CN113388181A - High-voltage-resistant heating material, preparation method thereof and self-heating deicing cable - Google Patents
High-voltage-resistant heating material, preparation method thereof and self-heating deicing cable Download PDFInfo
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
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Abstract
本发明提供了一种能够耐高压的发热材料及其制备方法和自发热除防冰电缆，所述发热材料由1～10％wt的表面改性石墨烯和余量的硅烷交联聚乙烯构成，发热材料的厚度为0.1～5mm，发热材料的耐压范围为1～8KV，发热材料的发热升温范围为4～80℃，发热材料的功率密度为1.0×10‑4～1.0×10‑1W/m m2。所述制备方法包括将表面改性的石墨烯和硅烷交联聚乙烯按质量百分数为1～10％wt混合均匀，在密炼机中以60～80rpm/min、180～210℃熔融共混5～60min后制得。本发明提供了一种兼具发热和耐高压的特性的发热材料以及防冰除冰电缆，在高电压电输送防冰、除冰领域等具有广阔的应用前景。The present invention provides a heating material capable of withstanding high pressure, a preparation method thereof, and a self-heating deicing and anti-icing cable. , the thickness of the heating material is 0.1～5mm, the withstand voltage range of the heating material is 1～8KV, the heating temperature range of the heating material is 4～80℃, and the power density of the heating material is 1.0×10 ‑4 ～1.0×10 ‑1 W/mm 2 . The preparation method comprises the steps of uniformly mixing the surface-modified graphene and the silane cross-linked polyethylene according to the mass percentage of 1-10% wt, and melt-blending at 60-80 rpm/min and 180-210 DEG C in an internal mixer for 5 Made after ~60min. The invention provides a heating material and an anti-icing and deicing cable with both heating and high-voltage resistance properties, which have broad application prospects in the fields of high-voltage electrical transmission anti-icing and deicing.
Description
Technical Field
The invention belongs to the technical field of high-voltage power transmission, and particularly relates to a high-voltage-resistant heating material, a preparation method thereof and a self-heating deicing cable.
Background
Electric power transportation is a system with important global energy, and particularly, a high-voltage overhead power transmission line is a lifeline of electric power systems of various countries. However, due to the existence of extreme ice storm climate, the icing of the line is a great challenge for the high-voltage overhead power transmission line, and the line falling, the ice-removing vibration of the line, the line galloping, the flashover and the like cause great economic loss to the production and the life of countries in the world. Therefore, the method has important significance for solving the line icing problem in the field of high-voltage power transmission, and related technologies are continuously proposed.
The application number is CN201610867150.1, the name is a self-melting ice conductor and ice melting equipment, and discloses a self-melting ice conductor adopting the structure of the conductor as a heating power supply conductor. However, CN201610867150.1 only shows the structure of the cable, and the heat-generating material used therein is not described. At present, although the research on graphene heating materials, including graphene composite materials, graphene films and the like, for defogging, antifogging, anti-icing and deicing is more, there are also a lot of graphene heating materials on the market, such as a graphene multifunctional heating table, a graphene intelligent physiotherapy pestle needle, a graphene transparent heating film, a graphene automobile heating seat and the like. However, most of these materials can only operate at low voltage and are not resistant to high voltage (1KV or more), and the heat generating material used as a heat generating material of a high-voltage transmission cable needs to have both heat generating and high voltage resistance. In addition, certain mechanical properties, weather resistance and the like are required.
Disclosure of Invention
The present invention aims to address at least one of the above-mentioned deficiencies of the prior art. For example, an object of the present invention is to provide a heat-generating material having both heat generation and high-pressure resistance. Another object of the present invention is to provide a method for preparing a heat-generating material capable of withstanding high pressure.
In order to achieve the above object, an aspect of the present invention provides a heat generating material capable of withstanding high pressure. The heating material is composed of 1-10 wt% of surface modified graphene and the balance of silane crosslinked polyethylene, the thickness of the heating material is 0.1-5 mm, the withstand voltage range of the heating material is 1-8 KV, the heating temperature range of the heating material is 4-80 ℃, and the power density of the heating material is 1.0 x 10-4～1.0×10-1W/mm2。
In one exemplary embodiment of an aspect of the present invention, the heat generating material may be composed of 3 to 5% wt of surface-modified graphene and the balance silane crosslinked polyethylene.
In one exemplary embodiment of an aspect of the present invention, the surface-modified graphene may be obtained by:
mixing graphene with ethanol with the volume fraction of 60-95% according to the mass-volume ratio of 1: mixing 50-100 g/ml, adding a long-chain alkane coupling agent solution accounting for 5-10 wt% of graphene, stirring at 20-60 ℃ for 0.5-2 h, and drying to obtain the surface modified graphene.
In an exemplary embodiment of an aspect of the present invention, the heat-generating material has a tensile strength of 10 to 20MPa and a room-temperature impact property of 8.8KJ/m2Above, low temperature impact property of 3.7KJ/m2The above.
In one exemplary embodiment of an aspect of the present invention, as the mass fraction of the surface-modified graphene in the heat-generating material increases, the microstructure of the heat-generating material transitions from the state that the distance between the surface-modified graphene sheet layers is greater than 10 μm, no mutual contact is made, no conductive network is formed, to the state that the distance between the surface-modified graphene sheet layers is 10nm to 10 μm, partial mutual contact is made, a discontinuous conductive network is formed, and finally, to the state that the graphene sheet layers are closely contacted with each other and stacked to form a continuous conductive network.
In one exemplary embodiment of an aspect of the present invention, the heat generating material may have a conductivity of 1 × 108～1×1013Ω·cm。
The invention also provides a preparation method of the high-pressure-resistant heating material. The method comprises the following steps: mixing the surface modified graphene and polyethylene according to the mass percent of 1-10 wt%, melting and blending at 180-210 ℃, and performing silane crosslinking to convert the polyethylene into silane crosslinked polyethylene, thereby preparing the heating material with the thickness of 0.1-5 mm.
In an exemplary embodiment of another aspect of the present invention, the melt blending may be performed in an internal mixer, the rotation speed of the internal mixer may be 30 to 100rpm/min, and the stirring time may be 5 to 60 min.
In one exemplary embodiment of another aspect of the present invention, the performing silane crosslinking to convert polyethylene in the heat generating material into silane crosslinked polyethylene may include the steps of: and (3) steaming the heating material in purified water at 100 ℃ for 5-10 hours, and drying at 50-80 ℃ for 8-12 hours.
Still another aspect of the present invention provides a self-heating deicing and anti-icing cable including a heat-generating material capable of withstanding high voltage as described above formed between an inner conductor and an outer conductor.
Compared with the prior art, the beneficial effects of the invention can comprise at least one of the following:
(1) the heating material has heating and high-pressure resistance, and can be applied to the fields of deicing and anti-icing of high-voltage cables;
(2) the self-heating deicing and anti-icing cable solves the problems of tower falling, line deicing vibration, line galloping, flashover and the like of a high-voltage overhead power transmission line caused by extreme snowstorm weather;
(3) the deicing and anti-icing cable is used as a high-voltage transmission line, and a heating wire is not required to be additionally arranged, so that the weight of the high-voltage transmission line can be reduced, and the cost is reduced.
Detailed Description
Hereinafter, the heat-generating material capable of withstanding high pressure, the method of preparing the same, and the self-heat-generating deicing cable of the present invention will be described in detail with reference to exemplary embodiments.
One aspect of the present invention provides a heat generating material capable of withstanding high pressure.
In an exemplary embodiment of the invention, the heat-generating material capable of resisting high pressure is composed of 1-10 wt% of surface-modified graphene and the balance of silane crosslinked polyethylene, the thickness of the heat-generating material is 0.1-5 mm, the withstand voltage range of the heat-generating material is 1-8 KV, the heat-generating temperature rise range of the heat-generating material is 4-80 ℃, and the power density of the heat-generating material is 1.0 × 10-4～1.0×10-1W/m m2. Further, the power density of the heat-generating material was 6.4 × 10-4～6.4×10-2W/m m2. For example, the heat-generating material may be composed of 3 to 5% by weight of surface-modified graphene and the balance of silane crosslinked polyethylene. The normal temperature conductivity of the heating film can be 1 multiplied by 108～1×1013Omega cm. In this embodiment, as the mass fraction of the surface-modified graphene in the heat-generating material increases, the microstructure of the heat-generating material is formed by the transition from the surface-modified graphene sheets having a distance greater than 10 μm, no mutual contact, no formation of a conductive network to the transition from the surface-modified graphene sheets having a distance of 10nm to 10 μm, partial mutual contact, formation of a discontinuous conductive network, and finally the transition to the transition from the graphene sheets being in close contact with each other and stacked to form a continuous conductive network. Specifically, when the addition content of the surface-modified graphene in the heat-generating material is 1-3 wt%, the distance between most surface-modified graphene sheet layers in the heat-generating material is greater than 10 μm, the distance between the most surface-modified graphene sheet layers in the heat-generating material is smaller than 10 nm-10 μm, and the graphene sheet layers are not in contact with each other to form a conductive network. At this time, the conduction mechanism of the heating material can be explained by the field emission theory, that is, when the distance between the conductive particles is more than 10nm, an electric field is applied to the conductive particles, the generation of the emission electric field between the conductive particles can be induced, and the free electrons are influenced by the electric field to move directionally, so that the generation of conductionElectrical behavior.
When the graphene addition content in the heating material is 6.5-10 wt%, the surface-modified graphene sheets are in close contact with each other or even stacked to form a continuous and compact conductive network, and the heating material has high conductivity and can conduct and heat. Thus, the mechanism of conduction with the addition of high levels of graphene can be explained by the percolation mechanism.
When the addition content of the surface modified graphene in the heating material is 3-5 wt%, the microstructure of the heating material is that graphene sheet layers are not completely contacted with each other, the distance between most of the surface modified graphene is within the range of 10 nm-10 um, the distance between a few of the surface modified graphene sheets is 1-10 nm or are contacted with each other, and the surface modified graphene sheet layers are contacted with each other but do not form a completely continuous conductive network. The distance between a small part of surface modified graphene sheets is 1-10 nm, and the conduction condition can be explained by a tunneling effect, namely, the conduction phenomenon when the conductive particles in the composite material are not in contact and the distance between the conductive particles is slightly smaller (1-10 nm), at the moment, the conduction of free electrons in the conductive composite material is completed through the migration of the free electrons, and the migration is caused by thermal vibration among the particles. And the conduction mechanism of the distance between most of the surface modified graphene is 10 nm-10 um is the field emission mechanism. Therefore, under the action of a high-voltage electric field, the composite material has conductivity due to the 3-5 wt% of graphene, and the conductivity of the heating material is combined action of a tunnel effect and a field emission effect.
In this embodiment, to achieve the effect of melting ice and snow (for example, calculated according to the thickness of ice being 1mm and the thickness of heating cable being increased by 0.5mm every 30min in the temperature raising stage), the minimum electrothermal conversion power required for the 1km homemade heating wire is 8922W, and the corresponding power density is 1.4 × 10-4W/mm2. Refer to homemade heat conducting wire and theory and technology for online anti-icing and de-icing, mo si te, li bi xiong, liu tian qi, university press. The power required for a 1km long self-heating wire is 8922W, and the power required for a 1mm long self-heating wire is 0.008922W. For the thickness of the heat-generating material is2mm self-made heat conducting wire with the actual section increased area of 63.55mm2The power density of the self-made heat conducting wire is 0.008922W/63.55mm2＝1.4×10-4W/mm2。
In this embodiment, the surface-modified graphene can be obtained by the following steps:
mixing graphene with ethanol with the volume fraction of 60-95% according to the mass-volume ratio of 1: mixing 50-100 g/ml, adding a long-chain alkane coupling agent solution accounting for 5-10 wt% of the reduced graphene oxide, stirring at 20-60 ℃ for 0.5-2 h, and drying to obtain the surface modified graphene. Wherein the long-chain alkane coupling agent solution can comprise at least one of silane coupling agent and phthalate coupling agent. The graphene can be graphene oxide or reduced graphene oxide, and the graphene can be in a single-layer or multi-layer form. For example, 20g of graphene is dispersed in 2000ml of 95% ethanol, 2g of silane coupling agent is dropped into the solution, magnetic stirring is carried out for 1 hour at 60 ℃, and the graphene is taken out and dried in an oven at 60 ℃ to obtain the surface modified graphene.
Here, the long-chain alkane coupling agent is first hydrolyzed by water, alcohols, and the like, then dehydrated and condensed into a polymer, and then hydrated with hydroxyl groups on the surface of graphene, and then heated and dried to cause a dehydration reaction on the surface of graphene, and finally covered with a silane coupling agent. After blending, the organic active groups of the coupling agent react with the polymer matrix. The purpose of surface modification is to obtain good cohesive force and binding force by coupling two kinds of graphene with greatly different properties of a silane coupling agent and a polymer matrix through chemical bonds, solve the problem of interface, improve the wettability of a polymer on the graphene, and solve the agglomeration between graphene sheets through the combination of long-chain silane macromolecules. The poor agglomeration and bonding force can cause large bonding gap between the graphene and the matrix, poor mechanical property, and incapability of forming uniform and effective conductive 'paths', namely incapable of forming current to do work and generate heat.
In this embodiment, the surface modification can improve the binding force and adhesion between graphene and silane crosslinked polyethylene. Specifically, the surface modification is performed to solve the interface problem between graphene and a substrate, improve the binding force and adhesion between graphene and silane crosslinked polyethylene, and improve the mechanical properties of the heating material. On the other hand, the graphene agglomeration is prevented, the graphene is promoted to be uniformly dispersed in the matrix, so that an effective conductive 'path' can be formed, and meanwhile, the graphene agglomeration can also cause the heating and the non-uniform breakdown strength of the material, so that the breakdown strength of places with more graphene is low, and the breakdown strength of places with less graphene is high. The invention also provides a preparation method of the high-pressure-resistant heating material.
In the present exemplary embodiment, the heat-generating material has a tensile strength of 10 to 20MPa and a room-temperature impact property of 8.8KJ/m2Above, low temperature impact property of 3.7KJ/m2The above. The mechanical property parameters of different surface modified graphene addition content patterns are given in table 1. Wherein the tensile properties are measured according to GB/T1040.2-2006 and the sample size is 150 x 10 x 4mm3(ii) a The impact properties were tested according to standard GB/T1043.1-2008, with a standard size of 80 x 10 x 4mm3。
Table 1 mechanical properties of samples with different surface modified graphene addition contents.
As can be seen from table 1, the elongation at break, room temperature impact property and low temperature impact property of the sample all show a tendency to decrease gradually with the increase of the content of the surface modified graphene, and the tensile strength is enhanced. The sample with the surface modified graphene added in an amount of 3-5 wt% has good mechanical properties.
In another exemplary embodiment of the present invention, a method of preparing a heat generating material capable of withstanding high pressure includes the steps of: uniformly mixing the surface modified graphene and polyethylene according to the mass percent of 1-10 wt%, melting and blending at 180-210 ℃ to prepare a heating material with the thickness of 0.1-5 mm, and performing silane crosslinking to convert the polyethylene in the heating material into silane crosslinked polyethylene. The melt blending can be carried out in an internal mixer, the rotating speed of the internal mixer can be 30-100 rpm/min, and the stirring time can be 5-60 min. Specifically, the surface-modified graphene and polyethylene are added into an internal mixer according to the mass fraction ratio of 1-10 wt%, the mixture is melted and blended at 180-210 ℃ at 30-100 rpm/min, the mixture is stirred and mixed for 5-60 min, and the mixture obtained after the internal mixer is melted and blended is made into a film with the thickness of 0.1-5 mm. And (3) crosslinking the film by using silane to obtain the required heating material.
In this embodiment, the performing silane crosslinking to convert polyethylene in the heat-generating material into silane-crosslinked polyethylene may include the steps of: and (3) steaming the heating material in purified water at 100 ℃ for 6-10 hours, and drying at 50-80 ℃ for 8-12 hours. However, the invention is not limited thereto, and other silane crosslinking means are possible, such as ultraviolet irradiation.
Still another aspect of the present invention provides a self-heating deicing and anti-icing cable including a heat-generating material capable of withstanding high voltage as described above formed between an inner conductor and an outer conductor.
In order that the above-described exemplary embodiments of the invention may be better understood, further description thereof with reference to specific examples is provided below.
Example 1
The surface modified graphene and polyethylene are added into an internal mixer according to the proportion of 1 wt%, 3 wt%, 4 wt%, 5 wt%, 6.5 wt% and 10 wt% (namely samples 1-6 in table 1), are melted and blended at 210 ℃, and are mixed for 20min at the stirring speed of 80 rpm/min. The melt blended mixture was cooked in purified water at 100 ℃ for 8 hours and dried at 60 ℃ for 12 hours. The dried mixture was formed into a 25 × 0.5mm rectangular sheet, and subjected to high voltage resistance and heat generation temperature rise experiments using a dc-plate electrode.
Example 2
The surface modified graphene and polyethylene are added into an internal mixer according to the proportion of 1 wt%, 3 wt%, 4 wt%, 5 wt%, 6.5 wt% and 10 wt% (namely, samples 7-12 in table 1), and are melted and blended at 210 ℃ and mixed for 20min at the stirring speed of 80 rpm/min. The melt blended mixture was cooked in purified water at 100 ℃ for 8 hours and dried at 60 ℃ for 12 hours. The dried mixture was fabricated into 25 × 2mm rectangular sheets, and high voltage and heat resistance temperature rise experiments were performed using dc-plate electrodes.
Example 3
The surface modified graphene and polyethylene are added into an internal mixer according to the proportion of 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt% and 6.5 wt% (namely samples 13-18 in Table 1), are melted and blended at 210 ℃, and are mixed for 20min at the stirring speed of 80 rpm/min. The melt blended mixture was cooked in purified water at 100 ℃ for 8 hours and dried at 60 ℃ for 12 hours. The dried mixture was fabricated into 25 × 5mm rectangular sheets, and high voltage and heat resistance temperature rise experiments were performed using dc-plate electrodes.
Comparative example
Polyethylene (i.e., samples 19-21 in Table 1) was added to an internal mixer, melt blended at 210 deg.C, and mixed at 80rpm/min for 20 min. The melt blended mixture was cooked in purified water at 100 ℃ for 8 hours and dried at 60 ℃ for 12 hours. The dried mixture was formed into rectangular sheets of 25 × 0.5mm, 25 × 2mm, and 25 × 5mm, and subjected to high-voltage resistance and heat generation temperature rise tests using dc-plate electrodes.
The results of the temperature rise and high pressure resistance experiments of the heat-generating material samples prepared in examples 1 to 3 and comparative example are given in table 2.
Table 2 examples and comparative ramp temperatures and withstand voltages.
Here, the temperature of the environment was set to 12 ℃ and the pressurizing and energizing time was set to 25 min. However, for safety reasons, when the temperature of the sample is raised at a high rate (e.g., ten minutes to 60 ℃ or higher), the temperature of the sample is not prevented from rising beyond the temperature resistance limit of the material, and the temperature rise is stopped.
As can be seen from tables 1 and 2, when the surface modified graphene is added in an amount of 3-5 wt%, the heating material has good conductivity and compressive strength, good mechanical properties (tensile strength, elongation at break, room temperature impact property and low temperature impact property), and can be used in the fields of deicing and anti-icing of high-voltage cables.
In summary, the beneficial effects of the invention can include at least one of the following:
(1) the heating material has heating and high-pressure resistance, and can be applied to the fields of deicing and anti-icing of high-voltage cables;
(2) the self-heating deicing and anti-icing cable solves the problems of tower falling, line deicing vibration, line galloping, flashover and the like of a high-voltage overhead power transmission line caused by extreme snowstorm weather;
(3) the deicing and anti-icing cable is used as a high-voltage transmission line, and a heating wire is not required to be additionally arranged, so that the weight of the high-voltage transmission line can be reduced, and the cost is reduced.
While the present invention has been described above in connection with exemplary embodiments, it will be apparent to those of ordinary skill in the art that various modifications may be made to the above-described embodiments without departing from the spirit and scope of the claims.
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