CN108521683B - Nano-cellulose graphene oxide electric heating material and preparation method thereof - Google Patents
Nano-cellulose graphene oxide electric heating material and preparation method thereof Download PDFInfo
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- CN108521683B CN108521683B CN201810462147.0A CN201810462147A CN108521683B CN 108521683 B CN108521683 B CN 108521683B CN 201810462147 A CN201810462147 A CN 201810462147A CN 108521683 B CN108521683 B CN 108521683B
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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—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater 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—Heater 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
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Abstract
The invention provides a nano-cellulose graphene oxide electric heating material and a preparation method thereof, wherein the preparation method comprises the following steps: a substrate; the heating layer is formed on the substrate and contains graphene, graphene oxide and nano-cellulose; and an electrode connected to the heat generating layer. The preparation method comprises selecting a substrate; coating or brushing a coating on the molded surface of the substrate to form a first insulating layer; mixing and dispersing the nano-cellulose and the graphene oxide to obtain a mixed system; carrying out ultrasonic dispersion on graphene, mixing the graphene with the mixed system, continuing to carry out ultrasonic dispersion to obtain a composite dispersion system, and coating the composite dispersion system on the first insulating coating by an ink-jet printing or spraying or brushing film-forming method to form a heating layer; arranging an electrode to be connected with the heating layer; and spraying or brushing the coating on the heating layer to form a second insulating layer to obtain the nano-cellulose graphene oxide electric heating material.
Description
Technical Field
The invention relates to the field of nano-cellulose electrothermal functional materials. More specifically, the invention relates to a nano-cellulose graphene oxide electric heating material with hydrophobicity, stable working temperature and uniform temperature distribution and a preparation method thereof.
Background
The graphene electrothermal material has high electrothermal conversion efficiency and quick heating response, can be used in the fields of snow melting and deicing, defogging and defrosting, heating and warming, microelectronic device heating and heat preservation, micro-region heating analysis and the like, and is an important direction for graphene application. At present, in related research, carbon fibers and slurry are compounded to obtain a base material, graphene and other auxiliaries are mixed to form slurry, the slurry is attached to the base material according to a preset process, and the graphene electric heating material is obtained through a series of curing and drying. The graphene obtained by the process has the advantages of good flexibility, difficult oxidation and the like; in addition, related research utilizes particles such as carbon fibers, graphite powder and carbon nanotubes added in a high polymer material to prepare a high polymer electrothermal material. The electric heating material solves the problem that the heat insulation effect of the high-molecular electric heating material is influenced by unstable electric resistance value caused by uneven mixing of the conductive particles. The electric heating material has larger resistance value, and is more suitable for a heating and heat-preserving device which is heated at low temperature and is in close contact with a human body; in addition, related researches also utilize the graphene aerogel to heat up to a certain temperature at a certain speed in an inert atmosphere and then cool down, so that the graphene electrothermal film with a certain density and hole size is obtained. The preparation method obtains the pressure-sensitive electrothermal film based on graphene. The pressure-sensitive electrothermal film comprises a graphene electrothermal film and insulating protective layers coated on the upper side and the lower side of the high-efficiency pressure-sensitive graphene electrothermal film. The pressure-sensitive electrothermal film can make quick electrothermal response under different stress strains, and the larger the stress is, the higher the electrothermal response saturation temperature is. The technology is simple in preparation process, and the prepared graphene-based pressure-sensitive electrothermal material is excellent in performance and has quick electrothermal response. Is suitable for large-scale production in production. Has wide application in the aspects of absorbent regeneration, catalytic framework and the like.
The inventor also applied for a Chinese patent of a nano-cellulose graphene composite electrothermal film and a green preparation process thereof before, wherein the application number of the patent is 2017104727432, the patent discloses that a composite film is prepared by mixing graphene and nano-cellulose, and the composite film can be used as the electrothermal film after being attached to an electrode and an insulating layer. In the technical scheme, when the nano-cellulose is blended with the graphene, under the cross-linking action, the nano-cellulose is equivalent to a skeleton tissue to support the graphene, but the simple use of the nano-cellulose as the skeleton tissue has the following problems: the space network framework structure formed by the nano-cellulose is not obvious, the dispersion degree of the graphene in the nano-cellulose framework structure is not high, the film uniformity formed by cross-linking and mixing of the nano-cellulose and the graphene is not high, and the heat conductivity and the stability of the prepared electric heating film are not good enough.
Similarly, the related researches have the defects that the dispersion degree of graphene is not high, the temperature is not uniform, water is easy to absorb and seep, and the stability of the working process is not facilitated. In addition, the prior art is rarely applicable to the preparation of the electrothermal material on the surface of the special-shaped substrate.
Disclosure of Invention
It is an object of the present invention to address at least the above-mentioned deficiencies and to provide at least the advantages which will be described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a nanocellulose graphene oxide electrocaloric material, comprising:
a substrate; different materials can be selected as the substrate according to the requirements, such as wood plate, iron plate, plastic and the like
The heating layer is formed on the substrate and contains graphene, graphene oxide and nano-cellulose; after the graphene oxide and the nano-cellulose are mixed and dispersed, a three-dimensional reticular framework structure can be formed in a cross-linking mode, the three-dimensional reticular framework structure is compared with a framework structure formed by directly utilizing the nano-cellulose in a traditional method, on one hand, the stability of the framework structure is increased, on the other hand, gaps in the three-dimensional reticular framework structure are more regular and uniform, the dispersion uniformity of the graphene in the framework structure is favorably improved, the heating uniformity of the prepared electric heating material is higher, and further, the mechanical property and the thermal stability of the electric heating material are improved.
And the electrode is connected to the heating layer and used for electrifying and heating.
Preferably, in the nano-cellulose graphene oxide electric heating material, the substrate has a certain molded surface, and the molded surface is a curved surface, a circular arc surface or a plane. For accommodating substrates of different profiles.
Preferably, the nanocellulose graphene oxide electric heating material further comprises a first insulating layer formed between the substrate and the heating layer, and a second insulating layer formed on the other surface of the heating layer, so that electric leakage of the heating layer is avoided.
Preferably, in the nano-cellulose graphene oxide electric heating material, the first insulating layer and the second insulating layer are made of epoxy resin, polyurethane, heterocyclic polymer and organic polymer paint, and the thickness is 0.02-0.3 mm.
Preferably, in the nanocellulose graphene oxide electrothermal material, the electrode is longer than the second insulating layer and shorter than the first insulating layer, so that the electrode is partially exposed, and the electric connection and the electrifying work are facilitated.
Preferably, the mass ratio of the graphene in the heating layer is 25-65%, and the mass ratio of the graphene oxide and the nano-cellulose is 35-75%; wherein the graphene oxide accounts for 10-60% of the total mass of the graphene oxide and the nano-cellulose.
Preferably, in the nano-cellulose graphene oxide electric heating material, the heating layer further comprises a hydrophobic agent, the hydrophobic agent is any one of fluoropolymer, fluorine-containing silane, fluorinated amphiphobic polyurethane, a mixed solution of nano-silica and perfluoroalkyl methacrylic acid copolymer, and an emulsion mixture of beeswax and palm wax, and the addition amount of the hydrophobic agent is 0.08-4.2% of the weight of the heating layer material.
A preparation method of a nano-cellulose graphene oxide electric heating material comprises the following steps:
selecting a substrate;
coating or brushing a coating on the molded surface of the substrate to form a first insulating layer;
mixing and dispersing the nano-cellulose and the graphene oxide to obtain a mixed system or mixing and dispersing the nano-cellulose, the graphene oxide and a hydrophobic agent to obtain a mixed system; carrying out ultrasonic dispersion on graphene, mixing the graphene and the mixed system, continuing to carry out ultrasonic dispersion to obtain a composite dispersion system, and coating the composite dispersion system on the first insulating coating by an ink-jet printing or spraying or brushing film forming method to form a heating layer; the graphene oxide and the nanocellulose are fully utilized to form a three-dimensional net through mutual crosslinking, and the surfaces of the graphene oxide and the nanocellulose in an aqueous phase system both have negative potential characteristics, so that the dispersion uniformity and the electric heating temperature uniformity of the graphene in the system are improved, the mechanical property and the thermal stability of the electric heating material are enhanced, and particularly, the adhesive force to a substrate is enhanced.
Arranging an electrode to be connected with the heating layer;
and spraying or brushing a coating on the heating layer to form a second insulating layer to obtain the nano-cellulose graphene oxide electric heating material.
Preferably, the preparation method of the nano-cellulose graphene oxide electric heating material specifically comprises the following steps:
selecting a substrate, and spraying or brushing paint on the surface of the substrate to form a first insulating layer after the substrate is coated with a surfactant and dried, wherein the coating weight is 50-200 g/m2And then the mixture is placed in a vacuum drying oven to be dried for 3 to 6 hours at the temperature of 70 to 90 ℃;
adhering copper foil or copper sheet on the substrate insulating coating to form an electrode, or printing or coating conductive paint or conductive colloid on the first insulating layer and drying to form the electrode;
preparing a mixed solution of graphene oxide and nano-cellulose or a mixed solution of graphene oxide, nano-cellulose and a hydrophobic agent into a water dispersion solution with the concentration of 0.1-2 mg/ml, and performing ultrasonic dispersion for 10-70 min at the power of 300-1000W to obtain a mixed system;
preparing graphene aqueous dispersion with the concentration of 0.1-3 mg/ml, and performing ultrasonic dispersion for 10-70 min under the power of 500-1000W to obtain the graphene aqueous dispersion, wherein the graphene accounts for 25-65% of the weight of the heating layer material;
step five, mixing the mixed system with the graphene aqueous dispersion, and carrying out ultrasonic treatment for 20-100 min at the power of 300-1200W to obtain a composite dispersion system;
sixthly, ink-jet printing or spraying or brushing the composite dispersion system on the first insulating layer, wherein the printing amount is 4-26 g/m2Then, againDrying in a vacuum drying oven at 50-80 ℃ for 6-24 h to form a heating layer;
seventhly, manually or mechanically polishing by using sand paper to remove redundant heating layers according to the preset effective heating surface shape and size;
step eight, spraying or brushing a second insulating layer on the surface of the heating layer, wherein the coating weight is 50-200 g/m2And drying the mixture in a vacuum drying oven at 70-90 ℃ for 3-6 h to obtain an electric heating material;
and step nine, quenching the obtained electric heating material, and electrifying for 2-12 hours by 1.5-2.5 times of the rated power of the electric heating material, partially removing defect groups on graphene and graphene oxide sheets, improving the conductivity, and forming the nano-cellulose graphene oxide electric heating material with a stable structure and stable power.
Preferably, in the preparation method of the nano-cellulose graphene oxide electric heating material, the graphene oxide accounts for 10-60% of the total weight of the nano-cellulose and the graphene oxide, and the nano-cellulose and the graphene oxide account for 35-75% of the mass of the heating layer; if the water repellent agent is used, the addition amount of the water repellent agent is 0.08-4.2% of the mass of the material of the heat-generating layer.
The invention at least comprises the following beneficial effects:
firstly, the graphene oxide and the nano-cellulose with better film forming capability are adopted, and a certain amount of hydrophobic agent is mixed with the graphene, so that the compactness and the humidity resistance stability of the surface of the electric heating material are improved, and the working stability is enhanced.
According to the invention, the graphene oxide dispersion liquid and the nano-cellulose are mixed to prepare the dispersion system, and the graphene oxide dispersion liquid and the nano-cellulose are independently dispersed and then are blended and dispersed, so that the graphene oxide and the nano-cellulose are fully utilized to form a three-dimensional net through mutual crosslinking, and the surfaces of the graphene oxide and the nano-cellulose in an aqueous phase system are both negative potential characteristics, so that the dispersion uniformity and the electric heating temperature uniformity of the graphene in the system are improved, the mechanical property and the thermal stability of the electric heating material are enhanced, and particularly, the adhesive force to a substrate is enhanced.
The invention takes the coating as the insulating layer, and the method for preparing the electrothermal layer by ink-jet printing or spraying or brushing is suitable for the surfaces of various molded surface substrates.
The invention adopts the spraying process to be suitable for the surfaces of various profile substrates, and adopts the graphene oxide with certain hydrophobic property and the hydrophobic agent to improve the moisture-proof stability of the electric heating material and improve the adhesive force of the electric heating material to the substrate coating; the graphene oxide and the nano-cellulose with good film-forming performance are used as a dispersion system, so that the dispersion uniformity of the graphene is effectively improved, the distribution uniformity of the working temperature is improved, and the coating is used as a waterproof layer, so that the applicability of the coating is favorably improved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a scanning electron microscope picture of a nanocellulose graphene oxide electrothermal material prepared in example 1 of the present invention with a magnification of 1000 times;
FIG. 2 is a scanning electron microscope picture of comparative material 1 prepared according to comparative example 1 of the present invention at a magnification of 1000 times;
FIG. 3 is a comparative graph of the current-carrying conditions of the nano-cellulose graphene oxide electric heating material prepared in example 1 of the present invention and the comparative material 1 prepared in comparative example 1;
FIG. 4 is a comparative graph of the current carrying situation of the nano-cellulose graphene oxide electric heating material prepared in example 2 of the present invention and the comparative material 2 prepared in comparative example 2;
FIG. 5 is a comparative graph of the current-carrying conditions of the nano-cellulose graphene oxide electric heating material prepared in example 3 and the comparative material 3 prepared in comparative example 3;
FIG. 6 is a thermogravimetric comparison graph of a nano-cellulose graphene oxide electric heating material prepared in example 1 and a comparative material 1 prepared in comparative example 1.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The main raw materials of the invention are:
example 1
Step one, selecting a substrate, spraying paint on the surface of the substrate to form a first insulating layer after the substrate is coated with a surfactant and dried, wherein the coating weight is 100g/m2And drying the mixture for 5 hours in a vacuum drying oven at the temperature of 80 ℃.
Adhering the copper foil on the substrate insulating coating to manufacture an electrode; the distance between two electrodes and the arrangement direction are determined according to the required effective heating breadth and the substrate profile.
Weighing 5g of graphene, 2.5g of graphene oxide and 2.5g of nanocellulose in a mass ratio of 0.5:0.25:0.25, mixing the weighed graphene oxide and nanocellulose to prepare a water dispersion liquid with the concentration of 0.5mg/ml, and performing ultrasonic dispersion for 50min at the power of 800W to obtain a mixed system.
And step four, preparing the graphene aqueous dispersion with the concentration of 0.5mg/ml by using the weighed graphene, and performing ultrasonic dispersion for 50min under the power of 800W to obtain the graphene aqueous dispersion.
And step five, mixing the mixed system with the graphene aqueous dispersion, and performing ultrasonic treatment for 50min at the power of 900W to obtain a composite dispersion system.
Sixthly, ink-jet printing is carried out on the composite dispersion system on the first insulating layer, and the coating amount is 15g/m2(by weight of dry matter)) Then placing the mixture in a vacuum drying oven to dry for 15 hours at 70 ℃ to form a heating layer; the size of the heating layer spans over 5mm of the electrodes at the two ends; parallel to the length direction of the electrode, one end of the electrode is smaller than the length of the electrode by 15mm (the electric connection end), and the other end of the electrode is smaller than the length of the electrode by 3 mm.
And seventhly, manually or mechanically polishing by using sand paper to remove redundant heating layers according to the preset shape and size of the effective heating surface.
Step eight, spraying or painting a second insulating layer on the surface of the heating layer, wherein the coating weight is 100g/m2And drying the mixture in a vacuum drying oven at 80 ℃ for 5 hours to obtain the electric heating material.
And step nine, quenching the obtained electric heating material, and after the electric heating material is electrified for 12 hours by 1.5 times of rated power, partially removing defect groups on graphene and graphene oxide sheets, improving the electric conductivity and the phase structure regularity, and forming the nano-cellulose graphene oxide electric heating film with a stable structure and stable power.
Example 2
Step one, selecting a substrate, spraying paint on the surface of the substrate to form a first insulating layer after the substrate is coated with a surfactant and dried, wherein the coating weight is 100g/m2And drying the mixture for 5 hours in a vacuum drying oven at the temperature of 80 ℃.
Adhering the copper foil on the substrate insulating coating to manufacture an electrode; the distance between two electrodes and the arrangement direction are determined according to the required effective heating breadth and the substrate profile.
Weighing 3.5g of graphene, 3.25g of graphene oxide and 3.25g of nanocellulose in a mass ratio of 0.35:0.325:0.325, mixing the weighed graphene oxide and nanocellulose to prepare a water dispersion liquid with the concentration of 0.5mg/ml, and performing ultrasonic dispersion for 50min at the power of 800W to obtain a mixed system.
And step four, preparing the graphene aqueous dispersion with the concentration of 0.5mg/ml by using the weighed graphene, and performing ultrasonic dispersion for 50min under the power of 800W to obtain the graphene aqueous dispersion.
And step five, mixing the mixed system with the graphene aqueous dispersion, and performing ultrasonic treatment for 50min at the power of 900W to obtain a composite dispersion system.
Sixthly, ink-jet printing is carried out on the composite dispersion system on the first insulating layer, and the coating amount is 15g/m2Drying at 70 deg.C for 15 hr to form a heating layer; the size of the heating layer spans over 5mm of the electrodes at the two ends; parallel to the length direction of the electrode, one end of the electrode is smaller than the length of the electrode by 15mm (the electric connection end), and the other end of the electrode is smaller than the length of the electrode by 3 mm.
And seventhly, manually or mechanically polishing by using sand paper to remove redundant heating layers according to the preset shape and size of the effective heating surface.
Step eight, spraying or painting a second insulating layer on the surface of the heating layer, wherein the coating weight is 100g/m2And drying the mixture in a vacuum drying oven at 80 ℃ for 5 hours to obtain the electric heating material.
And step nine, quenching the obtained electric heating material, and after the electric heating material is electrified for 12 hours by 1.5 times of rated power, partially removing defect groups on graphene and graphene oxide sheets, improving the electric conductivity and the phase structure regularity, and forming the nano-cellulose graphene oxide electric heating film with a stable structure and stable power.
Example 3
Step one, selecting a substrate, spraying paint on the surface of the substrate to form a first insulating layer after the substrate is coated with a surfactant and dried, wherein the coating weight is 100g/m2And drying the mixture for 5 hours in a vacuum drying oven at the temperature of 80 ℃.
Adhering the copper foil on the substrate insulating coating to manufacture an electrode; the distance between two electrodes and the arrangement direction are determined according to the required effective heating breadth and the substrate profile.
Weighing 5.5g of graphene, 2.25g of graphene oxide and 2.25g of nanocellulose in a mass ratio of 0.55:0.225:0.225, mixing the weighed graphene oxide and nanocellulose to prepare a water dispersion liquid with the concentration of 0.5mg/ml, and performing ultrasonic dispersion for 50min at the power of 800W to obtain a mixed system.
And step four, preparing the graphene aqueous dispersion with the concentration of 0.5mg/ml by using the weighed graphene, and performing ultrasonic dispersion for 50min under the power of 800W to obtain the graphene aqueous dispersion.
And step five, mixing the mixed system with the graphene aqueous dispersion, and performing ultrasonic treatment for 50min at the power of 900W to obtain a composite dispersion system.
Sixthly, ink-jet printing is carried out on the composite dispersion system on the first insulating layer, and the coating amount is 15g/m2Drying at 70 deg.C for 15 hr to form a heating layer; the size of the heating layer spans over 5mm of the electrodes at the two ends; parallel to the length direction of the electrode, one end of the electrode is smaller than the length of the electrode by 15mm (the electric connection end), and the other end of the electrode is smaller than the length of the electrode by 3 mm.
And seventhly, manually or mechanically polishing by using sand paper to remove redundant heating layers according to the preset shape and size of the effective heating surface.
Step eight, spraying or painting a second insulating layer on the surface of the heating layer, wherein the coating weight is 100g/m2And drying the mixture in a vacuum drying oven at 80 ℃ for 5 hours to obtain the electric heating material.
And step nine, quenching the obtained electric heating material, and after the electric heating material is electrified for 12 hours by 1.5 times of rated power, partially removing defect groups on graphene and graphene oxide sheets, improving the electric conductivity and the phase structure regularity, and forming the nano-cellulose graphene oxide electric heating film with a stable structure and stable power.
Example 4
Selecting a substrate, and spraying or brushing paint on the surface of the substrate to form a first insulating layer after the substrate is coated with a surfactant and dried, wherein the coating weight is 50g/m2And then the mixture is placed in a vacuum drying oven to be dried for 6 hours at the temperature of 70 ℃;
adhering copper foil or copper sheet on the substrate insulating coating to form an electrode, or printing or coating conductive paint or conductive colloid on the first insulating layer and drying to form the electrode;
weighing 0.5:0.25:0.25 mass ratio of graphene, graphene oxide and nanocellulose, namely 5g of graphene, 2.5g of graphene oxide and 2.5g of nanocellulose, weighing a hydrophobizing agent accounting for 0.8% of the total weight of the graphene, the graphene oxide and the nanocellulose, namely 0.08g of hydrophobizing agent, mixing the weighed graphene oxide, the nanocellulose and the hydrophobizing agent to prepare an aqueous dispersion with the concentration of 0.35mg/ml, and ultrasonically dispersing for 70min under 300W power to obtain a mixed system;
preparing graphene aqueous dispersion with the concentration of 0.25mg/ml by using the weighed graphene, and performing ultrasonic dispersion for 70min under the power of 500W to obtain the graphene aqueous dispersion;
step five, mixing the mixed system with the graphene water dispersion, and carrying out ultrasonic treatment for 100min at the power of 300W to obtain a composite dispersion system;
sixthly, the composite dispersion system is subjected to ink-jet printing or spraying or brushing on the first insulating layer, wherein the printing quantity is 4g/m2Then drying the mixture in a vacuum drying oven at 50 ℃ for 24 hours to form a heating layer;
seventhly, manually or mechanically polishing by using sand paper to remove redundant heating layers according to the preset effective heating surface shape and size;
step eight, spraying or painting a second insulating layer on the surface of the heating layer, wherein the coating weight is 50g/m2And then the mixture is placed in a vacuum drying oven to be dried for 6 hours at 70 ℃ to obtain an electric heating material;
and step nine, quenching the obtained electric heating material, and after the electric heating material is electrified for 12 hours by 1.5 times of rated power, partially removing defect groups on graphene and graphene oxide sheets, improving the electric conductivity and the regularity of phase structure, and forming the nano-cellulose graphene oxide electric heating material with stable structure and stable power.
Example 5
Selecting a substrate, and spraying or brushing paint on the surface of the substrate to form a first insulating layer after the substrate is coated with a surfactant and dried, wherein the coating weight is 200g/m2And then the mixture is placed in a vacuum drying oven to be dried for 3 hours at the temperature of 90 ℃;
adhering copper foil or copper sheet on the substrate insulating coating to form an electrode, or printing or coating conductive paint or conductive colloid on the first insulating layer and drying to form the electrode;
weighing 0.5:0.25:0.25 mass ratio of graphene, graphene oxide and nanocellulose, namely 5g of graphene, 2.5g of graphene oxide and 2.5g of nanocellulose, weighing a hydrophobing agent accounting for 4.2% of the total weight of the graphene, the graphene oxide and the nanocellulose, namely 0.42g of the hydrophobing agent, mixing the weighed graphene oxide, the nanocellulose and the hydrophobing agent to prepare an aqueous dispersion with the concentration of 0.75mg/ml, and ultrasonically dispersing for 10min at 1000W to obtain a mixed system;
step four, preparing graphene water dispersion with the concentration of 0.65mg/ml, and performing ultrasonic dispersion for 10min under the power of 1000W to obtain the graphene water dispersion;
step five, mixing the mixed system with the graphene water dispersion, and carrying out ultrasonic treatment for 20min at the power of 1200W to obtain a composite dispersion system;
sixthly, the composite dispersion system is subjected to ink-jet printing or spraying or brushing on the first insulating layer, and the printing quantity is 26g/m2Then placing the mixture in a vacuum drying oven to be dried for 24 hours at the temperature of 80 ℃ to form a heating layer;
seventhly, manually or mechanically polishing by using sand paper to remove redundant heating layers according to the preset effective heating surface shape and size;
step eight, spraying or painting a second insulating layer on the surface of the heating layer, wherein the coating weight is 200g/m2And then the mixture is placed in a vacuum drying oven to be dried for 3 hours at the temperature of 90 ℃ to obtain an electric heating material;
and step nine, quenching the obtained electric heating material, and after electrifying for 2 hours by 2.5 times of the rated power of the electric heating material, partially removing defect groups on the graphene and graphene oxide sheets, improving the conductivity and the phase structure regularity, and forming the nano-cellulose graphene oxide electric heating material with a stable structure and stable power.
Example 6
A nanocellulose graphene oxide electrocaloric material, comprising: a substrate; the heating layer is formed on the substrate and contains graphene, graphene oxide and nano-cellulose; and an electrode connected to the heat generating layer. The mass ratio of graphene in the heating layer is 50%, and the mass ratio of graphene oxide and nanocellulose is 50%; wherein the graphene oxide accounts for 50% of the total mass of the graphene oxide and the nanocellulose.
Example 7
A nanocellulose graphene oxide electrocaloric material, comprising: a substrate; the heating layer is formed on the substrate and contains graphene, graphene oxide, nano-cellulose and a hydrophobic agent; and an electrode connected to the heat generating layer. The heating element also comprises a first insulating layer formed between the substrate and the heating layer and a second insulating layer formed on the other surface of the heating layer. The first insulating layer and the second insulating layer are made of epoxy resin, polyurethane, heterocyclic polymer and organic polymer paint, and the thickness of the first insulating layer and the second insulating layer is 0.02-0.3 mm. The mass ratio of graphene in the heating layer is 50%, the mass ratio of graphene oxide and nano-cellulose is 49%, and the mass ratio of a water repellent agent is 1%; wherein the graphene oxide accounts for 50% of the total mass of the graphene oxide and the nanocellulose.
Comparative example 1
Comparative example 1 differs from example 1 in that: the comparative material 1 was prepared using only nanocellulose and graphene without adding graphene oxide, and the content of graphene was 50%, i.e. the mass ratio of nanocellulose to graphene was 1: 1.
The method specifically comprises the following steps: step one, selecting a substrate, spraying paint on the surface of the substrate to form a first insulating layer after the substrate is coated with a surfactant and dried, wherein the coating weight is 100g/m2And drying the mixture for 5 hours in a vacuum drying oven at the temperature of 80 ℃.
Adhering the copper foil on the substrate insulating coating to manufacture an electrode; the distance between two electrodes and the arrangement direction are determined according to the required effective heating breadth and the substrate profile.
Weighing 5g of graphene and 5g of nanocellulose in a mass ratio of 1:1, mixing the weighed nanocellulose to prepare an aqueous dispersion with a concentration of 0.5mg/ml, and performing ultrasonic dispersion for 50min at a power of 800W to obtain a mixed system.
And step four, preparing the graphene aqueous dispersion with the concentration of 0.5mg/ml by using the weighed graphene, and performing ultrasonic dispersion for 50min under the power of 800W to obtain the graphene aqueous dispersion.
And step five, mixing the mixed system with the graphene aqueous dispersion, and performing ultrasonic treatment for 50min at the power of 900W to obtain a composite dispersion system.
Sixthly, ink-jet printing is carried out on the composite dispersion system on the first insulating layer, and the coating amount is 15g/m2Drying the obtained product for 15 hours in a vacuum drying oven at 70 ℃ to form a heating layer (according to the dry weight of the graphene, the graphene oxide and the nano-cellulose); the size of the heating layer spans over 5mm of the electrodes at the two ends; parallel to the length direction of the electrode, one end of the electrode is smaller than the length of the electrode by 15mm (the electric connection end), and the other end of the electrode is smaller than the length of the electrode by 3 mm.
And seventhly, manually or mechanically polishing by using sand paper to remove redundant heating layers according to the preset shape and size of the effective heating surface.
Step eight, spraying or painting a second insulating layer on the surface of the heating layer, wherein the coating weight is 100g/m2And drying the mixture for 5 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain a dry material;
and step nine, carrying out quenching treatment on the obtained dried material, electrifying for 12 hours by 1.5 times of rated power, and partially removing defect groups on the graphene and graphene oxide sheets to obtain a comparative material 1.
Comparative example 2
Comparative example 2 differs from example 2 in that: the comparative material 2 was prepared using only nanocellulose and graphene without adding graphene oxide, and the content of graphene was 35%, i.e. the mass ratio of nanocellulose to graphene was 0.65: 0.35.
The method specifically comprises the following steps: step one, selecting a substrate, spraying paint on the surface of the substrate to form a first insulating layer after the substrate is coated with a surfactant and dried, wherein the coating weight is 100g/m2And drying the mixture for 5 hours in a vacuum drying oven at the temperature of 80 ℃.
Adhering the copper foil on the substrate insulating coating to manufacture an electrode; the distance between two electrodes and the arrangement direction are determined according to the required effective heating breadth and the substrate profile.
Step three, according to the mass ratio of 0.35: 0.65 weighing 3.5g of graphene and 6.5g of nanocellulose, mixing the weighed nanocellulose to prepare a water dispersion liquid with the concentration of 0.5mg/ml, and performing ultrasonic dispersion for 50min at the power of 800W to obtain a mixed system.
And step four, preparing the graphene aqueous dispersion with the concentration of 0.5mg/ml by using the weighed graphene, and performing ultrasonic dispersion for 50min under the power of 800W to obtain the graphene aqueous dispersion.
And step five, mixing the mixed system with the graphene aqueous dispersion, and performing ultrasonic treatment for 50min at the power of 900W to obtain a composite dispersion system.
Sixthly, ink-jet printing is carried out on the composite dispersion system on the first insulating layer, and the coating amount is 15g/m2Drying the obtained product for 15 hours in a vacuum drying oven at 70 ℃ to form a heating layer (according to the dry weight of the graphene, the graphene oxide and the nano-cellulose); the size of the heating layer spans over 5mm of the electrodes at the two ends; parallel to the length direction of the electrode, one end of the electrode is smaller than the length of the electrode by 15mm (the electric connection end), and the other end of the electrode is smaller than the length of the electrode by 3 mm.
And seventhly, manually or mechanically polishing by using sand paper to remove redundant heating layers according to the preset shape and size of the effective heating surface.
Step eight, spraying or painting a second insulating layer on the surface of the heating layer, wherein the coating weight is 100g/m2And drying the mixture in a vacuum drying oven at 80 ℃ for 5 hours to obtain a dry material.
And step nine, carrying out quenching treatment on the obtained dried material, electrifying for 12 hours by 1.5 times of rated power, and partially removing defect groups on the graphene and graphene oxide sheets to obtain a comparative material 2.
Comparative example 3
Comparative example 3 differs from example 3 in that: the comparative material 3 was prepared using only nanocellulose and graphene without adding graphene oxide, and the content of graphene was 55%, i.e. the mass ratio of nanocellulose to graphene was 0.45: 0.55.
The method specifically comprises the following steps: step one, selecting a substrate, and spraying paint on the surface of the substrate to form the paint after the substrate is coated with a surfactant and driedA first insulating layer coated at a weight of 100g/m2And drying the mixture for 5 hours in a vacuum drying oven at the temperature of 80 ℃.
Adhering the copper foil on the substrate insulating coating to manufacture an electrode; the distance between two electrodes and the arrangement direction are determined according to the required effective heating breadth and the substrate profile.
Step three, according to the mass ratio of 0.55: 0.45, weighing 5.5g of graphene and 4.5g of nanocellulose, mixing the weighed nanocellulose to prepare a water dispersion liquid with the concentration of 0.5mg/ml, and performing ultrasonic dispersion for 50min at the power of 800W to obtain a mixed system.
And step four, preparing the graphene aqueous dispersion with the concentration of 0.5mg/ml by using the weighed graphene, and performing ultrasonic dispersion for 50min under the power of 800W to obtain the graphene aqueous dispersion.
And step five, mixing the mixed system with the graphene aqueous dispersion, and performing ultrasonic treatment for 50min at the power of 900W to obtain a composite dispersion system.
Sixthly, ink-jet printing is carried out on the composite dispersion system on the first insulating layer, and the coating amount is 15g/m2Drying the obtained product for 15 hours in a vacuum drying oven at 70 ℃ to form a heating layer (according to the dry weight of the graphene, the graphene oxide and the nano-cellulose); the size of the heating layer spans over 5mm of the electrodes at the two ends; parallel to the length direction of the electrode, one end of the electrode is smaller than the length of the electrode by 15mm (the electric connection end), and the other end of the electrode is smaller than the length of the electrode by 3 mm.
And seventhly, manually or mechanically polishing by using sand paper to remove redundant heating layers according to the preset shape and size of the effective heating surface.
Step eight, spraying or painting a second insulating layer on the surface of the heating layer, wherein the coating weight is 100g/m2And drying the mixture in a vacuum drying oven at 80 ℃ for 5 hours to obtain the dry material.
And step nine, carrying out quenching treatment on the obtained dried material, electrifying for 12 hours by 1.5 times of rated power, and partially removing defect groups on the graphene and graphene oxide sheets to obtain a comparative material 3.
Data comparison analysis
(A)
FIG. 1 is a scanning electron microscope image of the nano-cellulose graphene oxide electrothermal material prepared by the embodiment at 1000 times magnification. It can be seen from fig. 1 that the surface dispersity of the material is relatively uniform, and the mixing degree is high, because the graphene fully enters the skeleton structure formed by the mixed system of the graphene oxide and the nanocellulose, a structure with uniform and stable dispersity is formed.
FIG. 2 is a scanning electron microscope photograph of comparative example 1 at 1000 times magnification. Fig. 2 shows that spider web-like structures are present on the surface of the material, and the spider web structures are formed by floating on the surface of the material due to incomplete mixing of the nanocellulose and the graphene, and the fundamental reason is that the nanocellulose cannot form a cross-linked structure obviously enough, the graphene cannot be uniformly dispersed in the nanocellulose, and therefore the prepared material is poor in stability.
And secondly, carrying out an electrifying test and thermogravimetric analysis on the materials prepared in the examples 1-3 and the comparative examples 1-3, and recording the electrifying condition and the thermogravimetric condition.
FIG. 3 is a comparative graph of the current-carrying conditions of the nano-cellulose graphene oxide electric heating material prepared in example 1 of the present invention and the comparative material 1 prepared in comparative example 1; wherein, the graphene content is 50%, the thick line without adding graphene oxide corresponds to the electrification condition of the material of the embodiment 1, the graphite content is 50%, the thin line without adding graphene oxide corresponds to the electrification condition of the comparative material 1, as can be seen from fig. 3, the temperature of the material corresponding to the embodiment 1 rises faster and higher with the increase of the electrification time, which shows that the nanocellulose graphene oxide electrothermal material prepared in the embodiment 1 has better heat conductivity, and has a certain degree of improvement compared with the comparative material 1.
FIG. 4 is a comparative graph of the current carrying situation of the nano-cellulose graphene oxide electric heating material prepared in example 2 of the present invention and the comparative material 2 prepared in comparative example 2; wherein, the graphene content is 35%, the thick line without adding graphene oxide corresponds to the electrification condition of the material of the embodiment 2, the graphite content is 35%, the thin line without adding graphene oxide corresponds to the electrification condition of the comparative material 2, as can be seen from fig. 4, the temperature of the material corresponding to the embodiment 2 rises faster and higher with the increase of the electrification time, which shows that the nanocellulose graphene oxide electrothermal material prepared by the embodiment 2 has better heat conduction performance, and has a certain degree of improvement compared with the comparative material 2.
FIG. 5 is a comparative graph of the current-carrying conditions of the nano-cellulose graphene oxide electric heating material prepared in example 3 and the comparative material 3 prepared in comparative example 3; wherein, the graphene content is 55%, the thick line without adding graphene oxide corresponds to the electrification condition of the material of the embodiment 3, the graphite content is 55, the thin line without adding graphene oxide corresponds to the electrification condition of the comparative material 3, as can be seen from fig. 5, the temperature of the material corresponding to the embodiment 3 rises faster and higher with the increase of the electrification time, which shows that the nanocellulose graphene oxide electrothermal material prepared by the embodiment 3 has better heat conduction performance, and has a certain degree of improvement compared with the comparative material 3.
FIG. 6 is a thermogravimetric comparison graph of a nano-cellulose graphene oxide electric heating material prepared in example 1 and a comparative material 1 prepared in comparative example 1. Wherein the line corresponding to the added graphene oxide represents the thermogravimetric condition of the material of the embodiment 1; the thermogravimetric condition of the comparative material 1 represented by the line corresponding to the non-added graphene oxide can be seen from fig. 6, and the mass loss of the film material added with the graphene oxide is smaller than that of the film material without the graphene oxide along with the increase of the temperature. Therefore, the nano-cellulose graphene oxide electric heating material prepared in the embodiment 1 has more excellent thermal stability.
In conclusion, compared with the traditional electric heating material, the nano-cellulose graphene oxide electric heating material has the advantages that the heat conduction performance and the heat stability are improved qualitatively.
While embodiments of the invention have been disclosed above, it is not intended to be limited to the uses set forth in the specification and examples. It can be applied to all kinds of fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art. The invention is not limited to the specific details.
Claims (1)
1. A preparation method of a nano-cellulose graphene oxide electric heating material specifically comprises the following steps:
selecting a substrate, and spraying or brushing paint on the surface of the substrate to form a first insulating layer after the substrate is coated with a surfactant and dried, wherein the coating weight is 50-200 g/m2And then the mixture is placed in a vacuum drying oven to be dried for 3 to 6 hours at the temperature of 70 to 90 ℃;
adhering copper foil or copper sheet on the substrate insulating coating to form an electrode, or printing or coating conductive paint or conductive colloid on the first insulating layer and drying to form the electrode;
mixing graphene oxide and nano-cellulose or mixing the graphene oxide, the nano-cellulose and a hydrophobic agent to prepare a water dispersion liquid with the concentration of 0.1-2 mg/ml, and performing ultrasonic dispersion for 10-70 min at the power of 300-1000W to obtain a mixed system;
step four, preparing graphene water dispersion liquid with the concentration of 0.1-3 mg/ml, and performing ultrasonic dispersion for 10-70 min under the power of 500-1000W to obtain the graphene water dispersion liquid;
step five, mixing the mixed system with the graphene aqueous dispersion, and carrying out ultrasonic treatment for 20-100 min at the power of 300-1200W to obtain a composite dispersion system;
sixthly, ink-jet printing or spraying or brushing the composite dispersion system on the first insulating layer, wherein the printing amount is 4-26 g/m2Then drying the mixture in a vacuum drying oven at the temperature of 50-80 ℃ for 6-24 hours to form a heating layer;
seventhly, manually or mechanically polishing by using sand paper to remove redundant heating layers according to the preset effective heating surface shape and size;
step eight, spraying or brushing a second insulating layer on the surface of the heating layer, wherein the coating weight is 50-200 g/m2And drying the mixture in a vacuum drying oven at 70-90 ℃ for 3-6 h to obtain an electric heating material;
step nine, quenching the obtained electric heating material, and electrifying for 2-12 hours by 1.5-2.5 times of rated power of the electric heating material, partially removing defect groups on graphene and graphene oxide sheets, and improving conductivity and phase structure regularity to obtain the nano-cellulose graphene oxide electric heating material with a stable structure and stable power;
wherein the graphene oxide accounts for 10-60% of the total weight of the graphene oxide and the nano-cellulose, and the graphene oxide and the nano-cellulose account for 35-75% of the mass of the heating layer; if the water repellent agent is used, the addition amount of the water repellent agent is 0.08-4.2% of the mass of the heat-generating layer.
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| CN110191523A (en) * | 2019-04-17 | 2019-08-30 | 中国林业科学研究院木材工业研究所 | A kind of low-voltage high-efficiency nano-carbon material Electric radiant Heating Film preparation method and application |
| CN112021893A (en) * | 2020-09-08 | 2020-12-04 | 北京康烯科技创新研究有限公司 | Palladium nanosheet/graphene-based hot compress medicine pillow |
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