CN111083814A - Graphene-based flexible heating cable with PTC effect and preparation method thereof - Google Patents
Graphene-based flexible heating cable with PTC effect and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/145—Carbon only, e.g. carbon black, graphite
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/02—Details
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/40—Heating elements having the shape of rods or tubes
- H05B3/54—Heating elements having the shape of rods or tubes flexible
- H05B3/56—Heating cables
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- Resistance Heating (AREA)
Abstract
The invention relates to the field of flexible electric heating and warming, and discloses a graphene-based flexible heating cable with a PTC (positive temperature coefficient) effect and a preparation method thereof, wherein the graphene-based flexible heating cable is wound by one or more heating fibers to form a heating inner core, and the heating inner core is coated with a resin layer with the PTC function; the heating fiber comprises chemical fiber or natural fiber, and the periphery of the chemical fiber or the natural fiber is coated with a conductive layer. The connection between the electrode for power supply and the heating cable adopts a concentrated ring type connection mode, the number of connection parts is small, the connection is tight, and ignition or open fire does not occur. The graphene-based flexible heating cable with the structure has the characteristics of PTC effect, uniform heating, flexibility, telescopic performance and adjustable temperature range.
Description
Technical Field
The invention relates to the field of electric heating, in particular to a graphene-based flexible heating cable with a PTC effect and a preparation method thereof, and particularly relates to an electric heating cable which can be manufactured into flexible and PTC electric heating cables and can be applied to heating floor heating, kang heating, wall heating, murals, sofas and other heating products.
Background
In the field of electric heating, resistance heating is a common heating technique. Among them, a metal resistance wire represented by nichrome is widely used in various fields as an electrothermal conversion medium. As resistance heating media gradually shift to lightweight and flexibility, electrothermal conversion media, mainly carbon fibers, ceramics, and the like, have come out.
CN108012349A discloses a high-efficient energy-conserving ground of graphite alkene carbon fiber warms up heating wire and manufacturing process thereof, and this heating wire includes carbon fiber layer, insulating layer, graphite alkene layer and the protective layer that sets gradually from inside to outside, the carbon fiber layer is carbon fiber bundle, carbon fiber bundle's outer parcel has the insulating layer, the outer parcel of insulating layer has graphite alkene layer, graphite alkene layer's periphery parcel has the protective layer. Although it can improve the heat transfer performance to some extent, it is poor in flexibility and weak in impact resistance. When the carbon fiber is assembled into a device, the stress at the connecting position of the power supply electrode and the heating wire is large, and the carbon fiber is easy to break.
Disclosure of Invention
The invention aims to solve the problems of poor flexibility, nonuniform heating, low resistance and overhigh heating temperature of a heating wire in the prior art, and provides a graphene-based flexible heating cable with a PTC effect and a preparation method thereof.
In order to achieve the above object, an aspect of the present invention provides a graphene-based flexible heat-generating cable having a PTC effect, wherein the heat-generating cable includes a heat-generating core and an insulating layer wrapped around the heat-generating core, the heat-generating core includes at least one heat-generating fiber and optionally a second fiber line; the heating fiber comprises a first fiber line, and the periphery of the first fiber line sequentially wraps the conductive layer and the resin layer which generates the PTC effect from inside to outside.
The second aspect of the present invention provides a method for preparing a graphene-based flexible heating cable having a PTC effect, the method comprising:
forming a conductive layer on the periphery of a first fiber wire by dip-coating conductive slurry on the first fiber wire to obtain a conductive heating fiber wire; the two ends of the conductive heating fiber wire are respectively fixed with a closed-loop electrode, and the conductive heating fiber wire forms a resin layer on the periphery of the conductive heating fiber wire through dip-coating resin slurry to obtain heating fibers generating PTC effect;
one or more heating fibers and optional second fiber line form the heating inner core through plying, and the periphery parcel insulating layer of heating inner core forms the heating cable.
According to the invention, the conductive layer and the resin layer are sequentially wrapped from the periphery of the first fiber wire to form the heating fiber, then the fiber is stranded to form the heating inner core, and the insulating layer is wrapped on the periphery of the heating inner core to form the heating cable. The heating cable prepared by the method has good flexibility and tensile property (the expansion ratio reaches 110-.
Drawings
Fig. 1 is a schematic structural view of a heat-generating cable in embodiment 1;
FIG. 2 is a schematic cross-sectional view of a heat-generating cable in embodiment 1;
fig. 3 is a schematic structural view of the heat-generating cable in embodiment 2.
Description of the reference numerals
1. Heating inner core 2, heating fiber 21 and first fiber line
22. Conductive layer 23, resin layer 3, and closed-loop electrode
4. Insulating layer 5, second fiber line
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a graphene-based flexible heating cable with PTC effect, wherein the heating cable comprises a heating inner core 1 and an insulating layer 4 wrapped on the periphery of the heating inner core 1, the heating inner core 1 comprises at least one heating fiber 2 and an optional second fiber line 5; the heating fiber 2 comprises a first fiber line 21, and the periphery of the first fiber line 21 is sequentially wrapped with a conductive layer 22 and a resin layer 23 generating PTC effect from inside to outside.
In the invention, the conductive layer 22 is wrapped on the periphery of the first fiber line 21 to form the conductive heating fiber line, the conductive heating fiber line has better conductivity, and the line resistance of the conductive heating fiber line is 50-1000 omega/cm. The periphery of the first fiber line 21 is sequentially wrapped with the conductive layer 22 and the resin layer 23, and the conductive layer and the resin layer are matched, so that the heating fiber 2 has a PTC effect, and the breaking elongation of the heating fiber can reach 21-25%.
In the invention, the heating cable formed by adopting the structure has better flexibility and expansion performance (the expansion ratio can reach 110-130%), the temperature can be adjusted in a larger range (30-300 ℃), the PTC effect is better, and the application is wider.
Preferably, the heat-generating inner core 1 comprises one heat-generating fiber 2; or a plurality of heating fibers 2 are twisted; or a plurality of the heating fibers 2 and the second fiber threads 5 are twisted.
The heating core 1 of the present invention may optionally include one heating fiber 2, or may be formed by stranding a plurality of heating fibers 2 (as shown in fig. 1 and fig. 2), where stranding may refer to twisting a plurality of heating fibers 2 to form a spiral, or may be braided or other winding forms in the prior art. The heat-generating core 1 may be formed by twisting the conductive heat-generating fiber thread and the second fiber thread 5 (as shown in fig. 3), where the twisting means that the conductive heat-generating fiber thread and the second fiber thread 5 are mixed and woven to form a tubular shape, or may be formed by other weaving methods or other winding methods in the prior art.
Preferably, the first fiber line 21 and the second fiber line 5 are made of chemical fibers and/or natural fibers, and the average molecular weight of the chemical fibers is 15000-25000;
preferably, the chemical fiber is polyethylene terephthalate, polyamide, polyacrylonitrile or polyvinyl chloride, and the natural fiber is viscose fiber, cellulose ester fiber or acetate fiber.
The first fiber thread 21 and the second fiber thread 5 may be the same or different, and may be adjusted according to actual needs.
Preferably, the thickness of the conductive layer 22 is 0.1-10 μm, preferably 1-5 μm.
Preferably, the conductive slurry used to form the conductive layer 22 includes graphene, a conductive filler, a flexible resin, and a solvent; relative to 100 parts by weight of solvent, the content of the graphene is 3-10 parts by weight, the content of the conductive filler is 0-10 parts by weight, and the content of the flexible resin is 10-20 parts by weight;
preferably, the conductive filler is at least one selected from the group consisting of carbon nanotubes, conductive carbon black, graphite, carbon fibers, and carbon microspheres; the flexible resin is at least one of polyurethane resin, acrylic resin, fluorocarbon resin, polyester resin and polyether resin; the solvent is at least one of water, tetrahydrofuran, dimethyl sulfoxide, N-methyl pyrrolidone and N, N-dimethylformamide.
In the invention, the graphene can be prepared by graphite through an intercalation stripping method, or can be prepared by graphite through a chemical oxidation reduction method. The conductive slurry can be a mixture of graphene, a flexible resin and a solvent, and can also be a mixture of graphene, a conductive filler, a flexible resin and a solvent.
In the invention, the graphene and the conductive filler in the conductive slurry can be uniformly dispersed in the solution after being dispersed, and the formed conductive slurry can be uniformly coated on the surface of the first fiber wire 21 in a dipping manner, so that the formed heating cable can uniformly heat.
The conductive slurry in the present invention is formed by mixing a graphene-containing dispersion liquid and a flexible resin emulsion, and may be formed by mixing a graphene-containing dispersion liquid, a conductive filler-containing dispersion liquid and a flexible resin emulsion. The graphene-containing dispersion, the conductive filler-containing dispersion, and the flexible resin emulsion are commercially available.
Preferably, the resin raw material used to form the resin layer 23 includes polyethylene having a number average molecular weight of 2000-500 ten thousand;
further preferably, the resin raw material comprises, based on the total amount of the resin raw material: 65-75 parts of polyethylene with the number average molecular weight of 2000-4000, 15-25 parts of polyethylene with the number average molecular weight of 100-150 ten thousand and 8-15 parts of polyethylene with the number average molecular weight of 150-500 ten thousand.
According to the invention, the resin layer 23 is combined with the conductive layer 22, so that the heating cable has a better PTC effect, the heating temperature of the heating cable has better self-control performance, and the overheating phenomenon is prevented.
Preferably, the line resistance of the heat generating fiber 2 is 10 to 10000 Ω/cm, preferably 50 to 1000 Ω/cm.
In the invention, the conductive layer 22 is formed on the surface of the first fiber line 21, so that the resistance of the heating fiber 2 is adjustable, the heating temperature of the heating cable can be regulated and controlled at 30-300 ℃, the heating cable can be regulated and controlled from low position to high temperature at will, and the application is wider.
Preferably, the heat-generating fibers 2 have a PTC coefficient of 104-106(ii) a Preferably, the diameter of the heat-generating inner core 1 is 0.1-100mm, preferably 1-10 mm.
In the present invention, the first fiber wire 21, the conductive layer 22 and the resin layer 23 are matched with each other so that the PTC coefficient of the heating fiber 2 can be adjusted within the above range, so that the heating cable of the present invention has a better PTC performance.
Preferably, the closed-loop electrodes 3 are respectively fixed at two ends of the heating inner core 1, and the closed-loop electrodes 3 are conducted with the heating fibers 2.
In the present invention, the closed-loop electrode 3 is formed in a ring shape around the heat-generating cable around the outer periphery of the heat-generating core 1. The closed-loop electrodes 3 are fixed at two ends of the heating inner core 1, and the closed-loop electrodes 3 and the heating fibers 2 are in a circuit conduction state. Closed loop electrode 3 is connected more firmly with the inner core 1 that generates heat, and the cable structure that generates heat that makes is more stable, avoids striking sparks or open fire because of contact failure leads to take place.
In order to further improve the connection stability of the heating inner core 1 and the closed-loop electrode 3 and the connection tightness between the heating fibers 2 in the heating inner core 1, the two ends of the heating inner core 1 are coated with conductive slurry, and the conductive slurry is conductive metal slurry and/or conductive carbon slurry.
And after the two ends of the heating inner core 1 are coated with the conductive slurry, fixing the closed-loop electrode 3. If the conductive paste is conductive metal paste, preferably conductive silver paste is adopted; if the conductive slurry is conductive carbon slurry, conductive graphene slurry is preferably adopted, and the conductive graphene slurry is obtained by concentrating the conductive slurry by 3 times.
The invention provides a preparation method of a heating cable, wherein the preparation method comprises the following steps:
forming a conductive layer 22 on the periphery of a first fiber wire 21 by dip-coating a conductive slurry on the first fiber wire 21 to obtain a conductive heating fiber wire; the two ends of the conductive heating fiber line are respectively fixed with the closed-loop electrodes 3, and the conductive heating fiber line forms a resin layer 23 on the periphery of the conductive heating fiber line through dip-coating resin slurry to obtain the heating fiber 2 generating PTC effect;
one or more heating fibers 2 and an optional second fiber line 5 are stranded to form a heating inner core 1, and an insulating layer 4 is wrapped on the periphery of the heating inner core 1 to form a heating cable.
The heating cable manufactured by the method has good flexibility and telescopic performance, is uniform in heating, adjustable in heating temperature and long in service life, and has a PTC function.
In the invention, the conductive heating fiber wire prepared by the method has better flexibility, the resistance can be adjusted between 50 and 1000 omega/cm, and the elongation at break is 18 to 30 percent. By adopting the method, the resin layer 23 is wrapped on the periphery of the conductive heating fiber line, so that the heating fiber 2 has a good PTC effect and uniform heating temperature.
Preferably, the preparation method comprises:
(1) forming a conductive layer 22 on the periphery of a first fiber wire 21 by dip-coating a conductive slurry on the first fiber wire 21 to obtain a conductive heating fiber wire;
(2a) combining a plurality of conductive heating fiber wires to form a wire bundle, respectively fixing closed-loop electrodes 3 at two ends of the wire bundle, immersing the wire bundle in resin slurry, and forming a resin layer 23 on the periphery of the conductive heating fiber wires to obtain heating fibers 2 with PTC function;
a plurality of heating fibers 2 are stranded to form a heating inner core 1;
(2b) a plurality of conductive heating fiber wires and second fiber wires 5 are mixed and woven to form a wire harness, closed-loop electrodes 3 are respectively fixed at two ends of the wire harness, the wire harness is immersed in resin slurry, and a resin layer 23 is formed on the peripheries of the conductive heating fiber wires and the second fiber wires 5 to obtain a heating inner core 1 with a PTC function;
(3) the periphery of the heating inner core 1 is wrapped by the insulating layer 4 to form a heating cable.
The heating fibers 2 form the heating core 1 in various ways, and may be formed by dip-coating a resin slurry around the periphery of the single conductive heating fiber wire. Or a plurality of conductive heating fiber wires are firstly combined to form a wire harness, and the closed-loop electrodes 3 are fixed at two ends of the wire harness, so that the closed-loop electrodes 3 are stably connected with the conductive heating fiber wires. The middle part is dipped into the resin slurry, so that the periphery of the conductive heating fiber line forms a uniform resin layer 23, and the resin layer 23 and the conductive layer 22 are tightly combined. Then, the wire harness is twisted (in this embodiment, the twisting may be a spiral shape) to form the heat-generating core 1. Or the conductive heating fiber wire and the second fiber wire 5 are mixed and braided firstly (in the scheme, the mixed and braided can be a cylindrical bundling body formed by braiding a cylindrical braiding machine) to form a wire harness, the closed-loop electrode 3 is fixed at two ends of the wire harness, and resin slurry is dip-coated in the middle of the wire harness to obtain the heating inner core 1.
In the present invention, the dip coating in step (1) means that the first fiber line 21 passes through the conductive slurry at a certain speed under the action of the traction force, so that part of the conductive slurry is coated on the surface of the first fiber line 21. In the steps (2a) and (2b), the step of immersing the wiring harness into the resin slurry means that the wiring harness passes through the resin slurry at a certain speed under the action of traction force, so that part of the resin slurry is wrapped on the surface of the conductive heating fiber wire.
The heating cable prepared by the method has good PTC effect, stable and adjustable heating temperature (30-300 ℃), high average heating rate (the average heating rate is 1-5 ℃/s) from room temperature to constant temperature and good expansion performance (the expansion rate reaches 110-.
In order to further improve the bonding stability of the conductive layer 22 and the first fiber line 21, it is preferable that the first fiber line 21 is dried at 100-.
In order to further improve the bonding stability of the conductive layer 22 and the resin layer 23 and to allow the heat generating cable to have a stable PTC effect, it is preferable that the resin layer 23 is formed on the outer circumference of the conductive heat generating fiber wire through the processes of sizing, infiltration and film formation after the wire harness is immersed in the resin slurry in the steps (2a) and (2 b).
In the invention, the conventional methods in the prior art are adopted for the methods of sizing, permeating and film forming.
The present invention will be described in detail below by way of examples. In the following examples and comparative examples,
the expansion and contraction rate of the heating core is determined by measuring the length L1 of the heating core under the natural length and the length L2 of the heating core under the stretching state under the action of external force, wherein L2/L1 is the expansion and contraction rate of the heating core;
the elongation at break of the heat-generating fiber is measured according to GB/T14344;
the line resistance of the heating fiber is measured by an ohm method;
PTC coefficient of heating fiber is measured by measuring normal temperature RlAnd volume resistivity R of the heat-generating fiber at high temperatureh，Rh/RlThe ratio of (A) to (B) is the PTC coefficient.
The following examples are all conventional materials unless otherwise specified.
Example 1
This example was conducted to provide a graphene-based flexible heat-generating cable having a PTC effect, which was prepared as follows, as shown in fig. 1 and 2:
(1) uniformly stirring 90g of dispersion liquid (purchased from a new materials and industry technology Beijing institute, model Graphene-W-6) containing 5.4g of Graphene and 10g of polyurethane emulsion (purchased from Aza, model AH-1618) to form conductive slurry;
the first fiber line 21(300D96F terylene) was dip-coated with conductive slurry and then dried at 100 ℃ to form a conductive layer 22 with a thickness of 3 μm on the surface of the first fiber line 21 to obtain a conductive heating fiber line.
(2) Melting 75 parts by weight of polyethylene with the number average molecular weight of 2000-4000, 15 parts by weight of polyethylene with the number average molecular weight of 100-150 ten thousand and 10 parts by weight of polyethylene with the number average molecular weight of 150-500 ten thousand at 130 ℃ to form resin slurry;
50 conductive heating fiber wires with the length of 2m are bundled to form a wire bundle, closed-loop electrodes 3 (copper electrode plates with the thickness of 1mm and the width of 15 mm) are respectively fixed at two ends of the wire bundle, the middle of the wire bundle is immersed in resin slurry, and a resin layer 23 with the thickness of 3 mu m is formed on the surface of the conductive heating fiber wires through slurry coating, infiltration and film forming treatment to obtain heating fibers 2; then, the heating core 1 (5 mm in diameter) is formed into a spiral shape by winding and twisting.
The line resistance of the heating fiber 2 is 500 +/-10 omega/cm, the elongation at break is 21 percent, and the PTC coefficient of the heating fiber 2 is 106The expansion and contraction rate of the heating core 1 is 120%.
(3) The periphery of the heating inner core 1 is wrapped by the insulating layer 4 to form a heating cable.
The surface temperature of the heating element was raised from 23 ℃ to 81 ℃ by applying a voltage of 220V to the electrodes at both ends and was kept constant at 81 ℃ with an average temperature rise rate of 2.9 ℃/s.
Example 2
This example is intended to provide a graphene-based flexible heat-generating cable having PTC effect, which is prepared as follows, as shown in fig. 3:
(1) uniformly stirring 50g of dispersion liquid (purchased from Beijing institute of New materials and Industrial technologies, model Graphene-W-6) containing 3.0g of Graphene, 38g of dispersion liquid (purchased from Beijing institute of New materials and Industrial technologies, model CNT-W-5) containing 1.9g of carbon nanotubes and 12g of polyurethane emulsion (purchased from Andatai, model AH-1618) to form conductive slurry;
the first fiber line 21(300D96F terylene) was dip-coated with conductive slurry and then dried at 100 ℃ to form a conductive layer 22 with a thickness of 3 μm on the surface of the first fiber line 21 to obtain a conductive heating fiber line.
(2) Melting 75 parts by weight of polyethylene with the number average molecular weight of 2000-4000, 15 parts by weight of polyethylene with the number average molecular weight of 100-150 ten thousand and 10 parts by weight of polyethylene with the number average molecular weight of 150-500 ten thousand at 130 ℃ to form resin slurry;
weaving 32 conductive heating fiber wires and 32 second fiber wires 5 (nylon wires with the mark of 180D 32F) by adopting a drum type weaving machine to form a cylindrical bundle body with the thickness of 10mm to form a wire bundle, coating conductive silver paste at two ends of the wire bundle, winding a closed loop electrode 3 (a copper electrode plate with the thickness of 1mm and the width of 15 mm), immersing the middle of the wire bundle into resin slurry, and forming a resin layer 23 with the thickness of 3 mu m on the surface of the conductive heating fiber wires to obtain a heating inner core 1 through slurry hanging, permeating and film forming treatment;
the line resistance of the heating fiber 2 is 500 +/-10 omega/cm, the elongation at break is 21 percent, and the PTC coefficient of the heating fiber 2 is 106The expansion and contraction rate of the heat-generating core 1 is 110%.
(3) The periphery of the heating inner core 1 is wrapped by the insulating layer 4 to form a heating cable.
The surface temperature of the heating element was raised from 23 ℃ to 73 ℃ by applying a voltage of 220V to the electrodes at both ends and was kept constant at 73 ℃ with an average heating rate of 2.5 ℃/s.
Example 3
In the manner of example 1, the difference is that:
in the step (2), conductive silver paste is coated before the closed-loop electrodes 3 are fixed at the two ends of the wire harness.
The prepared heating fiber 2 has line resistance of 500 +/-10 omega/cm, elongation at break of 21 percent and PTC coefficient of 106The expansion and contraction rate of the heating core 1 is 120%.
The surface temperature of the heating element was raised from 23 ℃ to 88 ℃ by applying a voltage of 220V to the electrodes at both ends and was kept constant at 88 ℃ with an average heating rate of 3.3 ℃/s.
Example 4
In the manner of example 1, the difference is that:
in the step (2), conductive graphene slurry is coated before the closed-loop electrodes 3 are fixed at the two ends of the wire harness.
The prepared heating fiber 2 has line resistance of 500 +/-10 omega/cm, elongation at break of 21 percent and PTC coefficient of 106The expansion and contraction rate of the heating core 1 is 120%.
The surface temperature of the heating element was raised from 23 ℃ to 86 ℃ by applying a voltage of 220V to the electrodes at both ends and was kept constant at 86 ℃ with an average heating rate of 3.2 ℃/s.
Example 5
In the manner of example 2, the difference is that:
in the step (2), a cylindrical bundle body of 10mm is formed by knitting 32 conductive heating fiber wires and 32 second fiber wires 5 (polyethylene wires, the trade name is 200D16F) by a cylindrical knitting machine, and no resin layer is coated on the periphery of the cylindrical bundle body.
The expansion rate of the prepared heating inner core 1 is 110%.
After the heat generating cable was formed, a voltage of 220V was applied to the electrodes at both ends, and the surface temperature of the heat generating element was raised from 23 ℃ to 63 ℃ and kept constant at 63 ℃ with an average temperature rising rate of 2.1 ℃/s.
Example 6
The embodiment is used for providing a graphene-based flexible heating cable, and the heating cable is prepared according to the following method:
(1) uniformly stirring 45g of dispersion liquid (purchased from Beijing institute of New materials and Industrial technologies, model Graphene-W-10) containing 4.5g of Graphene, 45g of dispersion liquid (purchased from Beijing institute of New materials and Industrial technologies, model CNT-W-10) containing 4.5g of carbon nanotubes and 10g of polyurethane emulsion (purchased from Andatai, model AH-1618) to form conductive slurry;
the first fiber line (300D96F terylene) is dipped and coated with conductive slurry, and then is dried at 100 ℃, and a conductive layer with the thickness of 3 μm is formed on the surface of the first fiber line to obtain the conductive heating fiber line.
(2) Melting 75 parts by weight of polyethylene with the number average molecular weight of 2000-4000, 15 parts by weight of polyethylene with the number average molecular weight of 100-150 ten thousand and 10 parts by weight of polyethylene with the number average molecular weight of 150-500 ten thousand at 130 ℃ to form resin slurry;
weaving 32 conductive heating fiber wires and 32 second fiber wires (PI fiber wires with the mark of 180D 32F) by adopting a cylindrical weaving machine to form a cylindrical bundle body with the thickness of 10mm to form a wire bundle, coating conductive silver paste at two ends of the wire bundle, and winding a closed-loop electrode (a copper electrode plate with the thickness of 1mm and the width of 15 mm) to obtain a heating inner core;
the line resistance of the heating fiber is 200 +/-5 omega/cm, the elongation at break is 21 percent, and the expansion and contraction rate of the heating inner core is 110 percent.
(3) The periphery of the heating inner core is wrapped with an insulating layer to form a heating cable.
The surface temperature of the heating element was raised from 23 ℃ to 175 ℃ by applying a voltage of 220V to the electrodes at both ends and was kept constant at 175 ℃ with an average heating rate of 3.8 ℃/s.
Example 7
The present embodiment is directed to providing a graphene-based flexible heating cable having a PTC effect, which is prepared as follows:
(1) uniformly stirring 90g of dispersion liquid (purchased from a new materials and industrial technology Beijing institute, model Graphene-W-10) containing 9g of Graphene and 10g of polyurethane emulsion (purchased from Aza, model AH-1618) to form conductive slurry;
the first fiber line (300D96F terylene) is dipped and coated with conductive slurry, and then is dried at 100 ℃, and a conductive layer with the thickness of 3 μm is formed on the surface of the first fiber line to obtain the conductive heating fiber line.
(2) Melting 75 parts by weight of polyethylene with the number average molecular weight of 2000-4000, 15 parts by weight of polyethylene with the number average molecular weight of 100-150 ten thousand and 10 parts by weight of polyethylene with the number average molecular weight of 150-500 ten thousand at 130 ℃ to form resin slurry;
combining 18 conductive heating fiber wires with the length of 2m to form a wire bundle, respectively fixing closed-loop electrodes (copper electrode plates with the thickness of 1mm and the width of 15 mm) at two ends of the wire bundle, immersing the middle of the wire bundle into resin slurry, and forming a resin layer with the thickness of 3 mu m on the surface of the conductive heating fiber wires through slurry coating, permeation and film forming treatment to obtain heating fibers; then, a spiral heating core (with the diameter of 2mm) is formed by winding and twisting.
The line resistance of the heating fiber is 200 +/-5 omega/cm, the elongation at break is 21 percent, and the PTC coefficient of the heating fiber is 106The expansion rate of the heating inner core is 120%.
(3) The periphery of the heating inner core is wrapped with an insulating layer to form a heating cable.
The surface temperature of the heating element was raised from 23 ℃ to 81 ℃ by applying a voltage of 220V to the electrodes at both ends and was kept constant at 81 ℃ with an average temperature rise rate of 2.9 ℃/s.
Example 8
In the manner of example 1, the difference is that:
uniformly stirring 80g of dispersion liquid (purchased from a new material and industrial technology Beijing research institute, model Graphene-W-5) containing 4g of Graphene and 20g of polyurethane emulsion (purchased from Andataai, model AH-1618) to form conductive slurry;
the heating fiber has a line resistance of 1000 Ω/cm, an elongation at break of 21%, and a PTC coefficient of 106The expansion rate of the heating inner core is 120%.
After the heating cable was manufactured, a voltage of 220V was applied to the electrodes at both ends, and the surface temperature of the heating element was raised from 23 ℃ to 52 ℃ and kept constant at 52 ℃ with an average heating rate of 1.8 ℃/s.
Comparative example 1
The process according to example 1, with the difference that: the surface of the conductive heating fiber line is not coated with the resin layer 23.
The line resistance of the heating fiber 2 is 500 +/-10 omega/cm, the elongation at break is 21 percent, and the expansion and contraction rate of the heating core 1 is 100 percent.
After the heating cable was manufactured, a voltage of 220V was applied to the electrodes at both ends, and the surface temperature of the heating element was raised from 23 ℃ to 105 ℃ and kept constant at 105 ℃ with an average heating rate of 4.1 ℃/s.
From the above results, the heating cables manufactured by the methods of the embodiments all have the PTC effect, and have good flexibility and elasticity, and the heating temperature and the resistance can be adjusted in a wide range, so that the heating cables can be applied to the field of electric heating.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. A graphene-based flexible heating cable with PTC effect, wherein the heating cable comprises a heating core and an insulating layer wrapped around the heating core, the heating core comprises at least one heating fiber and optionally a second fiber wire; the heating fiber comprises a first fiber line, and the periphery of the first fiber line sequentially wraps the conductive layer and the resin layer which generates the PTC effect from inside to outside.
2. The heat-generating cable according to claim 1, wherein the heat-generating inner core includes one of the heat-generating fibers; or a plurality of heating fibers are stranded; or a plurality of the heating fibers and the second fiber threads are twisted.
3. The heating cable according to claim 1 or 2, wherein the first fiber thread and the second fiber thread are made of chemical fibers and/or natural fibers, and the number average molecular weight of the chemical fibers is 15000-25000;
preferably, the chemical fiber is polyethylene terephthalate, polyamide, polyacrylonitrile or polyvinyl chloride, and the natural fiber is viscose fiber, cellulose ester fiber or acetate fiber.
4. A heat-generating cable according to claim 1 or 2, wherein the thickness of the conductive layer is 0.1-10 μ ι η, preferably 1-5 μ ι η.
5. The heat-generating cable according to claim 4, wherein a conductive paste used for forming the conductive layer includes graphene, a conductive filler, a flexible resin, and a solvent; relative to 100 parts by weight of solvent, the content of the graphene is 3-10 parts by weight, the content of the conductive filler is 0-10 parts by weight, and the content of the flexible resin is 10-20 parts by weight;
preferably, the conductive filler is at least one selected from the group consisting of carbon nanotubes, conductive carbon black, graphite, carbon fibers, and carbon microspheres; the flexible resin is at least one of polyurethane resin, acrylic resin, fluorocarbon resin, polyester resin and polyether resin; the solvent is at least one of water, tetrahydrofuran, dimethyl sulfoxide, N-methyl pyrrolidone and N, N-dimethylformamide.
6. A heat-generating cable according to claim 1 or 2, wherein the resin raw material for forming the resin layer generating the PTC effect comprises polyethylene having a number average molecular weight of 2000-500 ten thousand;
preferably, the resin raw material comprises, based on the total amount of the resin raw material: 65-75 parts of polyethylene with the number average molecular weight of 2000-4000, 15-25 parts of polyethylene with the number average molecular weight of 100-150 ten thousand and 8-15 parts of polyethylene with the number average molecular weight of 150-500 ten thousand.
7. A heat generating cable according to claim 1 or 2, wherein the line resistance of the heat generating fibers is 10-10000 Ω/cm, preferably 50-1000 Ω/cm.
8. A heat-generating cable according to claim 1 or 2, wherein the heat-generating fiber has a PTC coefficient of 104-106(ii) a Preferably, the diameter of the heat-generating inner core is 0.1-100mm, preferably 1-10 mm.
9. A heating cable according to claim 1 or 2, wherein closed-loop electrodes are fixed to both ends of the heating core, respectively, and are in electrical communication with the heating fibers.
10. A heat-generating cable according to claim 9, wherein the closed-loop electrode is fixed after both ends of the heat-generating inner core are coated with conductive paste, the conductive paste being conductive metal paste and/or conductive carbon paste.
11. A method of manufacturing a heat-generating cable according to any one of claims 1 to 10, wherein the method of manufacturing comprises:
forming a conductive layer on the periphery of a first fiber wire by dip-coating conductive slurry on the first fiber wire to obtain a conductive heating fiber wire; the two ends of the conductive heating fiber wire are respectively fixed with a closed-loop electrode, and the conductive heating fiber wire forms a resin layer on the periphery of the conductive heating fiber wire through dip-coating resin slurry to obtain heating fibers generating PTC effect;
one or more heating fibers and optional second fiber line form the heating inner core through plying, and the periphery parcel insulating layer of heating inner core forms the heating cable.
12. The production method according to claim 11, wherein the production method comprises:
(1) forming a conductive layer on the periphery of a first fiber wire by dip-coating conductive slurry on the first fiber wire to obtain a conductive heating fiber wire;
(2a) combining a plurality of conductive heating fiber wires to form a wire bundle, respectively fixing closed-loop electrodes at two ends of the wire bundle, immersing the wire bundle in resin slurry, and forming a resin layer on the periphery of the conductive heating fiber wires to obtain heating fibers with the PTC function;
a plurality of heating fibers are stranded to form a heating inner core;
(2b) a plurality of conductive heating fiber wires and second fiber wires are mixed and woven to form a wiring harness, closed-loop electrodes are fixed at two ends of the wiring harness respectively, the wiring harness is immersed in resin slurry, and a resin layer is formed on the peripheries of the conductive heating fiber wires and the second fiber wires to obtain a heating inner core with a PTC function;
(3) the periphery of the heating inner core is wrapped with an insulating layer to form a heating cable.
13. The preparation method according to claim 12, wherein in the step (1), the first fiber wire is dried at 200 ℃ and 100 ℃ after being dipped in the conductive slurry, so that the conductive layer is formed on the periphery of the first fiber wire.
14. The manufacturing method according to claim 12, wherein, in the steps (2a) and (2b), after the wire harness is immersed in the resin slurry, a resin layer generating the PTC effect is formed on the outer circumference of the conductive heat emitting fiber wire through the processes of sizing, infiltrating, and film forming.
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