KR20210046327A - Manufaturing method of carbon nano dispersion for heating, and heater thereof - Google Patents

Abstract

The present invention relates to a method for manufacturing a carbon nano-dispersion solution for heat generation and a method for manufacturing a heating element using the same, which use a structure-linked carbon nanomaterial in which a linear carbon nanowire is inserted between planar graphene layers, and in particular, a carbon nano-dispersion solution for heat generation is manufacturing by using a structural-linked carbon nano material, and a heating element is manufactured by coating the carbon nano-dispersion solution on metal, ceramic (tile, board, marble), polymer (film, plate, fiber, non-woven fabric), glass, or paper, and then forming an electrode on the upper or lower part of the coating layer. In addition, if necessary, by additionally coating the carbon nano-dispersion solution on an appropriate part of a material constituting the heating element, so that it is possible to improve the thermal diffusivity and obtain an electromagnetic wave shielding effect.

Description

Manufacturing method of carbon nano dispersion for heating, and method of manufacturing a heating element using the same {Manufaturing method of carbon nano dispersion for heating, and heater thereof}

The present invention relates to a method of manufacturing a heating element using a structure-linked carbon nanomaterial in which a linear carbon nanowire is inserted between a layer of graphene on a plane, and a method of manufacturing a heating element using the same. Using a carbon nanodispersion solution for heating, coating it on metal, ceramic (tile, board, marble), polymer (film, plate material, fiber, non-woven fabric), glass, and paper, and then forming an electrode on the top or bottom of the coating layer. It relates to a method of manufacturing a heating element by a method. In addition, if necessary, by adding a carbon nanodispersion solution to an appropriate part of the material constituting the heating element, it is possible to expect improved thermal diffusion and shielding effects from electromagnetic waves.

Carbon nanomaterials such as carbon nanotube, graphene, and fullerene, which are positioned as next-generation core materials, are applied in various industrial fields due to their excellent electrical conductivity, thermal conductivity, durability, and shape characteristics. It is expanding its width.

In particular, when a carbon nanomaterial is dispersed in various solvents and coated on an appropriate target material to manufacture a heating element, excellent energy efficiency can be expected, so many studies and commercializations are being attempted.

Carbon black is used to manufacture conductive inks for conventional heating elements. Graphite, etc. were used, but in recent years, due to the mass production of carbon nanomaterials, attempts to use carbon nanotubes and graphene as conductive materials are expanding.

The planar structure graphene has good conductivity in the XY (horizontal) direction when coated, but the conductivity in the Z direction (vertical direction), which can maximize the heating effect, is relatively inferior. If the structure of the graphene and the carbon nanowire is connected by inserting the carbon nanowire in the coating layer, the conductivity in the XYZ direction (horizontal and vertical direction) is improved, thereby maximizing the heating efficiency.

The prior art related to the production of dispersion and heating element using carbon nanotubes is "portable low-power heater having a planar heating element formed from CNT paste" (Korean Patent No. 10-1803194), "A planar heating glass panel using nanomaterials" (Korea Patent No. 10-1895008), etc., and “Dispersant for carbon nanotubes and composition containing the same” (Korean Patent Registration No. 10-0815028), “Conductive Ink and Conductive Substrate” (Korean Registration Patent No. 10-0599053 ), “Carbon Nanotube Dispersion Method” (PCT International Application No. PCT/EP2007/008193)”, etc. Most of these are technologies related to the selection of a dispersant and dispersion process and a method of manufacturing a heating element when using carbon nanotubes alone. admit,

As the prior art related to the production of the dispersion liquid and the heating element using graphene, "the graphene planar heating element and the method of manufacturing the graphene planar heating element" (Korean Patent Application No. 10-2013-0113097), "Fever including graphene oxide Composition and heating element using the same" (Korean Patent Application No. 10-2017-0098341), "Method for preparing a stable dispersion solution of reduced graphene and a reduced graphene dispersion solution prepared thereby" (Korean Patent Laid-Open Patent 10-2012-0039799) And the like, but these suggest a heating composition and a method of manufacturing a heating element when graphene is used alone.

The prior art related to the production of dispersions and heating elements using a mixture of carbon materials includes "conductive ink composition for heating elements using carbon nanotubes" (Korean Patent No. 10-1209174), and "planar heating elements including three-dimensional carbon structures. And manufacturing method" (Korean Patent No. 10-1447077), "Carbon-containing planar heating structure" (Korean Patent No. 10-2017-0066770), etc. These are simply mixed with carbon nanotubes and carbon black or graphite powder, or The method of vertical growth of carbon nanotubes on the carbon coating layer is presented, but it is distinguished from the method of manufacturing a dispersion and heating element using a structure-linked carbon nanomaterial in which a carbon nanowire is inserted between the graphene layers presented in the present invention. .

An object of the present invention is a dispersion liquid using a structure-linked carbon nanomaterial that links the structures of graphene and carbon nanowires to improve the electron transfer superheat diffusivity in the XYX direction in a heating layer using a carbon nanomaterial, and such a carbon nanodispersion liquid. It is to provide a method of manufacturing a heating element.

The gist of the present invention for achieving the above object is as follows.

(1) A method for preparing a carbon nano-dispersion for heating, comprising dispersing 0.1 to 30 wt% of a structure-linked carbon nanomaterial in which a linear carbon nanowire is inserted between the planar graphene layers in a solvent.

(2) The linear carbon nanowire used in the structure-linked carbon nanomaterial is a carbon nanotube, carbon nanofiber, or carbon fiber, and the planar carbon nanomaterial is graphene or graphite. Method for producing carbon nanodispersion for heating according to 1)..

(3) The solvent is distilled water, alcohol, DMF, MEK, or a method for producing a carbon nanodispersion for heating according to the above (1), characterized in that any one or more selected from Polyol.

(4) The dispersion step is from ultrasonic, roll milling, ball milling, jet milling, screw mixing, or attrition milling. Method for producing a carbon nanodispersion for heating according to (1), characterized in that carried out by any one or more selected methods.

(5) The carbon nanodispersion prepared according to any one of the above (1) to (4) is coated on metal, ceramic (tile, board, marble), polymer (film, plate, fiber, non-woven fabric), glass, paper, and Curing to form a carbon nanocoating layer; A method of manufacturing a carbon nano heating element comprising the step of manufacturing a heating element by forming an electrode on the carbon nano coating layer.

(6) The coating process is a method for manufacturing a carbon nano heating element according to (5), characterized in that the coating process is performed by any one of a spray coating method, a doctor blade method, a screen printing method, or an immersion method.

(7) The method of manufacturing a carbon nano heating element according to (5), wherein the curing process of the carbon nanomaterial coating layer is performed by thermal curing, natural curing, or ultraviolet curing.

(8) The method for manufacturing a carbon nano heating element according to (5), characterized in that by additionally coating a carbon nano dispersion liquid on an appropriate part of the material constituting the heating element to improve thermal diffusivity and shield electromagnetic waves.

According to the structure-linked carbon nanodispersion according to the present invention, a structure-linked carbon nanomaterial in which a linear carbon nanowire is inserted for the purpose of improving the conductivity in the vertical direction between graphene layers having good horizontal conductivity By using it, the heat dissipation of the coating layer can be improved by improving electron transfer and thermal diffusion in the XYX direction in the coating layer.

In addition, by forming an electrode on the coating layer formed of the carbon nanodispersion liquid, it is possible to manufacture a carbon nano heating element.

1 is an overall flowchart of a method for manufacturing a carbon nanodispersion for heating using the structure-linked carbon nanomaterial according to the present invention and a method for manufacturing a heating element using the same.
Figure 2 is a schematic diagram of the structure-linked carbon nanomaterial used in the present invention.
Figure 3 is a SEM photograph of the structure-linked carbon nanomaterial used in the present invention.
Figure 4 is a flow chart of a method for producing a carbon nano-dispersion for heating using a structure-linked carbon nanomaterial according to the present invention.
Figure 5 is a schematic diagram of a heating element using a carbon nanodispersion for heating according to the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Meanwhile, throughout the specification, when a certain part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

FIG. 1 is a flow chart showing a method of manufacturing a carbon nanodispersion for heating using a structurally-linked carbon nanomaterial according to the present invention and a method of manufacturing a heating element using the same, and FIG. It shows the flow chart of.

First, the method of manufacturing a carbon nanodispersion for heating according to the present invention includes the step 100 of providing a structure-linked carbon nanomaterial, as shown in FIGS. 1 and 4; And dispersing the structure-linked carbon nanomaterial in a solvent together with a dispersant (200, 300).

2 is a schematic diagram of a structure-linked carbon carbon nanomaterial, and FIG. 3 is a SEM photograph. Planar graphene has excellent electron transfer and thermal diffusivity in the horizontal direction, but is relatively inferior in the vertical direction, so in the present invention, a structure-linked carbon nanomaterial in which a linear carbon nanowire is inserted into a planar graphene. Was used as a material for heating.

Figure 4 is a method for producing a carbon nanodispersion for heating using a structure-linked carbon nanomaterial according to the present invention. The structure-linked carbon nanomaterial is mixed with a dispersant in a solvent and then manufactured through the first and second dispersion processes. This dispersion process goes through the first dispersion step 200 of adjusting the initial dispersion and viscosity in the mechanical mixing process, and finally, the second dispersion step 300 of preparing the carbon nanodispersion according to the purpose in the ultrasonic dispersion process. It consists of Dispersion method is ultrasonic (Ultrasonic), bead milling (Bead Milling), roll milling (Roll Milling), ball milling (Ball Milling), jet milling (Zet Milling), screw mixing (Screw Mixing), or attrition milling ( Attrition Milling) can be performed by any one or more methods selected from.

The amount of the structure-linked carbon nanomaterial dispersed in the solvent is preferably dispersed in the range of 0.1 to 30 wt% with respect to the solvent. 0.1 wt. If it is less than or equal to, it is difficult to expect the target heat generation performance, and if it exceeds 30 wt%, the viscosity of the dispersion is excessively high, making it difficult to form a coating layer, which is not preferable.

The solvent used in the dispersion may be any one or more selected from distilled water, alcohol, DMF, MEK, or Polyol, and is not particularly limited.

The dispersant may be any one or more selected from Triton-X, CMC, PVB, PAB, or EAB, and the amount of the dispersant is preferably in the range of 0.1 to 3 times the content of the carbon nanomaterial. If it is less than 0.1 times, re-aggregation of the carbon nanomaterial occurs over time, and if it is more than 3 times, the content of the dispersant attached to the surface of the carbon nanomaterial is excessively increased, resulting in poor conductivity.

In the manufacture of the heating element, a solid material such as metal, ceramic (tile, board, marble), polymer (film, plate, fiber, non-woven fabric), glass, and paper may be used as the coating base material.

The coating method of the carbon nanodispersion solution for manufacturing the heating element may be performed by any one or more of a spray coating method, a doctor blade method, a screen printing method, or a dipping method. The curing method of the coating layer may be performed by thermal curing, natural curing, or ultraviolet curing.

The methods of forming an electrode on the coated surface of the carbon nanodispersion solution include forming an electrode on the surface of the base material before coating the carbon nanodispersion solution, and then coating the carbon nanodispersion solution, and forming an electrode thereon after coating the carbon nanodispersion solution. Can be

In addition, if necessary, by adding a carbon nanodispersion solution to an appropriate part of the material constituting the heating element, it is possible to expect improved thermal diffusion and shielding effects from electromagnetic waves.

(Example)

After preparing a carbon nanodispersion using a structure-linked carbon nanomaterial, the exothermic properties of the carbon nanodispersion prepared using each of carbon nanotubes and graphene alone were compared.

When the structure-linked carbon nanomaterial was mixed with distilled water, alcohol, or an organic solvent with a dispersant, the concentration of the carbon nanomaterial was 3 wt.% and the dispersant was 1 wt.%. Even when carbon nanotubes and graphene were used alone, the concentrations were the same and compared.

The carbon nanomaterial and the dispersant were first mechanically mixed with distilled water, and then dispersed for 5 hours in an ultrasonic process to prepare a carbon nanodispersion solution, and the manufacturing conditions are summarized in Table 1 below.

division Contents Types of carbon nanomaterials Carbon nanotube, graphene, structure-linked carbon nanomaterial Type of solvent Distilled water Type of dispersant CMC Carbon nanomaterial concentration (wt.%) 3 Dispersion method Mechanical mixing, ultrasonic (5 hours)

As a method of forming the heating layer, a heating element was manufactured by coating the same amount of a carbon nanodispersion solution on a building tile (300x300mm) preheated to 60°C by a spray method and then attaching a copper electrode. In general, the heating characteristics (electrical characteristics) of the coating layer can be controlled by controlling the coating thickness of the carbon nanodispersion liquid and the amount of carbon nanomaterials added.

Table 2 is a result of comparing the heat generation characteristics of the structure-controlled carbon nanodispersion according to the present invention with a dispersion prepared using conventional carbon nanotubes and graphene. In the case of coating the structure-controlled carbon nanodispersion in the present invention, the electric resistance is lower, the heating rate is faster, and the power consumption is reduced compared to the case where the carbon nanotubes and graphene dispersions are coated respectively, so that the structure-controlled carbon nanomaterials of the present invention It was confirmed that the heating characteristics can be improved when is applied.

Dispersion type Carbon nanotube Graphene Structure-linked type
Carbon nanomaterial Electrical resistance
(Ohm/Sq.) 1.4 x 10 ³ 1.2 x 10 ³ 0.64 x 10 ³ Heating rate up to 40℃
(second) 52 55 43 Power consumption (WH) 21 22 17

Claims (6)

Providing a structure-linked carbon nanomaterial in which a linear carbon nanowire is inserted between the planar graphene layers;
Dispersing the structure-linked carbon nanomaterial in a weight ratio of 0.1 to 30wt% and a dispersant in a solvent at a concentration of 0.1 to 3 times that of the carbon nanomaterial to prepare a carbon nanodispersion for exothermic use;
And producing a heating element by coating the carbon nanodispersion solution on a base material and then forming an electrode on or under the coating layer.
The method of claim 1,
In the constitution of the structure-linked carbon nanomaterial, carbon, characterized in that it contains at least one of graphene or graphite as a planar carbon nanomaterial, and a carbon nanotube, a carbon nanofiber, and a carbon fiber as a linear carbon nanowire. Nano dispersion manufacturing method and heating element manufacturing method
The method of claim 1,
The carbon nanodispersion manufacturing method comprises at least one of a method of mixing graphene and a carbon nanowire in a solvent and then mechanically mixing and dispersing by ultrasonic waves.
The method of claim 1,
The solvent is distilled water, alcohol, DMF, MEK or polyol, characterized in that any one or more selected from the carbon nanodispersion manufacturing method and heating element manufacturing method.
The method of claim 1,
A method for producing a carbon nanodispersion solution, characterized in that the base material coating the carbon nanodispersion solution for the production of the heating element is at least one of metal, ceramic (tile, board, marble), polymer (film, plate material, fiber, non-woven fabric), glass, and paper. And a heating element manufacturing method.
The method of claim 1,
A carbon nanodispersion manufacturing method and a heating element manufacturing method, characterized in that by further coating a carbon nanodispersion solution on an appropriate part of a material constituting the heating element to improve thermal diffusivity and shield electromagnetic waves.

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