KR102437360B1 - A novel large-area electrified complex film comprising fluoropolymers and sulfur polymers, a method for preparing the same and triboelectric generateor using the same - Google Patents

Abstract

The present invention relates to a novel polymer composite film, a method for manufacturing the same, and a use thereof, and more particularly, to a large-area charged composite film comprising a fluorine-based polymer and a sulfur polymer, a method for manufacturing the same, and a triboelectric generator using the same. Since the composite film according to an embodiment of the present invention can be manufactured at a low cost and has excellent triboelectric power generation characteristics, it can be usefully used as an electrical device such as various sensors.

Description

A novel large-area electrified complex film comprising fluoropolymers and sulfur polymers, a method for preparing the same and triboelectric generator using the same the same}

The present invention relates to a novel polymer composite film, a manufacturing method thereof, and uses thereof, and more particularly, to a large-area charged-body composite film comprising a fluorine-based polymer and a sulfur polymer, a manufacturing method thereof, and a triboelectric power generator using the same .

Sulfur, which can be obtained as a by-product in the desulfurization process of crude oil, has weak brittleness and high crystallinity, so its utilization was not high except to the extent that it is used in the manufacture of sulfuric acid or in the vulcanization process of rubber. Recently, as a study for using such sulfur, a macromolecule containing sulfur is a functional polymer, and research on it is being actively conducted.

On the other hand, triboelectric charging is a phenomenon in which two objects are charged with electric charges of different polarities when they are brought into contact or rubbed together. When two different materials are in contact, one side is negatively charged and the other side is positively charged according to the charge heat.

In general, the frictional electrification phenomenon often brings inconvenience in industrial fields and daily life, so many studies have been conducted to reduce the frictional electrification phenomenon.

On the other hand, however, studies on triboelectric power generators using triboelectric charging are being actively conducted. However, the current change in triboelectric properties is only prominent in carbon-based materials, so it is difficult to change the triboelectric properties of various materials used in industry and daily life.

If a conductor surface is attached to each material and the relative distance between the two friction surfaces is repeatedly changed, electrostatic induction occurs on the conductor surface. After that, when the conductors attached to the two materials are connected, an alternating current is generated. The current and voltage generated by triboelectric charging become stronger as the amount of electric charge on the surface of each material increases. Therefore, as the materials with relatively large heat of charge are combined, the power generation efficiency increases.

Accordingly, the present invention has been devised to solve various problems including the aforementioned problems, and an object of the present invention is to provide more efficient negative tribo-composite films and a manufacturing method thereof. However, these problems are exemplary, and the scope of the present invention is not limited thereto.

According to one aspect of the present invention, there is provided an electrified composite film comprising a fluorine-based polymer and a sulfur polymer.

According to another aspect of the present invention, after melting elemental sulfur (S8), a composite manufacturing step of preparing a composite including a fluorine-based polymer and a sulfur polymer by mixing and stirring a crosslinking agent and a fluorine-based polymer; and

There is provided a method for producing the electrified composite film comprising a fluorine-based polymer and a sulfur polymer comprising the step of molding the composite into a film shape.

According to another aspect of the present invention, there is provided a triboelectric electrode including the charged body composite film.

According to another aspect of the present invention, there is provided a triboelectric power generating element including the triboelectric electrode.

According to another aspect of the present invention, there is provided a method of manufacturing a charged body composite film with improved output, comprising the step of performing corona discharge treatment on the charged body composite film.

According to another aspect of the present invention, there is provided an electrified composite film with improved output produced by the manufacturing method.

An electrified composite film comprising a fluorine-based polymer and a sulfur polymer prepared according to an embodiment of the present invention is easy to manufacture and has the advantage that it can be manufactured inexpensively by using sulfur, which can be obtained as a by-product in the desulfurization process of crude oil. have. In addition, since it can be manufactured in a film form, it can be used to manufacture a large-area triboelectric power generator. Therefore, according to an embodiment of the present invention, it is possible to manufacture a sensor or a power generating element using triboelectricity at a low cost.

1 is a schematic diagram schematically showing the manufacturing process of PPFS and a sulfur-containing polymer composite film.
2 is a photograph of a charged body composite film including poly(pentafluorostyrene) {PPFS} and a sulfur polymer prepared according to Example 7 of the present invention.
3 is a result of elemental analysis of fluorine and sulfur atoms on the surface of a composite film containing a fluorine-based polymer and a sulfur polymer using energy dispersive spectroscopy (EDX) using a scanning electron microscope (SEM). Using the Image J program, the area with a lot of sulfur polymer was shown in yellow, and the area with a lot of fluorine molecules was shown by changing the color map to blue.
4 is a schematic view schematically illustrating corona discharge treatment for a composite film electrified body including PPFS and a sulfur polymer.
5 is a schematic diagram schematically showing the structure of a triboelectric power generating element.
6 is a series of diagrams showing the output voltage (left) and current (right) measured in a triboelectric generator made of a composite film containing PPFS and a sulfur polymer prepared according to Example 7 of the present invention as a negative charge; is the graph of
7 is a circuit diagram for a PPFS-based triboelectric device LED connection circuit.
FIG. 8 shows 400 LEDs with power consumption of 40 mW (not lit: left) using a triboelectric power generator manufactured with a composite film electrified body of a 4-inch size (diagonal length) manufactured according to Example 7 of the present invention. It is a series of pictures taken at the same time as the result (right).

Definition of Terms:

As used herein, the term “sulfur polymer” refers to a polymer in which the main chain of the polymer is formed of bonds between sulfur atoms rather than bonds between carbons. Elemental sulfur (octasulfur) usually has 8 sulfur atoms in a ring (S ₈ ), but when melted at a high temperature, it is converted into a linear reactive molecule. This reactive sulfur molecule reacts with a crosslinking agent molecule having a carbon double bond to form a polymer will do In the case of such a polymer, it has a high refractive index due to the characteristics of sulfur and is known to have mid-infrared transmission properties (Chung, WJ et al ., J. Nat. Chem . 2013, 5(6): 518-524, 2013). ; Griebel, JJ et al ., Adv. Mater . 26(19): 3014-3018, 2014).

As used herein, the term “fluoropolymer” refers to a polymer in which some or all of the hydrogen atoms of a hydrocarbon-based polymer are substituted with fluorine. Fluorine-based polymers are used as water-repellent coatings because they do not adhere well to other materials due to their large contact angle and extremely low release force, and they are also used as ion-exchange membranes for fuel cells because of their strong chemical resistance.

The term "triboelectric generation" used in this document means that two materials with different degrees of charge have a specific charge through friction, and accordingly, an alternating current is generated by accumulating a compensating charge to generate electrical energy. It refers to the power generation technology to produce.

As used herein, the term "corona discharge" is an electrical discharge that occurs due to the ionization of a fluid around a conductor, in which the potential gradient (strength of an electric field) exceeds a certain value but is not sufficient to cause complete dielectric breakdown or arcing. Occurs when conditions are insufficient.

DETAILED DESCRIPTION OF THE INVENTION:

According to one aspect of the present invention, there is provided an electrified composite film comprising a fluorine-based polymer and a sulfur polymer.

In the electrified composite film, the fluorine-based polymer is poly(pentafluorostyrene) {poly(pentafluorostyrene), PPFS}, poly(tetrafluoroethylene) {polytetrafluoroethylene, PTFE}, terafluoroethylene perfluoroalkyl vinyl Ether copolymer [{poly[tetrafluoroethylene-co-perfluoro (alkyl vinyl ether)}, PFA}), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy alkane (PFA), polyvinyl Fluoride (polyvinyl fluoride, PVF), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE) , and ethylene-chlorotrifluoroethylene copolymer (ethylene-chlorotrifluoroethylene copolymer, ECTFE) may be one or two or more complexes selected from the group consisting of.

According to another aspect of the present invention, after melting elemental sulfur (S ₈ ), a composite manufacturing step of preparing a composite including a fluorine-based polymer and a sulfur polymer by mixing and stirring a crosslinking agent and a fluorine-based polymer; and

There is provided a method for producing the electrified composite film comprising a fluorine-based polymer and a sulfur polymer comprising a film forming step of forming the composite into a film shape.

In the preparation method, the crosslinking agent may be any compound having an alkene group at the terminal or inside, preferably limonene, ENB (5-ethylidene-2-norbornene), DCPD (dicyclopentadiene), or DIB (1,3-diisopropenyl benzene).

In the manufacturing method, the fluorine-based polymer is poly(pentafluorostyrene) {poly(pentafluorostyrene), PPFS}, poly(tetrafluoroethylene) {polytetrafluoroethylene, PTFE}, terafluoroethylene perfluoroalkyl vinyl ether air Copolymer [{poly[tetrafluoroethylene-co-perfluoro (alkyl vinyl ether)}, PFA}), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy alkane (PFA), polyvinyl fluoride (polyvinyl fluoride, PVF), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), and It may be one or two or more complexes selected from the group consisting of ethylene-chlorotrifluoroethylene copolymer (ECTFE).

In the manufacturing method, the mixing ratio of the fluorine-based polymer and the sulfur polymer is 1:100 to 1:5, 1:80 to 1:6, 1:50 to 1:7, 1:20 to 1:8, 1 by weight. :15 to 1:9, or 1:12 to 1:10.

In the manufacturing method, the film forming step may be performed by a high temperature family press, high temperature rolling molding, spin coating or extrusion molding.

According to another aspect of the present invention, there is provided a triboelectric electrode including the charged body composite film.

According to another aspect of the present invention, there is provided a triboelectric power generating element including the triboelectric electrode.

The triboelectric generator includes a first electrode and a second electrode that is spaced apart from the first electrode and faces, and the electrified composite film is attached to the opposite surface of any one of the first electrode and the second electrode It may have a structure, and preferably, the first electrode is a platinum electrode, the second electrode is an aluminum electrode, and the first electrode may be manufactured by depositing platinum on the electrified composite film.

According to another aspect of the present invention, there is provided a method of manufacturing a charged body composite film with improved output, comprising the step of corona discharge treating the charged body composite film.

In the manufacturing method, the corona discharge is performed by connecting the negative electrode and the positive electrode to the tungsten probe and the aluminum foil electrode, respectively, and placing the charged body composite film between the positive electrodes while maintaining the distance between the positive electrodes at 2 to 4 mm It can be carried out by applying a voltage of 5 to 7 kV for 20 to 40 minutes.

According to another aspect of the present invention, there is provided an electrified composite film with improved output produced by the manufacturing method.

Hereinafter, the present invention will be described in more detail through the accompanying Examples and Experimental Examples. However, the Examples and Experimental Examples of the present invention are provided to more fully explain the present invention to those of ordinary skill in the art, and the following examples may be modified in various other forms, The scope of the invention is not limited to the following examples. Rather, these embodiments are provided so as to more fully and complete the present disclosure, and to fully convey the spirit of the present invention to those skilled in the art. In addition, in the drawings, the thickness or size of each layer is exaggerated for convenience and clarity of description.

Example 1: Synthesis of fluorine-based polymer

The present inventors prepared 15 g of 2,3,4,5,6-pentafluorostyrene (PFS) as a monomer and 2,2'-azobisisobutyronitrile as an initiator Poly(pentafluorostyrene) {PPFS} was synthesized by dissolving 0.45 g of (2,2'-azobisisobutyronitrile, AIBN) in 30 mL toluene as a solvent in a nitrogen atmosphere and then polymerization at 70° C. for 20 hours. The molecular weight and polydispersity index (PDI) of the polymerized PPFS were measured by gel permeation chromatography (GPC) method. The polymerized PPFS had a number average molecular weight of 5,200 g/mol and a polydispersity index (PDI) of 1.2.

Example 2: Preparation of sulfur polymer film

The present inventors put 23.4 g of sulfur in a flask, melted it at 185° C., added 6.6 g of 1,3-diisopropenyl benzene (DIB) as a crosslinking agent, and stirred vigorously for 7 minutes to obtain a sulfur polymer was prepared. The prepared sulfur polymer was prepared as a charged body film with a thickness of about 0.6 mm at 150° C. using a hot press.

Example 3: Preparation of a composite film comprising a sulfur polymer and a fluorine-based polymer

After putting 23.4 g of sulfur in a flask and melting it at 185° C., 6.6 g of DIB and 0.3 g of PPFS synthesized in Example 1 were mixed and vigorously stirred for 7 minutes to prepare a composite of a fluorine-based polymer and a sulfur polymer. The prepared composite was manufactured as a charged body film having a thickness of about 0.6 mm at 150° C. using a hot press.

Example 4: Preparation of Composite Film Containing Sulfur Polymer and Fluorine-Based Polymer

In the same manner as in Example 3, 0.61 g of PPFS was added to prepare a composite of a fluorine-based polymer and a sulfur-containing polymer, and then filmed by a hot press press.

Example 5: Preparation of a composite film containing a sulfur polymer and a fluorine-based polymer

In the same manner as in Example 3, 1.09 g of PPFS was added to prepare a composite of a fluorine-based polymer and a sulfur-containing polymer, and then filmed by a hot press press.

Example 6: Preparation of Composite Film Containing Sulfur Polymer and Fluorine-Based Polymer

In the same manner as in Example 3, 1.58 g of PPFS was added to prepare a composite of a fluorine-based polymer and a sulfur-containing polymer, and then filmed by a hot press press.

Example 7: Preparation of composite film containing sulfur polymer and fluorine-based polymer

In the same manner as in Example 3, 2.43 g of PPFS was added to prepare a composite of a fluorine-based polymer and a sulfur-containing polymer, and then filmed by a hot press press.

Example 8: Preparation of composite film containing sulfur polymer and fluorine-based polymer

In the same manner as in Example 3, but 3.33 g of PPFS was added to prepare a composite of a fluorine-based polymer and a sulfur-containing polymer, and then filmed by a high-temperature press.

Comparative Example 1: Preparation of an electrified film using PTFE

PTFE, known as a material with a high negative charge heat, was used as a control in this experiment. In this case, under the same conditions, the open-circuit voltage and short-circuit current were measured to be 19.7 V and 0.35 uA, respectively. Therefore, it was confirmed that the PPFS polymer showed better tribological power generation performance.

Example 9: Corona Discharge Treatment

The present inventors additionally performed corona discharge treatment on the surface of the PPFS polymer. The output voltage of the PPFS polymer treated with corona discharge as described above was significantly improved. Specifically, after treatment, the open circuit voltage and short circuit current of the PPFS triboelectric charging device were measured to be 362.78 V and 8.21 μA, respectively, and the maximum power density was measured to be 832.89 mW/m ² at 60 MΩ. Experimental Example 1: Energy Dispersive Spectroscopy

The present inventors performed elemental analysis of the surface of a composite film of a fluorine-based polymer and a sulfur polymer using an energy dispersive X-ray spectroscopy (EDX) using a scanning electron microscope (SEM).

EDX performed surface analysis at a scale of 200 magnification under the conditions of an acceleration voltage of 15 kV and a working distance of 15 mm. The SEM image shown in FIG. 3 is a pseudo-coloring technique after dividing the boundary using the Image J program for clear contrast of the separated phase. It is shown by changing the map.

Experimental Example 2: Corona Discharge on Composite Film of Fluorine-Based Polymer and Sulfur Polymer

As a method for improving the performance of the power generation device, the surface of the negatively charged body of the PPFS and sulfur-containing polymer composite film was subjected to corona discharge as shown in FIG. 4 . Corona discharge is a phenomenon that occurs when a high voltage is applied to both ends of which charge densities are significantly different. By injecting electrons and ions into the surface of a material using a tungsten probe, the surface charge density can be maximized. In this demonstration, during corona treatment, the cathode and anode were connected to the probe and the aluminum foil electrode, respectively, and the charged composite film was placed between the electrodes while the gap was maintained at 3 mm. Then, a current of 6 kV was applied for 30 minutes. Corona discharge treatment was performed.

Example 10: Fabrication of a triboelectric power generator

As shown in FIG. 5 , in order to manufacture a triboelectric generator of a vertical contact type, two substrates to which electrodes are connected are required. The surface to be used as a cathode during friction is a PPFS and sulfur polymer composite film, and aluminum foil is attached thereto and heated to 60° C.) to complete the PPFS-Al surface. On the other side to be used as an anode, an Al-PTFE side was prepared by depositing 100 nm of metallic aluminum on a PTFE substrate through thermal evaporation. At this time, the deposited aluminum was used as the anode material. After each side was completed, the two sides were combined to fabricate a device. The device was installed on a sample stage made with a 3D printer, and at this time, the surface of the PPFS and sulfur polymer composite film and the deposited aluminum surface were in contact.

Experimental Example 3: LED lighting demonstration method

In the case of a triboelectric generator, AC power is produced during power generation by using triboelectric charging and electrostatic induction. In order to show an example of practical use using this, a commercial LED can be driven by connecting a rectifier circuit.

Accordingly, the present inventors constructed an LED circuit to demonstrate power generation using the triboelectric generator manufactured according to an embodiment of the present invention. At this time, the rectifier uses a device having a bridge rectifier circuit, and the bridge rectifier circuit uses the characteristics of a diode to allow forward current to flow and block reverse current to connect four light emitting diodes as shown in FIG. The current was aligned in one direction as well.

After connecting the DC power through the rectification circuit to 400 LEDs connected in series, a force of 30 N was applied to the triboelectric generator at a cycle of 1.3 Hz to demonstrate LED lighting. As a result, it was confirmed that all 400 LED elements were turned on.

Experimental Example 4: Analysis of power generation characteristics

The present inventors measured the amount of voltage and current generated using the triboelectric generator manufactured by the method of Example 10 using the composite films prepared in Examples 2 to 8. Specifically, the amount of voltage and current generated after applying a uniform force and a constant speed (30 N, 1.3 Hz) so that the two materials installed on the sample stage could be repeatedly contacted-separated from each other were measured. The dimensions of the devices used here are all 2 cm × 5 cm in contact area.

Preparation of a composite film electrified body of a fluorine-based polymer and a sulfur-containing polymer and electrical power generation characteristics of a triboelectric power generator manufactured using the same Example Sulfur content (g) DIB (g) PPFS (g) Surface fluorine content (wt%) open voltage (V) Short circuit current (μA) 2 23.4 6.6 0 0 5.00 0.04 3 23.4 6.6 0.30 3.3±1.0 6.25 0.15 4 23.4 6.6 0.61 5.4±2.1 85.89 1.84 5 23.4 6.6 1.09 9.8±2.0 90.51 1.85 6 23.4 6.6 1.58 16.2±2.9 143.38 2.57 7 23.4 6.6 2.43 29.5±3.0 164.00 3.53 8 23.4 6.6 3.33 21.8±1.6 153.41 3.21

As a result, as shown in Table 1, as the PPFS input increased, the PPFS derived on the surface of the composite film of the fluorine-based polymer and the sulfur-containing polymer increased, so that the surface fluorine content increased until Example 7 and decreased in Example 8.

The electrical power generation characteristics of triboelectric power generators manufactured using a composite film electrified body of a fluorine-based polymer and a sulfur-containing polymer were different according to the PPFS mixing ratio. The charged film without PPFS showed the lowest voltage output, and the open-circuit voltage and short-circuit current showed the maximum at the 7.5 wt% PPFS input ratio of Example 7. Thereafter, the output decreased again at a higher mass mixing ratio as in Example 8. These results are determined to be closely related to the fluorine content of the surface of the composite film of the fluorine-based polymer and the sulfur-containing polymer.

Although the present invention has been described with reference to the above-described examples and experimental examples, which are merely exemplary, those of ordinary skill in the art realize that various modifications and equivalent other examples and experimental examples are possible therefrom. will understand Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims.

Claims (14)

Poly(pentafluorostyrene) {poly(pentafluorostyrene), PPFS}, and an electrified composite film comprising a sulfur polymer. delete After melting elemental sulfur (S ₈ ), a composite manufacturing step of preparing a composite including PPFS and a sulfur polymer by mixing and stirring a crosslinking agent and poly (pentafluorostyrene); and
The method of claim 1 comprising a film forming step of forming the composite into a film shape. 4. The method of claim 3,
The crosslinking agent is a compound having an alkene group at the end or inside, the manufacturing method. 4. The method of claim 3,
The crosslinking agent is limonene (limonene), ENB (5-ethylidene-2-norbornene), DCPD (dicyclopentadiene), or DIB (1,3-diisopropenyl benzene), the manufacturing method. delete The method according to claim 3, wherein the mixing ratio of the fluorine-based polymer and the sulfur polymer is 1:100 to 1:5 by weight. 4. The method of claim 3,
The film forming step is performed by hot pressing, hot rolling molding, spin coating or extrusion molding. A triboelectric electrode comprising the composite film of claim 1 . A triboelectric power generating element comprising the triboelectric electrode of claim 9 . 11. The method of claim 10,
Friction comprising a first electrode and a second electrode facing the first electrode and spaced apart from the first electrode, and having a structure in which the charged body composite film is attached to an electrode-facing surface of any one of the first electrode and the second electrode electric power plant. A method of manufacturing a charged body composite film with improved output, comprising the step of corona discharge treating the charged body composite film of claim 1 . 13. The method of claim 12,
The corona discharge is performed by connecting the negative electrode and the positive electrode to the tungsten probe and the aluminum foil electrode, respectively, and placing the charged body composite film between the both electrodes while maintaining the distance between the positive electrodes at 2 to 4 mm, and then 5 to 40 minutes for 20 to 40 minutes. A manufacturing method performed by applying a voltage of 7 kV. An electrified composite film with improved output produced by the manufacturing method of claim 12 or 13.

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