WO2006006771A1 - Aqueous conductive polymer composition with ptc of resistivity and preparation thereof - Google Patents

Aqueous conductive polymer composition with ptc of resistivity and preparation thereof Download PDF

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Publication number
WO2006006771A1
WO2006006771A1 PCT/KR2005/002003 KR2005002003W WO2006006771A1 WO 2006006771 A1 WO2006006771 A1 WO 2006006771A1 KR 2005002003 W KR2005002003 W KR 2005002003W WO 2006006771 A1 WO2006006771 A1 WO 2006006771A1
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WO
WIPO (PCT)
Prior art keywords
weight
parts
polymer composition
conductive polymer
ptc
Prior art date
Application number
PCT/KR2005/002003
Other languages
French (fr)
Inventor
Chul-Yong Park
Yong-Chul Kim
Original Assignee
Chul-Yong Park
Yong-Chul Kim
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chul-Yong Park, Yong-Chul Kim filed Critical Chul-Yong Park
Publication of WO2006006771A1 publication Critical patent/WO2006006771A1/en

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Classifications

    • 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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising 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
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an aqueous conductive polymer composition with positive temperature coefficients (PTC) of resistivity, and more particularly, to an aqueous conductive polymer composition used for preparation of a plane heater and having PTC characteristics (self-temperature control characteristics) where it is heated only to an initial heating temperature of 60-70 0 C and no longer heated, as well as a preparation method thereof.
  • PTC positive temperature coefficients
  • a plane heater is a novel material which is formed by uniformly applying fine ceramic particles and conductive carbon particles on a fibrous fabric and generates heat upon the application of electricity.
  • the plane heater is widely used as not only a heating material for general homes or offices but also a material for road snow removal, agricultural heating, car sheets, various mattresses and heating clothes.
  • a conductive polymer is generally used.
  • the present inventors developed a conductive polymer paste with PTC characteristics and a method of coating the same (US patent Nos. 5,556,576 and 5,728,322).
  • PTC is an abbreviated word of positive temperature co ⁇ efficients of resistivity, which indicates that resistance is increased with an increase in temperature.
  • the term PTC characteristics refer to self-temperature control charac ⁇ teristics.
  • the conductive polymer paste disclosed in the above-mentioned US patents has various material advantages, including low electrical resistance, PTC flexibility, and easy moldability. Nevertheless this polymer paste contains no organic diluent having strong volatility, and thus, requires very limited conditions in its handling, transport and storage. Particularly, working environments for the preparation of the polymer paste and for the production of the plane heater are harmful to the health of workers, and the polymer paste is always exposed to the risk of fire, and thus, it is actually difficult to produce the polymer paste and the plane heater in large quantities. Disclosure of Invention
  • the present invention has been made to solve the above-described problems occurring in the prior art, and it is an object of the present invention to provide an aqueous conductive polymer composition which is based on an aqueous polymer, so that its handling, transport and storage are easy, processes for preparing the polymer and for producing the composition are very safe, and the composition has a very low fire risk which makes the mass production of the composition possible, as well as a preparation method thereof.
  • the present invention provides an aqueous conductive polymer composition with PTC of resistivity, comprising: 80-100 parts by weight of a water- soluble polymer; 80-100 parts by weight of alcohol paraffin wax; 20-40 parts by weight of carbon black powder with a particle size of 0.02-0.06 D; and 0.05-0.1 part by weight of a surfactant.
  • the present invention provides a method for preparing an aqueous conductive polymer composition with PTC of resistivity, the method comprising the steps of: mixing 80-100 parts by weight of a water-soluble polymer with 80-100 parts by weight of alcohol paraffin wax; dissolving the mixture by heating at a temperature of 80-100 0 C; adding 80-800 parts by weight of hot water to the mixture solution, and stirring and cooling the aqueous mixture; and sequentially adding 20-40 parts by weight of carbon black with a particle size of 0.02-0.06 D and 0.05-0.1 part by weight of a surfactant to the cooled mixture with stirring.
  • the aqueous conductive polymer composition according to the present invention comprises: a water-soluble polymer which is a basic resin material acting as both a binder and an emulsifier; alcohol paraffin wax which is a monomolecular crystalline material for imparting PTC characteristics; carbon black powder for imparting con ⁇ ductivity to the polymer; and a surfactant for finely dispersing these components in an aqueous solvent.
  • Examples of the water-soluble polymer which can be used as the basic resin material in the present invention include polyethylene glycol, polyethylene oxide and a mixture thereof.
  • This water-soluble polymer after cured, functions to provide mechanical strength. Namely, after cured by heating, the polymer has sufficient intrinsic resistance to heat and oxygen and particularly, stably maintains its physical a nd mechanical strengths against repeated heating and cooling.
  • the content of the water-soluble polymer is 80-100 parts by weight. If the content of the water-soluble polymer is less than 80 parts by weight, the mechanical strength of the cured polymer will become weak, and if it is more than 100 parts by weight, the characteristics of the other components will be adversely affected.
  • a material used to impart PTC characteristics to the composition is a monomolecular crystalline compound having the maximum volume at its melting point, and preferably alcohol paraffin wax. Paraffin having no impurity has higher resistance in the cured polymer.
  • the content of paraffin wax in the inventive composition is 80-100 parts by weight which is the same as the content of the water- soluble polymer. If the content of the paraffin wax is less than 80 parts by weight, the desired PTC characteristics cannot be obtained, and if it is more than 100 parts by weight, it will be difficult to expect an increase in effects caused by an increase in the content.
  • the material for imparting PTC characteristics must have good compatibility with the basic resin material, and if the kind of the basic resin material varies, the kind of the material for imparting PTC characteristics should also vary in order to realize the physical and mechanical properties of the basic resin material.
  • Carbon black powder used to impart conductivity to the polymer preferably has a particle size of 0.02-0.06 D and a content of 20-40 parts by weight. If the content of the conductive carbon black in the inventive composition is less than 20 parts by weight, the conductivity of the polymer will become poor, so that the desired heating effect cannot be achieved, and if the content is more than 40 parts by weight, the content of the other components will be relatively reduced so that the overall physical properties of the composition will be adversely affected.
  • a surfactant a nonionic dispersing and leveling agent is used.
  • the surfactant functions to finely disperse the above-described components in an aqueous solvent, and its content is preferably 0.05-0.1 part by weight.
  • the conductive polymer composition according to the present invention is prepared in the following manner.
  • the conductive polymer composition thus prepared is used to prepare a plane heater according to the present invention.
  • the conductive polymer composition is prepared in the form of an impregnable paste, and the paste is im ⁇ pregnated into a fibrous substrate, thus preparing a plane heater.
  • the surface of the prepared plane heater may also be treated with styrene-butadiene rubber (SBR) latex as a moisture-proofing agent.
  • SBR styrene-butadiene rubber
  • Example 1 except that polyethylene oxide in place of polyethylene glycol is used as the water-soluble polymer.
  • Example 1 except that a 1 : 1 (w/w) mixture of polyethylene oxide and polyethylene glycol is used as the water-soluble polymer.
  • a paste of the aqueous conductive compositions prepared in each of Examples 1-3 is impregnated into a fibrous fabric.
  • the resulting fabric is dried at 130 0 C and cured to prepare a plane heater.
  • the surface of the prepared plane heater is applied with latex as a moisture-proofing agent.
  • the plane heater thus prepared was measured for R /R (R : p r p peak resistance, and R r : resistance at room temperature), and as a result, the R p /R r was about 10 and had no significant difference between Examples 1-3.
  • the aqueous conductive polymer composition according to the present invention contains no volatile organic diluent.
  • a working process for preparing the composition is safe and the composition is not exposed to the risk of fire so that it can be produced in large amounts.
  • the aqueous conductive polymer composition is very excellent in thermal stability since it has PTC characteristics where it is heated to an initial heating temperature of 60-70 0 C and no longer heated.
  • the composition allows the mass production of dyeable plane heaters.

Abstract

The present invention relates to an aqueous conductive polymer composition with positive temperature coefficients (PTC) of resistivity, and more particularly, to an aqueous conductive polymer composition used for preparation of a plane heater and having PTC characteristics (self-temperature control characteristics) where it is heated only to an initial heating temperature of 60-70 0C and no longer heated, as well as a preparation method thereof.

Description

Description
AQUEOUS CONDUCTIVE POLYMER COMPOSITION WITH PTC OF RESISTIVITY AND PREPARATION THEREOF
Technical Field
[1] The present invention relates to an aqueous conductive polymer composition with positive temperature coefficients (PTC) of resistivity, and more particularly, to an aqueous conductive polymer composition used for preparation of a plane heater and having PTC characteristics (self-temperature control characteristics) where it is heated only to an initial heating temperature of 60-70 0C and no longer heated, as well as a preparation method thereof.
Background Art
[2] A plane heater is a novel material which is formed by uniformly applying fine ceramic particles and conductive carbon particles on a fibrous fabric and generates heat upon the application of electricity. The plane heater is widely used as not only a heating material for general homes or offices but also a material for road snow removal, agricultural heating, car sheets, various mattresses and heating clothes. In order to prepare this plane heater, a conductive polymer is generally used. Prior to the present invention, the present inventors developed a conductive polymer paste with PTC characteristics and a method of coating the same (US patent Nos. 5,556,576 and 5,728,322). In this regard, PTC is an abbreviated word of positive temperature co¬ efficients of resistivity, which indicates that resistance is increased with an increase in temperature. The term PTC characteristics refer to self-temperature control charac¬ teristics.
[3] The conductive polymer paste disclosed in the above-mentioned US patents has various material advantages, including low electrical resistance, PTC flexibility, and easy moldability. Nevertheless this polymer paste contains no organic diluent having strong volatility, and thus, requires very limited conditions in its handling, transport and storage. Particularly, working environments for the preparation of the polymer paste and for the production of the plane heater are harmful to the health of workers, and the polymer paste is always exposed to the risk of fire, and thus, it is actually difficult to produce the polymer paste and the plane heater in large quantities. Disclosure of Invention
Technical Solution
[4] Therefore, the present invention has been made to solve the above-described problems occurring in the prior art, and it is an object of the present invention to provide an aqueous conductive polymer composition which is based on an aqueous polymer, so that its handling, transport and storage are easy, processes for preparing the polymer and for producing the composition are very safe, and the composition has a very low fire risk which makes the mass production of the composition possible, as well as a preparation method thereof.
[5] Hereinafter, the present invention will be described in detail.
[6] In one aspect, the present invention provides an aqueous conductive polymer composition with PTC of resistivity, comprising: 80-100 parts by weight of a water- soluble polymer; 80-100 parts by weight of alcohol paraffin wax; 20-40 parts by weight of carbon black powder with a particle size of 0.02-0.06 D; and 0.05-0.1 part by weight of a surfactant.
[7] In another aspect, the present invention provides a method for preparing an aqueous conductive polymer composition with PTC of resistivity, the method comprising the steps of: mixing 80-100 parts by weight of a water-soluble polymer with 80-100 parts by weight of alcohol paraffin wax; dissolving the mixture by heating at a temperature of 80-100 0C; adding 80-800 parts by weight of hot water to the mixture solution, and stirring and cooling the aqueous mixture; and sequentially adding 20-40 parts by weight of carbon black with a particle size of 0.02-0.06 D and 0.05-0.1 part by weight of a surfactant to the cooled mixture with stirring.
[8] The aqueous conductive polymer composition according to the present invention comprises: a water-soluble polymer which is a basic resin material acting as both a binder and an emulsifier; alcohol paraffin wax which is a monomolecular crystalline material for imparting PTC characteristics; carbon black powder for imparting con¬ ductivity to the polymer; and a surfactant for finely dispersing these components in an aqueous solvent.
[9] Examples of the water-soluble polymer which can be used as the basic resin material in the present invention include polyethylene glycol, polyethylene oxide and a mixture thereof. This water-soluble polymer, after cured, functions to provide mechanical strength. Namely, after cured by heating, the polymer has sufficient intrinsic resistance to heat and oxygen and particularly, stably maintains its physical a nd mechanical strengths against repeated heating and cooling. In the composition of the present invention, the content of the water-soluble polymer is 80-100 parts by weight. If the content of the water-soluble polymer is less than 80 parts by weight, the mechanical strength of the cured polymer will become weak, and if it is more than 100 parts by weight, the characteristics of the other components will be adversely affected.
[10] A material used to impart PTC characteristics to the composition is a monomolecular crystalline compound having the maximum volume at its melting point, and preferably alcohol paraffin wax. Paraffin having no impurity has higher resistance in the cured polymer. The content of paraffin wax in the inventive composition is 80-100 parts by weight which is the same as the content of the water- soluble polymer. If the content of the paraffin wax is less than 80 parts by weight, the desired PTC characteristics cannot be obtained, and if it is more than 100 parts by weight, it will be difficult to expect an increase in effects caused by an increase in the content. The material for imparting PTC characteristics must have good compatibility with the basic resin material, and if the kind of the basic resin material varies, the kind of the material for imparting PTC characteristics should also vary in order to realize the physical and mechanical properties of the basic resin material.
[11] Carbon black powder used to impart conductivity to the polymer preferably has a particle size of 0.02-0.06 D and a content of 20-40 parts by weight. If the content of the conductive carbon black in the inventive composition is less than 20 parts by weight, the conductivity of the polymer will become poor, so that the desired heating effect cannot be achieved, and if the content is more than 40 parts by weight, the content of the other components will be relatively reduced so that the overall physical properties of the composition will be adversely affected.
[12] In addition, as a surfactant, a nonionic dispersing and leveling agent is used. The surfactant functions to finely disperse the above-described components in an aqueous solvent, and its content is preferably 0.05-0.1 part by weight.
[13] The conductive polymer composition according to the present invention is prepared in the following manner.
[14] First, 80-100 parts by weight of the water-soluble polymer is sufficiently mixed with 80-100 parts by weight of the alcohol paraffin wax, and the mixture is dissolved by heating at a temperature of 80-100 0C. Then, 80-800 parts by weight of hot water is added to the mixture and cooled to room temperature with sufficient stirring. Then, 20-400 parts by weight of carbon black powder with a particle size of 0.02-0.06 D is added to the cooled mixture and stirred until a smooth paste is formed. To the paste, 0.05-0.1 part by weight of the surfactant is added and sufficiently stirred until the carbon black powder is substantially uniformly dispersed.
[15] The conductive polymer composition thus prepared is used to prepare a plane heater according to the present invention. For this purpose, the conductive polymer composition is prepared in the form of an impregnable paste, and the paste is im¬ pregnated into a fibrous substrate, thus preparing a plane heater. The surface of the prepared plane heater may also be treated with styrene-butadiene rubber (SBR) latex as a moisture-proofing agent. Best Mode for Carrying Out the Invention
[16] Hereinafter, the present invention will be described in further detail by examples. It is to be understood, however, that the scope of the present invention is not limited to or by the examples.
[17] Example 1
[18] 95 parts by weight of polyethylene glycol and 95 parts by weight of paraffin wax are mixed with each other and dissolved in a stirring vessel by heating to about 90 0C. Then, 200 parts by weight of hot water is added to the solution, and the mixture is stirred until solids are finely dispersed. Then, the stirred mixture is cooled to room temperature. Then, 30 parts by weight of carbon black powder with a particle size of 0.02-0.06 D is added to the cooled mixture and stirred at about 1,500 rpm for about 3 hours. Then, 0.08 parts by weight of a surfactant (Disperol UDL-200 manufactured by Shinyoung Chemical Industrial Co., Ltd.) is added to the stirred mixture, and the resulting mixture is passed through three rolling mills, thus obtaining an aqueous conductive polymer composition.
[19] Example 2
[20] An aqueous conductive polymer composition is prepared in the same manner as in
Example 1 except that polyethylene oxide in place of polyethylene glycol is used as the water-soluble polymer.
[21] Example 3
[22] An aqueous conductive polymer composition is prepared in the same manner as in
Example 1 except that a 1 : 1 (w/w) mixture of polyethylene oxide and polyethylene glycol is used as the water-soluble polymer.
[23] A paste of the aqueous conductive compositions prepared in each of Examples 1-3 is impregnated into a fibrous fabric. The resulting fabric is dried at 130 0C and cured to prepare a plane heater. The surface of the prepared plane heater is applied with latex as a moisture-proofing agent. The plane heater thus prepared was measured for R /R (R : p r p peak resistance, and R r : resistance at room temperature), and as a result, the R p /R r was about 10 and had no significant difference between Examples 1-3. Industrial Applicability
[24] As described above, the aqueous conductive polymer composition according to the present invention contains no volatile organic diluent. Thus, a working process for preparing the composition is safe and the composition is not exposed to the risk of fire so that it can be produced in large amounts. Also, the aqueous conductive polymer composition is very excellent in thermal stability since it has PTC characteristics where it is heated to an initial heating temperature of 60-70 0C and no longer heated. In addition, the composition allows the mass production of dyeable plane heaters.

Claims

Claims
[1] An aqueous conductive polymer composition with PTC of resistivity, comprising:
80-100 parts by weight of a water-soluble polymer;
80-100 parts by weight of alcohol paraffin wax;
20-40 parts by weight of carbon black powder with a particle size of 0.02-0.06 D; and
0.05-0.1 part by weight of a surfactant. [2] The polymer composition of Claim 1, wherein the water-soluble polymer is polyethylene glycol, polyethylene oxide or a mixture thereof. [3] A method for preparing an aqueous conductive polymer composition with PTC of resistivity, the method comprising the steps of: mixing 80-100 parts by weight of a water-soluble polymer with 80-100 parts by weight of alcohol paraffin wax; dissolving the mixture by heating at a temperature of 80-100 0C; adding 80-800 parts by weight of hot water to the mixture solution and stirring and cooling the aqueous mixture; and sequentially adding 20-40 parts by weight of carbon black with a particle size of
0.02-0.06 D and 0.05-0.1 part by weight of a surfactant to the cooled mixture with stirring. [4] A plane heater prepared by impregnating a fibrous fabric with an aqueous conductive polymer composition prepared according to the method of Claim 3. [5] The plane heater of Claim 4, which has a surface treated with styrene -butadiene rubber (SBR) and finally finished.
PCT/KR2005/002003 2004-07-08 2005-06-27 Aqueous conductive polymer composition with ptc of resistivity and preparation thereof WO2006006771A1 (en)

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KR1020040053166A KR20060004158A (en) 2004-07-08 2004-07-08 Aqueous conductive polymer composition with ptc of resistivity and preparation therof
KR10-2004-0053166 2004-07-08

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017113884A1 (en) 2016-06-22 2017-12-28 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Electrically conductive moldings with a positive temperature coefficient
CN108440777A (en) * 2018-03-19 2018-08-24 河北中烯科技有限公司 Novel graphite alkene water-based electric heating film and preparation method thereof

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US5286415A (en) * 1992-12-28 1994-02-15 Advanced Products, Inc. Water-based polymer thick film conductive ink
US5658499A (en) * 1994-11-07 1997-08-19 Heraeus, Incorporated Aqueous silver compositions
JP2002179954A (en) * 2000-10-10 2002-06-26 Deha Manteku Co Ltd Photo-setting transparent conductive coating material containing aqueous conductive polymer solution, and transparent conductive film formed by using it
US6586041B1 (en) * 1998-11-06 2003-07-01 Goex Corporation Transparent static dissipative coating compositions
US6692663B2 (en) * 2001-02-16 2004-02-17 Elecon, Inc. Compositions produced by solvent exchange methods and uses thereof
US20040124504A1 (en) * 2002-09-24 2004-07-01 Che-Hsiung Hsu Electrically conducting organic polymer/nanoparticle composites and methods for use thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5286415A (en) * 1992-12-28 1994-02-15 Advanced Products, Inc. Water-based polymer thick film conductive ink
US5658499A (en) * 1994-11-07 1997-08-19 Heraeus, Incorporated Aqueous silver compositions
US6586041B1 (en) * 1998-11-06 2003-07-01 Goex Corporation Transparent static dissipative coating compositions
JP2002179954A (en) * 2000-10-10 2002-06-26 Deha Manteku Co Ltd Photo-setting transparent conductive coating material containing aqueous conductive polymer solution, and transparent conductive film formed by using it
US6692663B2 (en) * 2001-02-16 2004-02-17 Elecon, Inc. Compositions produced by solvent exchange methods and uses thereof
US20040124504A1 (en) * 2002-09-24 2004-07-01 Che-Hsiung Hsu Electrically conducting organic polymer/nanoparticle composites and methods for use thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017113884A1 (en) 2016-06-22 2017-12-28 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Electrically conductive moldings with a positive temperature coefficient
WO2017220747A1 (en) 2016-06-22 2017-12-28 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Electrically conductive shaped body with a positive temperature coefficient
CN109328390A (en) * 2016-06-22 2019-02-12 纺织和塑料研究协会图林根研究院 Conductive formed body with positive temperature coefficient
US10468164B2 (en) 2016-06-22 2019-11-05 Thueringisches Institut Fuer Textil-Und Kunststoff-Forschung E.V. Electrically conductive shaped body with a positive temperature coefficient
CN108440777A (en) * 2018-03-19 2018-08-24 河北中烯科技有限公司 Novel graphite alkene water-based electric heating film and preparation method thereof
CN108440777B (en) * 2018-03-19 2021-02-12 河北中烯科技有限公司 Graphene water-based electrothermal film and preparation method thereof

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