CN106710890A - Copper nanowire/graphene composite material and preparation method and application thereof - Google Patents
Copper nanowire/graphene composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 116
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 93
- 239000010949 copper Substances 0.000 title claims abstract description 93
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000002070 nanowire Substances 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005253 cladding Methods 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 claims 1
- 239000012065 filter cake Substances 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 13
- 238000003828 vacuum filtration Methods 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- -1 nitrogen doped Chemical compound 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of copper nanowire/graphene composite material. The preparation method comprises the following steps that (1) a copper nanowire and graphene are dispersed in deionized water so as to obtain mixed dispersion liquid, wherein the average sheet thickness of graphene is 0.5-5nm; and (2) the mixed dispersion liquid obtained in the step (1) is filtered and then a filter cake is dried so as to obtain the copper nanowire/graphene composite material. The preparation method is simple and efficient, convenient and rapid in experimental flow, simple in process, moderate in condition and high in universality. Compared with the method of reduction of graphene oxide in the prior art, reduction of the graphene oxide is not required so that the limitation of conductivity of the composite material by using binders can be avoided, the electric conductivity of the prepared copper nanowire/graphene composite material can be more than 5x103S/m, the composite material also has great oxidation resistance, and the electric conductivity can still be maintained for over 90% of the initial electric conductivity after the composite material is arranged in room temperature for 60 days.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, and in particular to copper nano-wire/graphene composite material and its
Preparation method and application.
Background technology
Using low-dimensional materials excellent electric conductivity can be obtained as the filler of conducing composite material.Metal nanometer line because
For its specific surface area greatly, the advantages of conducting electricity very well is widely used.Wherein the superior performance of gold, silver nano wire but its
Expensive price is the principal element for limiting its application, and copper nano-wire conducts electricity very well because of its cheap, rich reserves
Advantage has obtained increasing concern, while it also has highly important application prospect in association area.But copper nanometer
The oxidizable problem of line limits its application in some aspects.Graphene effectively can grind preservation antioxidation material as a kind of
Study carefully and be increasingly becoming focus.When Graphene is covered to metal surface, its can improve in environment oxidation material from graphenic surface to
The activation energy of lower metal interface diffusion, forms a barrier, so as to improve the antioxygenic property of metal.
CN105023629A discloses a kind of Graphene-copper nano-wire laminated film and preparation method thereof, the THIN COMPOSITE
Film includes：Substrate, copper nano-wire layer and graphene layer, the copper nano-wire layer are located on substrate or are partially submerged into substrate,
The graphene layer is located on copper nano-wire layer.Methods described includes：Using ethylene glycol and water mixed solution as turn
Move the copper nano-wire that medium will be transferred on substrate or be partially submerged into substrate by the Graphene of polymer Auxiliary support
On film；To drain after the transfer medium in reducing atmosphere and/or inert atmosphere and be heat-treated 30 in 100~200 DEG C~
60min is so that Graphene is fitted on copper nano-wire film；And it is placed in the organic solvent of the polymer that can dissolve Auxiliary support
In removing the polymer of graphenic surface.Graphene and copper nano-wire are laminating, structure in the product that the method is prepared
It is unstable, and preparation process is related to high-temperature step, energy consumption is big, and needs to remove polymer, and technique is cumbersome.
CN105583408A is by by copper nano-wire graphene oxide of the addition containing ascorbic acid, obtaining copper after reduction
Nano wire-redox graphene hydrogel, then there is three-dimensional porous pattern with suction filtration film forming, acquisition by washing, blending
Copper nano-wire/oxidation graphene film.Oxygen content in the compound that the method is obtained in redox graphene is difficult to
In low-level, electric conductivity is restricted for control.
The content of the invention
In view of problems of the prior art, an object of the present invention is to provide a kind of copper nano-wire/Graphene
The preparation method of composite, comprises the following steps：
(1) copper nano-wire and graphene dispersion are obtained into mixed dispersion liquid in deionized water；The average piece of the Graphene
Thickness degree is 0.5~10nm；
(2) by step (1) gained mixed dispersion liquid filtering, then by filtration cakes torrefaction, copper nano-wire/Graphene composite wood is obtained
Material.
For example, the average platelet thickness of the Graphene be 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1nm,
1.2nm、1.4nm、1.6nm、1.8nm、2nm、2.2nm、2.3nm、2.5nm、2.7nm、2.9nm、3nm、3.1nm、3.4nm、
3.5nm、3.8nm、4nm、4.1nm、4.2nm、4.3nm、4.4nm、4.5nm、4.6nm、4.7nm、4.8nm、4.9nm、5nm、
5.5nm, 6nm, 6.5nm, 7nm, 7.4nm, 8nm, 8.7nm, 9nm, 9.5nm or 10nm etc..
Preparation method of the invention is simple, efficient, realizes that flow is convenient and swift, process is simple, mild condition, universality
It is high.Both the method for being different from the prior art being reduced graphene oxide, it is not necessary to which graphene oxide is reduced, and is also kept away
The limitation to conductivity of composite material using binding agent, the copper nano-wire that the present invention is prepared/graphene composite material electricity are exempted from
Conductance is up to 5 × 103More than S/m, reaches as high as 2.88 × 104S/m, due to the synergy between copper nano-wire and Graphene, institute
Copper nano-wire (4.2 of the electrical conductivity of the copper nano-wire/graphene composite material for obtaining higher than the one-component used in the present invention
×103S/m) and grapheme material electrical conductivity (3.19 × 103S/m), while the composite has good inoxidizability,
Electrical conductivity remains to keep more than the 90% of initial conductivity after placing 60 days at room temperature.
The average length of copper nano-wire described in step (1) of the present invention is 5~50 μm, such as 5 μm, 6 μm, 7 μm, 8 μm, 9 μ
m、10μm、11μm、13μm、15μm、17μm、19μm、20μm、22μm、24μm、26μm、28μm、29μm、30μm、31μm、35μm、
40 μm, 45 μm or 50 μm etc., the average diameter of the copper nano-wire is 50~300nm, such as 50nm, 60nm, 70nm, 80nm,
90nm、95nm、100nm、105nm、110nm、120nm、130nm、140nm、145nm、148nm、150nm、160nm、180nm、
200nm, 210nm, 230nm, 250nm, 270nm, 290nm or 300nm etc., preferably 50~100nm.
In the present invention, when the average length of copper nano-wire is 5~50 μm, copper nano-wire/Graphene that the present invention is prepared
The electrical conductivity of composite is up to 5.3 × 103More than S/m, electrical conductivity remains to keep initial conductance after placing 60 days at room temperature
More than the 90.5% of rate.
During a diameter of 50~300nm of copper nano-wire, the conduction of copper nano-wire/graphene composite material is can further improve
Property and inoxidizability.
The average platelet thickness of Graphene is preferably 0.5~5nm described in step (1) of the present invention.The present invention is not to described
The slice plane size of Graphene is defined.
Average platelet thickness is dispersed good in the water Graphene of 0.5~5nm, can further improve copper nano-wire/
The electric conductivity of graphene composite material.
Graphene described in step (1) of the present invention is prepared by the non-oxide peeling of graphite.
Preferably, the Graphene is doped with nitrogen and/or element sulphur, such as nitrogen doped, doping element sulphur or
While nitrogen doped and element sulphur.
The less Graphene of lamellar spacing can be directly obtained by the non-oxide peeling of graphite, compared to general by aoxidizing stripping
The method that graphene oxide obtains Graphene through reduction again is obtained from graphite, this method eliminates the experimentation for restoring, and system
The standby Graphene oxygen content for obtaining is low, and good conductivity, the electrical conductivity of the copper nano-wire/graphene composite material finally prepared reaches
5.2×103More than S/m.
Graphene doped with nitrogen and/or sulphur further improves the electric conductivity of copper nano-wire/graphene composite material.
The mass ratio of copper nano-wire, Graphene and deionized water described in step (1) of the present invention is (1~10):(1~
10):(50~400), such as 1:1:50、1:10:50、1:1:400、10:1:50、1:2:50、1:5:50、1:2:100、1:5:
100、1:3:60、1:4:70、5:1:50、6:1:50、1:1:50、1:1:100、6:1:100、2:1:50、3:1:50、4:1:50、
5:1:100、2.5:1:100、1:3:80、1:6:200、1:8:250、8:1:350、10:1:400、1:10:400、1:9:380 or
1:5:80 etc., preferably (1~6):1:(50~100).
The mass ratio of copper nano-wire, Graphene and deionized water is (1~10):(1~10):When (50~400), final system
Ratio for two components in the copper nano-wire/graphene composite material for going out shows preferably electric conductivity and inoxidizability.
Wherein, the mass ratio of copper nano-wire, Graphene and deionized water is (1~6):1:When (50~100), further carry
The electric conductivity of high-copper nano wire/graphene composite.
Dispersion includes in step (1) of the present invention：Copper nano-wire and Graphene addition deionized water are carried out into ultrasonic disperse, i.e.,
Obtain the mixed dispersion liquid.
Step (2) filtering of the present invention includes vacuum filtration.
In view of the oxidative factors in technical process, composite is further improved using the filter type of vacuum filtration
Electric conductivity.
Preferably, the aperture of filter membrane used by the filtering be 0.1 μm~1 μm, such as 0.1 μm, 0.22 μm, 0.45 μm,
0.65 μm or 0.8 μm etc..
The second object of the present invention is to provide copper nano-wire/Graphene prepared by the preparation method as described in the first purpose
Composite, including copper nano-wire and cladding copper nano-wire Graphene, the cladding includes：The copper nano-wire is scattered in
The surface of the Graphene, is attached to the edge of the Graphene, and/or between being bound by the graphene layer.
Copper nano-wire/graphene composite material of the present invention is film.
The third object of the present invention is to provide copper nano-wire/graphene composite material as described in the second purpose in flexibility
Application in electronic device, sensor, ultracapacitor, water process.
Compared with prior art, the present invention at least has the advantages that：
Preparation method of the invention is simple, efficient, realizes that flow is convenient and swift, process is simple, mild condition, universality
It is high.Both the method for being different from the prior art being reduced graphene oxide, it is not necessary to which graphene oxide is reduced, and is also kept away
The limitation to conductivity of composite material using binding agent, the copper nano-wire that the present invention is prepared/graphene composite material electricity are exempted from
Conductance is up to 5 × 103More than S/m, reaches as high as 2.88 × 104S/m, due to the synergy between copper nano-wire and Graphene, institute
Copper nano-wire (4.2 of the electrical conductivity of the copper nano-wire/graphene composite material for obtaining higher than the one-component used in the present invention
×103S/m) and grapheme material electrical conductivity (3.19 × 103S/m), while the composite has good inoxidizability,
Electrical conductivity remains to keep more than the 90% of initial conductivity after placing 60 days at room temperature.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the gained laminated film of embodiment 1.
Fig. 2 is the big multiple scanning electron microscope (SEM) photograph of the gained laminated film of embodiment 1.
Fig. 3 is that the gained laminated film of embodiment 1 places X-ray diffraction (XRD) figure after 4 weeks in atmosphere.
Fig. 4 is that change of the sheet resistance of embodiment 1, comparative example 1 and the gained film of comparative example 2 in atmosphere with standing time is bent
Line.
Fig. 5 is the sheet resistance rate of change of embodiment 1, comparative example 1 and the gained film of comparative example 2 at room temperature with standing time
Change curve.
The present invention is described in more detail below.But following examples are only simple example of the invention, are not represented
Or the scope of the present invention is limited, protection scope of the present invention is defined by claims.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
For the present invention is better described, technical scheme is readily appreciated, it is as follows that the present invention enumerates embodiment.Ability
Field technique personnel it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to concrete restriction of the invention.
The test of electrical conductivity
Finally obtained composite is tested into its sheet resistance R with contactless resistance metersq, then use micrometer caliper
Its thickness d is measured, finally by formula σ=1/ (RsqD), the conductivityσ of film is obtained.
Embodiment 1
1) it is copper nano-wire and the 20mg Graphenes ultrasonic disperse of 50nm in 1.2mL deionized waters by 30mg average diameters
In, obtain mixed dispersion liquid；Wherein Graphene is prepared by the non-oxide peeling of graphite, and its average platelet thickness is 1nm, is mixed
The nitrogen of the miscellaneous element sulphur and 10wt% for having a 3wt%；
2) by step 1) gained mixed dispersion liquid carries out vacuum filtration, and the aperture of filter membrane used is 0.45 μm, then by filter cake
Dry, obtain laminated film, thickness is 40 μm, and its electrical conductivity is 2.88 × 104S/m。
The product of the gained of embodiment 1 is observed under ESEM, as depicted in figs. 1 and 2, it is seen that laminated film remains stone
Black alkene it is laminar structured, copper nano-wire is embedded on each graphene sheet layer, and is covered by graphene layer.So cause
Protective barrier together with having between copper nano-wire and the external world, hinders erosion of the moisture and oxygen in air to copper nano-wire,
So as to serve the effect of protection to copper nano-wire, the oxidation of copper nano-wire is further prevented.
After the gained film of embodiment 1 is placed into 4 weeks in atmosphere, XRD tests are carried out to it, as a result as shown in figure 3,2 θ=
Corresponding to 26.5 ° of position is carbon peak in Graphene.Three positions of main peak (2 θ=43.3 °, 50.4 °, 74.3 °) are respectively
Corresponding is that copper (111), (200), (220) crystal face, and the peak position without cupric oxide and cuprous oxide are present, obtained by illustrating
Copper nano-wire/graphene composite film there is good inoxidizability.
Comparative example 1
1) 50mg Graphenes ultrasonic disperse obtains mixed dispersion liquid in 1.2mL deionized waters；Wherein Graphene passes through stone
The non-oxide peeling of ink is prepared, and its average platelet thickness is 1nm, the nitrogen of element sulphur and 10wt% doped with 3wt%；
2) by step 1) gained mixed dispersion liquid carries out vacuum filtration, and the aperture of filter membrane used is 0.45 μm, then by filter cake
Dry, obtain graphene film, thickness is 36 μm.
Comparative example 2
1) 50mg average diameters for 50nm copper nano-wire ultrasonic disperse in 1.2mL deionized waters, obtain mixing dispersion
Liquid；
2) by step 1) gained mixed dispersion liquid carries out vacuum filtration, and the aperture of filter membrane used is 0.45 μm, then by filter cake
Dry, obtain copper nano-wire film, thickness is 50 μm.
Distinguish the sheet resistance of testing example 1, comparative example 1 and the gained film of comparative example 2, then test these three films respectively and exist
The sheet resistance after 1d, 2d, 3d, 5d, 8d, 27d, 32d, 36d, 60d is placed at room temperature, and Fig. 4 is embodiment 1, comparative example 1 and comparative example
The sheet resistance of 2 gained films is in atmosphere with the change curve of standing time, it is seen then that compared to same thickness copper nano-wire film and
Graphene film, small many of the sheet resistance of copper nano-wire/graphene composite film, and copper nano-wire film is placing first three day sheet resistance just
Rapid increase, its sheet resistance is up to 850 Ω/sq after placing 5 days.Fig. 5 is embodiment 1, comparative example 1 and the gained film of comparative example 2
Sheet resistance rate of change at room temperature with the change curve of standing time, from Fig. 4 and Fig. 5, the copper nano-wire of the gained of embodiment 1/
Sheet resistance is the 105% of initial sheet resistance after graphene composite film can be placed 60 days in atmosphere at room temperature, and electrical conductivity is first
The 95% of beginning electrical conductivity, further illustrates the copper nano-wire/graphene composite film of the gained of embodiment 1 with anti-oxidant well
Property.
Embodiment 2
With differing only in for embodiment 1：The average platelet thickness of Graphene is 5nm.Obtaining laminated film electrical conductivity is
1.5×104S/m, its electrical conductivity is the 90% of initial conductivity after placing 60 days in atmosphere at room temperature.
Embodiment 3
With differing only in for embodiment 1：The average platelet thickness of Graphene is 8nm.Obtaining laminated film electrical conductivity is
1.3×104S/m, its electrical conductivity is the 92% of initial conductivity after placing 60 days in atmosphere at room temperature.
Embodiment 4
With differing only in for embodiment 1：The average platelet thickness of Graphene is 10nm.Obtaining laminated film electrical conductivity is
1.1×104S/m, its electrical conductivity is the 91% of initial conductivity after placing 60 days in atmosphere at room temperature.
Embodiment 5
1) it is copper nano-wire and the 20mg Graphenes ultrasonic disperse of 100nm in 2mL deionized waters by 120mg average diameters
In, obtain mixed dispersion liquid；Wherein Graphene is prepared by the non-oxide peeling of graphite, and its average platelet thickness is 5nm, is mixed
The nitrogen of the miscellaneous element sulphur and 8wt% for having a 2wt%；
2) by step 1) gained mixed dispersion liquid carries out vacuum filtration, and the aperture of filter membrane used is 0.45 μm, then by filter cake
Dry, obtain copper nano-wire/graphene composite film, its electrical conductivity is 1.02 × 104S/m, and can at room temperature in sky
Electrical conductivity is the 96% of initial conductivity after being placed 60 days in gas.
Embodiment 6
1) it is copper nano-wire and the 50mg Graphenes ultrasonic disperse of 70nm in 2.5mL deionized waters by 50mg average diameters
In, obtain mixed dispersion liquid；Wherein Graphene is prepared by the non-oxide peeling of graphite, and its average platelet thickness is 3nm, is mixed
The nitrogen of the miscellaneous element sulphur and 9wt% for having a 3wt%；
2) by step 1) gained mixed dispersion liquid carries out vacuum filtration, and the aperture of filter membrane used is 0.45 μm, then by filter cake
Dry, obtain copper nano-wire/graphene composite film, its electrical conductivity is 1.43 × 104S/m, and can at room temperature in sky
The 95% of initial conductivity is kept after being placed 60 days in gas.
Embodiment 7
1) it is copper nano-wire and the 40mg Graphenes ultrasonic disperse of 300nm in 1mL deionized waters by 20mg average diameters,
Obtain mixed dispersion liquid；Wherein Graphene is prepared by the non-oxide peeling of graphite, and its average platelet thickness is 7nm, doping
There are the element sulphur of 2.8wt% and the nitrogen of 6.9wt%；
2) by step 1) gained mixed dispersion liquid carries out vacuum filtration, and the aperture of filter membrane used is 0.45 μm, then by filter cake
Dry, obtain copper nano-wire/graphene composite film, its electrical conductivity is 6.3 × 103S/m, and can at room temperature in air
It is middle place 60 days after electrical conductivity for initial conductivity 95%.
Embodiment 8
1) it is copper nano-wire and the 100mg Graphenes ultrasonic disperse of 5nm in 4mL deionized waters by 10mg average diameters,
Obtain mixed dispersion liquid；Wherein Graphene is prepared by the non-oxide peeling of graphite, and its average platelet thickness is 10nm；
2) by step 1) gained mixed dispersion liquid carries out vacuum filtration, and the aperture of filter membrane used is 0.1 μm, then filter cake is done
It is dry, copper nano-wire/graphene composite film is obtained, its electrical conductivity is 5.19 × 103S/m, and can at room temperature in air
It is middle place 60 days after electrical conductivity for initial conductivity 98%.
Comparative example 3
Copper nano-wire and 20mg Graphenes that 30mg average diameters same as Example 8 are 50nm are weighed, bonding is dissolved in
In the propanol solution of agent polyvinylpyrrolidone (PVP), 250 DEG C process 120min, the laminated film for obtaining under an argon atmosphere
Electrical conductivity is 4 × 103S/m, its electrical conductivity is the 75% of initial conductivity after placing 60 days in atmosphere at room temperature.
Comparative example 4
With differing only in for embodiment 8：The average platelet thickness of Graphene is 20nm.Obtaining laminated film electrical conductivity is
1×103S/m, its electrical conductivity is the 78% of initial conductivity after placing 60 days in atmosphere at room temperature.
Embodiment 9
1) it is copper nano-wire and the 50mg Graphenes ultrasonic disperse of 10nm in 2mL deionized waters by 10mg average diameters,
Obtain mixed dispersion liquid；Wherein Graphene is prepared by oxidation-reduction method, and its average platelet thickness is 9nm；
2) by step 1) gained mixed dispersion liquid carries out vacuum filtration, and the aperture of filter membrane used is 0.22 μm, then by filter cake
Dry, obtain copper nano-wire/graphene composite film, its electrical conductivity is 5.1 × 103S/m, and can at room temperature in air
It is middle place 60 days after electrical conductivity for initial conductivity 97%.
Embodiment 10
1) it is copper nano-wire and the 20mg Graphenes ultrasonic disperse of 200nm in 1.6mL deionized waters by 60mg average diameters
In, obtain mixed dispersion liquid；Wherein Graphene is prepared by the non-oxide peeling of graphite, and its average platelet thickness is 6nm；
2) by step 1) gained mixed dispersion liquid carries out vacuum filtration, and the aperture of filter membrane used is 0.8 μm, then filter cake is done
It is dry, copper nano-wire/graphene composite film is obtained, its electrical conductivity is 2.3 × 104S/m, and can at room temperature in atmosphere
Electrical conductivity is the 90% of initial conductivity after placing 60 days.
Applicant states that the present invention illustrates detailed construction feature of the invention by above-described embodiment, but the present invention is simultaneously
Above-mentioned detailed construction feature is not limited to, that is, does not mean that the present invention has to rely on above-mentioned detailed construction feature and could implement.Institute
Category those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of part selected by the present invention
And increase, the selection of concrete mode of accessory etc., within the scope of all falling within protection scope of the present invention and disclosing.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of copper nano-wire/graphene composite material, it is characterised in that comprise the following steps：
(1) copper nano-wire and graphene dispersion are obtained into mixed dispersion liquid in deionized water；The average platelet of the Graphene is thick
It is 0.5~10nm to spend；
(2) by step (1) gained mixed dispersion liquid filtering, then by filtration cakes torrefaction, copper nano-wire/graphene composite material is obtained.
2. preparation method as claimed in claim 1, it is characterised in that the average length of copper nano-wire described in step (1) is 5
~50 μm, the average diameter of the copper nano-wire is 50~300nm, preferably 50~100nm.
3. preparation method as claimed in claim 1 or 2, it is characterised in that the average platelet of Graphene described in step (1) is thick
It is 0.5~5nm to spend.
4. the preparation method as described in any one of claims 1 to 3, it is characterised in that Graphene described in step (1) passes through stone
The non-oxide peeling of ink is prepared；
Preferably, the Graphene is doped with nitrogen and/or element sulphur.
5. the preparation method as described in any one of Claims 1 to 4, it is characterised in that copper nano-wire, stone described in step (1)
Black alkene is (1~10) with the mass ratio of deionized water:(1~10):(50~400), preferably (1~6):1:(50~100).
6. the preparation method as described in any one of Claims 1 to 5, it is characterised in that disperse to include described in step (1)：Will
Copper nano-wire and Graphene addition deionized water carry out ultrasonic disperse, that is, obtain the mixed dispersion liquid.
7. the preparation method as described in any one of claim 1~6, it is characterised in that step (2) filtering includes that vacuum is taken out
Filter；
Preferably, the aperture of filter membrane used by the filtering is 0.1 μm~1 μm.
8. copper nano-wire/graphene composite material that prepared by the preparation method as described in any one of claim 1~7, including copper
The Graphene of nano wire and cladding copper nano-wire, the cladding includes：The copper nano-wire is scattered in the table of the Graphene
Face, is attached to the edge of the Graphene, and/or between being bound by the graphene layer.
9. copper nano-wire/graphene composite material as claimed in claim 8, it is characterised in that the copper nano-wire/Graphene
Composite is film.
10. copper nano-wire/graphene composite material as claimed in claim 8 or 9 is in flexible electronic device, sensor, super
Application in capacitor, water process.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107324312A (en) * | 2017-06-29 | 2017-11-07 | 南京开钰安全科技有限责任公司 | Bridging materials and its bridging method for improving commercial graphites alkene film layer electric conductivity |
| CN114989789A (en) * | 2022-03-09 | 2022-09-02 | 北京创新爱尚家科技股份有限公司 | Three-dimensional graphene-based composite heat conduction material and preparation method thereof |
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| CN102821554A (en) * | 2012-08-27 | 2012-12-12 | 中国科学院理化技术研究所 | Flexible circuit suction filtration forming method |
| CN103426494A (en) * | 2012-05-15 | 2013-12-04 | 中国科学院上海有机化学研究所 | Conducting film combined by graphene and metal nanowires, preparing method thereof and application for preparing transparent conducting film |
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| CN103426494A (en) * | 2012-05-15 | 2013-12-04 | 中国科学院上海有机化学研究所 | Conducting film combined by graphene and metal nanowires, preparing method thereof and application for preparing transparent conducting film |
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| CN107324312A (en) * | 2017-06-29 | 2017-11-07 | 南京开钰安全科技有限责任公司 | Bridging materials and its bridging method for improving commercial graphites alkene film layer electric conductivity |
| CN107324312B (en) * | 2017-06-29 | 2019-11-15 | 南京开钰安全科技有限责任公司 | For improving the bridging materials and its bridging method of commercial graphites alkene film layer electric conductivity |
| CN114989789A (en) * | 2022-03-09 | 2022-09-02 | 北京创新爱尚家科技股份有限公司 | Three-dimensional graphene-based composite heat conduction material and preparation method thereof |
| CN114989789B (en) * | 2022-03-09 | 2023-07-11 | 北京创新爱尚家科技股份有限公司 | Three-dimensional graphene-based composite heat conduction material and preparation method thereof |
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