CN108461177A - A kind of preparation method of the composite and flexible conductive film of carbon nanotube loaded graphene-copper nano particles - Google Patents
A kind of preparation method of the composite and flexible conductive film of carbon nanotube loaded graphene-copper nano particles Download PDFInfo
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- CN108461177A CN108461177A CN201810250732.4A CN201810250732A CN108461177A CN 108461177 A CN108461177 A CN 108461177A CN 201810250732 A CN201810250732 A CN 201810250732A CN 108461177 A CN108461177 A CN 108461177A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 48
- 239000010949 copper Substances 0.000 title claims abstract description 48
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 42
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 42
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010408 film Substances 0.000 claims abstract description 41
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000010409 thin film Substances 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 150000001879 copper Chemical class 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 235000015424 sodium Nutrition 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 238000000889 atomisation Methods 0.000 abstract 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract 1
- 238000005118 spray pyrolysis Methods 0.000 abstract 1
- 239000002238 carbon nanotube film Substances 0.000 description 25
- 239000000523 sample Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- -1 Graphite alkene Chemical class 0.000 description 1
- ZIALXKMBHWELGF-UHFFFAOYSA-N [Na].[Cu] Chemical compound [Na].[Cu] ZIALXKMBHWELGF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002079 double walled nanotube Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/04—Nanotubes with a specific amount of walls
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/30—Purity
Abstract
The invention discloses a kind of preparation methods of the composite and flexible conductive film of carbon nanotube loaded graphene copper nano particles, belong to conductive film preparation and technical field of composite preparation.This method is on the basis of carbon nanotube conductive thin film well prepared in advance, using spray pyrolysis by copper salt solution, graphene oxide suspension atomization, after heat resolve on carbon nanotube conductive thin film carrier forming core, growing up generates graphene cuprous oxide, it finally restores, obtains copper graphene carbon nanotube flexible conductive film band.Testing result show the grain size of copper in 200nm hereinafter, and graphene copper be uniformly distributed and be embedded on carrier；The conductivity of copper graphene carbon nanotube flexible conductive film band improves an order of magnitude, and the flexible conductive film is simple to operation with the preparation method of carbon nanotube loaded graphene copper, does not need large scale equipment, and technological process is shorter.
Description
Technical field
The present invention relates to a kind of preparation sides of the composite and flexible conductive film of carbon nanotube loaded graphene-copper nano particles
Method belongs to conductive film preparation and technical field of composite preparation.
Background technology
With the development of economy, the demand of people increasingly diversification, the position that flexible conducting material occupies on the market
More and more important and development is rapidly.Flexible conducting material has both excellent mechanical tensility and high conduction performance, that is,
Say it in larger elongation strain（100%）Lower and electric conductivities variation and little after stretching up to a hundred times repeatedly, thus passed in flexibility
Sensor, flexible thin-film solar cell, flexible super capacitor etc. have potential applying value.
Although but carbon nanotube conductive thin film has met ductility and tensile property, in terms of conduction
Still there is the space promoted, for now, it is more preferably conductive how with relatively simple easy-operating method to prepare performance
Film is a research hotspot.
It is well known that the conductivity of copper is very high, because it contains a large amount of free electron, thus copper is added to carbon nanometer
Pipe film enhances its electric conductivity, can better meet the needs of conductive film, and graphene has good flexibility, and still
Possess very high electric conductivity, there is high specific surface area, associativity can be improved.Therefore, graphene and copper are added to when simultaneously
In carbon nano-tube film, the conductivity and its flexibility of carbon nanotube can be improved, to reach common enhancing conductive film electricity
The effect of conductance.But how the two is uniformly incorporated to carbon nanotube, make its evenly dispersed, uniform deposition makes material
It is still a problem that performance, which reaches best performance,.
Someone deposits copper once using carbon nano-tube film as template in different electroplate liquids, the results showed that, copper can be embedded into
In carbon nano-tube film, and show that the carbon nano-tube film of this method preparation deposits the conductance of carbon/carbon-copper composite material through survey calculation
Rate reaches 1.7*105S*m-1.But such operation needs to pre-process carbon nano-tube film, that is, purifies, is sensitized, and holds very much
Fragile carbon nano-tube film brings certain difficulty to the operability of experiment, it is difficult to control, thus to the material of preparation
It can affect.
Invention content
The purpose of the present invention is to provide a kind of composite and flexible conductive films of carbon nanotube loaded graphene-copper nano particles
Preparation method, specifically include following steps：
（1）Using chemical vapor deposition for carbon nanotubes conductive film, it is cut into arbitrary dimension.
（2）Graphene oxide is dissolved in deionized water in the ratio of 0.1-0.2g/3000mL, ultrasonic disperse 0.2-2h,
Obtain graphene oxide suspension.
（3）Mantoquita is dissolved in deionized water and obtains copper salt solution, a concentration of 0.0017-0.01mol/L of copper salt solution
Magnetic agitation is stirred for uniformly at room temperature（1-3min）.
（4）It is respectively poured into after graphene oxide suspension and copper salt solution are stirred evenly in an atomizer, by carbon nanometer
Pipe film is fixed on tube furnace low temperature zone position after being fixed with fixture, temperature is 150-250 DEG C, waits for the high-temperature region temperature of tube furnace
When degree rises to 400-900 DEG C, while two atomizers are opened into spray patterns, is atomized the precursor liquid droplet of generation by high-temperature region
After chemistry thermal decomposition, synthesis cuprous oxide-graphene, spreads, moves, being loaded to forming core on the carrier of low-temperature space, growing up, to
Obtain the carrier of carbon nanotube loaded graphene-cuprous oxide nano particle.
（5）By step（4）Obtained complex carrier is placed in vacuum tube furnace, leads to reducing atmosphere, and reduction temperature is arranged
It it is 250-300 DEG C, the time is that 3-8h is restored to obtain the composite and flexible conduction of carbon nanotube loaded graphene-copper nano particles
Film.
Preferably, step of the present invention（1）The carbon nanotube conductive thin film thickness is 1-20 microns, can be bent repeatedly, electricity
Conductance is 3-8*104S/m。
Preferably, of the present invention that there are a large amount of oxygen-containing groups, there is good Solvent Solubility, graphene oxide purity
It is 99% or more, the number of plies is less than three layers.
Preferably, step of the present invention（3）Described in mantoquita be copper acetate, copper stearate, copper sulphate, copper nitrate, ethylenediamine
One or more of tetraacethyl sodium copper, EDTA copper sodiums are mixed to get according to arbitrary proportion.
Preferably, step of the present invention（5）Described in reducibility gas be hydrogen, decompose ammonia, carbon monoxide, hydrogen with it is lazy
One kind in the mixed gas of property gas.
Preferably, during using chemical vapor deposition for carbon nanotubes conductive film, the carbon nanotube of selection is
One or more of single wall, double-walled or multi-walled carbon nanotube are mixed to get according to arbitrary proportioning, the major diameter of carbon nanotube
Than for arbitrary draw ratio, can also be the carbon nanotube by being surface-treated or modifying, the purity of carbon nanotube be 95% with
On.
The beneficial effects of the invention are as follows：
（1）Carbon nanotube loaded graphene prepared by the method for the invention-copper conductive film band method is simple to operation, is not required to
Large scale equipment is wanted, it is cheap.
（2）The graphene being prepared, copper grain diameter size are substantially at nanoscale fine grained, without other field trashes,
And graphene-copper is uniformly distributed and is embedded on carrier；The conductivity of copper-graphite alkene-carbon nano tube flexible conductive film band carries
High an order of magnitude.
Description of the drawings
Fig. 1 is the SEM figures of the composite conductive thin film prepared in embodiment 1；
Fig. 2 is the SEM figures of the composite conductive thin film prepared in embodiment 1.
Specific implementation mode
Invention is further described in detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously
It is not limited to the content.
Embodiment 1
The preparation method of carbon nanotube loaded graphene-copper nano particles of flexible conductive film described in the present embodiment, specifically includes
Following steps：
（1）Carbon nanotube conductive thin film prepared by advance chemical vapour deposition technique is cut into the blockage of 20*20mm, passes through four
Square probe measuring resistance measures its sheet resistance, is fixed later with fixture.
（2）The graphene oxide 0.1g prepared using Hummers methods are improved is weighed, the deionized water of 3000ml is dissolved in
In, ultrasonic disperse 0.2h obtains graphene oxide suspension.
（3）Configuration concentration is the copper acetate solution of 0.0017mol/L, and magnetic stirring apparatus is sufficiently stirred work.
（4）By step（2）（3）Obtained suspension and copper salt solution respectively pours into an atomizer after stirring
In；The carbon nano-tube film cut is fixed on to the low temperature zone position of tube furnace with fixture（Temperature is 150 DEG C）, wait for tube furnace
When high-temperature region temperature is warming up to 400 DEG C, while two atomizers are opened into spray patterns, the precursor liquid droplet for being atomized generation passes through
High-temperature region chemistry thermal decomposition after being synthetically generated graphene-cuprous oxide, spreads, moves, being supported on to shape on the carrier of low-temperature space
Core is grown up, particle studded in carbon nano-tube film carrier, microscopic appearance such as Fig. 1 and 2 institutes to obtain graphene-cuprous oxide
Show, copper particle is in nanometer scale as seen from the figure, and evenly dispersed and be embedded in conductive film, and the carbon on conductive film is received
Mitron and graphene are high-visible.
（5）By step（4）Obtained graphene-cuprous oxide is particle studded to be placed in vacuum tube in carbon nano-tube film carrier
Lead to hydrogen atmosphere in formula stove to be restored to obtain the conductive film that graphene-copper is supported on carbon nanotube；Reducing atmosphere is argon hydrogen
Body, temperature are 250 DEG C, time 3h.
By graphene-copper nano particles that this experiment is prepared be embedded in the conductive film of carbon nano-tube film by using
Cubic probe surveys its sheet resistance, and conversion obtains its conductivity；It is computed, graphene-copper nano particles of preparation are embedded in carbon nanometer
The conductivity of the conductive film of pipe film is 1.21*105 S*m-1, the conductivity of flexible conductive film prepared by this method is substantially better than
Not plus the carbon nanotube conductive film of graphene and copper.
Embodiment 2
（1）Carbon nanotube conductive thin film is cut into the blockage of 20*20mm with stainless steel scissors, passes through cubic probe measuring resistance
Its sheet resistance is measured, the fixture made of copper sheet fixes later.
（2）0.2g graphene oxides are dissolved in 3000ml deionized waters, ultrasonic disperse 2h obtains the oxidation stone of brown color
Black alkene suspension.
（3）Compound concentration is the copper acetate solution of 0.01mol/L, magnetic agitation 30min.
（4）By step（2）（3）Obtained suspension and copper salt solution respectively pours into an atomizer after stirring evenly respectively
In；Carbon nano-tube film is fixed on to the low temperature zone position of tube furnace with copper fixture（Temperature is 250 DEG C）, wait for tube furnace high temperature
When area's temperature rises to 900 DEG C, two atomizers are opened into spray patterns, the drop for being atomized generation is thermally decomposed by high-temperature region chemistry
And spread, move, being supported on to forming core on the carrier of low-temperature space and grow up after generation graphene-cuprous oxide after combining, to
Obtain the composite material that graphene-cuprous oxide nano particle is embedded in carbon nano-tube film carrier.
（5）Again by step（4）Obtained graphene-cuprous oxide nano particle is embedded in answering for carbon nano-tube film carrier
Condensation material is put in vacuum tube furnace, and logical CO gas is restored, and reduction temperature is 300 DEG C, and the time is 5h；Obtain stone
Black alkene-copper nano particles are embedded in the flexible conductive film of carbon nano-tube film carrier.
（6）The flexibility that graphene-copper nano particles that this example is prepared are embedded in carbon nano-tube film carrier is led
Electrolemma surveys its sheet resistance by using cubic probe, then it is 1.32*10 to obtain its conductivity by conversion5 S*m-1。
Embodiment 3
（1）Carbon nanotube conductive thin film is cut into the blockage of 20*20mm with stainless steel scissors, passes through cubic probe survey side
Resistance, the fixture made of copper sheet fixes later.
（2）0.1g graphene oxides are dissolved in 3000ml deionized waters, ultrasonic disperse 1h obtains the oxidation stone of brown color
Black alkene suspension.
（3）Compound concentration is the copper acetate solution of 0.003mol/L, magnetic agitation 10min.
（4）By step（2）（3）Obtained suspension and copper salt solution respectively pours into an atomizer after stirring evenly respectively
In；Carbon nano-tube film is fixed on to the low temperature zone position of tube furnace with copper fixture（Temperature is 210 DEG C）, wait for tube furnace high temperature
When area's temperature rises to 480 DEG C, two atomizers are opened into spray patterns, the drop for being atomized generation is thermally decomposed by high-temperature region chemistry
And spread, move, being supported on to forming core on the carrier of low-temperature space and grow up after generation graphene-cuprous oxide after combining, to
Obtain the composite material that graphene-cuprous oxide nano particle is embedded in carbon nano-tube film carrier.
（5）Again by step（4）Obtained graphene-cuprous oxide nano particle is embedded in answering for carbon nano-tube film carrier
Condensation material is put in vacuum tube furnace, and reduction of fractions to a common denominator solution ammonia gas is restored, and reduction temperature is 270 DEG C, and the time is 5h.Obtain stone
Black alkene-copper nano particles are embedded in the flexible conductive film of carbon nano-tube film carrier.
Graphene-copper nano particles that this example is prepared are embedded in the flexible conductive film of carbon nano-tube film carrier
Its sheet resistance is surveyed by using cubic probe, then it is 1.18*10 to obtain its conductivity by conversion5 S*m-1。
Embodiment 4
（1）Carbon nanotube conductive thin film is cut into the blockage of 20*20mm with stainless steel scissors, passes through cubic probe survey side
Resistance, the fixture made of copper sheet fixes later.
（2）0.1g graphene oxides are dissolved in 3000ml deionized waters, ultrasonic disperse 120min obtains the oxygen of brown color
Graphite alkene suspension.
（3）Compound concentration is the copper acetate solution of 0.003mol/L, magnetic agitation 3min.
（4）By step（2）（3）Obtained suspension and copper salt solution respectively pours into an atomizer after stirring evenly respectively
In；Carbon nano-tube film is fixed on to the low temperature zone position of tube furnace with copper fixture（Temperature is 180 DEG C）, wait for tube furnace high temperature
When area's temperature rises to 500 DEG C, two atomizers are opened into spray patterns, the drop for being atomized generation is thermally decomposed by high-temperature region chemistry
And spread, move, being supported on to forming core on the carrier of low-temperature space and grow up after generation graphene-cuprous oxide after combining, to
Obtain the composite material that graphene-cuprous oxide nano particle is embedded in carbon nano-tube film carrier.
（5）Again by step（4）Obtained graphene-cuprous oxide nano particle is embedded in answering for carbon nano-tube film carrier
Condensation material is put in vacuum tube furnace, and logical argon hydrogen mixture is restored, and reduction temperature is 280 DEG C, and the time is 5h；Obtain stone
Black alkene-copper nano particles are embedded in the flexible conductive film of carbon nano-tube film carrier.
Graphene-copper nano particles that this example is prepared are embedded in the flexible conductive film of carbon nano-tube film carrier
Its sheet resistance is surveyed by using cubic probe, then it is 1.2*10 to obtain its conductivity by conversion5S*m-1；Therefore, the experimental method
The conductivity of the flexible conductive film of preparation is not substantially better than not plus graphene and copper.
Contrast experiment
Carbon nanotube conductive thin film is cut into the blockage of 20*20mm with stainless steel scissors, is surveyed by using cubic sonde method
It is 602.30 Ω cm to measure its sheet resistance（Survey is averaged again three times）；It is 5.0908*10 that its conductivity is obtained after conversion4S*m-1。
Claims (5)
1. a kind of preparation method of the composite and flexible conductive film of carbon nanotube loaded graphene-copper nano particles, it is characterised in that：
Specifically include following steps：
（1）Using chemical vapor deposition for carbon nanotubes conductive film, it is cut into required arbitrary dimension；
（2）Graphene oxide is dissolved in deionized water in the ratio of 0.1-0.2g/3000mL, ultrasonic disperse 0.2-2h is obtained
Graphene oxide suspension；
（3）Mantoquita is dissolved in deionized water and obtains copper salt solution, a concentration of 0.0017-0.01mol/L room temperatures of copper salt solution
Lower magnetic agitation is stirred for uniformly；
（4）It is respectively poured into after graphene oxide suspension and copper salt solution are stirred evenly in an atomizer, carbon nanotube is thin
Film is fixed on tube furnace low temperature zone position after being fixed with fixture, temperature is 150-250 DEG C, waits for the high-temperature region temperature liter of tube furnace
When to 400-900 DEG C, while two atomizers are opened into spray patterns, is atomized the precursor liquid droplet of generation by high-temperature region chemistry
After thermal decomposition, synthesis cuprous oxide-graphene, spreads, moves, being loaded to forming core on the carrier of low-temperature space, growing up, to obtain
The carrier of carbon nanotube loaded graphene-cuprous oxide nano particle；
（5）By step（4）Obtained complex carrier is placed in vacuum tube furnace, leads to reducing atmosphere, and setting reduction temperature is
250-300 DEG C, the time is that 3-8h is restored to obtain the composite and flexible conduction of carbon nanotube loaded graphene-copper nano particles
Film.
2. the preparation side of the composite and flexible conductive film of carbon nanotube loaded graphene-copper nano particles according to claim 1
Method, it is characterised in that：Step（1）The carbon nanotube conductive thin film thickness is 1-20 microns, can be bent repeatedly, conductivity 3-
8*104S/m。
3. the preparation side of the composite and flexible conductive film of carbon nanotube loaded graphene-copper nano particles according to claim 1
Method, it is characterised in that：The graphene oxide purity is 99% or more, and the number of plies is less than three layers.
4. the preparation side of the composite and flexible conductive film of carbon nanotube loaded graphene-copper nano particles according to claim 1
Method, it is characterised in that：Step（3）Described in mantoquita be copper acetate, copper stearate, copper sulphate, copper nitrate, sodium ethylene diamine tetracetate
One or more of copper, EDTA copper sodiums are mixed to get according to arbitrary proportion.
5. the preparation side of the composite and flexible conductive film of carbon nanotube loaded graphene-copper nano particles according to claim 1
Method, it is characterised in that：Step（5）Described in reducibility gas be hydrogen, decompose ammonia, carbon monoxide, hydrogen and inert gas
Mixed gas in one kind.
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| CN110576187A (en) * | 2019-09-19 | 2019-12-17 | 天津大学 | preparation method for in-situ synthesis of three-dimensional graphene/one-dimensional carbon nanotube loaded copper nanoparticle material |
| CN110686589A (en) * | 2019-10-18 | 2020-01-14 | 南京理工大学 | High-sensitivity large-strain flexible strain sensor and preparation method thereof |
| CN115124030A (en) * | 2022-08-02 | 2022-09-30 | 武汉市碳翁科技有限公司 | Method for preparing flexible self-supporting carbon nanotube film on large scale |
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| JP2015143165A (en) * | 2014-01-31 | 2015-08-06 | 株式会社日本触媒 | Metal-containing carbon nanotube and carbon nanotube film |
| CN105081312A (en) * | 2015-08-17 | 2015-11-25 | 天津大学 | Method for preparing grapheme/copper composite material by loading solid carbon source on copper powder surface in impregnation manner |
| CN106622236A (en) * | 2017-01-03 | 2017-05-10 | 昆明理工大学 | Preparation method of nanometer cuprous oxide particle-loaded type carbon nanotube-graphene material for photocatalysis |
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| JP2015143165A (en) * | 2014-01-31 | 2015-08-06 | 株式会社日本触媒 | Metal-containing carbon nanotube and carbon nanotube film |
| CN105081312A (en) * | 2015-08-17 | 2015-11-25 | 天津大学 | Method for preparing grapheme/copper composite material by loading solid carbon source on copper powder surface in impregnation manner |
| CN106622236A (en) * | 2017-01-03 | 2017-05-10 | 昆明理工大学 | Preparation method of nanometer cuprous oxide particle-loaded type carbon nanotube-graphene material for photocatalysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110576187A (en) * | 2019-09-19 | 2019-12-17 | 天津大学 | preparation method for in-situ synthesis of three-dimensional graphene/one-dimensional carbon nanotube loaded copper nanoparticle material |
| CN110686589A (en) * | 2019-10-18 | 2020-01-14 | 南京理工大学 | High-sensitivity large-strain flexible strain sensor and preparation method thereof |
| CN115124030A (en) * | 2022-08-02 | 2022-09-30 | 武汉市碳翁科技有限公司 | Method for preparing flexible self-supporting carbon nanotube film on large scale |
| CN115124030B (en) * | 2022-08-02 | 2023-12-22 | 武汉市碳翁科技有限公司 | Method for preparing flexible self-supporting carbon nano tube film on large scale |
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