KR102289596B1 - Layer by layer electrostatic generator and its manufacturing method - Google Patents

Abstract

The present invention relates to an electrostatic generator having a large area and polymorphism and a manufacturing method, and more particularly, it can be applied to various substrates such as fibers by applying a layered lamination technique, and nano/micro-sized structures are formed on the substrate. It relates to a layered electrostatic generator and a manufacturing method having stable output characteristics through uniform deposition, comprising: a substrate, a first solution for applying the substrate, and a second solution for applying the substrate after the first solution is dried Including, wherein the first solution helps the second solution to be deposited on the substrate, and the second solution is made of a polymer material that forms an electrode on the substrate to have conductivity.

Description

LAYER BY LAYER ELECTROSTATIC GENERATOR AND ITS MANUFACTURING METHOD

The present invention relates to an electrostatic generator having a large area and polymorphism and a manufacturing method, and more particularly, it can be applied to various substrates such as fibers by applying a layered lamination technique, and nano/micro-sized structures are formed on the substrate. It relates to a layered electrostatic generator and a manufacturing method having stable output characteristics through uniform deposition.

Triboelectric power generation is to generate electricity by friction, and unlike the existing eco-friendly energy such as solar cells, hydraulic power, wind power, etc., it is possible to extract consumable mechanical energy generated during minute vibrations or motions occurring in the surroundings as electrical energy. For example, whenever people walk, pressure energy that presses the floor with their feet and vibration and thermal energy are generated when cars, trains, and airplanes move. is about

In other words, it is a technology that harvests small amounts of energy that are routinely discarded or not used and converts it into usable electrical energy. If it is not used, it is eventually converted into sound or heat and disappears in the air. Therefore, it is possible to collect such fine-sized energy and utilize it as electrical energy.

In particular, triboelectric nanogenerators (TENGs) are evaluated as promising next-generation mechanical energy harvesting devices due to their desirable characteristics such as light weight, portability, environmental friendliness, and low cost. technology is proposed.

For example, Korean Patent Publication No. 10-1244058 (registration date: March 8, 2013) relates to a method for manufacturing a graphene transparent thin film using a layered self-assembly method, and graphene using a layered self-assembly method of reduced graphene oxide It is applied to a method for manufacturing a transparent thin film and an organic light emitting device (OLED) using a graphene transparent thin film obtained according to the manufacturing method.

However, the existing flexible electrostatic power generator utilizes a specific flexible material substrate or is mostly composed of a polymer material, and thus requires pretreatment or a specific material in the electrode formation and surface manufacturing process. Such pretreatment or the use of specific materials may impair the economics of manufacturing an electrostatic generator. In addition, a conductive fabric is used to induce high deformability, but the conductive fabric is difficult to manufacture and has low economic efficiency.

On the other hand, as technology advances, flexible electrostatic generators require a cost-effective, scalable, and easy-to-manufacture method for the commercialization of fiber-type triboelectric nanogenerators (TENGs) compatible with various textile products. the current situation.

Korean Patent Publication No. 10-1244058 (Registration Date: 2013.03.08.)

An object of the present invention is to provide a layered electrostatic generator and a manufacturing method that solve the problems of the conventional flexible electrostatic power generation device development mentioned above.

An object of the present invention is to provide a layered electrostatic generator and a manufacturing method for manufacturing an electrostatic generator having a large area and high deformability.

An object of the present invention is to provide a layered electrostatic generator and a manufacturing method that are compatible with various textile products and are manufactured on a polymer substrate having a surface of various shapes.

A layered electrostatic generator according to the present invention for achieving this object includes a substrate, a first solution for applying the substrate, and a second solution for applying the substrate on which the first solution is dried, the first solution helps the second solution to be deposited on the substrate, and the second solution is made of a polymer material that forms an electrode on the substrate to have conductivity.

Preferably, in the present invention, the first solution and the second solution are sequentially applied to the substrate as one cycle, and the cycle is repeated multiple times.

Preferably, in the present invention, the first solution and the second solution are deposited on the substrate through a wet process that is a hydrogen bond-based multilayer thin film stacking method (layer-by-layer (LbL) assembly). do.

Preferably, in the present invention, the substrate is made of a fabric or a structure is formed on the surface.

Preferably, in the present invention, the substrate has a PET substrate, and a protective film is attached to one surface and then subjected to oxygen plasma treatment to prevent application of the first solution and the second solution.

Preferably, in the present invention, the first solution is a PVA solution mixed with 0.25wt% PVA powder and deionized water, and serves as a negative friction material, and the second solution is 0.1wt% GNP and 0.1wt% A PSS solution and a GNP-PSS dispersion in which graphene is mixed with deionized water at the concentration of PSS is used as a positive friction material.

* Preferably, in the present invention, a PSS solution is further included in the graphene to improve the dispersion and adhesion of the graphene deposited on the substrate.

Preferably, in the present invention, each time the first solution and the second solution are applied to the substrate, the substrate is rinsed with deionized water and then dried.

Preferably, in the present invention, preparing a substrate, applying the substrate by immersing the substrate in a first solution, rinsing the substrate coated with the first solution in deionized water, and drying the substrate Then, immersing the second solution for application, and rinsing the substrate coated with the second solution in deionized water.

Preferably, in the present invention, the process of applying the substrate with the first solution and the second solution is one cycle, and the cycle is repeated multiple times.

Preferably, in the present invention, the first solution and the second solution are deposited on the substrate through a wet process that is a hydrogen bond-based multilayer thin film stacking method (layer-by-layer (LbL) assembly). do.

Preferably, in the present invention, the substrate is made of a fabric or a structure is formed on the surface.

Preferably, in the present invention, both surfaces of the substrate are coated with the first solution and the second solution, or a protective film is attached to one surface of the substrate and subjected to oxygen plasma treatment so that the other surface of the substrate is formed with the first solution and , is applied as a second solution.

Preferably, in the present invention, the first solution is a PVA solution mixed with 0.25wt% PVA powder and deionized water, and applied to the substrate by immersion for 5 minutes.

Preferably, in the present invention, the second solution is a GNP-PSS dispersion in which a PSS solution and graphene are mixed with deionized water at a concentration of 0.1 wt% GNP and 0.1 wt% PSS, and is applied by soaking the substrate for 5 minutes. .

The layered electrostatic generator and manufacturing method according to the present invention have a cost-effective, scalable effect with proven high performance and durability

The present invention is easy to apply to multi-dimensional substrates such as planar surfaces, fine concavo-convex surfaces and fiber surfaces.

The present invention forms a maximum output performance of 100 V and 5 μA at 9 N due to the proper shape and electrical properties of the 3BL graphene layer.

According to the present invention, the layered electrostatic generator of the fiber platform is easy to use as a power source for wearable electronic products.

The present invention can be applied to the commercialization of a layered electrostatic generator and the manufacture of the electronic textile industry through a multilayer thin film lamination method of graphene multilayers.

1 is a schematic diagram of a manufacturing process of a layered electrostatic generator according to the present invention;
2 is a layered structure stacked on a layered electrostatic generator according to the present invention;
3 is a view of the type of substrate used in the layered electrostatic generator according to the present invention;
4 is a perspective view of a contact-type triboelectric nanogenerator using a layered electrostatic generator according to the present invention and a simulation according to an operating mechanism;
5 is an enlarged image coated with a graphene layer of 3BL and an image coated with a graphene layer of 10BL on the substrate surface of the layered electrostatic generator according to the present invention;
6 is a graph showing the thickness of the thin film measured by ellipsometric measurement of the layered electrostatic generator according to the present invention and optoelectronic characteristics;
7 is a graph showing the work function of the multilayer graphene of the layered electrostatic generator according to the present invention;
8 is a graph expressing the sheet resistance bending cycle of the layered electrostatic generator according to the present invention as a function;
9 is a comparison of an image coated with a graphene film on a microrelief PET substrate of a layered electrostatic generator according to the present invention and a triboelectric contact, and output voltage and output current accordingly;
10 is various enlarged images of the triboelectric nanogenerator based on the fabric of the layered electrostatic generator according to the present invention and an embodiment thereof;
11 is a view of the operation process and performance of the triboelectric nanogenerator based on the fibers of the layered electrostatic generator according to the present invention;
12 is a flowchart for the manufacturing process of the layered electrostatic generator according to the present invention.

Specific structural or functional descriptions presented in the embodiments of the present invention are only exemplified for the purpose of describing embodiments according to the concept of the present invention, and the embodiments according to the concept of the present invention may be implemented in various forms. In addition, it should not be construed as being limited to the embodiments described herein, and should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

1 relates to a schematic diagram of a perspective view and a manufacturing process of a layered electrostatic generator according to the present invention.

The layered electrostatic generator 1 is an electrostatic generator using a layer-by-layer method of assembling a conductive material on a substrate 10 , and uniform deposition is possible even if a nano- or micro-sized structure is formed on the substrate 10 . Because it is possible, it has the characteristic of having stable output performance.

The layered electrostatic generator 1 is positioned on the deposition layer 22 by coating the substrate 10 with the first solution 20 and the deposition layer 22 formed by applying the first solution 20 and the substrate 10 with the second solution 40 . It includes a graphene layer 42 that is. At this time, the deposition layer 22 allows the second solution 40 to be deposited on the substrate 10 , and the graphene layer 42 is made of a polymer material that forms an electrode on the substrate 10 to have conductivity.

The substrate 10 is made of a fabric or a structure is formed on the surface, so that the mass production or manufacturing area can be freely controlled. The details of the substrate 10 will be dealt with in detail with reference to FIG. 3 below.

The first solution 20 is a PVA solution in which 0.25 wt% PVA powder and deionized water 30 are mixed, and serves as a negative friction material.

The second solution 40 uses a GNP-PSS dispersion in which a PSS solution and graphene are mixed with deionized water 30 at a concentration of 0.1wt% GNP and 0.1wt% PSS as a positive friction material, and is deposited on the substrate 10 . PSS solution is further included in graphene to improve the dispersion and adhesion of graphene.

In addition to the PVA solution and the GNP-PSS dispersion used as the first solution 20 and the second solution 40, various materials may be used, and the types of materials are as follows.

Deposition target material first solution second solution note Graphene Polyvinyl alcohol (PVA) Poly(4-styrene-sulfonic acid) (PSS)-modified graphene nanoplatelets (GNP-PSS) G-TENG SWCNT Poly(diallyldimethylammonium chloride) (PDDA) Single walled Carbon nanotube dispersed by Sodium deoxycholate (DOC) Transparent Electrode MMT Cationic starch (CS) Montmorillonite (MMT) flame retardant BPEI-PAA
crosslinking Polyethylenimine (PEI) Poly(acrylic acid) (PAA) gas barrier MoS2 MWCNT MOS2 Electrocatalysis GO Positive GO Negative GO Gas selectivity Emulsion Branched polyethylenimine (BPEI) Poly(acrylic acid) (PAA) Encapsulation and Controlled Release of Small Molecules to protocells

There may be changes in electrical properties such as the output of power. However, it will be preferable in manufacturing the layered electrostatic generator 1 to rinse the substrate 10 with deionized water 30 and then dry it whenever the first solution 20 and the second solution 40 are applied to the substrate 10 . On the other hand, when the first solution 20 and the second solution 40 are applied to the substrate 10 once, the substrate 10 has two layers composed of the first solution 20 and the second solution 40 . When this is formed and repeated twice, the first solution 20 and the second solution 40 form another layer to form a total of four layers. At this time, the first solution 20 and the second solution 40 are deposited on the substrate 10 through a wet process that is a hydrogen bonding-based multilayer thin film stacking method (layer-by-layer (LbL) assembly).

2 shows a layered structure stacked on a layered electrostatic generator according to the present invention.

The first solution 20 and the second solution 40 are sequentially applied to the substrate 10 in a total of two cycles, and the first solution 20 and the second solution 40 are It relates to the process of forming a layer.

When the first solution 20 and the second solution 40 are applied to the substrate 10 in one cycle, the first solution 20 and the second solution 40 are layered on the substrate 10 . Since the first solution 20 is first applied to the substrate 10 , a layer in which the first solution 20 is adhered to the substrate 10 is formed. Then, when the second solution 40 is applied, the second solution 40 is directly formed on the layer on which the first solution 20 is formed. Through this process, the production of the layered electrostatic generator 1 manufactured in one cycle is completed.

If one more cycle is applied with the first solution 20 and the second solution 40 in the layered electrostatic generator 1, the first solution 20 is directly on the layer on which the second solution 40 is formed. will form And when the second solution 40 is applied, the second solution 40 will further form a layer on the layer on which the first solution 20 is formed.

Since the layered electrostatic generator 1 manufactured in two cycles has a total of four layers, it may be formed to be thicker than the layered electrostatic generator 1 manufactured in one cycle, and electrical properties and effects may also be different.

That is, the first solution 20 and the second solution 40 will cross each other as many times as the number of cycles to form a layer on the substrate 10, and the thickness will also increase because a plurality of layers are formed.

3 shows the types of substrates used in the layered electrostatic generator according to the present invention.

The substrate 10 is made of fabric or has a structure formed on its surface. Specifically, the substrate 10 has a PET substrate, a protective film is attached to one surface, and then subjected to oxygen plasma treatment to treat the first solution ( 20) and the second solution 40 are prevented from being applied. Since a protective film is attached to one surface of the substrate 10, when the first solution 20 and the second solution 40 are applied, the solution is not applied to the surface to which the protective film is attached, and the protective film is not attached. Application is made only on the other side that is not. That is, when the protective film is attached, the solution is applied only to one side to which the protective film is not attached.

The substrate 10 will not necessarily have to coat one side. If it is necessary to apply a solution on both sides of the substrate 10 depending on the situation, it is not necessary to attach a protective film, but sequentially dip it in the first solution 20 and the second solution 40 and take it out and layer it on both sides of the substrate 10 may be formed.

The substrate 10 may be divided in various ways according to the shape of the surface. For example, in addition to the substrate 10 having a flat surface, the fine concavo-convex substrate 12 having an undulated shape on the surface may be used. In addition, the fabric substrate 16 made of a structure such as textile or cloth may be used.

This can be used not only on the substrate 10 having a simple surface, but also on the substrate 10 having a three-dimensional surface because the solution can be deposited using the multilayer thin film lamination method. However, since the surface of the substrate 10 is coated with a liquid material to form a layered layer, the surface of the substrate 10 may well absorb or be applied to the liquid. In addition, the substrate 10 may be applied to a multi-layer thin film lamination method such as a film, foam, fiber, etc., which are polymer materials in addition to PET material, and a substrate 10 made of ceramic or metal that can be applied with graphene may be used.

4 is a perspective view of a contact-type layered electrostatic generator using a layered electrostatic generator according to the present invention and a simulation according to an operating mechanism.

The contact-type layered electrostatic generator 50 uses a polyimide film 52 in which an air gap is formed in the hollow part as a spacer to facilitate contact and separation of the layered electrostatic generator 1 . The layered electrostatic generators 1 attached to the PET film 58 are positioned facing each other on both sides of the spacer. At this time, the layered electrostatic generator 1 is used not only as a positive friction material but also as an electrode, and the PET film 58 is used as a negative friction material.

And it would be good to put a soft polyurethane foam 56 between the PET film 58 and the acrylate substrate 54 in order to effectively increase the contact area in the step of pressing the contact-type layered electrostatic generator 50 .

When the contact-type layered electrostatic generator 50 is pressed by hand and then released, the layered electrostatic generator 1 comes into contact with each other and then separated.

In detail, when the layered electrostatic generator 1 located at the bottom comes into contact with the PET film 58 , the electrons of the layered electrostatic generator 1 located at the bottom move to the surface of the PET film 58 due to the difference in triboelectricity. However, since electrical equilibrium is maintained, electron flow does not occur in the external circuit.

Then, in the stage where the layer electrostatic generator 1 is separated, due to the strong potential difference between the two layer electrostatic generators 1, the electrons of the layer electrostatic generator 1 (negative potential) at the top are transferred through an external circuit to the bottom It flows into the layered electrostatic generator 1 (positive potential) to achieve electrical equilibrium.

5 relates to an image coated with a graphene layer of 3BL and an enlarged image coated with a graphene layer of 10BL on the substrate surface of the layered electrostatic generator according to the present invention.

An image of the layered electrostatic generator 1 stacked with three double layers (3BL) observed with a field emission scanning electron microscope (FE-SEM) and the first stacked with ten double layers (10BL) on a flat PET substrate 10 It relates to a cross-sectional image of a layered electrostatic generator 1 coated with a solution (PVA) 20 and a second solution (GNP-PSS) 40 observed with a transmission electron microscope (TEM).

Although the upper surface of the graphene layer 42 looks rough in the image of a scanning electron microscope (FE-SEM), it can be seen that the large area of the PET substrate 10 is uniform and the graphene layer 42 is well distributed.

Transmission electron microscopy (TEM) images show a layered electrostatic generator 10 made up of several layers, where the dark gray area is the PET substrate 10 area, the light gray area is the epoxy area, and the darkest black line is the multi-layered thin film stack ( LbL) is a cross-section of the graphene layer 42 deposited by the technique.

In the two images, a homogeneous network of the second solution (GNPs) 40 was observed and confirmed, and the addition of PSS for exfoliation of individual GNPs helps uniform distribution of the graphene layer 42 on the substrate 10, as a result The polymer-like entanglement results in a three-dimensional network. In this network, the graphene layer 42 provides an electron transport path through the substrate 10 so that a high conductivity is created.

6 is a graph showing the thickness of the thin film measured by the ellipsometric method of the layered electrostatic generator according to the present invention and relates to the optoelectronic characteristics.

When the layer consisting of PVA as the first solution 20 and GNP-PSS as the second solution 40 is referred to as a double layer (1BL), the layer thicknesses of 1, 3, 5 and 10BL are measured and compared by ellipsometric method. , showing the linear growth of the graphene multilayer thin film stacking method. Through this, it can be seen that the bonding degree of PVA and graphene in the layer and a constant component ratio are confirmed.

Also, through this graph, it can be seen that the average thickness of the region containing many particles in the place where the void space is formed between the layers and the surface roughness of the graphene-based layer can be seen.

The maximum value of 3BL measured by ellipsometric measurement was 46 nm, indicating that the deposition of PVA molecules and GNP-PSS particles produced a rough surface until the first 3BL, indicating that the roughness increased. However, after that, the roughness is reduced, which is because precipitation occurs in a part of the thinly created area in the previous deposition step, so that the roughness is reduced.

Like the thickness of the double layer BL, the linear growth of the graphene multilayer can be confirmed through the increased absorbance of the graphene layer 42 . The linear increase in the thickness of the bilayer and the absorbance results in the growth of the graphene layer 42 at a constant concentration regardless of the number of deposited bilayers.

(b) relates to a graph showing the optoelectronic properties of the graphene layer 42 assembled by the multilayer thin film stacking method. The x-axis shows a light transmittance of 1 to 10BL at 550 nm, and the transmittance decreases from 92.1% to 34.8% due to an increase in the thickness of the graphene layer 42 .

Since the thick layer has a 3D graphene network that provides more efficient electron transport and higher conductivity, resistivity (ρ) changes with resistance and thickness (RSt). Therefore, the resistivity decreases while the thickness of the graphene layer 42 increases up to 5BL, which maintains a similar resistivity up to 20BL.

In the case of the fabric-based layered electrostatic generator 4, the graphene layer 42 forms a resistance of a minimum of 3.8 kΩ sq-1 in 10BL and a minimum of 10.8 kΩ sq-1 in 3BL. As the layer thickness of the graphene layer 42 increases, the resistivity decreases, so that the output is improved.

7 is a graph showing the triboelectric output voltage of the layered electrostatic generator according to the present invention and the work function of the graphene multilayer.

The performance of planar layered electrostatic generators (FG-TENGs) 1 on a flat PET substrate 10 as a function of graphene layer 42 was investigated. A planar layered electrostatic generator 1 with three graphene layers 42 shows the maximum output voltage and current of 100V and 5 μA. This is significantly greater than the power of conventional graphene-based triboelectric nanogenerators (TENGs).

That is, it can be seen that the output performance of the planar layered electrostatic generator 1 greatly affects the number of BLs representing the thickness of the multilayer. However, due to the sensitivity to changes in temperature, humidity, substrate pretreatment, etc., which are wet manufacturing conditions at the nanometer level, the maximum output may occasionally occur in the planar layered electrostatic generator 1 made of 2 to 4BL.

The output performance of the layered electrostatic generator 1 in which a plurality of graphene layers 42 having the highest conductivity are stacked should have the highest output, but the maximum output in the layered electrostatic generator 1 formed of the graphene layers 42 of 3BL is showing

This can be seen through Kelvin Probe Force Microscopy (KPFM), which measures the output power of the planar lamellar electrostatic generator 1 .

That is, when the work function of the layered electrostatic generator 1 forming the 1, 3, and 10 graphene layers 42 is measured, the work function increases with the thickness of the graphene layer 42 . In addition, when the work function increases, more energy is required to extract electrons, and through this, the optimum of the graphene layer 42 that can maintain a balance between the resistivity and the work function due to the increase in the layers of the graphene layer 42 . It can be seen that the thickness of is 3BL.

8 is a graph expressing the sheet resistance bending cycle of the layered electrostatic generator according to the present invention as a function, and relates to a comparison of the output voltage and current of three planar layered electrostatic generators before and after the bending cycle.

The sheet resistance bending cycle of the planar lamellar electrostatic generator 1 of 3, 5, and 20BL is expressed as a function, and the triboelectric output voltage of the three planar lamellar electrostatic generators 1 before and after 1000 folding cycles. It shows the amount of change in overcurrent.

Since bending stability is becoming an increasingly important characteristic as the flexible electronic application market expands, the mechanical durability of the layered electrostatic generator 1 assembled by the multilayer thin film lamination method of the graphene layer 42 is very important in electrode or flexible electronic applications. will be.

When the layered electrostatic generator 1 was repeatedly bent to a radius of curvature of 1.0 cm to compare the bending stability of the layered electrostatic generator 1 composed of three different layers, the center of each layered electrostatic generator 1 after the bending cycle Measure the sheet resistance at At this time, it can be seen that all graphene layers 42 maintained a constant sheet resistance in bending deformation of up to 1000 cycles, and triboelectric output voltage and output current were maintained constant even after 1000 bending cycles.

Therefore, the mechanical stability of the layered electrostatic generator 1 will be very suitable for application to flexible electronic products.

9 is a comparison of an image coated with a graphene film on a micro-recessed PET substrate of a layered electrostatic generator according to the present invention, a triboelectric contact, and output voltage and output current accordingly.

(a) is assembled by a multilayer thin film lamination method of the graphene layer 42, and is etched with sodium hydroxide (NaOH-etched) to form a fine concavo-convex layered electrostatic generator coated with a graphene layer 42 on a substrate 10 (2) relates to the magnified image of the surface using a field emission scanning electron microscope (FE-SEM).

(b) is a comparison of graphene on a flat surface and wrinkled graphene with uniform curves formed on the entire surface of the layer, respectively.

On the other hand, the graphene layer 42 based on the corrugated surface is highly likely to have a rough surface compared to the graphene based on the flat surface due to the corrugated surface.

When the output performance of the fine concavo-convex lamellar electrostatic generator (UG-TENG) (2) and the fabric-based stratified electrostatic generator (TG-TENG) (4) were compared, The output voltage and current of -TENG) (2) are higher than the output voltage and current of the planar lamellar electrostatic generator (FG-TENG) (1) formed of three double layers (BL).

It can be seen that this phenomenon is due to the increased surface area due to the corrugated graphene layer 42 of the fine concavo-convex layered electrostatic generator (UG-TENG) 2 and the concentrated contact stress with the friction material on the opposite side. That is, it can be seen that the output performance of the layered electrostatic generator (G-TENG) 1 is greatly improved by applying the graphene layer 42 on the corrugated surface.

10 relates to various enlarged images of the layered electrostatic generator based on the fabric of the layered electrostatic generator according to the present invention and an embodiment thereof.

The multi-layer thin film lamination method relates to a method of forming a plurality of durable graphene layers 42 without limitation on the size of the substrate 10 made of a fabric, and a durable and expandable fabric-based layered electrostatic generator (TG-TENG) ( 4) can be produced.

(a) is a field emission scanning electron microscope (FE-SEM) enlarged image of the graphene layer 42 on the substrate 10 using cotton fibers as the substrate 10, in which the structure of the graphene layer 42 on the cotton fabric bundle is It can be seen that it is well formed. Another magnified image is of a graphene composite surface on a single fabric.

(b) and (c) are enlarged images of the surface of the graphene layer 42 formed of a plurality of layers after bending and rolling of 20,000 cycles, and it can be seen that there is no significant damage to the graphene layer 42 . Through this, it can be seen that the durability of the graphene layer 42 using the cotton fiber as the substrate 10 is high.

In addition, graphene thin films can be manufactured on the substrate 10 of various sizes as shown in (d), which is possible because of the multilayer thin film stacking method (LbL) of the graphene layer 42, which can easily expand the processing.

The multi-layer thin film lamination method can apply a fairly uniform coating over a large surface area using an immersion process, and the multi-layer thin film lamination method of the spray graphene layer 42 or the multi-layer thin film lamination method of the continuous graphene layer 42 can be applied to various applications. It will be applicable to the multilayer thin film lamination process of the graphene layer 42 on an industrial scale for It may also be applied to a fabric-based layered electrostatic generator (TG-TENG) 4 operating in a single electrode mode in which a graphene layer 42 is applied on a substrate 10 made of cotton fibers.

11 shows the operation process and performance of the triboelectric nanogenerator based on the fibers of the layered electrostatic generator according to the present invention.

It relates to the mechanism of the fabric-based layered electrostatic generator 4, when a finger to which a Teflon (PTFE) film is attached comes into contact with a fiber substrate 10 coated with a graphene layer 42, Teflon is triboelectrically stronger than graphene. Since it is negative, the electrons of the graphene layer 42 are extracted and transferred to the Teflon film. And when the contact is released, positive triboelectric and negative materials of a finite size are separated, and the positive charge induced in the graphene layer 42 is reduced. This is because electrons flow from the ground to the graphene layer 42 and stop in an equilibrium state.

If the Teflon comes closer to the fiber substrate 10 coated with the graphene layer 42 again, a positive charge is induced in the graphene layer 42 to balance the negative charge of the Teflon, and the electrons are from the graphene layer 42 to the ground. will flow to By repeating this process over and over again, the AC output of the fabric-based stratified electrostatic generator 4 will be generated.

The energy harvesting performance and durability of the fabric-based layered electrostatic generator 4 operating with a single electrode and exhibiting an output voltage of 20V at an external load of 9N are the same. Therefore, it will be suitable for use in the wearable fabric-based layered electrostatic generator 4 of the 3BL graphene layer 42 using the cotton fabric as the substrate 10 .

In addition, since there is no significant change in output voltage after 20,000 cycles of bending and rolling, it can be seen that the fabric-based layered electrostatic generator 4 has excellent mechanical durability. And it can be seen that the fabric-based layered electrostatic generator 4 made of three double layers (BL) connected in series with a rectifier circuit is a sustainable power source because 100 commercial green LEDs are emitting at the same time. There will be.

Figure 12 relates to a flow chart for the manufacturing process of the layered electrostatic generator according to the present invention.

The manufacturing process of the layered electrostatic generator 1 includes the steps of preparing a substrate (S10), immersing the substrate in a first solution (S20), and rinsing the substrate coated with the first solution in deionized water (S30). ), and drying the substrate and then dipping the substrate in the second solution (S40) and rinsing the substrate coated with the second solution in deionized water (S50).

In the step of preparing the substrate (S10), the substrate 10 may use a material or fabric having a flat surface, and a structure may be formed on the surface. In addition, it will be irrelevant to use the substrate 10 of various sizes.

In the step of applying the substrate with the first solution (S20), the first solution 20 is a PVA solution mixed with 0.25 wt% PVA powder and deionized water 30, and the substrate 10 is added to the first solution 20. Soak for 5 minutes.

In step S30 of rinsing the substrate in deionized water, the substrate 10 coated with the first solution 20 is taken out and rinsed sufficiently in deionized water 30 .

In the step of applying the dried substrate with the second solution (S40), the substrate 10 rinsed in deionized water 30 is dried in the air and dried. Then, in order to apply the substrate 10 as the second solution 40, a PSS solution and graphene at a concentration of 0.1 wt% GNP and 0.1 wt% PSS are mixed with deionized water 30 to make a GNP-PSS dispersion, and a tip The GNP-PSS dispersion is completed by sonicating for 3 hours using an ultrasonic disperser. When the preparation of the GNP-PSS dispersion is completed, the dried substrate 10 is immersed and maintained for 5 minutes.

In the step of rinsing the substrate in deionized water (S50), the substrate 10 is immersed in the second solution 40 for 5 minutes, taken out, and rinsed in deionized water 30 again. When the substrate 10 is sufficiently rinsed and dried, the second solution 40 will be applied to the substrate 10 .

The above process is one cycle, and the first solution 20 and the second solution 40 are sequentially layered on the substrate 10 that has undergone one cycle. If more layers are formed, the process of sequentially applying and rinsing with the first solution 20 and the second solution 40 may be repeated multiple times.

The present invention described above is not limited by the above-described embodiments and the accompanying drawings, and it is common in the technical field to which the present invention pertains that various substitutions, modifications, and changes are possible without departing from the technical spirit of the present invention. It will be clear to those who have the knowledge of

1: stratified electrostatic generator 2: fine irregularity stratified electrostatic generator
4: fabric-based layered electrostatic generator 10: substrate
20: first solution 22: deposition layer
30: deionized water 40: second solution
42: graphene layer 50: contact-type layered electrostatic generator
52: polyimide film 54: acrylate substrate
56: polyurethane foam 58: PET film

Claims (9)

A layered electrostatic power generation unit including a substrate, a deposition layer formed by coating one side of the substrate with a first solution, and a graphene layer positioned on the deposition layer by coating one side of the substrate with a second solution, into two to face each other is placed,
The deposition layer allows the second solution to be deposited on the substrate, and the graphene layer is made of a polymer material that forms an electrode on the substrate to have conductivity,
Both sides of the substrate are coated on both sides with the first solution and the second solution, or a protective film is attached to the other side of the substrate and subjected to oxygen plasma treatment so that one side of the substrate is single-sidedly coated with the first solution and the second solution,
The process of applying the substrate with the first solution and the second solution is one cycle, and the cycle is repeated three times to form three double layers of the deposition layer and the graphene layer,
The two layered electrostatic power generation units are electrically connected to each other,
One side and the other side of the substrate of any one of the two layered electrostatic power generation units are formed to be flat, the deposition layer and the graphene layer are also formed to be flat, and the substrate of the other one of the two layered electrostatic power generation units is on one side It is etched with sodium hydroxide (NaOH-etched) to uniformly form corrugated curves in the concave-convex shape, so that the deposited layer and the graphene layer are also curved,
The other side of any one of the two substrates and the graphene layer of the other one of the two substrates are in selective contact with each other,
The first solution is a PVA solution in which 0.25 wt% PVA powder and deionized water are mixed,
The second solution uses a GNP-PSS dispersion in which a PSS solution and graphene are mixed with deionized water at a concentration of 0.1 wt% GNP and 0.1 wt% PSS,
When the cycle is repeated three times to form the three double layers of the deposited layer and the graphene layer, the surface roughness of the graphene layer gradually increases, and the maximum when the deposited layer and the graphene layer form three double layers. Laminar electrostatic generator, characterized in that representing the output. According to claim 1,
The layered electrostatic generator, characterized in that the first solution and the second solution are deposited on the substrate through a wet process that is a hydrogen bonding-based multilayer thin film stacking method (layer-by-layer (LbL) assembly). According to claim 1,
The substrate is made of a fabric, or a layered electrostatic generator with a structure formed on the surface. 4. The method of claim 3,
The substrate has a PET substrate, and an oxygen plasma-treated protective film is attached to one surface to prevent application of the first solution and the second solution. delete According to claim 1,
The layered electrostatic generator further comprising a PSS solution in the graphene to improve the dispersion and adhesion of the graphene deposited on the substrate. According to claim 1,
A layered electrostatic generator for rinsing with deionized water and then drying the substrate each time the first solution and the second solution are applied to the substrate. A method for manufacturing a layered electrostatic generator for manufacturing two facing electrostatic generators, the method comprising:
Preparing two substrates to face;
etching one side of the substrate with sodium hydroxide to form irregularities;
applying the substrate by immersing it in a first solution for forming a deposition layer;
rinsing the substrate coated with the first solution in deionized water;
drying the substrate and then applying it by immersing it in a second solution for forming a graphene layer;
rinsing the substrate coated with the second solution in deionized water;
including,
The process of applying the substrate with the first solution and the second solution is one cycle, and the cycle is repeated 3 times, and the first solution and the second solution are hydrogen-bonded based multilayer thin film stacking method (layer-by-layer method) layer (LbL) assembly) is deposited on the substrate through a wet process, the deposition layer and the graphene layer to form three double layers,
Both sides of the substrate are coated on both sides with the first solution and the second solution, or a protective film is attached to the other side of the substrate and subjected to oxygen plasma treatment so that one side of the substrate is single-sidedly coated with the first solution and the second solution,
The first solution is a PVA solution mixed with 0.25wt% PVA powder and deionized water, immersed in the substrate for 5 minutes and applied, and the second solution is a PSS solution and graphene at concentrations of 0.1wt% GNP and 0.1wt% PSS. A GNP-PSS dispersion made by mixing the pins with deionized water and then sonicating them for 3 hours using a tip ultrasonicator, immersing them on the substrate for 5 minutes and applying them,
One side and the other side of the substrate of any one of the two substrates are formed to be flat, the deposition layer and the graphene layer are also formed to be flat, and the substrate of the other one of the two substrates is uniformly corrugated on one side. The deposition layer and the graphene layer are also formed to be curved,
The other flat side of any one of the two substrates and the graphene layer of the other one of the two substrates are in selective contact with each other,
When the cycle is repeated three times to form the three double layers of the deposited layer and the graphene layer, the surface roughness of the graphene layer gradually increases, and the maximum when the deposited layer and the graphene layer form three double layers. Layered electrostatic generator manufacturing method, characterized in that representing the output. 9. The method of claim 8,
The substrate is made of a fabric, or a structure is formed on the surface of the layered electrostatic generator manufacturing method.

Images