Polymer film comprising polymer nanofibers loaded with metal-organic frameworks, triboelectric-based nanogenerator comprising same, and method for manufacturing polymer nanofibers loaded with metal-organic frameworks

Abstract

According to an embodiment of the present application, a polymer film is provided. The polymer film comprises polymer nanofibers loaded with metal-organic frameworks, and may have a dielectric constant of at least 9.50 at 103Hz, a dielectric constant of at least 9.00 at 104Hz, a dielectric constant of at least 8.00 at 105Hz, and a dielectric constant of at least 6.00 at 106Hz.

Description

Polymer film comprising polymer nanofibers loaded with a metal-organic framework, triboelectric-based nanogenerator comprising the same, and method for manufacturing polymer nanofibers loaded with a metal-organic framework

[0001] The present application relates to a polymer film comprising polymer nanofibers loaded with a metal-organic framework, a triboelectric-based nanogenerator comprising the same, and a method for manufacturing polymer nanofibers loaded with a metal-organic framework.

[0002] Triboelectric-based nanogenerators are attracting attention for their eco-friendly and sustainable characteristics, but they currently lack energy efficiency in actual applications. To address this problem, research is being conducted to increase energy harvesting efficiency by incorporating nano-fillers with excellent electrical performance into triboelectric-based materials. In particular, carbon and metal-based nanomaterials are receiving significant attention, and among them, Metal-Organic Frameworks (MOFs) are being actively researched due to their excellent charge trapping performance and superior biocompatibility.

[0003] Most metal-organic framework-based nanogenerators currently under research utilize a method in which metal-organic frameworks are synthesized via solvothermal synthesis in a high-temperature organic solvent environment, dispersed in a polymer solution, and then fabricated into films through electrospinning. However, during this process, a problem arises where metal-organic frameworks aggregate on the polymer film. Consequently, while power generation efficiency increases in proportion to the load of metal-organic frameworks at low concentrations, it actually decreases beyond a certain concentration due to the aggregation of metal-organic frameworks. Thus, according to the current method, there are limitations to the load of metal-organic frameworks and performance improvement.

[0004] The present application aims to provide a polymer film comprising polymer nanofibers loaded with a metal-organic framework, a triboelectric-based nanogenerator comprising the same, and a method for manufacturing polymer nanofibers loaded with a metal-organic framework.

[0005] According to an embodiment of the present application, a polymer film is provided. The polymer film comprises polymer nanofibers loaded with a metal-organic framework, and 10 3 The dielectric constant at Hz is 9.50 or greater, and 10 4 The dielectric constant at Hz is 9.00 or greater, and 10 5 The dielectric constant at Hz is 8.00 or greater, and 10 6 The dielectric constant at Hz can be 6.00 or greater.

[0006] In addition, the metal-organic framework may be a Uio-66-based metal-organic framework.

[0007] According to an embodiment of the present application, a triboelectric-based nanogenerator is provided. The triboelectric-based nanogenerator comprises a polymer film and an open circuit voltage (β OC ) can be 18,000V or higher.

[0008] Additionally, the triboelectric-based nanogenerator comprises: a first film layer connected to a first conductor; and a second film layer opposite to the first triboelectric layer and connected to a second conductor; wherein the first film layer and the second film layer generate a voltage as they come into contact with or separate from each other by an external force, and at least one of the first film layer and the second film layer may include the polymer film.

[0009] According to an embodiment of the present application, a method for manufacturing a polymer nanofiber loaded with the metal-organic framework is provided. The method for manufacturing a polymer nanofiber loaded with the metal-organic framework may include the steps of: electrospinning a first solution containing a polymer and a metal compound to form a polymer nanofiber loaded with the metal compound; immersing the polymer nanofiber in a second solution containing a ligand compound; and reacting the metal compound with the ligand compound to grow the metal-organic framework on the polymer nanofiber.

[0010] In addition, the above polymer is polyvinylidene fluoride (PVDF), polyvinylidene fluoride / trifluoroethylene copolymer (PVDF-TrFE), polyvinyl alcohol (PVA), polyurethane (PU), polyacrylonitrile (PAN), polyethylene glycol (PEG), polystyrene (PS), polyimide (PI), polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene (ETFE), polyfluoroalkyl methacrylate, polychlorotrifluoroethylene (PCTFE), polyfluoroethylene (PFE), It may be polyvinyl fluoride (PVF), cellulose-based polymers, or any combination thereof.

[0011] In addition, the metal compound may include zirconium (Zr) hydrate.

[0012] In addition, the metal compound may be zirconium(IV) oxynitrate hydrate, zirconium oxychloride octahydrate, or any combination thereof.

[0013] In addition, the ligand compound may include at least one of an amino group (-NH2), a nitro group (-NO2), or a carboxyl group (-COOH).

[0014] In addition, the ligand compound is 2-aminoterephthalic acid, 2-nitroterephthalic acid, 1,2,4,5-benzenetetracarboxylic acid, tetrafluoroterephthalic acid, 2-fluoroterephthalic acid, 2,5-diethyloxyterephthalic acid, 2,3,5,6-tetrafluoro-1,4-benzenedicarboxylic acid, 2,5-dihydroxyterephthalic acid or thereof It can be any combination.

[0015] In addition, the step of growing the metal-organic framework can be carried out at a temperature of 40 to 100°C.

[0016] In addition, the weight ratio of the polymer and the metal compound in the first solution may be 1:0.01 to 1.

[0017] In addition, the concentration of the metal compound in the first solution may be 1 to 200 mM.

[0018] In addition, the concentration of the ligand compound in the second solution may be 0.1 to 50 mM.

[0019] In addition, the solvents of the first solution and the second solution are water, acetone, dimethylformamide (DMF), methyl ethyl ketone (MEK), isopropyl alcohol (IPA), ethyl acetate, methyl isobutyl ketone (MIBK), dioxane, cyclohexanone, methanol, ethanol, propanol, butanol, acetonitrile, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), and hexamethylphosphamide (Hexamethylphosphoramide, HMPA), propylene carbonate, glycerol, pyridine, triethylamine, 1,2-dichloroethane, acetic acid, 1,4-butanediol, ethylene glycol, or any combination thereof.

[0020] According to the embodiments of the present application, polymer nanofibers equipped with a metal-organic framework that suppresses aggregation and has excellent self-generating performance can be provided.

[0021] The effects obtainable from the embodiments of the present application are not limited to those mentioned above, and other unmentioned effects will be clearly understood by those skilled in the art to which the present application belongs from the description below.

[0022] FIG. 1 is a flowchart of a method for manufacturing polymer nanofibers loaded with a metal-organic framework according to an embodiment of the present application.

[0023] FIG. 2 is a schematic diagram illustrating a method for manufacturing polymer nanofibers loaded with a metal-organic framework according to an embodiment of the present application.

[0024] Figure 3 is an XRD graph of a polymer film loaded with a metal-organic framework according to an embodiment of the present application.

[0025] FIG. 4 is a graph showing the dielectric constant of a polymer film loaded with a metal-organic framework according to an embodiment of the present application.

[0026] Figure 5 is an SEM image of a polymer film loaded with a metal-organic framework according to an embodiment of the present application.

[0027] Figures 6 and 7 are SEM images of a polymer film loaded with a metal-organic framework according to a comparative example of the present application.

[0028] FIG. 8 is a graph of the open-circuit voltage measurements of a polymer film loaded with a metal-organic framework according to an example and a comparative example of the present application.

[0029] The structural or functional descriptions of the embodiments disclosed in this specification are merely illustrative for the purpose of explaining embodiments according to the technical concept of this application. Furthermore, embodiments according to the technical concept of this application may be implemented in various forms other than those disclosed in this specification. Additionally, the technical concept of this application is not to be interpreted as being limited to the embodiments described in this specification.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention pertains.

[0031] Among the physical properties mentioned in this specification, if the measurement temperature affects the property, the property is the one measured at room temperature and pressure unless otherwise specifically stipulated.

[0032] Unless otherwise specifically defined among the physical properties mentioned in this specification, said physical properties may basically follow the SI unit system. For example, weight may be expressed in kg units, and length may be expressed in m units.

[0033] The term "room temperature" as used in this specification refers to a natural temperature that is not heated or cooled, and may mean, for example, any temperature within the range of 10°C to 30°C, for example, about 15°C or higher, about 18°C ​​or higher, about 20°C or higher, about 23°C or higher, about 27°C or lower, or 25°C. Unless specifically defined in this specification, the unit of temperature is Celsius (°C).

[0034] The term "relatively high temperature relative to room temperature" as used in this specification refers to a temperature higher than room temperature, and may mean, for example, any temperature within the range of 30°C to 50°C, for example, about 35°C or higher, about 40°C or higher, or about 45°C or lower.

[0035] Among the physical properties mentioned in this specification, if the measured pressure affects the physical property, unless otherwise specifically defined, the physical property is the property measured at atmospheric pressure. The term atmospheric pressure used in this specification refers to natural pressure that is not pressurized or depressurized, and typically refers to atmospheric pressure within the range of about 700 mmHg to 800 mmHg.

[0036] As used in this specification, the terms a to b refer to a range between a and b, including a and b. For example, including a to b parts by weight is equivalent to including within the range of a to b parts by weight.

[0037] Throughout this specification, values ​​expressed in the form of ranges should be interpreted in a flexible manner to include not only numeric values ​​explicitly mentioned as limits of such ranges, but also all individual numeric values ​​or sub-ranges included within such ranges, as if each individual numeric value and sub-range were explicitly mentioned. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not only about 0.1% to about 5%, but also individual values ​​(e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. Unless otherwise indicated, a reference to “about X to Y” has the same meaning as “about X to about Y.” Likewise, unless otherwise indicated, a reference to “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z.”

[0038] The terms “about” or “approximately” as used herein mean that dimensions, sizes, formulations, parameters, shapes, and other quantities and characteristics may not be precise and may be approximate and / or larger or smaller by reflecting, as necessary, tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art. The terms “about” or “approximately” apply to the dimensions, sizes, formulations, parameters, shapes, or other quantities or characteristics described herein, generally, regardless of whether they are explicitly mentioned. The term “about” as used herein may allow for a degree of variability in a given value or range, for example, within 10%, within 5%, or within 1% of the stated value or stated range limit, and includes the stated precise value or range.

[0039] Where a method for measuring or evaluating specific dimensions, sizes, formulations, parameters, shapes, and other quantities and characteristics is not described in this specification, a person skilled in the art may readily recognize a previously known method for measuring or evaluating, or may readily derive such method by referring to prior art known prior to the filing date of this specification.

[0040] As used herein, the term “substantially” refers to a majority or most, such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. As used herein, the term “substantially absent” may mean having nothing, or having a negligible amount of a material present such that the amount of the material does not affect the substantial properties of the composition containing the material. At this time, a small amount is an amount of material in the composition of about 0% to about 5% by weight, or about 0% to about 1% by weight, or about 5% or less by weight, or about 4.5% or less by weight, or about 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or 0.001% by weight or less. The term “substantially absent” as used in this specification may mean that the composition has a material of about 0 weight % to about 5 weight %, or about 0 weight % to about 1 weight %, or about 5 weight % or less, or about 4.5 weight % or less, about 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01 or 0.001 weight % or less, or a minor amount having about 0 weight %.

[0041] As used in this specification, the term "generally" means 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more.

[0042] The terms used herein are for describing embodiments and are not intended to limit or / or restrict the present application. Singular expressions include plural expressions unless the context clearly indicates otherwise. Additionally, numbers used herein (e.g., First, Second, etc.) are merely identifiers to distinguish one component from another.

[0043] In this specification, when a part is described as being connected to another part, this includes not only cases where they are directly connected, but also cases where they are indirectly connected with other components in between. Furthermore, when a part is described as including a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0044] Furthermore, in this application, the term "or" is intended to mean an implicit "or" rather than an exclusive "or." That is, unless otherwise specified or evident from the context, "X uses A or B" is intended to mean one of the natural implicit substitutions. In other words, if X uses A; if X uses B; or if X uses both A and B, "X uses A or B" may apply to any of these cases. Additionally, the term "and / or" as used herein should be understood to refer to and include all possible combinations of one or more of the enumerated related configurations.

[0045]

[0046] FIG. 1 is a flowchart of a method for manufacturing polymer nanofibers loaded with a metal-organic framework according to an embodiment of the present application, and FIG. 2 is a schematic diagram showing a method for manufacturing polymer nanofibers loaded with a metal-organic framework according to an embodiment of the present application. Specifically, FIG. 2(a) shows a conventional method for manufacturing polymer nanofibers loaded with a metal-organic framework, and FIG. 2(b) shows a method for manufacturing polymer nanofibers loaded with a metal-organic framework according to an embodiment of the present application.

[0047] Referring to FIG. 1, a method (100) for manufacturing a polymer nanofiber loaded with a metal-organic framework may include steps S110 to S130.

[0048] Referring to FIG. 2, in the case of a conventional manufacturing method, a metal-organic framework is synthesized by solvothermal synthesis in a high-temperature organic solvent environment, dispersed in a polymer solution, and then produced into a film through electrospinning. During this process, a problem occurs in which the metal-organic framework aggregates on the nanofiber. In contrast, when using the manufacturing method (200) according to the embodiment of the present application, the aggregation phenomenon is suppressed by going through steps S110 to S230, and accordingly, a polymer nanofiber with improved self-power generation performance can be provided.

[0049] In step S110, a first solution containing a polymer and a metal compound can be electrospun to form a polymer nanofiber loaded with a metal compound.

[0050] In the examples, electrospinning is a technique that uses a high-voltage electric field to spin a polymer solution or molten polymer material into a nanofiber form, and through electrospinning, the diameter of the nanofiber can be controlled to a range from nanometers to several micrometers. Electrospinning generally proceeds through the processes of solution preparation, electric field generation, Taylor cone formation, and fiber spinning, but is not limited thereto, and any known electrospinning process may be applied.

[0051] In the examples, the electrospinning conditions are not particularly limited, but can be performed, for example, in a voltage range of greater than 0 kV to 60 kV, with a needle gauge of 10 to 50 G, a flow rate of 0.001 ml / h to 10 ml / h, a tip-collector distance of 5 to 30 cm, and a roller RPM of 10 to 1000.

[0052] In the examples, the polymer can form nanofibers as it is electrospun. When the polymer forms nanofibers, a metal compound included together in the first solution can be loaded onto the polymer nanofibers. As the material for the polymer, any known polymer material capable of manufacturing nanofibers while maintaining the physical and chemical properties of the metal compound and / or ligand compound can be used.

[0053] In the example, the polymer nanofibers formed by electrospinning can form a polymer film. That is, in step S110, a first solution containing a polymer and a metal compound can be electrospun to form a polymer film loaded with a metal compound. Hereinafter, the term "polymer nanofiber" is described as a concept encompassing a polymer film containing polymer nanofibers.

[0054] In the examples, the polymer is polyvinylidene fluoride (PVDF), polyvinylidene fluoride / trifluoroethylene copolymer (PVDF-TrFE), polyvinyl alcohol (PVA), polyurethane (PU), polyacrylonitrile (PAN), polyethylene glycol (PEG), polystyrene (PS), polyimide (PI), polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene (ETFE), polyfluoroalkyl methacrylate, polychlorotrifluoroethylene (PCTFE), polyfluoroethylene (PFE), It may be polyvinyl fluoride (PVF), cellulose-based polymers, or any combination thereof.

[0055] In the examples, the metal compound can react with the ligand compound to form a metal-organic framework. Any known metal compound capable of forming a metal-organic framework can be used as the material for the metal compound.

[0056] In the examples, the metal compound may include cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), manganese (Mn), iron (Fe), chromium (Cr), zirconium (Zr), or any combination thereof. For example, the metal compound may include a zirconium (Zr) compound.

[0057] In the examples, the metal compound may be a metal hydrate. For example, the metal compound may include cobalt (Co) hydrate, nickel (Ni) hydrate, zinc (Zn) hydrate, aluminum (Al) hydrate, manganese (Mn) hydrate, iron (Fe) hydrate, chromium (Cr) hydrate, zirconium (Zr) hydrate, or any combination thereof. For example, the metal compound may include zirconium (Zr) hydrate.

[0058] In the examples, the metal compound may be zirconium(IV) oxynitrate hydrate, zirconium oxychloride octahydrate, or any combination thereof.

[0059] In the example, the weight ratio of the polymer and the metal compound in the first solution may be 1:0.01 to 1. For example, the weight ratio of the polymer and the metal compound in the first solution is 1 : 0.01 to 1, 1 : 0.1 to 1, 1 : 0.3 to 1, 1 : 0.5 to 1, 1 : 0.7 to 1, 1 : 0.9 to 1, 1 : 0.01 to 0.8, 1 : 0.1 to 0.8, 1 : 0.3 to 0.8, 1 : 0.5 to 0.8, 1 : 0.7 to 0.8, 1 : 0.01 to 0.6, 1 : 0.1 to 0.6, 1 : 0.3 to 0.6, 1 : 0.5 to 0.6, 1 : 0.01 to 0.4, 1 : 0.1 to 0.4, 1 : 0.3 to 0.4, 1 : It may be 0.01 to 0.2 or 1 : 0.1 to 0.2.

[0060] In the example, the concentration of the metal compound in the first solution may be 1 to 200 mM. For example, the concentration of the metal compound in the first solution may be 1 to 200 mM, 10 to 200 mM, 50 to 200 mM, 100 to 200 mM, 150 to 200 mM, 1 to 150 mM, 10 to 150 mM, 50 to 150 mM, 100 to 150 mM, 1 to 100 mM, 10 to 100 mM, 50 to 100 mM, 1 to 50 mM, 10 to 50 mM, or 1 to 10 mM.

[0061] In step S120, the polymer nanofiber can be immersed in a second solution containing a ligand compound. At this time, if a polymer film is formed in step S110, the polymer film can be immersed in the second solution containing a ligand compound.

[0062] In the examples, the ligand compound can react with a metal compound to form a metal-organic framework. Any known ligand compound capable of forming a metal-organic framework can be used as the material for the ligand compound.

[0063] In the examples, the ligand compound may include at least one of an amino group (-NH2), a nitro group (-NO2), or a carboxyl group (-COOH).

[0064] In the examples, the ligand compound may be 2-aminoterephthalic acid, 2-nitroterephthalic acid, 1,2,4,5-benzenetetracarboxylic acid, or any combination thereof.

[0065] In the example, the concentration of the ligand compound in the second solution may be 0.1 to 50 mM. For example, the concentration of the ligand compound in the second solution may be 0.1 to 50 mM, 0.5 to 50 mM, 1 to 50 mM, 5 to 50 mM, 10 to 50 mM, 0.1 to 10 mM, 0.5 to 10 mM, 1 to 10 mM, 5 to 10 mM, 0.1 to 5 mM, 0.5 to 5 mM, 1 to 5 mM, 0.1 to 1 mM, 0.5 to 1 mM, or 0.1 to 0.5 mM.

[0066] In step S130, a metal compound can be reacted with a ligand compound to grow a metal-organic framework on a polymer nanofiber. Specifically, in step S130, a metal compound loaded on a polymer nanofiber immersed in a second solution can react with a ligand compound contained in the second solution to synthesize a metal-organic framework.

[0067] In the examples, the step of growing the metal-organic framework can be carried out at a temperature of 40 to 100°C. According to the examples of the present application, the metal-organic framework can be synthesized at a relatively low temperature. When synthesized at a low temperature, the aggregation phenomenon of the metal-organic framework can be suppressed. For example, the step of growing a metal-organic framework may be carried out at a temperature of 40 to 100°C, 50 to 100°C, 60 to 100°C, 70 to 100°C, 80 to 100°C, 90 to 100°C, 40 to 90°C, 50 to 90°C, 60 to 90°C, 70 to 90°C, 80 to 90°C, 40 to 80°C, 50 to 80°C, 60 to 80°C, 70 to 80°C, 40 to 70°C, 50 to 70°C, 60 to 70°C, 40 to 60°C, 50 to 60°C, or 40 to 50°C.

[0068] In the examples, the solvents of the first solution and the second solution may include any type of solvent capable of dissolving polymers, metal compounds and / or ligand compounds. For example, the solvents of the first solution and the second solution are water, acetone, dimethylformamide (DMF), methyl ethyl ketone (MEK), isopropyl alcohol (IPA), ethyl acetate, methyl isobutyl ketone (MIBK), dioxane, cyclohexanone, methanol, ethanol, propanol, butanol, acetonitrile, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), hexamethylphosphoramide, It may be HMPA), propylene carbonate, glycerol, pyridine, triethylamine, 1,2-dichloroethane, acetic acid, 1,4-butanediol, ethylene glycol, or any combination thereof.

[0069] The method (100) for manufacturing a polymer nanofiber equipped with a metal-organic framework according to FIG. 1 is exemplary, and various configurations may be applied according to the embodiments to which the present application applies.

[0070]

[0071] According to an embodiment of the present application, a polymer nanofiber is provided. The polymer nanofiber can be manufactured according to the manufacturing method (100) described herein.

[0072] In the examples, the metal-organic framework mounted on the polymer nanofiber may be a Uio-66 (Zirconium 1,4-dicarboxybenzene)-based metal-organic framework.

[0073] In the examples, the metal-organic framework can be uniformly loaded along the longitudinal direction of the polymer nanofiber. That is, the metal-organic framework may not aggregate in a portion of the polymer nanofiber or be non-uniformly loaded along the longitudinal direction of the polymer nanofiber.

[0074]

[0075] According to an embodiment of the present application, a polymer film is provided. The polymer film may comprise polymer nanofibers loaded with a metal-organic framework as described herein.

[0076] In the example, the polymer film can be formed by electrospinning. For example, as step S110 in the above-described manufacturing method (100) proceeds for a predetermined period, nanofibers can be spun over a predetermined area to form a film.

[0077] In the examples, the polymer film is 10 3 The dielectric constant at Hz can be 9.50 or greater. For example, a polymer film is 10 3 The dielectric constant at Hz can be 15.00 or less. For example, a polymer film is 10 3 The dielectric constant at Hz may be 9.50 or greater, 10.00 or greater, 10.50 or greater, 11.00 or greater, 11.50 or greater, or 12.00 or greater. For example, the polymer film is 10 3The dielectric constant at Hz may be 15.00 or less, 14.50 or less, 14.00 or less, 13.50 or less, 13.00 or less, 12.50 or less, 12.00 or less, 11.50 or less, 11.00 or less, 10.50 or less, or 10.00 or less.

[0078] In the examples, the polymer film is 10 4 The dielectric constant at Hz can be 9.00 or greater. For example, a polymer film is 10 4 The dielectric constant at Hz can be 12.00 or less. For example, a polymer film is 10 4 The dielectric constant at Hz may be 9.00 or greater, 9.50 or greater, 10.00 or greater, or 10.50 or greater. For example, a polymer film is 10 4 The dielectric constant at Hz may be 12.00 or less, 11.50 or less, 11.00 or less, 10.50 or less, 10.00 or less, or 9.50 or less.

[0079] In the examples, the polymer film is 10 5 The dielectric constant at Hz can be 8.00 or greater. For example, a polymer film is 10 5 The dielectric constant at Hz can be 10.00 or less. For example, a polymer film is 10 5 The dielectric constant at Hz may be 8.00 or more, 8.10 or more, 8.20 or more, 8.30 or more, 8.40 or more, 8.50 or more, 8.60 or more, 8.70 or more, 8.80 or more, 8.90 or more, 9.00 or more, 9.10 or more, 9.20 or more, 9.30 or more, 9.40 or more, or 9.50 or more. For example, the polymer film is 10 5The dielectric constant at Hz may be 10.00 or less, 9.90 or less, 9.80 or less, 9.70 or less, 9.60 or less, 9.50 or less, 9.40 or less, 9.30 or less, 9.20 or less, 9.10 or less, 9.00 or less, 8.90 or less, 8.80 or less, 8.70 or less, 8.60 or less, or 8.50 or less.

[0080] In the examples, the polymer film is 10 6 The dielectric constant at Hz can be 6.00 or greater. For example, a polymer film is 10 6 The dielectric constant at Hz can be 8.00 or less. For example, a polymer film is 10 6 The dielectric constant at Hz may be 6.00 or more, 6.10 or more, 6.20 or more, 6.30 or more, 6.40 or more, 6.50 or more, 6.60 or more, 6.70 or more, 6.80 or more, 6.90 or more, 7.00 or more, 7.10 or more, 7.20 or more, 7.30 or more, 7.40 or more, 7.50 or more, or 7.60 or more. For example, the polymer film is 10 6 The dielectric constant at Hz may be 8.00 or less, 7.90 or less, 7.80 or less, 7.70 or less, 7.60 or less, 7.50 or less, 7.40 or less, 7.30 or less, 7.20 or less, 7.10 or less, 7.00 or less, 6.90 or less, 6.80 or less, 6.70 or less, or 6.60 or less.

[0081]

[0082] According to an embodiment of the present application, a metal-organic framework application product is provided. The metal-organic framework application product may include a polymer film as described herein.

[0083] In the examples, the metal-organic framework application product may be at least one of a triboelectric-based nanogenerator, a gas adsorbent, a catalyst, or a drug delivery system. For example, the metal-organic framework application product may be a triboelectric-based nanogenerator.

[0084] In an embodiment, the triboelectric-based nanogenerator may include a first film layer connected to a first conductor; and a second film layer facing the first triboelectric layer and connected to a second conductor. The first film layer and the second film layer may generate a voltage as they come into contact with or separate from each other by an external force. At this time, at least one of the first film layer and the second film layer may include the polymer film. The voltage generated by the contact or separation between the first film layer and the second film layer may form a current, and the current may be transmitted to an external circuit through the first conductor and / or the second conductor.

[0085] In an example, the first film layer may be the polymer film and the second film layer may be nylon-6. In another example, the first film layer may be nylon-6 and the second film layer may be the polymer film. However, the materials of the first film layer and the second film layer are not limited thereto, and any known material capable of generating triboelectricity may be applied.

[0086] In the embodiments, the first conductor and the second conductor may be formed from copper, an acrylic polymer, polyimide, or any combination thereof. For example, the first conductor and / or the second conductor may comprise a first layer comprising copper and a second layer comprising an acrylic polymer. However, the materials of the first conductor and the second conductor are not limited thereto, and any type of material capable of transmitting triboelectricity may be applied.

[0087] In the example, the triboelectric-based nanogenerator has an open circuit voltage (△V OC ) can be 18,000V or higher. For example, triboelectric-based nanogenerators have an open-circuit voltage (△V OC) may be 30,000V or less. It may be 18,000V or more, 19,000V or more, 20,000V or more, 21,000V or more, 22,000V or more, 23,000V or more, or 24,000V or more. For example, a similarly electric-based nanogenerator has an open circuit voltage (△V OC ) may be 30,000V or less, 29,000V or less, 28,000V or less, 27,000V or less, 26,000V or less, or 25,000V or less.

[0088]

[0089] The present invention will be explained below through manufacturing examples and experimental examples, but the scope of the present invention is not limited by the contents presented below.

[0090]

[0091] Preparation Example

[0092]

[0093] Preparation Example 1: Preparation of Example 1

[0094] (1) Step 1: Manufacture of a polymer film loaded with a metal compound

[0095] 800 mg of PVDF-TrFE was dissolved in a 4 ml solution of acetone and DMF mixed in a 7:3 ratio (v / v). Then, 80 mg of zirconium(IV) oxynitrate hydrate was suspended in the solution and stirred evenly by ultrasonication. Subsequently, the solution was electrospun for 3 hours (voltage: 25 kV, needle gauge: 24G, flow rate: 1 ml / h, tip-collector distance: 10 cm, roller RPM: 100) to produce a PVDF-TrFE film loaded with zirconium hydrate, and the film was cut to 2.5 cm x 2.5 cm.

[0096] (2) Step 2: Growth of metal-organic framework in polymer film

[0097] 0.11 mmol of 2-aminoterephthalic acid was dissolved in 0.25 ml of DMF, and then 40 ml of deionized water (DI) was added to dissolve it. Subsequently, 1 ml of an aqueous solution of zirconium(IV) oxynitrate hydrate at a concentration of 0.2 mM was added to the solution. Then, the PVDF-TrFE film loaded with the zirconium hydrate prepared in Step 1 was immersed in the solution, and 3 ml of trifluoroacetic acid (TFA) solution was added. The metal-organic framework was then grown in a 70°C incubator for 24 hours to prepare Example 1.

[0098]

[0099] Preparation Example 2: Preparation of Example 2

[0100] Example 2 was prepared by growing a metal-organic framework using the same method as in Preparation Example 1, except that 0.1 mmol of 2-nitroterephthalic acid was dissolved instead of 0.11 mmol of 2-aminoterephthalic acid in Step 2.

[0101]

[0102] Preparation Example 3: Preparation of Example 3

[0103] Example 3 was prepared by growing a metal-organic framework using the same method as in Preparation Example 1, except that 0.2 mmol of 1,2,4,5-benzenetetracarboxylic acid was dissolved instead of 0.11 mmol of 2-aminoterephthalic acid in Step 2, and 1 ml of trifluoroacetic acid (TFA) solution was added instead of 3 ml.

[0104]

[0105] Preparation Example 4: Preparation of Comparative Example 1

[0106] 800 mg of PVDF-TrFE was dissolved in a 4 ml solution of acetone and DMF mixed in a 7:3 ratio (v / v). Subsequently, the solution was electrospun for 3 hours (voltage: 25 kV, needle gauge: 24G, flow rate: 1 ml / h, tip-collector distance: 10 cm, roller RPM: 100) to produce a PVDF-TrFE film, and the film was cut to 2.5 cm × 2.5 cm to produce Comparative Example 1.

[0107]

[0108] Preparation Example 5: Preparation of Comparative Example 2 - Uio-66-NH2(L)

[0109] (1) Step 1: Preparation of a polymer film loaded with a ligand compound

[0110] 800 mg of PVDF-TrFE was dissolved in a 4 ml solution of acetone and DMF mixed in a 7:3 ratio (v / v). Subsequently, 0.692 mmol of 2-aminoterephthalic acid was suspended in the solution and then ultrasonically stirred. The solution was then electrospun for 3 hours (voltage: 25 kV, needle gauge: 24G, flow rate: 1 ml / h, tip-collector distance: 10 cm, roller RPM: 100) to produce a PVDF-TrFE film loaded with a ligand compound, and the film was cut to a size of 2.5 cm × 2.5 cm.

[0111] (2) Step 2: Growth of metal-organic framework in polymer film

[0112] 0.2 mmol of 2-aminoterephthalic acid was dissolved in 0.5 ml of DMF, and then 30 ml of deionized water (DI) was added to dissolve it. Subsequently, 10 ml of an aqueous solution of zirconium(IV) oxynitrate hydrate at a concentration of 0.1 mM was added to the solution. Then, a PVDF-TrFE film loaded with the ligand compound prepared in Step 1 was immersed in the solution, and 3 ml of trifluoroacetic acid (TFA) solution was added. A metal-organic framework was then grown in a 70°C incubator for 24 hours to prepare Comparative Example 2.

[0113]

[0114] Preparation Example 6: Preparation of Comparative Example 3 - Uio-66-NO2(L)

[0115] Comparative Example 3 was prepared by growing a metal-organic framework using the same method as in Preparation Example 5, except that 0.692 mmol of 2-nitroterephthalic acid was suspended instead of 0.692 mmol of 2-aminoterephthalic acid in Step 1, 0.3 mmol of 2-nitroterephthalic acid was dissolved instead of 0.2 mmol of 2-aminoterephthalic acid in Step 2, and 10 ml of deionized water was additionally added instead of 30 ml of deionized water.

[0116]

[0117] Preparation Example 6: Preparation of Comparative Example 4 - Uio-66-COOH(L)

[0118] Comparative Example 4 was prepared by growing a metal-organic framework using the same method as in Preparation Example 5, except that 0.692 mmol of 1,2,4,5-benzenetetracarboxylic acid was suspended instead of 0.692 mmol of 2-aminoterephthalic acid in Step 1, 0.3 mmol of 1,2,4,5-benzenetetracarboxylic acid was dissolved instead of 0.2 mmol of 2-aminoterephthalic acid in Step 2, 10 ml of deionized water was added instead of 30 ml of deionized water, and 1 ml of trifluoroacetic acid (TFA) solution was added instead of 3 ml.

[0119]

[0120] Experimental Example

[0121]

[0122] (1) Experimental Example 1: Measurement of X-ray diffraction pattern

[0123] X-ray diffraction (XRD) patterns of Examples 1 to 3 and Comparative Example 1 were measured using a SmartLab device from Rigaku by applying a voltage of 3 kW and measuring within a 2θ range between 3 and 60°, and the results are shown in FIG. 3. In FIG. 3, (a) shows the graph of Example 1, (b) shows the graph of Example 2, (c) shows the graph of Example 3, and (d) shows the graph of Comparative Example 1.

[0124] As a result of the experiment, the X-ray diffraction peak of Uio-66-NH2 was observed in Example 1, the X-ray diffraction peak of Uio-66-NO2 was observed in Example 2, and the X-ray diffraction peak of Uio-66-COOH was observed in Example 3, so it can be confirmed that Uio-66-based metal-organic frameworks were synthesized in Examples 1 to 3.

[0125]

[0126] (2) Experimental Example 2: Measurement of dielectric constant

[0127] Using Keysight's Dielectric Test Fixture device, 10 3 Hz ~ 10 8 The dielectric constants of Examples 1 to 3 and Comparative Example 1 were measured in the Hz frequency range, and the results are shown in FIG. 4 and Table 1. In FIG. 4, (a) shows the graph of Example 1, (b) shows the graph of Example 3, (c) shows the graph of Example 2, and (d) shows the graph of Comparative Example 1.

[0128]

[0129] Dielectric constant 10 by distinguishing frequency (Hz) 3 10 4 10 5 10 6 Example 1 12.110.99.537.67 Example 29.889.388.496.71 Example 3 12.110.48.656.56 Comparative Example 17.316.846.124.83

[0130] As a result of the experiment, it can be confirmed that in the case of Examples 1 to 3, the dielectric constant generally increased as the metal-organic framework was synthesized, and it is confirmed that the electrical properties of the polymer film were improved.

[0131]

[0132] (3) Experimental Example 3: SEM Analysis

[0133] The surface morphology of polymer films loaded with metal-organic frameworks prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was observed using a scanning electron microscope (SEM) of JEOL Ltd., and the results are shown in FIGS. 5 to 7. Specifically, FIG. 5(a) is the SEM image of Example 1, FIG. 5(b) is the SEM image of Example 2, FIG. 5(c) is the SEM image of Example 3, FIG. 6 is the SEM image of Comparative Example 1, FIG. 7(a) is the SEM image of Comparative Example 2, FIG. 7(b) is the SEM image of Comparative Example 3, and FIG. 7(c) is the SEM image of Comparative Example 4.

[0134] Experimental results confirm that in the case of Examples 1 to 3, the metal-organic framework does not aggregate on the surface of the polymer nanofiber, and the metal-organic framework is evenly distributed throughout along the longitudinal direction of the nanofiber.

[0135] On the other hand, in Comparative Examples 1 and 2, metal-organic frameworks are not observed on the surface of the nanofibers, and in Comparative Examples 3 and 4, metal-organic frameworks are aggregated on the surface of the polymer nanofibers and are unevenly distributed throughout along the longitudinal direction of the nanofibers.

[0136]

[0137] (4) Experimental Example 4: Open Circuit Voltage Measurement

[0138] After fabricating a triboelectric-based nanogenerator using a polymer film, triboelectricity was induced in the nanogenerator at a constant speed, and the open-circuit voltages of Examples 1 to 3 and Comparative Examples 1 to 4 were measured using an oscilloscope, and the results are shown in FIG. 8 and Table 2. FIG. 8 shows the graphs of Comparative Example 1 (a), Example 1 (b), Example 3 (c), Example 2 (d), Comparative Example 2 (e), Comparative Example 4 (f), and Comparative Example 3 (g).

[0139]

[0140] Separated open circuit voltage (△V OC △V compared to Comparative Example 1 OC Increase Amount (%) Example 1 21.028 70.51 Example 2 23.08 38 7.18 Example 3 24.8 22 10 1.28 Comparative Example 1 12.33 20 Comparative Example 2 15.178 23.07 Comparative Example 3 12.174 -1.28 Comparative Example 4 12.96 45.13

[0141] As a result of the experiment, the polymer films of Examples 1 to 3 had an open circuit voltage (△V) of 23.083 V or higher. OCAs indicated by ), it can be confirmed that the power generation performance of the triboelectric-based nanogenerator has improved by more than 70.51% compared to Comparative Example 1.

[0142] On the other hand, no significant improvement in power generation performance was found in the polymer films of Comparative Examples 1 to 4 when compared to Comparative Example 1.

[0143]

[0144] Foregoing, specific parts of the contents of this application have been described in detail. It will be apparent to those skilled in the art that such specific descriptions are merely preferred embodiments and do not limit the scope of this application. Accordingly, the actual scope of this application is defined by the appended claims and their equivalents.

Claims

1. Includes polymer nanofibers loaded with a metal-organic framework, and 10 3 The dielectric constant at Hz is 9.50 or greater, and 10 4 The dielectric constant at Hz is 9.00 or greater, and 10 5 The dielectric constant at Hz is 8.00 or greater, and 10 6 A polymer film having a dielectric constant of 6.00 or greater at Hz.

2. In Paragraph 1, The above metal-organic framework is a polymer film that is a Uio-66-based metal-organic framework.

3. Comprising the polymer film of claim 1, Open circuit voltage (△V OC A triboelectric-based nanogenerator with a voltage of 18,000V or higher.

4. In Paragraph 3, A first film layer connected to a first conductor; and A second film layer facing the first friction layer and connected to a second conductor; comprising The first film layer and the second film layer generate a voltage as they come into contact with or separate from each other due to an external force, and A triboelectric-based nanogenerator, wherein at least one of the first film layer and the second film layer comprises the polymer film.

5. A method for manufacturing polymer nanofibers loaded with a metal-organic framework according to claim 1, A step of electrospinning a first solution containing a polymer and a metal compound to form a polymer nanofiber loaded with said metal compound; A step of immersing the polymer nanofiber in a second solution containing a ligand compound; and A step of reacting the metal compound with the ligand compound to grow a metal-organic framework on the polymer nanofiber; A method for manufacturing polymer nanofibers loaded with a metal-organic framework, comprising 6. In Paragraph 5, The above polymers are polyvinylidene fluoride (PVDF), polyvinylidene fluoride / trifluoroethylene copolymer (PVDF-TrFE), polyvinyl alcohol (PVA), polyurethane (PU), polyacrylonitrile (PAN), polyethylene glycol (PEG), polystyrene (PS), polyimide (PI), polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene (ETFE), polyfluoroalkyl methacrylate, polychlorotrifluoroethylene (PCTFE), and polyfluoroethylene (PFE). A method for manufacturing polymer nanofibers loaded with a metal-organic framework, which is polyvinyl fluoride (PVF), cellulose-based polymers, or any combination thereof.

7. In Paragraph 5, A method for manufacturing polymer nanofibers loaded with a metal-organic framework, wherein the metal compound comprises zirconium (Zr) hydrate.

8. In Paragraph 5, A method for manufacturing polymer nanofibers loaded with a metal-organic framework, wherein the metal compound is zirconium(IV) oxynitrate hydrate, zirconium oxychloride octahydrate, or any combination thereof.

9. In Paragraph 5, A method for preparing polymer nanofibers loaded with a metal-organic framework, wherein the ligand compound comprises at least one of an amino group (-NH2), a nitro group (-NO2), or a carboxyl group (-COOH).

10. In Paragraph 5, A method for preparing polymer nanofibers loaded with a metal-organic framework, wherein the ligand compound is 2-aminoterephthalic acid, 2-nitroterephthalic acid, 1,2,4,5-benzenetetracarboxylic acid, or any combination thereof.

11. In Paragraph 5, A method for manufacturing polymer nanofibers loaded with a metal-organic framework, wherein the step of growing the metal-organic framework is carried out at a temperature of 40 to 100°C.

12. In Paragraph 5, A method for manufacturing polymer nanofibers loaded with a metal-organic framework, wherein the weight ratio of the polymer and the metal compound in the first solution is 1:0.01 to 1.

13. In Paragraph 5, A method for manufacturing polymer nanofibers loaded with a metal-organic framework, wherein the concentration of the metal compound in the first solution is 1 to 200 mM.

14. In Paragraph 5, A method for manufacturing polymer nanofibers loaded with a metal-organic framework, wherein the concentration of the ligand compound in the second solution is 0.1 to 50 mM.

15. In Paragraph 5, The solvents of the first solution and the second solution are water, acetone, dimethylformamide (DMF), methyl ethyl ketone (MEK), isopropyl alcohol (IPA), ethyl acetate, methyl isobutyl ketone (MIBK), dioxane, cyclohexanone, methanol, ethanol, propanol, butanol, acetonitrile, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), and hexamethylphosphoramide. A method for manufacturing polymer nanofibers loaded with a metal-organic framework, wherein the metal-organic framework is HMPA), propylene carbonate, glycerol, pyridine, triethylamine, 1,2-dichloroethane, acetic acid, 1,4-butanediol, ethylene glycol, or any combination thereof.

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