KR20200021147A - Layer by layer electrostatic generator and its manufacturing method - Google Patents

Abstract

The present invention relates to an electrostatic generator having large-area and polygonality, and a manufacturing method thereof. More specifically, the present invention relates to a layered electrostatic generator and a manufacturing method thereof. The layered electrostatic generator is applied to various substrates such as fibers by applying a layered stacking technique, and has stable output characteristics through uniform deposition even when nano/micro sized structures are formed on the substrate. The layered electrostatic generator comprises: a substrate; a first solution applied to the substrate; and a second solution applied to 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 to form an electrode on the substrate to have conductivity.

Description

Layered electrostatic generator and manufacturing method {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 in particular, 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. The present invention relates to a layered electrostatic generator and a manufacturing method having stable output characteristics through uniform deposition.

The triboelectric power generation generates electricity by friction, and unlike conventional eco-friendly energy such as solar cells, hydropower, wind power, etc., it is possible to extract the consumable mechanical energy generated during the minute vibration or movement generated as electric energy. For example, whenever people walk, the pressure energy that presses the floor to the sole and vibration and heat energy are generated when the car, train, or airplane moves. Collecting this discarded energy and converting it into electricity generates triboelectric and electrostatic induction power generation. It is about.

In other words, it is a technology that harvests and converts small energy that is discarded or unused daily into usable electric energy. The vibrations and heat of machines operating in factories or power plants, and electromagnetic waves are continuously emitted from mobile phone base stations and broadcasting stations. If not used, it eventually turns into sound or heat and disappears from the air. Therefore, it is possible to collect the energy of this fine size and use it as electrical energy.

In particular, triboelectric nanogenerators (TENGs) are considered to be the next generation of dynamic energy harvesting devices that are promising due to their desirable characteristics such as light weight, portability, environmental friendliness, and low cost. Techniques have been proposed.

For example, Korean Patent Publication No. 10-1244058 (Registration Date: 2013.03.08) relates to a method for manufacturing a graphene transparent thin film using a layered self-assembly, graphene using a layered self-assembled method of reduced graphene oxide It is applied to an organic light emitting device (OLED) using a method for producing a transparent thin film and a graphene transparent thin film obtained according to the manufacturing method.

However, existing flexible electrostatic power generators utilize a specific flexible material substrate, or mostly composed of a polymer material, requiring pretreatment or a specific material during electrode formation and surface fabrication. Such pretreatment or the use of certain materials can impede the economics of manufacturing electrostatic generators. And, in order to use a conductive fabric to induce high deformation, the conductive fabric is difficult to manufacture, economical inferior.

On the other hand, with the development of technology, flexible electrostatic generators are required to be a cost-effective, scalable, and easily manufactured method for commercializing fibrous triboelectric nanogenerators (TENGs) compatible with various textile products. It is true.

Korean Registered Patent Publication No. 10-1244058 (Registration Date: March 8, 2013)

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

The present invention is to provide a layered electrostatic generator and a manufacturing method for manufacturing a electrostatic generator having a large area, high deformation.

The present invention provides a layered electrostatic generator and a manufacturing method which is compatible with various textile products and is manufactured on a polymer substrate having a surface of various shapes.

The layered electrostatic generator according to the present invention for achieving the above object comprises 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 The second solution helps the second solution to be deposited on the substrate, and the second solution is made of a polymer material to form 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 in one cycle, and the cycle is repeated many times.

Preferably, in the present invention, the first solution and the second solution is deposited on the substrate through a wet process, which is a layer-by-layer (LbL) assembly based on hydrogen bonding. 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, the protective film is attached to one surface and then subjected to oxygen plasma treatment to prevent the 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, the second solution is 0.1wt% GNP, 0.1wt% The PSS solution at the concentration of PSS and the GNP-PSS dispersion mixed with graphene in deionized water are used as a positive friction material.

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

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

Preferably, in the present invention, preparing a substrate, immersing and applying the substrate in a first solution, rinsing the substrate coated with the first solution in deionized water, and drying the substrate. And then immersing and applying the second solution 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 is deposited on the substrate through a wet process, which is a layer-by-layer (LbL) assembly based on hydrogen bonding. 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 separated from the first solution. And a second solution.

Preferably, in the present invention, the first solution is a PVA solution mixed with 0.25 wt% PVA powder and deionized water, and soaked on the substrate 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 in deionized water at a concentration of 0.1 wt% GNP and 0.1 wt% PSS, and soaked on the substrate for 5 minutes. .

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

The invention is easy to apply to multidimensional substrates such as flat, fine surface and fiber surface.

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

The invention makes it easy to use a layered electrostatic generator of a fiber platform as a power source for wearable electronics.

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

1 is a schematic diagram of a manufacturing process of a layered electrostatic generator according to the present invention;
2 is a layered structure laminated to 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 generator using a layered electrostatic generator according to the present invention and the simulation according to the operating mechanism,
5 is an enlarged image coated with a graphene layer of 3BL and 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 a thin film measured by an ellipsometric method and a photoelectric characteristic of the layered electrostatic generator according to the present invention,
7 is a graph showing the work function of the graphene multilayer of the layered electrostatic generator according to the present invention,
8 is a graph representing the sheet resistance bending cycle of the layered electrostatic generator according to the present invention as a function;
9 is a view comparing the image and the frictional electrical contact and the resulting output voltage and output current coated with a graphene film on the fine uneven PET substrate of the layered electrostatic generator according to the present invention,
10 is an enlarged image and various embodiments of the triboelectric nanogenerator based on the fabric of the layered electrostatic generator according to the present invention;
11 is a view of the operation and performance of the triboelectric nano-generator based on the fiber of the layered electrostatic generator according to the present invention,
12 is a flow chart 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 illustrated for the purpose of describing the embodiments according to the inventive concept, and the embodiments according to the inventive concept may be implemented in various forms. In addition, it should not be construed as limited to the embodiments described herein, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

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

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

The layered electrostatic generator 1 is an electrostatic generator using layered self-assembly (Layer-by-Layer) of a conductive material on the substrate 10. Even if a nano- or micro-sized structure is formed on the substrate 10, uniform deposition is performed. Because of this, there is a characteristic that has a stable output performance.

The layered electrostatic generator 1 is deposited on the deposition layer 22 by coating the substrate 10 with the first solution 20 and the substrate 10 with the second solution 40. The graphene layer 42 is included. In this case, 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 having conductivity by forming an electrode on the substrate 10.

The substrate 10 is made of a fabric, or the structure is formed on the surface, it is possible to freely control the mass production or manufacturing area. Details of the substrate 10 will be described in detail later with reference to FIG. 3.

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 mixture of PSS solution and graphene in deionized water 30 at a concentration of 0.1 wt% GNP and 0.1 wt% PSS as a positive friction material, and is deposited on the substrate 10. PSS solution is further included in the graphene to improve the dispersion and adhesion of the graphene.

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

Deposition target material First solution Second solution Remarks 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

Variations in electrical characteristics, such as power output, can occur. However, whenever the first solution 20 and the second solution 40 are applied to the substrate 10, rinsing with deionized water 30 and then drying may be preferable in manufacturing the layered electrostatic generator 1.

Meanwhile, when the first solution 20 and the second solution 40 are applied to the substrate 10 once, two layers of the first solution 20 and the second solution 40 are applied to the substrate 10. When the second solution is repeated, the first solution 20 and the second solution 40 form another layer to form a total of four layers. In this case, the first solution 20 and the second solution 40 are deposited on the substrate 10 through a wet process, which is a layer-by-layer (LbL) assembly based on hydrogen bonding.

Figure 2 shows a layered structure laminated to a layered electrostatic generator according to the present invention.

It is a state of the board | substrate 10 which carried out 2 cycles of apply | coating the 1st solution 20 and the 2nd solution 40 sequentially, and the 1st solution 20 and the 2nd solution 40 are applied to the board | substrate 10. FIG. 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 form a layered layer on the substrate 10. Since the first solution 20 is first applied to the substrate 10, a layered state 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 forms a layer on the layer on which the first solution 20 is formed. Through this process, the production of the layered electrostatic generator 1 produced in one cycle is completed.

If the layered electrostatic generator 1 is further coated with the first solution 20 and the second solution 40, the first solution 20 is directly layered on the layer on which the second solution 40 is formed. Will form. When the second solution 40 is applied, the second solution 40 may 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 layered layers, the layered electrostatic generator 1 may have a thicker thickness than the layered electrostatic generator 1 manufactured in one cycle, and electrical properties and effects may also be different.

That is, in the substrate 10, the first solution 20 and the second solution 40 cross each other as many times as the number of cycles, thereby forming a layered layer, and since the plurality of layered layers are formed, the thickness will also be thick.

Figure 3 shows the type of substrate used in the layered electrostatic generator according to the present invention.

Substrate 10 is made of a fabric, or the structure is formed on the surface, in detail, the substrate 10 has a PET substrate, a protective film is attached to one surface and then subjected to oxygen plasma treatment to the first solution ( 20) and the application of the second solution 40 is prevented. One surface of the substrate 10 is attached with a protective film, and when the first solution 20 and the second solution 40 are applied, the solution is not applied to the surface on which the protective film is attached, and the protective film is not attached. Only the other side is applied. That is, when the protective film is attached, it is applied as a solution only on one surface not to attach the protective film.

The substrate 10 will not necessarily need to coat one side. If both sides of the substrate 10 need to be applied as a solution according to a situation, the first solution 20 and the second solution 40 are sequentially immersed in the first solution 20 and the second solution 40 without the need to attach a protective film. May form.

The substrate 10 may be divided in various ways according to the shape of the surface. As an example, the microconvex substrate 12 having an undulated shape on the surface may be used, including the substrate 10 having a flat surface. It is also possible to use a fabric substrate 16 made of a structure such as a fabric or cloth.

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

Figure 4 relates to a perspective view of the contact type layered electrostatic generator using the layered electrostatic generator according to the present invention and the appearance of the simulation according to the operating mechanism.

The contact type layer electrostatic generator 50 uses a polyimide film 52 having an air gap in the hollow portion as a spacer to facilitate contact and separation of the layer electrostatic generator 1. On both sides of the spacer, the layered electrostatic generator 1 attached to the PET film 58 is located facing each other. 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.

In addition, in order to effectively increase the contact area in the step of pressing the contact type layered electrostatic generator 50, it may be better to put a soft polyurethane foam 56 between the PET film 58 and the acrylate substrate 54.

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

In detail, when the layered electrostatic generator 1 located at the bottom contacts the PET film 58, 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 frictional electricity. However, since the electrical balance is maintained, no electron flow occurs in the external circuit.

The electrons of the layered electrostatic generator 1 (cathode potential) at the top through the external circuit due to the strong potential difference between the two layered electrostatic generators 1 in the stage where the layered generator 1 is then separated It flows into the layered electrostatic generator 1 (anode 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 a substrate surface of a layered electrostatic generator according to the present invention.

The layered electrostatic generator 1 laminated with three bilayers 3BL is observed with a field emission scanning electron microscope (FE-SEM) and the first bilayers 10BL are laminated on a flat PET substrate 10. The layered electrostatic generator 1 coated with the solution (PVA) 20 and the second solution (GNP-PSS) 40 is a cross-sectional image observed with a transmission electron microscope (TEM).

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

The image of the transmission electron microscope (TEM) shows a multi-layered layered electrostatic generator 10, where the dark gray part is the PET substrate 10 area, the light gray part is the epoxy area, and the darkest black line is the multilayer thin film laminate ( LbL) is a cross section of the graphene layer 42 deposited by the technique.

A homogeneous network of second solutions (GNPs) 40 was observed and confirmed in both images, and PSS addition for the separation of individual GNPs assisted in the uniform distribution of the graphene layer 42 on the substrate 10. Entanglings such as polymers form a three-dimensional network. In this network, the graphene layer 42 provides high conductivity by providing an electron transfer path through the substrate 10.

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

When the layered layer consisting of PVA, which is the first solution 20, and GNP-PSS, which is the second solution 40, is called a double layer (1BL), the layer thicknesses of 1, 3, 5, and 10BL are measured and compared by ellipsometric methods. The graph shows the linear growth of graphene multilayer thin-film lamination. Through this, it can be seen that the degree of coupling between PVA and graphene and a constant component ratio in the layered layer.

In addition, the graph shows the average thickness of the region containing many particles and the surface roughness of the graphene-based layer where the void space is formed between the layers.

The maximum value of 3BL measured by ellipsometric method is 46 nm, indicating that the deposition of PVA molecules and GNP-PSS particles produces a rough surface until the first 3BL, increasing the roughness. However, thereafter, the roughness decreases, which reduces the roughness because precipitation occurs in some of the thinly formed regions in the previous deposition step.

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

(b) relates to a graph showing the optoelectronic properties of the graphene layer 42 assembled by the multilayer thin film lamination 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 the increase in the thickness of the graphene layer 42.

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

In the fabric based layered electrostatic generator 4, the graphene layer 42 will form a resistance of at least 3.8 kΩ sq-1 at 10BL and at least 10.8 kΩ sq-1 at 3BL. Since the resistivity decreases as the layer thickness of the graphene layer 42 becomes thicker, the output is improved.

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

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

In other words, it can be seen that the output performance of the planar layered electrostatic generator 1 greatly influences the number of BLs representing the thickness of the multilayer. However, due to the sensitivity to changes in wet manufacturing conditions such as temperature, humidity, substrate pretreatment, etc. at the nanometer level, a maximum output may sometimes occur in the planar layer electrostatic generator 1 composed of 2 to 4 BL.

Although the output performance of the layered electrostatic generator 1 in which a plurality of graphene layers 42 having the highest conductivity are stacked should be the highest, the maximum output is obtained from the layered electrostatic generator 1 formed of the 3BL graphene layer 42. Is showing.

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

That is, when the work function of the layered electrostatic generator 1 forming 1, 3, 10 graphene layers 42 is measured, the work function increases with the thickness of the graphene layer 42. In addition, as the work function becomes larger, more energy is required to extract electrons, thereby increasing the layer of the graphene layer 42, thereby optimizing the graphene layer 42 that can maintain a balance between resistivity and work function. It can be seen that the thickness of 3BL.

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

The triboelectric sheet voltage bending cycles of the planar layered electrostatic generators 1, 3, 5, and 20BL as a function, and the triboelectric output voltages of the three planar layered electrostatic generators 1, 3, 5, and 20 before and after 1000 folding cycles. The amount of change in over current is shown.

Since flexural stability is becoming more and more important as the market for flexible electronic applications expands, the mechanical durability of layered electrostatic generators (1) assembled by multilayer thin film lamination of graphene layers (42) may be very important in electrodes or flexible electronic applications. will be.

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

The mechanical stability of the layered electrostatic generator 1 will therefore be well suited for application in flexible electronics.

FIG. 9 compares an image coated with a graphene film and frictional electrical contact, and thus an output voltage and an output current, on a fine uneven PET substrate of a layered electrostatic generator according to the present invention.

(a) is assembled by the multilayer thin film lamination method of the graphene layer 42, and is a fine rough layered layer electrostatic generator coated with a graphene layer 42 on a substrate 10 on which NaOH-etched and fine irregularities are formed. The surface of (2) relates to an enlarged image using a field emission scanning electron microscope (FE-SEM).

(b) shows the comparison between making graphene on the flat surface and corrugated graphene with uniform curvature on the entire surface of the layer.

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

When comparing the output performance of the microstructured layered electrostatic generator (UG-TENG) (2) and the fabric-based layered electrostatic generator (TG-TENG) (4), the microstructured layered electrostatic generator (UG) formed of three double layers (BL) The output voltage and current of TENG) 2 are higher than the output voltage and current of the planar layered 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 and the concentrated contact stress with the opposite friction material due to the corrugated graphene layer 42 of the uneven uneven layered electrostatic generator (UG-TENG) 2. 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 to the corrugated surface.

Figure 10 relates to various enlarged images of a layered electrostatic generator based on the fabric of the layered electrostatic generator according to the invention and the embodiment accordingly.

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

(a) is an enlarged image of the field emission scanning electron microscope (FE-SEM) of the graphene layer 42 on the substrate 10 having the cotton fiber as the substrate 10, and the graphene layer 42 structure is formed on the cotton fabric bundle. You can see that it is well formed. Other magnified images relate to graphene composite surfaces on a single fabric.

(b) and (c) is an enlarged image 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 graphene layer 42 having cotton fibers as the substrate 10 has high durability.

In addition, it is possible to produce a graphene thin film on the substrate 10 of various sizes as shown in (d), which is possible because of the multilayer thin film lamination method (LbL) of the graphene layer 42 that can be easily expanded processing.

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

Figure 11 shows the operation and performance of the triboelectric nano-generator based on the fiber of the layered electrostatic generator according to the present invention.

The mechanism of the fabric-based layered electrostatic generator 4 is that when a finger with a Teflon (PTFE) film is in contact with the fibrous substrate 10 coated with the graphene layer 42, the Teflon is triboelectrically compared to graphene. As it is negative, the electrons in the graphene layer 42 are extracted and transferred to the Teflon film. When the contact is released, positive charge induced in the graphene layer 42 is reduced while positive and negative frictional and negative materials are separated. This is because electrons flow from the ground into the graphene layer 42 and stop at equilibrium.

If the Teflon is close to the fibrous 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, the electron is ground on the graphene layer 42 Will flow into. Repeating this process will produce the AC output of the fabric-based laminar generator 4.

The energy-harvesting performance and durability of the fabric-based layered electrostatic generator 4, operated from a single electrode and showing an output voltage of 20V at an external load of 9N, is the same. It would therefore be suitable for use in a wearable fabric based layered electrostatic generator 4 of 3BL graphene layer 42 with cotton fabric as substrate 10.

In addition, since there is no large change in output voltage after bending and rolling of 20,000 cycles, it can be seen that the mechanical durability of the fabric-based layered electrostatic generator 4 is excellent. In addition, the fabric-based laminar generator (4) consisting of three double layers (BL) connected in series with the rectifier circuit emits 100 commercial green LEDs simultaneously, indicating that the fabric-based laminar generator (4) is a sustainable power source. There will be.

12 is a flowchart of the manufacturing process of the layered electrostatic generator according to the present invention.

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

In preparing the substrate (S10), the substrate 10 may be formed of a material or fabric having a flat surface, and a structure may be formed on the surface. In addition, various sizes of substrate 10 may be used.

In the step of applying the substrate to 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 to the first solution 20 Soak for 5 minutes.

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

In step S40 of applying the dried substrate to the second solution, the substrate 10 rinsed in deionized water 30 is dried in air and dried. Then, to apply the substrate 10 to the second solution 40, the PSS solution and graphene were mixed with deionized water 30 at a concentration of 0.1 wt% GNP and 0.1 wt% PSS to form a GNP-PSS dispersion, and a tip Sonicate for 3 hours using an ultrasonic disperser to complete the GNP-PSS dispersion. After the preparation of the GNP-PSS dispersion is completed, soak the dried substrate 10 and hold for 5 minutes.

In the step S50 of rinsing the substrate in deionized water, the substrate 10 is immersed in the second solution 40 for 5 minutes, and then rinsed again in deionized water 30. After sufficiently rinsing and drying the substrate 10, the substrate 10 will be applied as the second solution 40.

The process is one cycle, and the first solution 20 and the second solution 40 are sequentially layered on the substrate 10 after one cycle. In order to form more layers, the process of sequentially applying and rinsing with the first solution 20 and the second solution 40 may be repeated many times.

The present invention described above is not limited to the above-described embodiments and the accompanying drawings, and various substitutions, modifications, and changes can be made without departing from the technical spirit of the present invention. It will be evident to those who have knowledge of.

1: Layered Blackout Generator 2: Fine Iron Layered Blackout 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 layer electrostatic generator
52 polyimide film 54 acrylate substrate
56 polyurethane foam 58 PET film

Claims (15)

Board;
A deposition layer formed by applying the substrate with a first solution;
A graphene layer disposed on the deposition layer by coating the substrate with a second solution;
Including;
The deposition layer is a layered electrostatic generator made of a polymer material to enable the second solution to be deposited on the substrate, the graphene layer is conductive by forming an electrode on the substrate. The method of claim 1,
In one cycle, the deposition layer and the graphene layer are sequentially stacked on the substrate, and the cycle is repeated three times to form a maximum output when the deposition layer and the graphene layer form three bilayers. Electrostatic generator. The method of claim 1,
And the first solution and the second solution are deposited on the substrate through a wet process, which is a hydrogen bond-based multilayer-by-layer (LbL) assembly. The method of claim 1,
The substrate is a layered electrostatic generator consisting of a fabric, the structure is formed on the surface. The method of claim 4, wherein
The substrate has a PET substrate, a protective film treated with an oxygen plasma treatment on one side, the layered electrostatic generator to prevent the application of the first solution and the second solution. The method of claim 1,
The first solution is a PVA solution mixed with 0.25 wt% PVA powder and deionized water, and serves as a negative friction material,
The second solution is a layered electrostatic generator using a GNP-PSS dispersion mixture of PSS solution and graphene in deionized water at a concentration of 0.1wt% GNP and 0.1wt% PSS as a positive friction material. The method of claim 6,
Layered electrostatic generator further comprises a PSS solution to the graphene to improve the dispersion and adhesion of the graphene deposited on the substrate. The method of claim 1,
The layered electrostatic generator rinsed with deionized water and dried every time the first and second solutions are applied to the substrate. Preparing a substrate;
Dipping and applying the substrate to a first solution;
Rinsing the substrate coated with the first solution in deionized water;
Drying the substrate and immersing it in a second solution;
Rinsing the substrate coated with the second solution in deionized water;
Layered electrostatic generator manufacturing method comprising a. The method of claim 9,
The process of coating the substrate with the first solution and the second solution as a cycle, and when the cycle is repeated three times, the method of producing a layered electrostatic generator, characterized in that to form a maximum output. The method of claim 9,
Wherein the first solution and the second solution are deposited on the substrate through a wet process, which is a layer-by-layer (LbL) assembly based on hydrogen bonding. The method of claim 9,
The substrate is made of a fabric, the structure of the layered electrostatic generator having a structure formed on the surface. The method of claim 9,
A layered electrostatic generator in which 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 oxygen plasma treatment is applied to the other surface of the substrate with the first solution and the second solution. Manufacturing method. The method of claim 9,
The first solution is a PVA solution mixed with 0.25 wt% PVA powder and deionized water, and soaked on the substrate for 5 minutes to apply a layered electrostatic generator. The method of claim 9,
The second solution is a method of producing a layered electrostatic generator applied by soaking for 5 minutes on the substrate as a dispersion of GNP-PSS mixed with PSS solution and graphene in deionized water at a concentration of 0.1wt% GNP and 0.1wt% PSS.

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