solution of 0.05 mol/L.
Further, in the preparation method of arch Graphene three-dimensional network of the present invention, quarter is continuously injected into described in step 3
The method for losing fluid refers to that the colloid for obtaining step 2 half wraps up the Graphene three-dimensional network containing copper core and is placed in container, holds
The etching fluid that flow velocity is 0.1 cel is persistently injected in device one end, and the other end discharges etching liquid with the flow velocity of 0.1 cel
Body, until copper core is removed completely.
Further, cleaned in the preparation method of arch Graphene three-dimensional network of the present invention, described in step 4 and refer to, will
Graphene three-dimensional network after step 3 removal copper core is placed in container, and one end persistently injects deionized water or distilled water,
Flow velocity is 0.2-0.5 cels, and the other end discharges liquid with the flow velocity of 0.2-0.5 cels, persistently cleans 60 minutes.
Further, in the preparation method of arch Graphene three-dimensional network of the present invention, drying described in step 4 refers to incite somebody to action
Graphene three-dimensional network after cleaning is inserted 25 DEG C of air dry ovens and is dried 2 hours.
Compared with prior art, technical solution of the present invention has the beneficial effect that：
（1）When growing Graphene due to the existing catalytic templating with copper as process for preparing graphenes by chemical vapour deposition, generally require
Copper catalysis substrate is processed by shot blasting, improving the surface quality of copper can just grow continuous, high-quality to a certain extent
Graphene, process is cumbersome, and the inventive method without excessive demand, only needs growth substrates to keep cleaning i.e. growth substrates
Can.
（2）The present invention on the basis of with copper as catalytic templating chemical vapor deposition growth Graphene, by Graphene
Trace meter nickel steam is introduced directly into vacuum growth furnace to regulate and control the number of plies and continuity of Graphene, makes it in three-dimensional copper
The Graphene three-dimensional network of online generation with optimal self-supporting and is suitable to the electronic transport of strain sensing detection in transfer
Performance, eliminates previously prepared this process of corronil substrate of needs, simplifies technique；And by the step control of nickel steam one
The number of plies, continuity of method control Graphene etc., can obtain Graphene of different nature.
（3）Be transferred to three-dimensional grapheme in flexible substrate by the step transfer method of soft gel one by the present invention, and process is simple can
With the geometrical morphology of intact reservation three-dimensional grapheme, and it is still in a state of use three-dimensional structure that can keep Graphene.
（4）The etching liquid of lasting injection flowing can make Graphene three-dimensional network in the effect of fluid during etching
Lower sustained suspension, to keep the connectivity and self-supporting of Graphene network, is conducive to the reservation of Graphene network three-dimensional structure；
And use the distilled water or deionized water of flowing to clean, and Graphene network structural integrity is on the one hand kept, on the other hand make miscellaneous
Matter is difficult to adhere to graphenic surface, improves degree of cleaning and efficiency.
Brief description of the drawings
Fig. 1 is the schematic diagram of the arch Graphene three-dimensional net structure that the experimental group of embodiment 1 is obtained.
Fig. 2 is the arch Graphene three-dimensional network SEM schematic diagram that the experimental group of embodiment 1 is obtained.
Fig. 3 is the Raman spectrum of the arch Graphene three-dimensional network of experimental group acquisition in embodiment 1.
Fig. 4 is the Raman spectrum of the arch Graphene three-dimensional network of control group acquisition in embodiment 1.
Fig. 5 is the optical microscope picture of the arch Graphene three-dimensional network of experimental group acquisition in embodiment 1.
Fig. 6 is the optical microscope picture of the arch Graphene three-dimensional network of control group acquisition in embodiment 1.
Fig. 7 is the Raman spectrum of the arch Graphene three-dimensional network of experimental group acquisition in embodiment 2.
Fig. 8 is the Raman spectrum of the arch Graphene three-dimensional network of control group acquisition in embodiment 2.
Fig. 9 is the optical microscope picture of the arch Graphene three-dimensional network of experimental group acquisition in embodiment 2.
Figure 10 is the optical microscope picture of the arch Graphene three-dimensional network of control group acquisition in embodiment 2.
Figure 11 is the Raman spectrum of the arch Graphene three-dimensional network of experimental group acquisition in embodiment 3.
Figure 12 is the Raman spectrum of the arch Graphene three-dimensional network of control group acquisition in embodiment 3.
Figure 13 is the optical microscope picture of the arch Graphene three-dimensional network of experimental group acquisition in embodiment 3.
Figure 14 is the optical microscope picture of the arch Graphene three-dimensional network of control group acquisition in embodiment 3.
Figure 15 is the Raman spectrum of the arch Graphene three-dimensional network of experimental group acquisition in embodiment 4.
Figure 16 is the Raman spectrum of the arch Graphene three-dimensional network of control group acquisition in embodiment 4.
Figure 17 is the optical microscope picture of the arch Graphene three-dimensional network of experimental group acquisition in embodiment 4.
Figure 18 is the optical microscope picture of the arch Graphene three-dimensional network of control group acquisition in embodiment 4.
Specific embodiment
The present invention is elaborated with reference to the accompanying drawings and detailed description, but the present invention is not limited to following reality
Example.Method described in following embodiments, unless otherwise specified, is conventional method；The reagent and material etc., such as without special theory
It is bright, commercially obtain.
Reagent and instrument involved by embodiment：
Key instrument：
Growth furnace：Nanjing Univ. Instrument Factory's OTL1200 tube furnaces；
Ultrasonic washing instrument：Kunshan Ultrasonic Instruments Co., Ltd.'s KQ-400KDE types；
Light microscope：NIKON Eclipse Lv100NO；
SEM：Zeiss EVO 18 ；
Raman spectrometer：HORIBA JY Labram HR Evolution；
Main agents and material：
Dimethyl silicone polymer and its curing agent silane coupler：From Dow corning company, model DC184；
Silicon rubber：Famous 704 silicon rubber in south；
Three-dimensional copper mesh：Hebei Hengshui Anping stainless (steel) wire products factory, specification is 100 mesh；
Nickel wire and nickel powder：Hebei Hengshui Anping stainless (steel) wire products factory, nickel wire specification is the mm of diameter 0.1, and nickel powder specification is 120
Mesh；
Remaining required reagent is all from the western Chemical Co., Ltd. of Alpha.
Embodiment 1
1st, arch Graphene three-dimensional network is prepared
Step one：Take three-dimensional copper mesh and be cut to the mm of 5 cm *, 5 cm * 0.25, take 100 milligrams of diameter 0.1mm nickel wires（Specifically
The nickel powder of 120 mesh specifications can also be used in practice process）, copper mesh and nickel wire are put into 1:The alcohol and third of 1 isometric mixing
In ketone mixed solution.Cleaned with ultrasonic wave 40-80 minutes with the power of 200-400W, rinse dry repeatedly with deionized water afterwards
Only, the impurity on surface, the three-dimensional copper mesh after being cleaned are removed.
Three-dimensional copper mesh and nickel wire after by cleaning（100 milligrams）Together it is put into chemical vapor deposition growth furnace, furnace cavity
Product is 1 liter, and nickel vapour concentration is about 0.13ppm in reaction temperature lower furnace chamber（In specific implementation process, it is ensured that nickel in reaction furnace chamber
The concentration of steam can all realize the purpose of the present invention in the range of 0.05 ~ 2 ppm）As experimental group；
While another group only by copper mold plate（Nickel is not added）It is put into growth furnace as a control group；
Two groups are all grown with typical growing condition, obtain 2 groups of Graphene three-dimensional networks；
The typical growing condition refers to：1000 degrees Celsius of furnace temperature, methane flow is 35sccm, hydrogen 8sccm, and growth time is
45 minutes.
Step 2：By dimethyl silicone polymer and its curing agent silane coupler in mass ratio 10:1 ratio is well mixed,
It is placed in container natural levelling 10 minutes, then inserts in vacuum sample tank, then is connected vacuum sample tank and vavuum pump with tracheae,
Vavuum pump is opened, vacuum outgas is put into 50 ~ 60 DEG C of baking ovens after 10 minutes, bakee -60 minutes 40 minutes time, form soft solidifying
Glue.
Transfer：Before soft gel solidification, the 2 groups of Graphene three-dimensional networks obtained in step one are placed in flexible glue table respectively
Face, natural subsidence obtains the Graphene three-dimensional network that soft gel half is coated after 5 minutes.
Step 3：The Graphene three-dimensional network that step 2 is obtained soft gel again half is coated is placed in container, to container
One end persistently inject the liquor ferri trichloridi that the concentration that flow velocity is 0.1 cel is 0.05 mol/L（Actual mechanical process
In can also concentration be 0.05 mol/L ammonium persulfate solution or other corrosive fluids）, while holding container is another
Etch liquids are discharged in one end with the flow velocity of 0.1 cel, until copper core is removed completely.
Step 4：After copper core is removed, then to one end in the container equipped with the graphene-containing three-dimensional network after removal copper core
The distilled water of lasting injection flowing（Deionized water can also be used in actual mechanical process）Clean repeatedly, flow rate of liquid is 0.2-
0.5 cel, while the other end flow velocity in container persistently discharges cleaning liquid for 0.2-0.5 cels, will lasting cleaning
Graphene three-dimensional network after at least 60 minutes is inserted 25 DEG C of air dry ovens and is dried 2 hours, obtains experimental group and control group arch
Shape Graphene three-dimensional network.
2nd, performance detection：
Fig. 1 is the schematic diagram of the arch Graphene three-dimensional net structure that the present embodiment experimental group is obtained.
Fig. 2 is the arch Graphene three-dimensional network SEM schematic diagram that the present embodiment experimental group is obtained（In figure
Scale is 100 μm）.
Fig. 3 and Fig. 4 are respectively experimental group (nickel steam is with the addition of in growth) and control group (without nickel steam) Graphene network
Raman spectrum, from Raman spectrum it can be seen that the Graphene that obtains of experimental group is multilayer, control group is individual layer.
Fig. 5 and Fig. 6 are respectively experimental group (nickel steam is with the addition of in growth) and control group (not adding nickel) Graphene network
Optical microscope photograph（Scale is 200 μm in figure）, it can be seen that when in control group growth without nickel, Graphene network pole
Easily cave in and damaged, it is difficult to maintain three-dimensional net structure.
Graphene network to experimental group and control group does electrical performance testing respectively, will obtain after the completion of step 4
2 groups of materials connect wire and prepare electrode, are bent 200 times with R=5 mm respectively.Result shows：Experimental group sample electricity before bending
It is 4.65 k Ω to hinder, and resistance is 4.65-4.75 k Ω after bending, and resistance drift is less than 5%；And resistance before control sample bending
It is 1.5 M Ω, resistance is 200 M Ω -500M Ω after bending, and electric current is almost nil after bending 40 times, and circuit disconnects.
Embodiment 2
The experiment basic skills of the present embodiment is substantially the same manner as Example 1, except that, in step one：Experimental group is reacted
At a temperature of grow furnace chamber in nickel vapour concentration be about 0.05ppm, control group is equally added without nickel wire.
The growth conditions of experimental group and control group is：1010 degrees Celsius of furnace temperature, methane flow is 50sccm, hydrogen flowing quantity
5sccm is controlled to, growth time is 60 minutes.Remaining condition and step are identical with specific embodiment 1.
Fig. 7 and Fig. 8 are respectively experimental group (nickel steam is with the addition of in growth) and control group (without nickel steam) Graphene network
Raman spectrum, from Raman spectrum it can be seen that the Graphene that obtains of experimental group is multilayer, control group is individual layer.
Fig. 9 and Figure 10 are respectively experimental group (nickel steam is with the addition of in growth) and control group (without nickel steam) Graphene network
Optical microscope photograph（Scale is 200 μm in figure）, it can be seen that when in growth without nickel, Graphene network easily caves in
And breakage, it is difficult to maintain three-dimensional net structure.
Graphene to experimental group and control group does electrical performance testing respectively, will the present embodiment step obtain experimental group
Wire is connected with 2 groups of materials of control group and prepare electrode, bent 200 times with R=5 mm respectively.Result shows：Experimental group sample exists
Resistance is 3.28 k Ω before bending, and resistance is 3.37 k Ω -3.54 k Ω after bending, and resistance drift is less than 7%；And control group sample
Resistance is 2.7M Ω before product bending, and resistance is 269M Ω -700 M Ω after bending, and electric current is almost nil after bending 37 times, circuit
Disconnect.
Embodiment 3
The present embodiment experiment basic skills is substantially the same manner as Example 1, except that, in step one：The present embodiment is tested
It is 2ppm that nickel vapour concentration in furnace chamber is grown under group reaction temperature, and control group is similarly and is added without nickel.
The growth conditions of experimental group and control group is：990 DEG C of furnace temperature, methane flow is 20sccm, hydrogen flowing quantity control
It is 15sccm, growth time is 50 minutes.Remaining condition and step are same as Example 1.
Figure 11 and Figure 12 are respectively experimental group (nickel steam is with the addition of in growth) and control group (without nickel steam) arch graphite
Raman spectrum after the transfer of alkene three-dimensional network, from Raman spectrum it can be seen that the Graphene that experimental group is obtained is multilayer, control group
It is individual layer.
Figure 13 and Figure 14 are respectively experimental group (nickel steam is with the addition of in growth) and control group (without nickel steam) arch graphite
Optical microscope photograph after the transfer of alkene three-dimensional network（Scale is 200 μm in figure）, it can be seen that when in growth without nickel, stone
Black alkene network easily caves in and damaged, it is difficult to maintain three-dimensional net structure.
Graphene to experimental group and control group does electrical performance testing respectively, 2 groups for will being obtained with the present embodiment
Material connects wire and prepares electrode, is bent 200 times with R=5 mm respectively.Result shows：Experimental group sample resistance before bending
It is 2.36 k Ω, resistance is 2.48 k Ω -2.56 k Ω after bending, resistance drift is less than 8%；And electricity before control sample bending
It is 1.67M Ω to hinder, and resistance is 339M Ω -600 M Ω after bending, and electric current is almost nil after bending 43 times, and circuit disconnects.
Embodiment 4
The present embodiment experimental technique is substantially the same manner as Example 1, except that, in step one：The present embodiment experimental group adds
Enter nickel for nickel powder, nickel vapour concentration in furnace chamber is reacted under reaction temperature and is about 1.39ppm, control group is equally added without nickel.
（Experimental group and control group）Growth conditions is：1020 DEG C of furnace temperature, methane flow is 30sccm, and hydrogen flowing quantity is controlled to
12sccm, growth time is a hour.
What the soft gel that step 2 transfer is used was obtained by：Silicon rubber is poured into appropriate container, natural levelling 2
After minute, bakeed under the conditions of 25 DEG C and obtain final product soft gel in 15 minutes, 2 groups of Graphene three dimensional networks that step one is obtained gently are placed in this
Soft gel surface, natural subsidence obtains the Graphene three-dimensional network that soft gel half is coated after 8 minutes.Gas-operated and embodiment
1 is identical.
Figure 15 and Figure 16 are respectively experimental group (nickel steam is with the addition of in growth) and control group (without nickel steam) arch graphite
The Raman spectrum of alkene three-dimensional network, from Raman spectrum it can be seen that the Graphene that experimental group is obtained is multilayer, control group is individual layer.
Figure 17 and Figure 18 are respectively experimental group (nickel steam is with the addition of in growth) and control group (without nickel steam) arch graphite
Optical microscope photograph after the transfer of alkene three-dimensional network（Scale is 200 μm in figure）, it can be seen that when in growth without nickel, stone
Black alkene network easily caves in and damaged, it is difficult to maintain three-dimensional net structure.
Graphene to experimental group and control group does electrical performance testing respectively, the 2 groups of materials that will be obtained with the present embodiment
Material connects wire and prepares electrode, is bent 200 times with R=5 mm respectively.Result shows：Experimental group sample resistance before bending is
6.78 k Ω, resistance is 6.94k Ω -7.85 k Ω after bending, and resistance drift is less than 15%；And resistance before control sample bending
It is 3.79M Ω, resistance is 457M Ω -893 M Ω after bending, and electric current is almost nil after bending 29 times, and circuit disconnects.
Claims (9)
1. a kind of preparation method of arch Graphene three-dimensional network, it is characterised in that specific preparation process is as follows：Step one, with
Three-dimensional copper mesh is template, is grown using nickel steam auxiliary Graphene three-dimensional network chemical vapor deposition：Growth temperature 990-1020
DEG C, methane flow 20-50 sccm, hydrogen flowing quantity 5-15 sccm growth time 30-60 minutes, are then cooled to room temperature, obtain final product
To the Graphene three-dimensional network being grown in three-dimensional copper mesh template；
Step 2, the Graphene three-dimensional network that step one is obtained is placed in soft gel surface, natural subsidence 5-8 minutes, obtains glue
Body half wraps up the Graphene three-dimensional network containing copper core；
Step 3, with the copper core being continuously injected into the Graphene three-dimensional network of the method removal step two of etch liquids acquisition；
Step 4, the Graphene three-dimensional network after the removal copper core of cleaning step three, dries, that is, obtain the arch Graphene three
Dimension network.
2. the preparation method of arch Graphene three-dimensional network according to claim 1, it is characterised in that temperature is reacted in step one
The nickel vapour concentration is 0.05 ~ 2 ppm in the lower growth furnace chamber of degree.
3. the preparation method of arch Graphene three-dimensional network according to claim 2, it is characterised in that utilized described in step one
The auxiliary Graphene three-dimensional network chemical vapor deposition growth of nickel steam refers to after three-dimensional copper mesh cleaning, to be put together with nickel wire or nickel powder
Entering carries out chemical vapor deposition growth in growth furnace.
4. the preparation method of arch Graphene three-dimensional network according to claim 3, it is characterised in that the cleaning refers to：
During three-dimensional copper mesh is put into alcohol and the isometric mixed solution of acetone, it is cleaned by ultrasonic 40-80 minutes, then rushed with deionized water
Wash.
5. according to the preparation method of one of the claim 1-4 arch Graphene three-dimensional networks, it is characterised in that step 2 institute
State what the soft gel of semi-solid preparation was obtained by：By dimethyl silicone polymer and its silane coupler in mass ratio 10:1 mixing is equal
It is even, natural levelling 10 minutes, then vacuum outgas 10 minutes, then 50-60 DEG C stands 40-60 minutes, that is, obtain the soft gel；
Or, by silicon rubber nature levelling 2 minutes, 15 minutes are stood then at 25 DEG C, that is, obtain the soft gel.
6. the preparation method of arch Graphene three-dimensional network according to claim 5, it is characterised in that etched described in step 3
Liquid refers to the liquor ferri trichloridi or ammonium persulfate that concentration is 0.05 mol/L.
7. the preparation method of arch Graphene three-dimensional network according to claim 6, it is characterised in that continuous described in step 3
The method for injecting etch liquids refers to that the colloid for obtaining step 2 half wraps up the Graphene three-dimensional network containing copper core and is placed in container
In, one end persistently injects the etching fluid that flow velocity is 0.1 cel, and the other end is discharged with the flow velocity of 0.1 cel and carved
Erosion liquid, until copper core is removed completely.
8. the preparation method of arch Graphene three-dimensional network according to claim 5, it is characterised in that cleaned described in step 4
Refer to, by step 3 remove copper core after Graphene three-dimensional network be placed in container, one end persistently inject deionized water or
Distilled water, flow velocity is 0.2-0.5 cels, and the other end discharges liquid with the flow velocity of 0.2-0.5 cels, persistently cleans 60 points
Clock.
9. the preparation method of arch Graphene three-dimensional network according to claim 8, it is characterised in that dried described in step 4
Refer to that the Graphene three-dimensional network after cleaning is inserted into 25 DEG C of air dry ovens dries 2 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109425367A (en) * | 2017-09-04 | 2019-03-05 | 北京清正泰科技术有限公司 | A kind of graphene sensor range protection system |
| CN109650381A (en) * | 2019-02-15 | 2019-04-19 | 湖南医家智烯新材料科技股份有限公司 | A kind of sea urchin shape graphene and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086360A (en) * | 2011-11-01 | 2013-05-08 | 海洋王照明科技股份有限公司 | Method for continuously preparing graphene |
| CN104986758A (en) * | 2015-06-25 | 2015-10-21 | 厦门凯纳石墨烯技术有限公司 | Three-dimensional network graphene for lithium battery and preparing method thereof |
-
2017
- 2017-03-02 CN CN201710119786.2A patent/CN106904601B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086360A (en) * | 2011-11-01 | 2013-05-08 | 海洋王照明科技股份有限公司 | Method for continuously preparing graphene |
| CN104986758A (en) * | 2015-06-25 | 2015-10-21 | 厦门凯纳石墨烯技术有限公司 | Three-dimensional network graphene for lithium battery and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109425367A (en) * | 2017-09-04 | 2019-03-05 | 北京清正泰科技术有限公司 | A kind of graphene sensor range protection system |
| CN109650381A (en) * | 2019-02-15 | 2019-04-19 | 湖南医家智烯新材料科技股份有限公司 | A kind of sea urchin shape graphene and preparation method thereof |
| CN109650381B (en) * | 2019-02-15 | 2022-04-05 | 湖南医家智烯新材料科技有限公司 | Sea urchin-shaped graphene and preparation method thereof |
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