CN107887070B - A kind of cable based on patterned graphene nanoribbons and preparation method thereof - Google Patents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B9/00—Power cables
- H01B9/006—Constructional features relating to the conductors
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B9/00—Power cables
- H01B9/02—Power cables with screens or conductive layers, e.g. for avoiding large potential gradients
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Abstract
本发明提供了一种基于图案化石墨烯纳米带的电缆及其制备方法，该电缆自内向外依次设有导电芯、绝缘层、屏蔽层、阻水层和护套，导电芯由多层石墨烯纳米带所制成，多层石墨烯纳米带为经过图案化处理过的石墨烯纳米带，所述屏蔽层、阻水层和护套三者的厚度自内向外依次递增，所述绝缘层的厚度大于屏蔽层与阻水层两者的厚度之和；本发明利用氢原子钝化的图像化石墨烯纳米带，用于导线中的导电芯承担电流的传输，能够有效提高导电芯中载流子的迁移率，大大减小导线的电阻率，从而降低功耗。
The invention provides a cable based on patterned graphene nanoribbons and a preparation method thereof. The cable is provided with a conductive core, an insulating layer, a shielding layer, a water blocking layer and a sheath in sequence from the inside to the outside, and the conductive core is made of multilayer graphite. Made of graphene nanoribbons, the multilayer graphene nanoribbons are patterned graphene nanoribbons. The thickness is greater than the sum of the thicknesses of the shielding layer and the water blocking layer; the present invention utilizes the imaged graphene nanoribbons passivated by hydrogen atoms, which is used for the conductive core in the wire to undertake current transmission, and can effectively improve the load in the conductive core. The mobility of the carrier greatly reduces the resistivity of the wire, thereby reducing power consumption.
Description
Technical Field
The invention relates to the technical field of cables prepared from new materials, in particular to a patterned graphene nanoribbon-based cable and a preparation method thereof.
Background
Cables are generally rope-like cables made by stranding several or groups of conductors (at least two in each group), each group being insulated from each other and often twisted around a center, the entire outer surface being coated with a highly insulating coating. The device is erected in the air or installed underground or underwater for telecommunication or power transmission. In 1832, the wire line of the refuge officer schooling is buried underground, and the six wires are insulated by rubber and then placed in a glass tube, which is the earliest underground cable in the world. The cable may be classified into a power cable, a communication cable, a control cable, and the like according to its use. Compared with an overhead line, the cable has the advantages of small insulating distance between lines, small occupied space, no occupation of space above the ground due to underground laying, no influence of pollution of the surrounding environment, high power transmission reliability, and small interference on personal safety and the surrounding environment. But the cost is high, the construction and the maintenance are troublesome, and the manufacture is complicated. Therefore, the cable is mostly applied to dense areas of population and power grids and places with heavy traffic; when the cable is laid in the river, the river and the seabed, the use of large-span overhead lines can be avoided. Cables may also be used where it is desirable to avoid interference of overhead lines with communications and where aesthetic considerations or exposure to objects are desired.
The power cable product is mainly characterized in that: and (3) extruding (winding) an insulating layer outside the conductor, such as an overhead insulated cable, or twisting a plurality of cores (corresponding to a phase line, a zero line and a ground wire of an electric power system), such as an overhead insulated cable with more than two cores, or adding a sheath layer, such as a plastic/rubber sleeve wire cable. The main process technologies include drawing, twisting, insulation extrusion (lapping), cabling, armoring, sheath extrusion and the like, and different process combinations of various products have certain differences. The product is mainly used for strong electric energy transmission in power generation, distribution, transmission, transformation and power supply lines, and the passing current is large (dozens of amperes to thousands of amperes) and the voltage is high (220V to 500kV or more). Since the loss of energy during transmission becomes a major performance point for use in power transmission, efforts are underway to find more energy efficient power cables.
2D materials with atomic layer thickness are widely studied due to their superior properties different from bulk materials, such as BN, MoS2And so on. Since 2004, the emergence of graphene has made it possible to find many fields. Graphene (Graphene) is a two-dimensional crystal consisting of carbon atoms only one layer atomic thick exfoliated from a graphitic material. Graphene is the thinnest material and the toughest material, and the breaking strength is 200 times higher than that of the best steel. Meanwhile, the elastic fabric has good elasticity, and the stretching amplitude can reach 20% of the size of the elastic fabric. It is currently the thinnest, highest strength material of nature and has ultra-high carrier mobility and low resistivity. Graphene, which is the thinnest, the greatest strength and the strongest novel nanomaterial of electric and thermal conductivity found at present, is called "black gold", which is the king of new materials, and scientists even predict that graphene will "thoroughly change the material in the 21 st century".
Disclosure of Invention
Aiming at the problems, the invention aims to provide a patterned graphene nanoribbon-based cable which is high in speed, low in resistance, high in wire transmission efficiency, low in loss and good in flexibility and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the cable based on the patterned graphene nanoribbon is sequentially provided with a conductive core, an insulating layer, a shielding layer, a water-blocking layer and a sheath from inside to outside, wherein the conductive core is made of multiple graphene nanoribbons, the multiple graphene nanoribbons are subjected to patterning treatment, the thicknesses of the shielding layer, the water-blocking layer and the sheath are sequentially increased from inside to outside, and the thickness of the insulating layer is greater than the sum of the thicknesses of the shielding layer and the water-blocking layer.
The patterned graphene nanoribbon is formed by patterning a graphene structure by adopting a nanowire oxygen plasma etching and probe stripping method. Compared with the ultrasonic chemical method and the carbon nanotube cutting method, the method has the advantages that the width of the nano-belt is easier to control, the width of the nano-belt can be narrower, and the patterned nano-belt is more advantageous and easier to control.
The graphene nanoribbon is subjected to patterning and hydrogen passivation treatment. The hydrogen passivation enables the dangling bonds at the edge of the graphene nanoribbon to be saturated, so that the edge effect can be eliminated, and the property of the graphene is more stable. And it can be seen from fig. 1, 4, 5, 6, 7, and 8 that the energy band structure of the patterned graphene nanoribbon is greatly changed, and the dirac point required by the present invention appears.
The insulating layer is prepared from polytetrafluoroethylene, the shielding layer is prepared from metal copper, the water-blocking layer is prepared from polyethylene, and the sheath is prepared from polyvinyl chloride.
The invention provides a preparation method of a cable based on a patterned graphene nanoribbon, which comprises the following steps:
1) preparing the conductive core: taking natural graphite as a raw material, carrying out oxidation treatment on the natural graphite to generate graphene oxide, and stirring, centrifuging and oscillating the graphene oxide to obtain the graphene oxide; in 3Reducing graphene oxide on a 00nm silicon wafer; carrying out nanowire etching on graphene on a Si substrate to obtain a graphene nanoribbon with corresponding width and patterning, and finally introducing H at high temperature2And passivating the graphene nanoribbon by H atoms to obtain the conductive core made of the graphene nanoribbon.
2) Preparing an insulating layer: preparing an insulating layer with a circular cross section by using polytetrafluoroethylene as a raw material; the material has good heat resistance and low temperature resistance, and has good moisture resistance, wear resistance and corrosion resistance.
3) Preparing a shielding layer: the shielding layer with the circular cross section is prepared by taking metal copper as a raw material and adopting a structure of additionally weaving a copper wire belt on a copper coating.
4) Preparation of a water-resistant layer: preparing a water-resistant layer by using polyethylene as a raw material; the material has water tightness hundreds times higher than that of polyvinyl chloride and good water-blocking effect.
5) Preparing a sheath: preparing a sheath by taking polyvinyl chloride as a raw material; the material has the advantages of good chemical stability, good weather resistance, excellent acid and alkali resistance, no conductivity, good flame retardance and no fire-fighting concerns.
6) And (3) sequentially coating and assembling the conductive core, the insulating layer, the shielding layer, the water-resistant layer and the sheath prepared in the steps 1) to 5) to obtain the patterned graphene nanoribbon-based cable.
In the preparation process of the conductive core in the step 1), the detailed preparation method of the hydrogen passivation imaging graphene nanoribbon comprises the following steps:
A) loading natural graphite into NaNO3Adding concentrated sulfuric acid and KMnO into the solution in ice bath4(ii) a Heating to 35 ℃ for 6 hours, adding deionized water, heating the solution to 95-100 ℃, and keeping for 15 minutes; adding deionized water and hydrogen peroxide into the solution; filtering, taking a filtrate, cleaning the filtrate with a large amount of ultrapure water, and then placing the filtrate in deionized water for ultrasonic treatment to obtain a graphene oxide solution; carrying out centrifugal treatment on the graphene oxide solution to obtain graphene oxide;
B) fishing out the graphene oxide film by using the Si substrate, and drying the graphene oxide film on a heating table at 50-60 ℃ to remove water between the graphene oxide film and the Si substrate;
C) placing the graphene oxide obtained in the step B) into a low-temperature area of a high-temperature quartz tube, and filling argon; heating to 400 ℃, continuously introducing argon, maintaining for 5 minutes, pulling the graphene oxide back to a low-temperature region, and rapidly cooling to room temperature; obtaining reduced multilayer graphene;
D) after obtaining multilayer graphene, taking the silicon dioxide nanowire with the required patterning width as an etching mask, placing the silicon dioxide nanowire above the surface of the graphene, and performing oxygen plasma etching on the silicon dioxide nanowire to obtain a patterned graphene nanoribbon;
E) putting the graphene nanoribbon obtained in the step D) into a low-temperature area of a quartz tube, and introducing H2And obtaining a passivated graphene nanoribbon, and cooling and then taking down the graphene nanoribbon.
The invention has the advantages that: the graphene nanoribbon utilized in the invention is a derivative of graphene material, and the superior performance of the graphene nanoribbon can be adjusted by patterning and passivating graphene.
For the single-layer graphene nanoribbon, the product of the invention is patterned in the specific graphene nanoribbon: (as shown in FIG. 1, where the main band has a width of 2.5565 nm, the edge sub-band has a width of 0.8241nm, and the edge is passivated with H atoms), the band exhibits the characteristics of a Dirac point. The effective mass of the carriers is theoretically zero, and the mobility of the carriers is theoretically infinite. The specific patterned graphene nanoribbon structure has high carrier mobility and low resistivity.
An ultra high speed cable constructed using a patterned graphene nanoribbon stack structure is provided, which produces a cable with less energy loss, better ductility and strength than cables made with conventional conductive cores.
According to the invention, the multilayer graphene nanoribbon is used as the conductive core of the conductive cable, so that the resistivity can be reduced, and the power consumption is reduced; the selected two-dimensional material graphene can be used for making the conductive cable very light and thin, and has higher ductility and strength; the patterned graphene nanoribbon is selected to form a Dirac point in an energy band, so that current carriers in the conductive core are greatly improved.
Drawings
Fig. 1 is a schematic diagram of a hydrogen passivated patterned graphene nanoribbon;
fig. 2 is a schematic structural diagram of a patterned graphene nanoribbon-based cable provided by the present invention;
fig. 3 is a schematic cross-sectional structure diagram of a patterned graphene nanoribbon-based cable provided by the present invention;
fig. 4 is a diagram of electron spin-up energy band structure of a hydrogen passivated patterned graphene nanoribbon;
fig. 5 is an electron spin-down energy band structure diagram of a hydrogen passivated patterned graphene nanoribbon.
Fig. 6 is a schematic illustration of hydrogen passivated unpatterned graphene nanoribbons;
fig. 7 is a diagram of electron spin-up structures of hydrogen passivated unpatterned graphene nanoribbons.
Fig. 8 is an electron spin up configuration diagram of a hydrogen passivated unpatterned graphene nanoribbon.
The gray spheres in fig. 1 and 6 represent that the white spheres at the edge of the C atom are hydrogen atoms, G in fig. 4, 5, 7 and 8 represents a highly symmetric gamma point in an energy band, Y represents a highly symmetric path from the gamma point of the first fabry-perot source region to the boundary of the first fabry-perot source region along the Y direction, and E is a unit of energy band symbol and has a unit of eV.
Detailed Description
The invention is described in further detail below with reference to the following description of the drawings and the detailed description.
Example 1: as shown in fig. 2 and 3, the patterned graphene nanoribbon-based cable is sequentially provided with a conductive core 1, an insulating layer 2, a shielding layer 3, a water blocking layer 4 and a sheath 5 from inside to outside, wherein the conductive core 1 is made of a plurality of graphene nanoribbons, the plurality of graphene nanoribbons are patterned graphene nanoribbons, the thicknesses of the shielding layer 3, the water blocking layer 4 and the sheath 5 are sequentially increased from inside to outside, and the thickness of the insulating layer 2 is greater than the sum of the thicknesses of the shielding layer 3 and the water blocking layer 4.
Example 2: as shown in fig. 2 and 3, a preparation method of a patterned graphene nanoribbon-based cable comprises the following steps:
1) preparation of the conductive core 1: taking natural graphite as a raw material, carrying out oxidation treatment on the natural graphite to generate graphene oxide, and stirring, centrifuging and oscillating the graphene oxide to obtain the graphene oxide; reducing graphene oxide on a 300nm silicon wafer; carrying out nanowire etching on graphene on a Si substrate to obtain a graphene nanoribbon with corresponding width and patterning, and finally introducing H at high temperature2And passivating the graphene nanoribbon by H atoms to obtain the conductive core made of the graphene nanoribbon.
2) Preparation of the insulating layer 2: preparing an insulating layer with a circular cross section by using polytetrafluoroethylene as a raw material; the material has good heat resistance and low temperature resistance, and has good moisture resistance, wear resistance and corrosion resistance.
3) Preparation of the shielding layer 3: the shielding layer with the circular cross section is prepared by taking metal copper as a raw material and adopting a structure of additionally weaving a copper wire belt on a copper coating.
4) Preparation of the water-resistant layer 4: preparing a water-resistant layer by using polyethylene as a raw material; the material has water tightness hundreds times higher than that of polyvinyl chloride and good water-blocking effect.
5) Preparation of the sheath 5: preparing a sheath by taking polyvinyl chloride as a raw material; the material has the advantages of good chemical stability, good weather resistance, excellent acid and alkali resistance, no conductivity, good flame retardance and no fire-fighting concerns.
6) And (2) sequentially coating and assembling the conductive core 1, the insulating layer 2, the shielding layer 3, the water-resistant layer 4 and the sheath 5 which are prepared in the steps 1) to 5) to obtain the patterned graphene nanoribbon-based cable.
Example 3: in the preparation process of the conductive core, the detailed preparation method of the hydrogen passivation imaging graphene nanoribbon comprises the following steps:
A) loading natural graphite into NaNO3Adding concentrated sulfuric acid and KMnO into the solution in ice bath4(ii) a Heating to 35 deg.C for 6 hours, adding deionized water and dissolvingHeating to 95-100 deg.c for 15 min; adding deionized water and hydrogen peroxide into the solution; filtering, taking a filtrate, cleaning the filtrate with a large amount of ultrapure water, and then placing the filtrate in deionized water for ultrasonic treatment to obtain a graphene oxide solution; carrying out centrifugal treatment on the graphene oxide solution to obtain graphene oxide;
B) fishing out the graphene oxide film by using the Si substrate, and drying the graphene oxide film on a heating table at 50-60 ℃ to remove water between the graphene oxide film and the Si substrate;
C) placing the graphene oxide obtained in the step B) into a low-temperature area of a high-temperature quartz tube, and filling argon; heating to 400 ℃, continuously introducing argon, maintaining for 5 minutes, pulling the graphene oxide back to a low-temperature region, and rapidly cooling to room temperature; obtaining reduced multilayer graphene;
D) after obtaining multilayer graphene, taking the silicon dioxide nanowire with the required patterning width as an etching mask, placing the silicon dioxide nanowire above the surface of the graphene, and performing oxygen plasma etching on the silicon dioxide nanowire to obtain a patterned graphene nanoribbon;
E) putting the graphene nanoribbon obtained in the step D) into a low-temperature area of a quartz tube, and introducing H2And obtaining a passivated graphene nanoribbon, and cooling and then taking down the graphene nanoribbon.
The performance of the hydrogen passivated imaged graphene nanoribbon obtained by the above method is shown in fig. 1, 4 and 5, and it can be known that there are three:
the graphene nanoribbon patterned by hydrogen passivation has a greatly changed energy band structure, and particularly generates a Dirac point at a Fermi level. The presence of dirac points allows the low-energy-banded fermions (here electrons) in the material to satisfy the two-dimensional dirac equation without mass. The electrons described by the energy band have zero mass in a static state and act like photons, so that the surface carrier of the hydrogen passivated graphene nanoribbon has high mobility which is close to the speed of light. This determines that hydrogen passivated graphene is much better conducting than conventional copper core wires. The measured electric conductivity is 10^ (-6) omega/m magnitude, which is much smaller than that of the existing copper core and aluminum alloy core cables, so that the voltage drop and the current loss of the same distance are greatly reduced, and the transmission speed is much higher.
Example 4: compared with the common copper and aluminum alloy conductive core, the graphene obtained by using the hydrogen passivated patterned graphene as the conductive core is finer and lighter in manufacture, and has lower power consumption due to extremely low resistivity under the same load current; and the transmission is greatly improved by about 5 times of that of copper; the flexibility and strength of the graphene are 20 times of those of the best steel, so that the hydrogen passivated graphene nanoribbon conductive core has good ductility.
Example 5: comparing the hydrogen passivated patterned graphene nanoribbons in fig. 1, 4 and 5 with the hydrogen passivated unpatterned graphene nanoribbons in fig. 6, 7 and 8, it can be seen that:
as can be seen from fig. 1 and 6, the patterned graphene nanoribbon has jagged edges, which enable the edges to have zigzag and arm-chair characteristics at the same time, while the unpatterned graphene nanoribbon has zigzag characteristics only, which enables the electronic characteristics of the patterned graphene nanoribbon to be greatly different.
As can be seen from the comparison of the band diagrams of fig. 4 and 5 and the band diagrams of 7 and 8, the patterned graphene nanoribbon is a semiconductor characteristic with a certain band gap, and the non-patterned graphene nanoribbon is a conductor characteristic with a zero band gap, and the non-patterned graphene nanoribbon forms a dirac point at the fermi level, so that the carrier transmission rate is greatly improved.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and any combination or equivalent changes made on the basis of the above-mentioned embodiments are also within the scope of the present invention.
Claims (4)
1. The patterned graphene nanoribbon-based cable is characterized in that a conductive core, an insulating layer, a shielding layer, a water-blocking layer and a sheath are sequentially arranged from inside to outside, the conductive core is made of a plurality of graphene nanoribbons, the graphene nanoribbons are subjected to patterning treatment, the thicknesses of the shielding layer, the water-blocking layer and the sheath are sequentially increased from inside to outside, and the thickness of the insulating layer is greater than the sum of the thicknesses of the shielding layer and the water-blocking layer;
the graphene nanoribbon is subjected to patterning and hydrogen passivation treatment; the step of patterning the graphene nanoribbon refers to patterning the graphene structure by adopting a nanowire oxygen plasma etching and probe stripping method.
2. The patterned graphene nanoribbon-based cable according to claim 1, wherein the insulating layer is made of polytetrafluoroethylene, the shielding layer is made of metallic copper, the water blocking layer is made of polyethylene, and the sheath is made of polyvinyl chloride.
3. A method for preparing the patterned graphene nanoribbon-based cable according to claim 1 or 2, wherein the method comprises the following steps:
1) preparing the conductive core: taking natural graphite as a raw material, carrying out oxidation treatment on the natural graphite to generate graphene oxide, and stirring, oscillating and centrifuging to obtain the graphene oxide; reducing graphene oxide on a 300nm Si substrate; carrying out nanowire etching on graphene on a Si substrate to obtain a graphene nanoribbon with corresponding width and patterning, and finally introducing H at a temperature of less than 400 DEG C2Passivating the graphene nanoribbon by H atoms to obtain a conductive core made of the graphene nanoribbon;
2) preparing an insulating layer: preparing an insulating layer with a circular cross section by using polytetrafluoroethylene as a raw material;
3) preparing a shielding layer: preparing a shielding layer with a circular cross section by taking metal copper as a raw material and adopting a structure of additionally weaving a copper wire belt on a copper coating;
4) preparation of a water-resistant layer: preparing a water-resistant layer by using polyethylene as a raw material;
5) preparing a sheath: preparing a sheath by taking polyvinyl chloride as a raw material;
6) sequentially coating and assembling the conductive core, the insulating layer, the shielding layer, the water-blocking layer and the sheath prepared in the steps 1) -5) to obtain the patterned graphene nanoribbon-based cable.
4. The method for preparing the patterned graphene nanoribbon-based cable according to claim 3, wherein in the step 1) of preparing the conductive core, the method comprises the following steps:
A) loading natural graphite into NaNO3Adding concentrated sulfuric acid and KMnO into the solution in ice bath4(ii) a Heating to 35 ℃ for 6 hours, adding deionized water, heating the solution to 95-100 ℃, and keeping for 15 minutes; adding deionized water and hydrogen peroxide into the solution; filtering, taking a filtrate, cleaning the filtrate with a large amount of ultrapure water, and then placing the filtrate in deionized water for ultrasonic treatment to obtain a graphene oxide solution; carrying out centrifugal treatment on the graphene oxide solution to obtain graphene oxide;
B) fishing out the graphene oxide film by using the Si substrate, and drying the graphene oxide film on a heating table at 50-60 ℃ to remove water between the graphene oxide film and the Si substrate;
C) placing the graphene oxide obtained in the step B) into a low-temperature area of a quartz tube, wherein the temperature is less than 400 ℃, and introducing argon; heating to 400 ℃ in a high-temperature area, continuously introducing argon, maintaining for 5 minutes, drawing the graphene oxide back to a low-temperature area, and rapidly cooling to room temperature; obtaining reduced multilayer graphene;
D) after obtaining multilayer graphene, taking the silicon dioxide nanowire with the required patterning width as an etching mask, placing the silicon dioxide nanowire above the surface of the graphene, and performing oxygen plasma etching on the silicon dioxide nanowire to obtain a patterned graphene nanoribbon;
E) putting the graphene nanoribbon obtained in the step D) into a low-temperature area of a quartz tube, wherein the temperature is less than 400 ℃, and introducing H2And obtaining a passivated graphene nanoribbon, and cooling and then taking down the graphene nanoribbon.
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