CN113354855B - Bendable electrothermal film device based on graphene and preparation method thereof - Google Patents
Bendable electrothermal film device based on graphene and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a bendable electrothermal film device based on graphene, which comprises a polyimide base layer and an organic electrothermal film coated on the surface of the base layer; the organic electrothermal film comprises the following components in parts by weight: 5 to 15 parts of graphene; 2 to 9 parts of an ionic liquid; 1 to 8 parts of multi-walled carbon nanotubes; 10 to 20 parts of carbon black particles; 260 to 300 parts of polytetrafluoroethylene; the invention also discloses a preparation method of the electrothermal film device; the invention provides a preparation method of an electrothermal film device; the electric heating film obtained by the invention is flexible and bendable, has stable structure and heating, and has higher heating efficiency.
Description
Technical Field
The invention relates to the field of electrothermal film devices, in particular to a bendable electrothermal film device based on graphene.
Background
The film-shaped electrothermal functional element is generally composed of an electrothermal functional film, an electrode and a substrate. The electrodes serve as conductors to reduce contact resistance and are connected to a power supply. The electrode is made of conductor slurry or metal foil or wire, and the base body mainly plays a role of supporting an electric heating functional film and also plays a role of a heat conductor or a heat insulator and an insulator separator. The properties of the matrix are determined mainly according to the design requirements of the product, and are not strictly limited. However, the production of the electrothermal functional film on the surface with edges and concave-convex surfaces brings some disadvantages, such as easy skin effect at sharp parts; the excessive concave-convex surface is difficult to ensure the uniformity of the film layer, and the uneven power distribution is easy to form. The conductivity of the electrothermal composite material is realized by forming a conductive network in a polymer matrix through a conductive filler;the materials commonly used for the substrate are glass, ceramics, high polymer resin and the like. The electric heating functional film is a heating body and is distinguished according to materials: metal film, inorganic film, organic material film. In general, for additive type electrocaloric materials, the conductive filler is a component of the electrocaloric material that functions as a conductor. After the electric heating slurry is dried and solidified, the binder and the conductive filler form a whole. Under the action of an applied voltage, free electrons inside the electric heating material move along the direction of an external electric field to form current, and heat is generated along with the prolonging of time according to Joule-Lenz law. Therefore its electric heat principle is the principle that when electric current passes through resistance with electric energy conversion heat energy, as formula: q = I 2 RT: q is the heating value of the electric heating material coating; i is the current flowing through the electrothermal material coating; r is the resistance of the electrothermal material coating; t is the heat generation time.
The organic heating film material is prepared by adding conductive particles into organic high molecular material, or preparing film material from conductive organic material, or coating organic material on the surface of insulating material to obtain organic conductive film. For example: the polytetrafluoroethylene is doped with carbon black to prepare a heating belt similar to a plastic film, which is not required to be attached to any base material, is flexible and bendable, and is conductive without an insulating layer. When in use, the polyimide film can be used as an insulating layer, and the organic film has bending performance and can be bent, but can only be used at a lower temperature.
Disclosure of Invention
The invention aims to provide a bendable electric heating film device based on graphene.
In order to solve the technical problem, the technical scheme of the invention is as follows: a bendable electrothermal film device based on graphene comprises a polyimide base layer and an organic electrothermal film coated on the surface of the base layer;
the organic electrothermal film comprises the following components in parts by weight:
in a further improvement, the surface of the polyimide-based layer is rubbed to obtain a rough surface with protrusions with the same orientation. According to the invention, the binding force of the base layer and the organic heating layer is effectively increased, meanwhile, the protrusions in the same orientation can guide the arrangement of the conductive fillers in three dimensions to a certain extent, because the protrusions in the same orientation exist, the one-dimensional multi-walled carbon nanotubes and the two-dimensional graphene coated on the base layer are uniformly and regularly arranged along the direction of the guide protrusions due to the limitation of the same guide protrusions, while the 0-dimensional carbon black particles and the ionic liquid are uniformly dispersed in the coating, and are uniformly dispersed in the film layer along with the regular arrangement of the guide protrusions in the internal structure of the coating and the multi-walled carbon nanotubes and graphene, so that the organic heating film with a closer structure and a stable structure is formed.
Preferably, the ionic liquid is [ Bmim ] [ BF ] 4 [ solution ] A. [ Bmim ] BF ] in the present invention 4 Not only exist as part of forming a conductive network, [ Bmim ] [ BF ] 4 Graphene, carbon nanotubes and carbon black particles are effectively promoted to be uniformly distributed in a polytetrafluoroethylene dispersion system through the adsorption effect of charges on the surface groups of the graphene, the carbon nanotubes and the carbon black particles, secondary agglomeration is prevented from occurring in the mixing process, and the stability and reliability of a conductive network are effectively guaranteed.
Preferably, the nano-cellulose accounts for 0.2 to 0.6 times of the sum of the mass of the graphene oxide, the mass of the multi-wall carbon nano-tubes and the mass of the carbon black particles. According to the invention, nanocellulose is added into a polytetrafluoroethylene system and acts as a system stabilizer from two aspects, on one hand, when the electric heating film is in a slurry state, the nanocellulose is embedded between the graphene directionally coated on the surface of the base layer through the characteristic of larger length-diameter ratio of the nanocellulose, and the nanocellulose and the multi-walled carbon nano tubes are inclined on the base layer together, so that the dispersion and gluing of the graphene and the multi-walled carbon nano tubes are promoted, and after the slurry is solidified into a film, the nanocellulose is used as a matrix skeleton due to the structure of the nanocellulose, so that the structural strength of the whole electric heating film is ensured.
Preferably, the organic electrothermal film comprises the following components in parts by weight:
the thickness of the organic electrothermal film is preferably 100 to 300 μm. The thickness of the organic electrothermal film can be adjusted according to different use environments so as to meet the requirements of specific products and applications.
The invention also aims to provide the preparation method of the electrothermal film device, which has good film forming effect, can be bent and has high heating efficiency.
In order to solve the technical problem, the technical scheme of the invention is as follows: a preparation method of an electrothermal film device comprises the following steps:
step one, adding the components into polytetrafluoroethylene according to parts by weight, and performing ball milling and uniform mixing;
step two, uniformly coating the mixture obtained in the step one on the surface of a polyimide base layer, and standing for defoaming;
and step three, performing thermocuring to obtain the target electrothermal film device.
Preferably, after the polyimide base layer is formed into a film, a friction roller is used for directional friction to obtain rough guide bulges. According to the invention, the rough guide film is prepared on the polyimide layer to promote the combination of the base layer and the organic heating layer, and the protrusions with the same orientation guide the arrangement of the conductive fillers with three dimensions, so that the high-quality bendable electric heating film device is obtained.
By adopting the technical scheme, the invention has the beneficial effects that:
the obtained electrothermal film comprises a polyimide base layer and an organic electrothermal film coated on the surface of the base layer, wherein the organic electrothermal film takes polytetrafluoroethylene as a binder, takes graphene, multi-walled carbon nanotubes, carbon black particles and ionic liquid as conductive fillers, wherein the graphene, the multi-walled carbon nanotubes and the carbon black particles form a conductive network dispersed in a polytetrafluoroethylene film layer from three dimensions of points, lines and surfaces, the ionic liquid is favorable for improving the stability of slurry in a coating layer, and the ionic liquid is mixed with the polytetrafluoroethylene together and uniformly dispersed among the conductive fillers with the three dimensions to promote the formation of the conductive network;
the electric heating film device has the advantages that the structural strength of the electric heating film device is effectively improved due to the matching of the base layer and the organic heating film, the electric heating film device can be bent, and the heating effect is not influenced; repeated bending is carried out, the heating is stable, and the relative position of the conductive filler in the internal structure of the obtained film layer is stable, the conductive performance is stable, and the film layer has wider application.
Thereby achieving the above objects of the present invention.
Drawings
FIG. 1 is a schematic cross-sectional view of a bendable electrothermal film device based on graphene according to the present invention;
FIG. 2 is an enlarged view at A in FIG. 1;
FIG. 3 is a U-I curve of the electrothermal film devices obtained in example 3 and example 4 of the present invention and comparative example 1 before and after 50 times of bending.
In the figure:
a polyimide base layer 1; an organic electrothermal film 2.
Detailed Description
In order to further explain the technical scheme of the invention, the invention is explained in detail by the specific embodiment.
Example 1
The embodiment discloses a bendable electrothermal film device based on graphene, and the specific components and parts by mass are shown in table 1, and the specific preparation method comprises the following steps:
step one, adding the components into polytetrafluoroethylene according to parts by weight, and performing ball milling and uniform mixing;
step two, uniformly coating the mixture obtained in the step one on the surface of a polyimide base layer, and standing for defoaming;
and step three, performing thermocuring to obtain a target electrothermal film device with the area of 100mm multiplied by 100mm.
And in the second step, after the polyimide base layer is formed into a film, a friction roller is used for directional friction to obtain the rough guide projection.
The cross-sectional structure of the obtained electrothermal film is shown in fig. 1 and fig. 2, and comprises a polyimide substrate 1 and an organic electrothermal film 2 coated on the surface of the substrate.
Example 2
The main differences between this example and example 1 are detailed in table 1.
Example 3
The main differences between this example and example 1 are detailed in table 1.
Example 4
The main differences between this example and example 1 are detailed in table 1.
Example 5
The main differences between this example and example 1 are detailed in table 1.
Example 6
The main differences between this example and example 1 are detailed in table 1.
Comparative example 1
The main differences between this example and example 1 are detailed in table 1.
Comparative example 2
The main differences between this example and example 1 are shown in table 1.
Table 1 materials and amounts (parts by mass) of electric heating films obtained in examples 1 to 6 and comparative examples 1 and 3
Respectively carrying out a heating efficiency test, a U-I curve test and a heating efficiency test after bending 50 times on the electrothermal film devices obtained in the examples 1 to 6 and the comparative examples 1 and 2;
the bending angle is larger than 90 degrees.
The method and the calculation mode for testing the heating efficiency are as follows:
connecting metal electrodes at two ends of the prepared electrothermal film, applying 15V voltage on the electrodes by using a direct current power supply, and heating for a period of time until the temperature is stable. According to the law of conservation of energy, when the temperature of heating is increased to the maximum value, the heating quantity of the electrothermal film is equal to the energy radiated outwards, so the heating efficiency
h＝IV 0 /[(T m -T 0 )*S]；
Wherein h is the film heating efficiency (W/(. Degree. C. Mm) 2 ))；
I is the current (A) when the temperature is stable;
V 0 voltage (V) for temperature stability
T m The highest temperature;
T 0 the environmental temperature is 25 ℃ in the invention;
s is the area of the heating zone.
TABLE 2 comparison of heating efficiency before and after bending of the electric heating films obtained in examples 1 to 6 and comparative examples 1 and 2
The electric heating films obtained in the example 3, the example 4 and the comparative example are subjected to a U-I curve test before and after bending respectively, and the specific details are shown in figure 1.
The electric heating film obtained by the invention has high heating efficiency, the U-I curve basically accords with ohm's law, and the main reasons are analyzed as follows by combining the following table 1, the table 2 and the figure 1: graphene, multi-walled carbon nanotubes, carbon black particles and ionic liquid are used as conductive fillers, wherein the graphene, the multi-walled carbon nanotubes and the carbon black particles form a conductive network dispersed in a polytetrafluoroethylene film layer from three dimensions of points, lines and surfaces, the ionic liquid is beneficial to improving the stability of slurry in a coating layer, and the ionic liquid and the polytetrafluoroethylene are mixed together and uniformly dispersed among the conductive fillers with the three dimensions to promote the formation of the conductive network; in addition, as can be seen from comparison between the embodiment 3 and the embodiment 4, the structure of the nanocellulose is used as the matrix skeleton, so that the structural strength of the whole electrothermal film is ensured, and after bending, the heating efficiency of the embodiments 4 to 6 is better maintained than that of the embodiments 1 to 3.
The above embodiments and drawings are not intended to limit the form and style of the present invention, and any suitable changes or modifications thereof by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (7)
1. The utility model provides a can buckle electric hot film device based on graphite alkene which characterized in that: comprises a polyimide base layer and an organic electrothermal film coated on the surface of the base layer;
the organic electrothermal film comprises the following components in parts by weight:
5-15 parts of graphene;
2-9 parts of ionic liquid;
1-8 parts of multi-wall carbon nano tube;
10 to 20 parts of carbon black particles;
260 to 300 parts of polytetrafluoroethylene;
rubbing the surface of the polyimide-based layer to obtain a rough surface with the same orientation protrusions;
arranging the same-orientation protrusions to guide the arrangement of the graphene, the multi-walled carbon nanotubes and the carbon black particles;
the projections with the same orientation exist, the one-dimensional multi-walled carbon nanotubes and the two-dimensional graphene coated on the base layer are uniformly and regularly arranged along the direction of the guide projections due to the limit of the same guide projections, and the 0-dimensional carbon black particles and the ionic liquid are uniformly dispersed in the coating and uniformly dispersed in the film layer along with the regular arrangement of the guide projections of the internal structure of the coating and the multi-walled carbon nanotubes and the graphene, so that the organic heating film with the tighter structure and the stable structure is formed.
2. The graphene-based bendable electrothermal film device of claim 1, wherein: the ionic liquid is [ Bmim ] [ BF4 ].
3. The graphene-based bendable electrocaloric film device of claim 1, wherein: the composite material also comprises nano-cellulose, wherein the mass of the nano-cellulose is 0.2 to 0.6 times of the sum of the mass of the graphene, the multi-walled carbon nano-tubes and the carbon black particles.
4. The graphene-based bendable electrothermal film device of claim 3, wherein: the organic electrothermal film comprises the following components in parts by weight:
7 parts of graphene;
6 parts of ionic liquid;
3 parts of multi-wall carbon nano tubes;
13 parts of carbon black particles;
6.9 parts of nano-cellulose;
280 parts of polytetrafluoroethylene.
5. The graphene-based bendable electrocaloric film device of claim 3, wherein: the thickness of the organic electrothermal film is 100-300 μm.
6. A method of making an electrocaloric film device according to any of claims 1 to 5, wherein: the method comprises the following steps:
step one, adding the components except for the polytetrafluoroethylene into the polytetrafluoroethylene according to the mass parts, and performing ball milling and mixing uniformly;
step two, uniformly coating the mixture obtained in the step one on the surface of the polyimide base layer, standing and defoaming;
and step three, performing thermocuring to obtain the target electrothermal film device.
7. The method of claim 6, wherein: and after the polyimide base layer is formed into a film, directionally rubbing the film by using a rubbing roller to obtain the rough guide bulges.
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