KR20210094805A - Fluorinated hydrophobic conductive metal oxide coated hydrophilic fiber membrane and superhydrophobic electrode based electrical energy generator and manufacturing method for the electrical energy generator - Google Patents

Abstract

The present invention relates to a fiber membrane energy generating device, which utilizes a potential difference caused by an electric double layer effect formed in a process in which a polar protic solvent containing a polar molecule or ion is adsorbed on the surface of a conductive oxide to which a hydrophobic fluorine-based functional group is bonded, to perform asymmetric adsorption of a solution that can be obtained from nature as well as a manufactured solution on a fiber membrane coated with a conductive oxide layer bonded with a fluorine-based functional group, maintains high potential difference and current, generated therefrom, for a long time, generates electric energy in the form of direct current, and has the conductive oxide layer bonded with the fluorine-based functional group bound to the surface of individual fibers, a manufacturing method of the energy generating device, a large-area energy generating device in which a plurality of energy generating devices are stacked or combined in parallel/series, and a manufacturing method thereof.

Description

FLUORINATED HYDROPHOBIC CONDUCTIVE METAL OXIDE COATED HYDROPHILIC FIBERICAL MEMBRANE AND SUPERHYDROPHOBIC ELECTRODE BASED TECHNICAL FIELD MANUFACTURING METHOD FOR THE ELECTRICAL ENERGY GENERATOR}

The present invention relates to a polar molecule or a conductive oxide surface to which a fluorine-based hydrophobic functional group is bonded by asymmetrically electrostatic physisorption of a polar solvent (preferably, a polar protic solvent containing ions) and flow of a fluid. In the process of continuously adsorbing ions and asymmetrically adsorbing a polar solvent to the electrode region connected to both sides of the conductive oxide to which the fluorine-based hydrophobic functional group is bonded, the high voltage generation efficiency is utilized by the potential difference on both electrodes and continuously In order to neutralize the potential difference generated, an energy generating device that converts electric current generated by electrons moving from a conductive material to an electrode, that is, high-performance electrical energy, and a method for manufacturing the energy generating device, and a device in which a plurality of energy generating devices are combined It relates to an area electric energy generating device. Specifically, an individual electrical energy generating device based on a hydrophilic fiber membrane coated with a conductive oxide applies a uniform conductive oxide layer to the fiber strand surface of the hydrophilic fiber membrane through a dipping process using a conductive oxide solution dispersed in ethanol. A fluorine-based functional group, a waterproof coating material, is chemically bonded to the surface of the conductive oxide coated on the hydrophilic fiber membrane and uniformly applied by vapor deposition. When a polar solvent is asymmetrically dropped on both electrodes of a hydrophilic fiber membrane coated with a conductive oxide to which a hydrophobic fluorine-based functional group is bonded, a potential difference due to an electric double layer caused by physical adsorption is formed between the adsorbed portion and the non-adsorbed portion. . At this time, the surface area of the water contained in the container is exposed to the air, and physical adsorption occurs continuously on the surface of the hydrophilic fiber membrane coated with the conductive oxide to which the hydrophobic fluorine-based functional group is bonded due to the continuous movement of water molecules inside the water due to the surface evaporation of the water. The potential difference can be maintained for a long time until the polar solvent is completely evaporated. At this time, the electron flow of the conductive oxide for maintaining charge neutrality to the electric double layer formed at the interface where the physical adsorption occurs may be induced to generate an electric current, thus generating electric power.

Energy that produces electric energy using waste and unused resources, such as light, heat, kinetic energy, water, and wind, in order to produce eco-friendly and sustainable electric energy and to build a self-contained power source required for the smart grid. _{The field of harvesting technology solves environmental problems related to the greenhouse effect caused by CO 2} generated in producing electric energy, and electronic devices based on sensor network technology and wireless data transmission and reception technology required for the Internet of Things, a pivotal technology of the car industrial revolution. It is a field with infinite potential to improve the quality of life by combining them.

Among the electric energy generating systems developed so far, solar cells and thermoelectric systems have the advantage of generating high power of 100 mW or more. However, in order to continuously generate electric energy, it is necessary to always maintain a temperature difference, or it is possible to generate electric energy only during the day when continuous and strong sunlight irradiation is possible. Due to this, in order to generate high-efficiency electric energy, the temperature difference must be sufficiently generated or the sunlight must be well received, so the installation site is also limited.

In addition, piezoelectric and triboelectric nanogenerators using a piezoelectric effect and a triboelectric effect by receiving energy from a mechanical energy source existing around, for example, a movement and vibration source of the human body are suggested as alternatives. Each energy generating device has the advantage of generating high voltage and high power of several tens of μW to mW. In particular, the piezoelectric and triboelectric energy generating devices can convert the movement of the human body into electrical energy, and thus can be used in a wearable energy generating device.

However, in the energy generating device by mechanical deformation and friction, electrical energy is generated in the form of high frequency alternating current (AC) voltage and current by the generating principle. An instantaneous voltage difference occurs only when mechanical deformation and friction are applied. When the applied mechanical action is removed, the voltage difference is re-established in the opposite direction, so that the electrical energy takes the form of a high-frequency alternating current. For this reason, piezoelectric and triboelectric energy generating devices must always be accompanied by a separate rectifier circuit and energy storage device, and must be installed in a limited place where mechanical energy sources exist to generate high-efficiency energy.

Therefore, as an alternative to the above issues, the generator design and large-area manufacturing technology that can stably produce direct current without damage to the energy generating device must be preceded. This enables the simplification of the energy generating device, thereby reducing production cost and improving the availability.

When a polar solvent is dropped on a hydrophilic fiber membrane coated with a conductive oxide bonded with a fluorine-based functional group, polar molecules or ions contained in the solvent are physically adsorbed on the fiber membrane surface to form an electric double layer, which results in the formation of an electric double layer on both sides of the fiber membrane A potential difference is induced asymmetrically in the electrode region connected to the polar solvent between the adsorbed portion and the non-adsorbed portion. The potential difference formed is maintained for a long time until the polar solvent is completely evaporated. In addition, the electrons inside the conductive oxide move to maintain the charge neutrality of the charge layer generated at the interface due to the physical adsorption of the polar solvent and the fluorine-based functional group, so that the current continues until the polar solvent is completely evaporated. will flow to In addition, by chemically bonding a hydrophobic fluorine-based functional group to the surface of the metal electrode used or by forming a physical structure on the surface of the electrode to have physical and chemical superhydrophobic properties, it prevents chemical reaction or oxidation between the polar solvent and the metal electrode for durability to improve In embodiments of the present invention, a high-performance, high-durability energy generating device and energy generation that have a high generated voltage and current in the form of direct current (DC) and prevent a chemical reaction with a polar solvent by using a hydrophobic fluorine-based functional group to generate electrical energy A method of manufacturing the device is provided.

Provided is a large-area electric energy generating device that combines a plurality of individual energy generating devices so that they can be utilized in various conditions and environments, such as supplying power to IoT electronic devices or storing energy generated in secondary batteries and supercapacitors.

In the hydrophilic membrane coated with a conductive oxide bonded to a hydrophobic fluorine-based functional group, an electric double layer is formed by the polar molecules adsorbed to the fluorine-based functional group and ions contained in the solvent, so that the potential difference between the adsorbed portion and the non-adsorbed portion is An energy generating device is provided, characterized in that electric energy in the form of direct current is induced and induced by the flow of electrons moving in a predetermined direction to maintain charge neutrality.

According to one side, the potential difference due to the electric double layer formed by polar molecules and ions adsorbed on the surface of the conductive oxide to which the fluorine-based functional group is bonded and the electrical neutrality of the electric charge formed at the interface between the fluorine-based functional group and the polar solvent are maintained. It may be characterized in that electrical energy is continuously generated by the flow of electrons for

According to another aspect, the fluorine-based functional group is chemically bonded to the hydrophilic oxide, and the polar solvent and the fluorine-based functional group do not chemically react or prevent oxidation, thereby increasing durability to continuously generate electrical energy. .

According to another aspect, the fibrous membrane having the hydrophobic surface is physically adsorbed with the fluorine-based hydrophobic functional group to form an electric double layer, but does not react chemically to minimize the evaporation of water resource energy used to generate electrical energy. It may be characterized in that electrical energy is generated for a long time.

According to another aspect, the area adsorbed to the fibrous membrane having a hydrophobic surface is a structure in which the surface of water is exposed to external air in a container containing water, or the flow of water molecules inside by evaporation of water occurring at the sea surface As the polar solvent is continuously adsorbed to the fluorine-based functional group by the

According to another aspect, the polar solvent comprises a polar protic solvent containing ions, and the ions contained in the polar protic solvent are additionally arranged on an outer Helmholtz plane of the adsorption region. can be done with

According to another aspect, the energy generating device may include a first electrode connected to a region adsorbed to the fibrous membrane having the hydrophobic surface; and a second electrode connected to the non-adsorbed area of the fibrous membrane having the hydrophobic surface.

According to another aspect, by chemically bonding a hydrophobic fluorine functional group to the first electrode and the second electrode or by forming a physical structure on the surface, the surface of the superhydrophobic metal electrode with extremely low surface energy is durable to a polar solvent. It may be characterized in that electrical energy is continuously generated by preventing oxidation and corrosion.

According to another aspect, the polar solvent is (1) formic acid, n-butanol (n-butanol), isopropanol (isopropanol), n-propanol (n-propanol), ethanol (ethanol), methanol ( It may be characterized as comprising a synthetic solution in which ions are dissolved in at least one of methanol) and water in a polar protic solvent, or (2) a solution existing in nature, such as at least one of seawater and sweat.

According to another aspect, the conductive oxide constituting the conductive oxide layer is at least one material selected from n-type or p-type oxide exhibiting conductivity due to oxygen vacancy and atomic doping effect. For example, the conductive oxide having oxygen vacancies is In ₂ O ₃ , which has electrical conductivity due to oxygen vacancies, and further includes a conductive oxide whose electrical conductivity is improved by the Sn atom doping effect.

According to another aspect, the hydrophobic functional group is -CF _{3, a} terminal group, -CH _2, as a material having a terminal group trichloro(1H,1H,2H,2H-perfluorooctyl)silane, trichloro(1H,1H,2H,2H -heptadecafluorodecyl)silane, 1H,1H,2H,2H-perfluorododecyltrichlorosilane, and a waterproof coating material containing non-polar functional groups are characterized.

According to another aspect, the metal electrode electrically connected to the fiber membrane coated with the conductive oxide to which the hydrophobic fluorine-based functional group is bonded uses a metal having a value equal to or lower than the work function (Φ) of the conductive oxide to provide high power. It is characterized in that it includes continuously generating.

According to another aspect, in the conductive oxide layer to which the fluorine-based functional group is bonded, the selected at least one conductive oxide material has zero-dimensional, one-dimensional or It may be characterized in that it is complexed in two dimensions.

According to another aspect, the conductive oxide layer is ^{coated by loading a conductive oxide in the range of 2.1 mg/cm 3} to 0.024 mg/cm ³ per unit volume on the hydrophilic fiber membrane, and the amount of the loaded conductive oxide is generated through the It may be characterized in that the voltage and current of the electrical energy to be regulated.

According to another aspect, the hydrophilic fiber membrane is selected from cotton fabric, mulberry paper, polypropylene membrane, oxygen plasma-treated nonwoven fabric, hydrophilic surface-treated fabric, and nanofiber. It may be characterized in that it is composed of at least one material.

According to another aspect, the hydrophilic fibrous membrane may be formed of fiber strands to improve a specific surface area and adsorption power to a polar protic solvent, and a conductive oxide may be bound to the surface of individual fibers.

According to another aspect, the diameter of the hydrophilic fiber strands included in the hydrophilic fiber membrane may be characterized in that it is included in the range of several tens of nm to several hundred mm.

According to another aspect, the thickness of the hydrophilic fiber membrane may be characterized in that it is included in the range of 5 mm to 1 mm.

According to another aspect, the hydrophilic fibrous membrane includes an electrode and one of the two electrodes connected to both ends of the membrane to maintain a voltage difference through asymmetric adsorption of both poles, and the length of the fibrous membrane from the part where the electrode is connected It is possible to asymmetrically adsorb the polar solvent up to the 1/2 point region.

According to another aspect, the amount of electrical energy generated by laminating at least one other hydrophobic fiber membrane on the conductive oxide-coated fiber membrane to which the hydrophobic fluorine-based functional group is bonded, or connecting in parallel or series, the amount, voltage, power density, It may be characterized in that at least one of the adsorption power to the polar protic solvent is controlled.

A method for manufacturing an energy generating device, comprising: (a) cutting a hydrophilic fiber membrane to a designed size; (b) coating the conductive oxide layer on the surface of individual fibers constituting the hydrophilic fibrous membrane by dipping the hydrophilic fibrous membrane in a conductive oxide coating solution; (c) drying the hydrophilic fibrous membrane coated with the conductive oxide layer; (d) chemically bonding a fluorine-based functional group to a conductive oxide and an electrode electrically connected to the conductive oxide layer, wherein the fluorine-based functional group is asymmetrically adsorbed by a polar solvent on the surface of the conductive oxide layer to which the conductive oxide layer is bonded. As the polar solvent is adsorbed to the fluorine-based functional group in the region where the polar solvent is adsorbed, a potential difference is induced between the non-adsorbed regions by the electric double layer effect generated in the adsorbed region to generate electrical energy, Provided is a method for manufacturing an energy generating device capable of generating energy for a long time by extremely minimizing evaporation by preventing a water resource used to generate electrical energy from chemically reacting with a hydrophobic surface.

According to one side, the method of manufacturing the energy generating device may further include (e) stacking two or more hydrophilic fiber membranes coated with a conductive oxide layer to which a hydrophobic functional group is bonded.

According to another aspect, the method of manufacturing the energy generating device may further include (f) connecting a plurality of hydrophilic fibrous membranes coated with a conductive oxide layer to which a fluorine-based functional group is bonded in parallel or in series.

According to another aspect, in step (b), as a conductive oxide material capable of adsorbing both cations and anions, an n-type or p-type oxide exhibiting conductivity by oxygen vacancy and atomic doping effects At least one conductive oxide material selected from among is dispersed in ethanol to generate the conductive oxide coating solution to have a mass ratio of 1 wt% to 5 wt%.

According to another aspect, the step (b) may be characterized in that the loading amount of the conductive oxide is controlled by controlling the number of times the hydrophilic fiber membrane is immersed in the conductive oxide coating solution.

According to another aspect, in step (c), the hydrophilic fiber membrane coated with the conductive oxide layer is placed flat on a tray and then dried in an oven.

According to another aspect, the polar solvent is asymmetrically adsorbed only to the portion connected to one of the two electrodes connected to the hydrophilic fiber membrane coated with the conductive oxide layer to which the fluorine-based functional group is bonded, so that the portion adsorbed by the polar solvent is It may be characterized in that DC power is generated by connecting the electrode and the electrode of the non-adsorbed portion to form a circuit.

According to another aspect, the polar solvent is a polar protic solvent containing ions, (1) formic acid, n-butanol (n-butanol), isopropanol (isopropanol), n-propanol (n- propanol), ethanol, methanol and water containing a synthetic solution in which ions are dissolved in a polar protic solvent selected from, or (2) containing a solution that exists in nature, such as seawater or sweat. can be characterized as

According to another aspect, the hydrophobic functional group is -CF _{3, a} terminal group, -CH _2, as a material having a terminal group trichloro(1H,1H,2H,2H-perfluorooctyl)silane, trichloro(1H,1H,2H,2H -heptadecafluorodecyl)silane, 1H,1H,2H,2H-perfluorododecyltrichlorosilane, and a waterproof coating material containing non-polar functional groups are characterized.

According to another aspect, the metal electrode electrically connected to the conductive oxide includes a material equal to or lower than the work function of the conductive oxide.

According to embodiments of the present invention, a polar solvent (preferably, a polar protic solvent containing ions) is asymmetrically dropped onto a hydrophilic fiber membrane coated with a conductive oxide layer to which a hydrophobic functional group is bonded, resulting in high-performance direct current. Electrical energy generating devices that generate electric power can be crafted.

Through the dipping process, the conductive oxide is uniformly applied to the fiber strand surface of the hydrophilic fiber membrane, which is easily absorbed by the polar solvent, and the fluorine-based functional group on the surface of the hydrophilic conductive oxide is chemically bonded through vapor deposition. Electric energy can be generated only in the presence of a polar solvent by It can generate electrical energy for driving.

For example, an energy generating device based on a hydrophilic fibrous membrane coated with a conductive oxide layer manufactured using an immersion process chemically contains a hydrophobic fluorine-based functional group on a metal oxide, which is a representative material that forms a hydrophilic hydroxyl (OH) functional group on the surface. Use a metal electrode with the same or lower work function as that of the conductive oxide, or use a hydrophobic fluorine-based functional group to the metal electrode. Or, by forming a physical shape on the surface to have superhydrophobicity, it is possible to generate high-performance, high-durability DC power in an environmentally friendly manner based on excellent durability by preventing chemical reaction or oxidation with polar solvents. In one embodiment, in the case of a hydrophilic fiber membrane coated with a conductive oxide layer having a size of 3 cm (vertical) × 9 cm (horizontal) in size, when water is completely evaporated in the surrounding environment while being immersed in 280 ml tap water DC power can be generated for up to 14 days, and mass production is easy, so it is highly likely to be used as a home energy auxiliary device, a portable power auxiliary device, and an auxiliary power device for wearable electronic devices.

BRIEF DESCRIPTION OF THE DRAWINGS The drawings, which are included as a part of the detailed description to help the understanding of the present invention, provide embodiments of the present invention, and together with the detailed description, explain the technical spirit of the present invention.
1 is a schematic diagram of a manufacturing process of a hydrophilic fiber membrane-based energy generating device coated with a conductive oxide layer to which a hydrophobic functional group is bonded, which is a manufacturing process of the present invention.
2 is a flowchart illustrating a method of manufacturing a hydrophilic fiber membrane-based energy generating device coated with a conductive oxide layer to which a hydrophobic functional group is bonded using an immersion process according to an embodiment of the present invention.
3 is a schematic diagram of a large-area energy generating device in which individual stacked energy generating devices are combined according to an embodiment of the present invention.
Figure 4 is a polar solvent of DI (deionized) water in the energy generating device according to the resistance value according to the loading amount of the conductive oxide and the energy generating device coated with ITO (indium tin oxide) nanoparticles, which is a conductive oxide according to asymmetric surface adsorption. This is the result of performing asymmetric adsorption and comparing the generated open circuit voltage using
Figure 5 is a polar solvent of DI (deionized) water in the energy generating device according to the resistance value according to the loading amount of the conductive oxide and the energy generating device coated with ITO (indium tin oxide) nanoparticles, which is a conductive oxide according to asymmetric surface adsorption. This is the result of performing asymmetric adsorption and comparing the generated short-circuit current.
6 is a result of measuring the short-circuit current generated while the energy generating device is asymmetrically adsorbed in a beaker containing tap water and the water is evaporated.
7 is a result of storing electric energy in a supercapacitor by using a power source generated by electrically connecting a plurality of energy generating devices.
FIG. 8 is a diagram illustrating a state in which a power source generated by electrically connecting a plurality of energy generating devices is stored in a plurality of supercapacitors to increase an output size to drive a power device.

The present invention can apply various transformations and can have various embodiments. Hereinafter, specific embodiments will be described in detail based on the accompanying drawings.

In describing the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

Hereinafter, an energy generating device based on a hydrophilic fiber membrane coated with a conductive oxide layer to which a hydrophobic functional group is bonded and a method for manufacturing the same will be described in detail with reference to the accompanying drawings.

The present invention relates to a conductive oxide surface bonded with a fluorine-based functional group capable of adsorbing a polar solvent to the surface by asymmetric adsorption of a polar solvent (preferably, a polar protic solvent containing ions) and flow of a fluid. Utilizing the unique high voltage generation efficiency that is formed in the process of adsorption, a polar solvent (preferably a polar protic solvent containing a small amount of ions) that is placed in a container and the surface of the polar solvent is exposed to air is treated with a fluorine-based function. It relates to an energy generating device that generates electrical energy through the act of asymmetrically contacting only the region where one of the two electrodes is connected to a hydrophilic fiber membrane coated with a conductive oxide layer coated with a group, and a method for manufacturing the same, A potential difference is formed between the adsorbed portion and the non-adsorbed portion by the electric double layer generated due to physical adsorption. The potential difference formed is continuously adsorbed to the fluorine-based functional group due to the flow of polar molecules inside the polar solvent by evaporation of the surface of the polar solvent contained in the container, and can be maintained for a long time until the polar solvent is completely evaporated.

And, in order to maintain the charge neutrality (charge neutrality) formed at the interface between the fluorine-based functional group and the polar solvent, it may be characterized by utilizing the continuous movement of electrons to the metal electrode through the conductive oxide. In addition, the hydrophobic functional group coupled to the conductive oxide layer and the metal electrode may not chemically react with the polar solvent, thereby increasing durability and stably generating power for a long time.

An embodiment of the present invention provides an individual energy generating device for generating high-performance DC voltage-current type electric energy, and a method for manufacturing a large-area electric energy generating device by combining a plurality of such individual energy generating devices. Electric energy in the form of direct current formed through a conductive oxide-based energy generating device coupled with a hydrophobic functional group can be driven by directly connecting it to a high-power electronic device without a separate rectifying circuit.

As such, embodiments of the present invention can mass-produce a fiber membrane in which a conductive oxide layer is coated by a simple immersion process and a fluorine-based functional group is bonded to a conductive oxide by vapor deposition at low cost, and a large-area energy generating device It is easy to manufacture and has the advantage of easy control of the generated voltage and current through lamination between fiber membranes.

More specifically, the energy generating device according to an embodiment includes a hydrophilic fiber membrane coated with a conductive oxide layer and a metal electrode electrically connected to the conductive oxide layer, and the hydrophilic surface of the hydrophilic fiber membrane is changed into a hydrophobic surface, and , on the surface of the conductive oxide layer to which the hydrophobic functional group is chemically bonded to the surface of each of the conductive oxide layer and the metal electrode, and to which the hydrophobic functional group is bonded, between the region to which the polar solvent is adsorbed and the region to which the polar solvent is not adsorbed. It may be characterized in that a miracle potential difference is induced to generate continuous electrical energy.

In this case, the conductive oxide layer may include an n-type or p-type oxide exhibiting conductivity due to an oxygen vacancy or atomic doping effect. For example, the conductive oxide layer may include _{In 2} O ₃ having electrical conductivity due to oxygen vacancies and improved electrical conductivity due to Sn atom doping effect. In addition, the hydrophilic fiber membrane is at least one material selected from cotton fabric, Korean paper (mulberry paper), polypropylene membrane, oxygen plasma-treated nonwoven fabric, hydrophilic surface-treated fabric, and nanofibers. can be composed of In addition, the diameter of the fiber strands included in the hydrophilic fiber membrane may be included in the range of 50 nm to 500 mm.

At this time, the hydrophilic surface of the hydrophilic fibrous membrane is _{a hydrophobic surface using a material having at least one of -CF 3,} terminal groups, -CH _2, terminal groups, or non-polar molecules that do not chemically react with water. can

In addition, the polar solvent is a polar protic solvent containing ions, (1) formic acid, n-butanol (n-butanol), isopropanol, n-propanol (n-propanol), ethanol ( ethanol), a synthetic solution in which ions are dissolved in at least one polar protic solvent of methanol, and water, or (2) a solution of at least one of seawater and sweat.

In addition, the conductive oxide layer and the metal electrode may include a metal having a value equal to or lower than the work function (?) of the conductive oxide. For example, the conductive oxide layer and the metal electrode are made of silver (Ag, φ = 4.26 eV) and aluminum (Al, φ = 4.28 eV) or mercury (Hg, φ = 4.49 eV).

In addition, the metal electrode includes, on the surface of the conductive oxide layer to which the hydrophobic functional group is bonded, the first metal electrode in contact with the region to which the polar solvent is adsorbed and the second metal electrode in contact with the region to which the polar solvent is not adsorbed. may include.

In this case, the conductive oxide layer is coated by loading the conductive oxide on the hydrophilic fiber membrane, and the voltage and current of the generated electrical energy can be controlled by controlling the amount of the conductive oxide loaded on the hydrophilic fiber membrane.

In addition, the hydrophobic functional group may include a fluorine-based hydrophobic functional group.

On the other hand, the method of manufacturing an energy generating device according to an embodiment comprises the steps of (a) cutting a hydrophilic fiber membrane to a designed size, (b) immersing the hydrophilic fiber membrane in a conductive oxide solution in which conductive nanoparticles are dispersed in a solvent. Coating a conductive oxide layer on the surface of individual fibers constituting the hydrophilic fiber membrane, (c) drying the hydrophilic fiber membrane coated with the conductive oxide layer, and (d) bonding a hydrophobic functional group to the surface of the conductive oxide layer may include steps.

At this time, the contact of the polar solvent to the hydrophilic fiber membrane coated with the conductive oxide layer to which the hydrophobic functional group is bonded forms an electric double layer on the surface of the conductive oxide layer to which the hydrophobic functional group is bonded, and the polar solvent is in contact with the hydrophilic fiber membrane. Continuous electrical energy can be generated by inducing a potential difference between the regions where the hyperpolar solvent is not in contact, generating a voltage, and generating a current by electrons moving through the conductive oxide layer.

Step (b) described above may be characterized in that the conductive nanoparticles are coated on the fiber strands constituting the hydrophilic fiber membrane using an ultrasonic disperser (sonicator).

In addition, the step (c) described above may be characterized in that the solvent remaining in the hydrophilic fiber membrane is removed by drying the hydrophilic fiber membrane coated with the conductive oxide layer in an oven.

The loading amount of the conductive oxide layer may be controlled by controlling the number of times the hydrophilic fiber membrane is immersed in the conductive oxide solution and dried in steps (b) and (c) described above.

In addition, step (d) comprises _{coating a material having at least one of -CF 3, an} end group, -CH _{2, an} end group, or a non-polar molecule that does not chemically react with water as a hydrophobic functional group to the conductive oxide layer. can be characterized as More specifically, step (d) is a step of oxygen plasma treatment of the hydrophilic fiber membrane and trichloro(1H,1H,2H,2H-perfluorooctyl)silane, trichloro(1H,1H, 2H,2H-heptadecafluorodecyl)silane, 1H,1H,2H,2H-perfluorododecyltrichlorosilane, or a waterproof coating material containing a non-polar functional group may include coating.

On the other hand, the diameter of the conductive nanoparticles may be included in the range of 20 nm to 100 nm.

The polar solvent may include a solvent containing polar molecules and ions, and the polar molecules and ions contained in the polar solvent may be asymmetrically adsorbed to the conductive oxide layer to which the hydrophobic functional group is bonded to form an electric double layer. In this case, in order to maintain charge neutrality, electrons may be continuously transferred through the conductive oxide layer to the metal electrode connected to the conductive oxide layer to which the polar solvent is adsorbed.

In addition, the method of manufacturing the energy generating device may further include connecting the first metal electrode and the second metal electrode to both ends of the hydrophilic fiber membrane coated with the conductive oxide layer to which the hydrophobic functional group is bonded. In this case, in the hydrophilic fiber membrane, the polar solvent is adsorbed to the portion to which the first metal electrode is connected, and the polar solvent is not adsorbed to the portion to which the second metal electrode is connected, thereby generating DC power according to asymmetric adsorption. .

The weight of the hydrophilic fibrous membrane coated with the conductive oxide layer to which the hydrophobic functional group is bonded may be included in the range of 0.01 g to 1000 g, and the hydrophilic fibrous membrane is placed on the polar solvent or the hydrophilic fibrous membrane is placed in the polar solvent by using a fixing frame. Partial soaking can asymmetrically adsorb with polar solvents.

1 is a schematic diagram of a manufacturing process of an energy generating device based on a hydrophilic fiber membrane coated with a conductive oxide layer according to an embodiment of the present invention. The hydrophilic fibrous membrane 101 cut to a predetermined size (eg, 3 cm (length) Х 9 cm (horizontal)) is immersed in the conductive oxide coating solution 102 in which the conductive oxide is dispersed. During the dipping process, the thickness and uniformity of the conductive oxide layer applied to the surface of the hydrophilic fiber membrane can be controlled by controlling the number of dipping. The hydrophilic fiber membrane 103 coated with the conductive oxide layer may be completed after the drying process 104 in a drying oven. The resistance of the dried hydrophilic fiber membrane 105 may be included in the range of 1 kΩ to 100 MΩ. In addition, the diameter of the hydrophilic fiber strands included in the dried hydrophilic fiber membrane 105 may be configured within a range of several tens of nm to several hundred mm (eg, a range of 50 nm to 500 mm).

Also, FIG. 1 shows an example of finally generating an energy generating device 107 through an oxygen plasma treatment process 106 and a vapor deposition process 107 on the dried hydrophilic fiber membrane 105 .

At this time, the energy generating device 107 physically adsorbs the polar solvent to the conductive oxide in the region where the polar solvent is adsorbed by asymmetric adsorption by the polar solvent on the surface of the conductive oxide layer, It may be characterized in that electric energy is generated by generating a potential difference between regions that are not adsorbed. For example, adsorption by a polar solvent, such as a solution containing a bipolar molecule or a cation, causes the surface to be negatively charged by an electric double layer on the surface of the conductive oxide to which the fluorine-based hydrophobic functional group is bonded and to form a negative potential. Due to this, a potential difference may be formed between the adsorbed portion and the non-adsorbed region by the polar solvent. In this case, when the first electrode connected to the adsorbed region of the fibrous membrane having the hydrophobic surface and the second electrode connected to the non-adsorbed region of the fibrous membrane having the hydrophobic surface are connected in a circuit, a direct current voltage, a direct current and power generation.

In addition, the energy generating device can continuously maintain a potential difference induced by the electric double layer between the first region and the second region, thereby continuously generating electric energy. For example, a hydrophilic fiber membrane coated with a conductive oxide to which a fluorine-based hydrophobic functional group is bonded induces a flow of electrons to maintain electrical neutrality from the conductive oxide, and evaporates on the surface of the polar solvent contained in the container. Due to the flow of polar molecules, it is possible to continuously generate electrical energy until the polar molecules are continuously adsorbed to the fluorine-based hydrophobic functional group and completely evaporated. Therefore, in the embodiments of the present invention, voltage and current are continuously generated in a constant direction, so that electric energy in the form of direct current can be continuously generated. The double-layer-based electric energy generating device proposed in the embodiments of the present invention can confirm various phenomena that do not appear in the existing evaporation driven streaming potential.

The existing evaporative flow potential has a characteristic that a flow is generated by continuous evaporation of a fluid, and a potential difference occurs in an environment in which the flow of the fluid is maintained. In an environment with high relative humidity, the evaporation rate is significantly reduced and the flow of the fluid is stagnant, so the existing evaporation flow potential is difficult to generate electric power. On the other hand, in the double-layer-based energy generating device according to the embodiments of the present invention, it is caused by physical adsorption of water, and the slow flow of the fluid inside the polar solvent is, for example, in the case of water, surface evaporation occurs at 0 ° C. or higher, so that the inside of the water Since there is a flow of fluid in the air and continuous adsorption is possible, the generation of electrical energy is less affected by humidity.

In addition, while the existing evaporative flow potential difference tends to decrease as the concentration of positive ions increases, the voltage and current of electrical energy generated through the double layer of the present invention both tend to increase with the addition of various types of ions. . For example, in the generated potential using the existing evaporative flow directly, the flow rate of the fluid is limited because the flow of the fluid completely depends on evaporation, and thus the amount of fluid itself is limited, so the positive ions included in the limited amount of the fluid. An increase in concentration leads to a decrease in the amount of evaporation of the fluid, for example by binding to water molecules and ions. Since the decrease in the evaporation amount can eventually reduce the velocity of the fluid, the voltage decreases as the concentration of cations increases in the potential difference that occurs depending on the velocity of the existing evaporative flow. On the other hand, in the fiber membrane to which the hydrophobic functional group is bonded according to the embodiments of the present invention, various cations can be arranged on the outer Helmholtz plane according to the asymmetric adsorption of the polar solvent to the hydrophobic functional group, and the increase in ion concentration is This can lead to a relatively larger potential difference. Therefore, both voltage and current may increase with an increase in cation concentration.

Meanwhile, as the conductive oxide, at least one conductive oxide material selected from n-type or p-type oxide exhibiting conductivity due to an oxygen vacancy and atomic doping effect may be used. Conductive oxide with excellent electrical conductivity and good bonding to chemically bond hydrophobic functional groups is not limited to a specific oxide material, and a conductive oxide layer coated in a thin layer can be used, The conductive oxide layer may be used alone or may be used in combination.

2 is a flow chart according to a method of manufacturing an energy generating device based on bonding a hydrophobic fluorine-based functional group to a conductive oxide by vapor deposition on a hydrophilic fiber membrane coated with a conductive oxide layer using an immersion process according to an embodiment of the present invention. show As can be seen in the flowchart of FIG. 2 , the manufacturing method of the energy generating device includes cutting the hydrophilic fiber membrane to a designed size ( 201 ), immersing the hydrophilic fiber membrane in a conductive oxide solution to coat the conductive oxide layer ( 202 ). ), removing moisture through oven drying on the hydrophilic fiber membrane coated with the conductive oxide layer (203), and oxygen plasma treatment on the surface of the fiber membrane and the metal electrode coated with the conductive oxide layer to form a hydrophilic surface ( 204), vapor-depositing the oxygen plasma-treated conductive oxide and the metal electrode to form a hydrophobic functional group surface (205). Individual energy generating devices may be manufactured through these steps 201 to 205 , and a large-area energy generating device may be manufactured by combining a plurality of individual energy generating devices. In order to manufacture such a large-area energy generating device, as shown in FIG. 2 , the method of manufacturing the energy generating device may further include step 206 . In addition, in order to generate electric energy through an individual energy generating device or a large-area energy generating device, the manufacturing method of the energy generating device is through asymmetric adsorption of a polar solvent to a membrane coated with a conductive oxide layer to which a fluorine-based functional group is bonded. It may further include generating 207 electrical energy.

Step 201 is a process of cutting a hydrophilic fibrous membrane, which becomes a frame of an individual energy generating device, containing a polar solvent in some regions, to a preset size (eg, 3 cm (length) × 9 cm (horizontal)) can be In this case, the thickness of the hydrophilic fiber membrane may be included in the range of 5 mm to 1 mm. The hydrophilic fiber membrane is made of at least one material selected from cotton fabric, Korean paper, polypropylene membrane, oxygen plasma-treated nonwoven fabric, hydrophilic surface-treated fabric, and nanofiber. can be configured.

Step 202 may be a process of coating a conductive oxide layer on the hydrophilic fiber membrane. To this end, as described with reference to FIG. 1 , the hydrophilic fiber membrane may be immersed in a conductive oxide solution in which a conductive oxide is dispersed in water. For example, the conductive oxide material may be dispersed in water to have a mass ratio of 1 wt% to 5 wt% to ethanol. As described above, the conductive oxide material constituting the conductive oxide layer may include at least one material selected from among n-type or p-type oxide exhibiting conductivity due to oxygen vacancy and atomic doping effect. . Such a conductive oxide layer may have excellent electrical conductivity and a hydrophilic surface property in which hydrophobic functional groups are easily chemically bonded, and may be combined in 0-dimensional, 1-dimensional, or 2-dimensional composite to a hydrophilic fiber membrane. The conductive oxide layer ^{can be coated by loading the hydrophilic fiber membrane with a conductive oxide in the range of 2.1 mg/cm 3} to 0.024 mg/cm ³ per unit volume, and the voltage and current of electrical energy generated through the amount of the loaded conductive oxide is can be adjusted. For example, in order to control the amount of conductive oxide loaded onto the hydrophilic fiber membrane, the number of times the hydrophilic fiber membrane is immersed in the conductive oxide coating solution may be controlled and/or the mass ratio of the conductive oxide to water may be controlled.

Step 203 may be a process for drying the hydrophilic fiber membrane coated with the conductive oxide layer. As described above, the area except for the area where the polar solvent is dropped must be dry to generate electrical energy through a potential difference with the area adsorbed by the polar solvent. It can be used in a dry state. In this process, the hydrophilic fibrous membrane coated with the conductive oxide layer may be placed flat on a tray and dried (eg, 60° C., 10 minutes) through an oven.

Step 204 may be a process for forming a hydrophilic surface by oxygen plasma treatment on the surface of the metal electrode and the hydrophilic fiber membrane coated with the conductive oxide layer. To this end, as described with reference to FIG. 1 , an oxygen plasma treatment process 106 (eg, 10 sccm O ₂ , 100W, 120s) may be performed. In this process, a hydrophilic hydroxyl radical (-OH) end group having a high surface energy may be chemically formed on the surface of the conductive oxide, and it may help to chemically bond with a hydrophobic functional group to be used in the next step (205).

Step 205 may be a process for forming a hydrophobic surface on the oxygen plasma-treated hydrophilic conductive oxide surface and the metal electrode surface. To this end, as described with reference to FIG. 1 , a hydrophobic fluorine-based functional group may be chemically bonded to the plasma-treated conductive oxide surface by vapor deposition. As described above, the material constituting the hydrophobic functional group is -CF _{3, a} terminal group, -CH _2, a material having a terminal group, trichloro(1H,1H,2H,2H-perfluorooctyl)silane, trichloro(1H,1H,2H) ,2H-heptadecafluorodecyl)silane, 1H,1H,2H,2H-perfluorododecyltrichlorosilane, and a waterproof coating material containing a non-polar functional group may be included. In this process, the hydrophobic functional group is chemically strongly bonded to the surface of the hydrophilic conductive oxide through an oven (for example, 90° C., 30 minutes), so that it has excellent durability against physical contact with polar solvents. You can make sure it doesn't peel off.

Step 206 may be a process of stacking two or more fibrous membranes coated with a conductive oxide layer to which a hydrophobic functional group is bonded, or combining them in parallel or in series to manufacture a large-area energy generating device. Stacking between individual energy generating devices can be utilized by increasing the amount of generated current. Also, connecting individual energy generating devices in parallel or series can be utilized to generate large area-maximized currents and voltages. Here, stacking between individual energy generating devices may mean physically stacking fiber membranes coated with a conductive oxide layer to which a hydrophobic functional group is bonded. On the other hand, parallel/series connection/coupling between individual energy generating devices may mean electrical connection/coupling.

Step 207 may be a process of asymmetrically adsorbing a polar solvent to a fiber membrane coated with a conductive oxide to which a hydrophobic functional group is bonded to generate electrical energy using the manufactured energy generating device. As already described, when the polar solvent is dropped on only a portion of the fiber membrane coated with the conductive oxide layer to which the hydrophobic functional group is bonded, the polar solvent is adsorbed to the fluorine-based functional group in the region to which the polar solvent is adsorbed. Electrical energy may be generated as a potential difference is induced between regions that are not adsorbed.

Additionally, as the polar solvent, polar protic solvents containing ions may be used. For example, polar solvents include (1) formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol and It may include a synthetic solution in which ions are dissolved in at least one polar protic solvent of water or (2) a solution existing in nature, such as at least one of seawater and sweat. For example, as polar protic solvents containing hydrogen ions (protons) having a dielectric constant of 20 or more, methanol, formic acid, water, etc. may be used, and in particular, dielectric constant ^{When H +} , Li ⁺ , Na ⁺ , and K ⁺ ions are dissolved in the water with the highest , additional ions are arranged on the outer Helmholtz surface to increase the current and voltage of electrical energy. The ions that are harmless even in contact with the human body and can improve the performance of the energy generating device include Na ⁺ , K ⁺ , and the like.

Additionally, as the metal electrode, a metal electrode having a work function equal to or lower than the work function of the metal oxide used may be used. For example, silver (Ag, φ = 4.26 eV), aluminum (Al, φ = 4.28 eV), mercury (Hg) with a work function lower than that of conductive oxide ITO loaded onto hydrophilic fibers (φ = 4.8 eV). , φ = 4.49 eV) and so on. The manufactured energy generating device can generate high-performance DC power for a long period of time even with a polar protic solvent containing a small amount of ions and is easy to mass-produce, so it can be used as a home energy auxiliary device, portable power auxiliary device, and wearable electronic device. It can be applied as a power supply.

3 is a schematic diagram of a large-area energy generating device in which individual stacked energy generating devices are combined according to an embodiment of the present invention. As described above, in order to drive a large-capacity electronic device using individual energy generating devices coated with conductive oxides, it is necessary to manufacture a large-area energy generating device through stacking or parallel/series connection of individual energy generating devices. 3 shows an energy generating device 301 in which a plurality of individual energy generating devices are stacked as an embodiment thereof, and a plurality of stacked energy generating devices are installed through a space provided by the support 302 to be installed in series and/or Alternatively, an embodiment in which the large-area energy generating device 303 is formed by being electrically connected/coupled in parallel is shown. Through such a large-area energy generating device 303, it is possible to drive an electronic device requiring high driving voltage and current with a polar solvent such as a polar protic solvent containing a small amount of ions.

Hereinafter, embodiments of the present invention will be described in detail through Examples and Comparative Examples. Examples and comparative examples are only for illustrating the present invention, and the present invention is not limited by the following examples.

Example 1: Fabrication of energy generation device using FDTS functionalized ITO immersion process and generation of voltage and current

4 is a cotton fabric energy generating device coated with a conductive oxide ITO (Indium Tin Oxide) layer to which a hydrophobic functional group FDTS (Perfluorodecyltrichlorosilane) is bonded. and power. The cotton fabric was controlled by varying the number of times of immersion in a solution in which ITO nanoparticles (30 nm to 50 nm) were sonicated for 30 minutes using sonication and evenly dispersed in ethanol. As The more the number of impregnation increases the amount of the ITO nanoparticles in the surface mounting lowers the resistance (resistance), 3cm (horizontal) × 9cm (vertical) having a size of resistance resistance of the R _#n (#n each impregnation number R _#2 :2.5MΩ~3.0MΩ, R _#3 :1.0MΩ~1.5MΩ, R _#4 :0.6MΩ~0.7MΩ, R _#5 :0.35MΩ~0.4MΩ, R _#6 : Energy generating devices were prepared as samples by electrically connecting gold (Au) electrodes to both sides of each sample as five individual devices with a resistance distribution of 0.15MΩ to 0.2MΩ. During the measurement, the same water (DI water, 1.0 mL) was dropped asymmetrically to the area connected to one gold electrode for measurement. As observed in the open circuit voltage graph of FIG. 4, the higher the resistance of the energy generating device, the higher the open voltage (1.0MΩ~1.5MΩ sample: 0.23V) characteristics appear, and the hydrophobic FDTS function of 0.15MΩ~0.2MΩ with the lowest resistance. A low open-circuit voltage of 0.1 V was observed in the sample in which a cotton fabric coated with a group-bonded conductive oxide layer was physically adsorbed by dropping 1.0 mL of DI water on one gold electrode area by connecting a gold electrode. It can be seen that it is important to control both the base contact resistance of the hydrophilic fiber membrane-based energy generating device and the loading amount of the conductive oxide in order to obtain high open-circuit voltage characteristics.

In addition, FIG. 4 is a result showing a short-circuit current according to a change in resistance of a cotton fabric energy generating device coated with a conductive oxide ITO layer. R _#2 :2.5MΩ~3.0MΩ, R _#3 :1.0MΩ~1.5MΩ, R _#4 :0.6MΩ~0.7MΩ, R _#5 :0.35MΩ~0.4MΩ, R _#6 : The generated short-circuit current of samples having a resistance distribution of 0.15 MΩ to 0.2 MΩ was measured. During the measurement, the same water (DI water, 1.0 mL) was dropped asymmetrically to the area connected to one gold electrode for measurement.

As observed in the graph of short-circuit current in Fig. 4, the lower the resistance of the energy generating device, the higher the short-circuit current (0.15MΩ~0.2MΩ, sample: ~600nA) characteristics, and the highest resistance 1.0MΩ~1.5MΩ A low short-circuit current characteristic of ~180 nA or less was observed in the sample of . It can be seen that the base contact resistance of the fiber membrane-based energy generating device loaded with the conductive oxide has a direct effect on the generated current.

Example 2: FTDS-coupled aluminum metal electrode and conductive oxide-coated energy generating device generation voltage and current generation

5 is a gold electrode (φ = 5.1 eV) and a low work function in which a conductive oxide having a work function (φ = 4.8 eV) is higher than the work function of the conductive oxide in an ITO-coated cotton fabric energy generating device. In order to connect an aluminum electrode (φ = 4.28 eV) with an energy generating device and check the degree of improvement in voltage and current generation, a gold electrode and an aluminum electrode were connected using a sample having the same resistance as #5 in FIG. 4 above. When connected, open voltage and short circuit current were measured. At this time, the same amount of water (DI water, 1 mL) was dropped and measured. First, as shown in the photo in FIG. 5, the open-circuit voltage and short-circuit current generated when the gold electrode was connected to both sides of the sample and measured were confirmed to be ~0.2 V and ~430 nA. Next, the aluminum electrode was connected to both sides of the sample and measured. The open-circuit voltage and short-circuit current generated during this time were confirmed to be ~0.65 V and ~930 nA, and it can be confirmed that the open-circuit voltage and short-circuit current increased by more than 200% and more than 100%. This is the energy formed at the interface according to the work function of the conductive oxide and the work function of the metal electrode electrically connected when electrons move from the conductive oxide to the electrode to maintain electrical neutrality from the potential difference caused by the electric double layer caused by the adsorption of water. It can be explained that it is possible by facilitating the movement of electrons generated by bending the band downward when an aluminum electrode having a band of the band gap lower than the work function of the conductive oxide is used. In addition, the aluminum electrode used is very inexpensive compared to the gold electrode, and when the hydrophobic FDTS is coated, it can have chemical durability against a polar solvent containing a certain amount of ions, so that electric energy can be stably generated for a long time. In addition, if the size of the energy generating device is enlarged and several are connected, it means that energy of mW or more can be generated, and it means that an energy source driven by a small electronic device can be generated environmentally and continuously.

Example 3: Asymmetrical immersion of an energy generating device in a beaker filled with tap water to generate a long-time generated current

In order to confirm the possibility of directly immersing the energy generating device of the aluminum metal electrode and conductive oxide coated with FTDS in a container containing tap water that is sufficiently present on Earth and can be obtained, the ITO nano of FIG. The open current was measured using a sample loaded with particles 5 times. Gold (Al) electrodes on both sides of the sample were electrically connected to an energy generating device, and 280 ml of tap water was added to a 500 ml beaker, and only half of the sample area was immersed in water to perform asymmetric adsorption. When 2.5 cm × 4.5 cm of the area of the energy generating device is immersed in water in an environment of 20 ° C to 25 ° C, a short-circuit current of close to 4 μA appears after about 6970 seconds, and 1.0 ml of water is dropped as in Example 2 In comparison, it can be seen that the increase is about 400%. The generated current can be generated continuously for about 2 weeks or more while the water evaporates from 280 ml to 100 ml. This shows that tap water can be used naturally as an energy source, and an eco-friendly and sustainable energy generating device can be utilized under a very simple energy generating system operated in a building in an environment where water evaporates under ambient indoor temperature and humidity conditions. .

Example 4: Electric energy storage in an energy storage supercapacitor using a power source generated by immersing a plurality of energy generating devices in water

7 is FDTS coated on ITO nanoparticles and electrically connected in parallel to 10 of the same samples of FIG. It was allowed to increase the short-circuit current, and the open-circuit voltage and the short-circuit current were measured. As in the example of FIG. 6 , when tap water was asymmetrically adsorbed, a voltage of 0.8 V was generated in 10 samples connected in electrical parallel, and it can be confirmed that 35 μA to 27 μA of current was generated for about 20 hours. This shows that it is possible to increase the open-circuit voltage and short-circuit current proportionally by connecting multiple energy generators. Therefore, it means that it can be applied to electronic devices driven at a micro power level by utilizing the power source generated by the generator. The DC output generated from a number of energy generators was directly connected to supercapacitors with capacities of 0.22 F and 1 F to perform energy storage. It can be seen that the 0.22 F supercapacitor takes about 1 hour and 30 minutes to charge energy up to 0.5 V, and the 1 F supercapacitor with a larger capacity takes about 5 hours and 30 minutes. The voltage and current of the large-area energy generating device can effectively generate electric energy using tap water from the inside of a building to a micro level, which shows that an eco-friendly and sustainable indoor energy generating device can be directly utilized. It is of great significance.

Example 5: Driving an electronic device using a plurality of energy generating devices and a power source stored in a plurality of supercapacitors

8 is a diagram to proportionally increase the generated current by connecting 10 energy generating devices in parallel, to be effectively stored in a supercapacitor as in the embodiment of FIG. 4, and to increase electrical energy. Shows the voltage measured by electrically connecting the supercapacitors of It takes about 1 hour and 30 minutes to store energy up to 0.5 V in one 0.22 F supercapacitor, and about 15 hours to charge 10 identical supercapacitors to the same voltage. A charged voltage of about 5 can be obtained by connecting them in series. This can sufficiently drive an electronic device consuming power from μW to mW by using the electrical energy stored in the 1F supercapacitor, and furthermore, it consumes up to W level by increasing the amount of energy stored using a larger number of supercapacitors. It means that electronic devices can also be operated. As in Example 5, the output terminal of 10 supercapacitors in which electrical energy is stored up to 5 V is directly connected to the input terminal of a 2.5 W class LED display having a driving voltage of 5 V and a driving current of 0.5 A capable of sensing the clock function and ambient temperature. connected. When the switch is turned on, it can be seen that the electronic function that detects the ambient temperature of 7:43 and 82 °F is activated.

As described above, in the energy generating device based on a hydrophilic fiber membrane coated with a conductive oxide layer, a conductive oxide is uniformly applied to the fiber strand surface of the hydrophilic fiber membrane through a dipping process to form a conductive oxide layer. . A hydrophilic fibrous membrane having high absorption capacity for a polar solvent (preferably a polar solvent containing ions) is capable of generating a potential difference induced by the capacitance caused by cation and anion adsorption between the polar solvent and the conductive oxide layer for a long time. can In particular, by using a polar protic solvent containing a small amount (0.25 ml) of ions to maintain asymmetric adsorption of a hydrophilic fiber membrane-based electric energy generating device coated with a conductive oxide layer, direct current can be created and maintained. A plurality of such high-performance energy generating devices may be stacked on each other or combined in series or parallel to maximize the generated voltage and current. The DC power generated in this way can drive Internet-of-Things-based electronic devices with high driving power without a separate rectifier circuit or energy storage device, and can be stored in an energy storage system to be used for driving electronic devices requiring high power. can In addition, the fact that sweat or seawater can be used as the polar solvent may mean that the energy generating device according to embodiments of the present invention can be used for power generation such as a wearable device or a structure on the sea.

The above description is merely illustrative of the technical spirit of the present invention, and various modifications and variations will be possible without departing from the essential characteristics of the present invention by those skilled in the art to which the present invention pertains. Accordingly, the embodiments described in the present invention are not intended to limit the technical spirit of the present invention, but to explain, and are not limited to these embodiments. The protection scope of the present invention should be construed by the following claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (26)

a hydrophilic fibrous membrane coated with a conductive oxide layer; and
a metal electrode electrically connected to the conductive oxide layer
including,
The hydrophilic surface of the hydrophilic fiber membrane is changed to a hydrophobic surface,
A hydrophobic functional group is chemically bonded to the surface of each of the conductive oxide layer and the metal electrode,
On the surface of the conductive oxide layer to which the hydrophobic functional group is bonded, an electrostatic potential difference is induced between the region to which the polar solvent is adsorbed and the region to which the polar solvent is not adsorbed to generate continuous electrical energy.
Energy generating device, characterized in that. According to claim 1,
The conductive oxide layer comprises an n-type or p-type oxide exhibiting conductivity due to an oxygen vacancy or atomic doping effect. According to claim 1,
The conductive oxide layer has electrical conductivity due to oxygen vacancies, and In ₂ O ₃ , wherein the electrical conductivity is improved by the Sn atom doping effect. According to claim 1,
The hydrophilic fiber membrane is a cotton fabric (cotton fabric), Korean paper (mulberry paper), polypropylene membrane (polypropylene membrane), oxygen plasma-treated nonwoven fabric, a fabric with a hydrophilic surface treatment, and at least one material selected from nanofibers. An energy generating device, characterized in that it is configured. According to claim 1,
The energy generating device, characterized in that the diameter of the fiber strand included in the hydrophilic fiber membrane is included in the range of 50 nm to 500 mm. The method of claim 1,
The hydrophilic surface of the hydrophilic fibrous membrane is _{a hydrophobic surface using a material having at least one of -CF 3,} terminal groups, -CH _2, terminal groups, or non-polar molecules that do not chemically react with water. Characterized by an energy generating device. According to claim 1,
The polar solvent is (1) formic acid, n-butanol (n-butanol), isopropanol (isopropanol), n-propanol (n-propanol), ethanol (ethanol), methanol (methanol) and water (water) ) of a synthetic solution in which ions are dissolved in at least one polar protic solvent or (2) a solution of at least one of seawater and sweat. According to claim 1,
The energy generating device, characterized in that the conductive oxide layer and the metal electrode include a metal having a value equal to or lower than the work function (?) of the conductive oxide. According to claim 1,
The conductive oxide layer and the metal electrode are formed of silver (Ag, φ = 4.26 eV), aluminum (Al, φ = 4.28 eV) having a work function lower than that of the conductive oxide indium tin oxide (ITO) (φ = 4.8 eV). ) or mercury (Hg, φ = 4.49 eV). According to claim 1,
The metal electrode, on the surface of the conductive oxide layer to which the hydrophobic functional group is bonded, includes a first metal electrode in contact with a region to which a polar solvent is adsorbed and a second metal in contact with a region to which the polar solvent is not adsorbed. An energy generating device comprising an electrode. According to claim 1,
The conductive oxide layer is coated by loading a conductive oxide on the hydrophilic fiber membrane, and the voltage and current of the generated electrical energy are controlled by controlling the amount of the conductive oxide loaded on the hydrophilic fiber membrane. Device. According to claim 1,
The hydrophobic functional group energy generating device, characterized in that it comprises a fluorine-based hydrophobic functional group. 13. A large-area energy generation, characterized in that at least one of an amount of generated electrical energy, a voltage, and a power density is regulated by stacking the energy generating devices of any one of claims 1 to 12 or connecting them in parallel or series Device. A method for manufacturing an energy generating device, comprising:
(a) cutting the hydrophilic fibrous membrane to a designed size;
(b) coating the conductive oxide layer on the surface of individual fibers constituting the hydrophilic fiber membrane by immersing the hydrophilic fiber membrane in a conductive oxide solution in which conductive nanoparticles are dispersed in a solvent;
(c) drying the hydrophilic fibrous membrane coated with the conductive oxide layer; and
(d) bonding a hydrophobic functional group to the surface of the conductive oxide layer
A method of manufacturing an energy generating device comprising a. 15. The method of claim 14,
Contacting the polar solvent to the hydrophilic fiber membrane coated with the conductive oxide layer to which the hydrophobic functional group is bonded forms an electric double layer on the surface of the conductive oxide layer to which the hydrophobic functional group is bonded,
generating a voltage by inducing a potential difference between a region in contact with a polar solvent and a region not in contact with a polar solvent in the hydrophilic fiber membrane;
A continuous electrical energy is generated by generating a current by electrons moving through the conductive oxide layer.
A method of manufacturing an energy generating device, characterized in that. 15. The method of claim 14,
Step (b) is,
A method of manufacturing an energy generating device, characterized in that the fiber strands constituting the hydrophilic fiber membrane are coated with conductive nanoparticles using an ultrasonic disperser (sonicator). 15. The method of claim 14,
The method of manufacturing an energy generating device, characterized in that the diameter of the conductive nanoparticles is included in the range of 20 nm to 100 nm. 15. The method of claim 14,
The step (c) is,
and drying the hydrophilic fiber membrane coated with the conductive oxide layer in an oven to remove the solvent remaining in the hydrophilic fiber membrane. 15. The method of claim 14,
Step (d) is,
Energy generating device, characterized in that the conductive oxide layer is coated with a material having at least one of -CF _{3 , a} terminal group, —CH _{2 , a} terminal group, or a non-polar molecule that does not chemically react with water as the hydrophobic functional group. manufacturing method. 15. The method of claim 14,
Step (d) is,
oxygen plasma treatment of the hydrophilic fiber membrane; and
trichloro(1H,1H,2H,2H-perfluorooctyl)silane, trichloro(1H,1H,2H,2H-heptadecafluorodecyl)silane, 1H,1H,2H,2H-perfluorododecyltrichlorosilane or Coating a waterproof coating material containing a non-polar functional group
A method of manufacturing an energy generating device comprising a. 15. The method of claim 14,
The polar solvent includes a solvent containing polar molecules and ions,
Polar molecules and ions contained in the polar solvent are asymmetrically adsorbed to the conductive oxide layer to which the hydrophobic functional group is bonded to form an electric double layer,
A method of manufacturing an energy generating device, characterized in that electrons continuously move through the conductive oxide layer to a metal electrode connected to the conductive oxide layer to which the polar solvent is adsorbed in order to maintain charge neutrality. 15. The method of claim 14,
Laminating two or more hydrophilic fibrous membranes coated with a conductive oxide layer to which the hydrophobic functional groups are bonded, or connecting them in parallel or in series
A method of manufacturing an energy generating device further comprising a. 15. The method of claim 14,
The method of manufacturing an energy generating device, characterized in that the loading amount of the conductive oxide layer is controlled by controlling the number of times the hydrophilic fiber membrane is immersed in the conductive oxide solution and dried. 15. The method of claim 14,
(e) connecting the first metal electrode and the second metal electrode to both ends of the hydrophilic fiber membrane coated with the conductive oxide layer to which the hydrophobic functional group is bonded
further comprising,
In the hydrophilic fiber membrane, a polar solvent is adsorbed to the portion to which the first metal electrode is connected, and DC power is generated according to asymmetric adsorption of the polar solvent to which the polar solvent is not adsorbed to the portion to which the second metal electrode is connected. A method for manufacturing an energy generating device. 15. The method of claim 14,
The weight of the hydrophilic fibrous membrane coated with the conductive oxide layer to which the hydrophobic functional group is bonded is included in the range of 0.1 g to 1000 g,
A method of manufacturing an energy generating device, characterized in that the hydrophilic fibrous membrane is placed on a polar solvent or partially immersed in the polar solvent using a fixed frame to adsorb the polar solvent asymmetrically. 15. The method of claim 14,
The polar solvent is a polar protic solvent containing ions, (1) formic acid, n-butanol (n-butanol), isopropanol, n-propanol (n-propanol), ethanol (ethanol) ), methanol (methanol) and water (water) comprising a synthetic solution in which ions are dissolved in a polar protic solvent selected from, or (2) an energy generating device comprising a solution of at least one of seawater and sweat manufacturing method.

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