WO2017155185A1

WO2017155185A1 - Method for manufacturing coated porous material, coated porous material and electrode comprising coated porous material

Info

Publication number: WO2017155185A1
Application number: PCT/KR2016/014214
Authority: WO
Inventors: 홍순형; 류호진; 케밥사렘야; 이빈
Original assignee: 한국과학기술원
Priority date: 2016-03-08
Filing date: 2016-12-06
Publication date: 2017-09-14
Also published as: KR101794440B1; KR20170104807A

Abstract

The present invention relates to a method for manufacturing a coated porous material, a coated porous material, and an electrode comprising the coated porous material. The method for manufacturing a coated porous material according to an embodiment of the present invention includes: a step of preparing a porous substrate; and a step of coating, on the porous substrate, at least one material selected from the group consisting of a metal, a metal oxide, a ceramic polymer, and a carbon material, wherein the porous substrate includes a crystalline polymer and an amorphous polymer.

Description

Process for preparing coated porous material, electrode comprising coated porous material and coated porous material

The present invention relates to a method of making a coated porous material, a coated porous material and an electrode comprising the coated porous material.

Research on energy storage devices such as batteries, batteries, and capacitors is being actively conducted by increasing demand for electrical devices and improving performance. Among them, supercapacitors have high power density, fast charging and discharging speed, and long life, which are essential technologies for the development of the electronics industry. Supercapacitors are mainly divided into pseudocapacitors that use carbon-based materials and exhibit high energy density using electrical double layer capacitors (EDLC) and metal oxide materials using high specific surface areas thereof. In addition, research on hybrid supercapacitors combining the advantages of the two supercapacitors has been extensively conducted, but it is limited to the direction of maximizing the physical properties using carbon-based nanomaterials and nanometal oxides. There is a bunch. Supercapacitors are expanding into areas such as communication equipment, automotive navigation systems, black box memory backup, solar street lights, wind power generation, emergency lights and hybrid electric vehicles, but the capacity per unit weight of electrodes using activated carbon is still Is a key challenge to be addressed in the future, which is significantly lower than that of conventional metal oxides and conductive polymers. Accordingly, by producing a porous material containing a large amount of mesopores in which activated carbon is easy to penetrate the electrolyte, it is possible to further improve the performance of the field being applied, inexpensive to maintain a wide range of use, and maintain high performance It is necessary to develop supercapacitor technology.

The present invention is to solve the above-mentioned problems, an object of the present invention, a method for producing a coated porous material that can be produced in a simple and environmentally friendly method of electrode material maintaining high capacitance and cycle stability, coated It is to provide an electrode comprising a porous material and a coated porous material.

However, the problem to be solved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.

According to a first aspect, a method of manufacturing a porous substrate; And coating at least one material selected from the group consisting of a metal, a metal oxide, a ceramic polymer, and a carbon material on the porous substrate, wherein the porous substrate includes a crystalline polymer and an amorphous polymer. Provided are methods for preparing phosphorus, coated porous materials.

The step of preparing the porous substrate according to one side, preparing a composite solution containing a polymer precursor; Forming the porous substrate using the composite solution; And heat treating the porous substrate.

The complex solution according to one side may be to include at least one of starch and organic acid.

Forming the porous substrate using the composite solution according to one side is by electrospinning, the viscosity of the composite solution may be 50 cp to 1,000 cp.

Coating the at least one material selected from the group consisting of metals, metal oxides, ceramic polymers and carbon materials on the porous substrate according to one side, the solvent, metal, metal oxides, ceramic polymers and carbon materials Dissolving the precursor of at least one material selected from the group consisting of to form a coating solution; Coating at least one material selected from the group consisting of metals, metal oxides, ceramic polymers, and carbon materials using the coating solution to form a coated porous material; And heat treating the coated porous material.

According to a second aspect, a porous substrate comprising a crystalline polymer and an amorphous polymer; And at least one material selected from the group consisting of metals, metal oxides, ceramic polymers, and carbon materials, coated on the porous substrate.

The porous substrate according to one side may be at least any one selected from the group consisting of fibers, thin films or bulk structures.

The carbon material according to one side includes at least one selected from the group consisting of graphite, graphene, graphene oxide, graphite, carbon nanorods, carbon fibers, carbon nanotubes, carbon black, activated carbon and fullerene, The at least one coated material may be at least one selected from the group consisting of particles, fibers, and flakes.

The specific surface area of the porous substrate according to one side may be 100 m ² / g to 2,000 m ² / g, and the pore volume per unit mass of the porous substrate may be 0.01 cm ³ / g to 5 cm ³ / g.

The pore size of the coated porous material according to one side may be from 0.1 nm to 10,000 nm.

The coated material of the coated porous material according to one side may be from 0.01% to 30% by weight.

According to a third aspect, there is provided an electrode comprising the coated porous material according to the second aspect.

According to an embodiment of the present invention, a method of manufacturing a coated porous material, an electrode including a coated porous material, and a coated porous material may prepare an environmentally friendly coated porous material that is environmentally friendly and contains a large amount of mesopores. have. When used as an electrode material, the specific surface area is large, so that penetration of the electrolyte is easy, and the storage capacity can be improved.

1 is a flow chart showing the manufacturing process of the coated porous material according to an embodiment of the present invention.

FIG. 2 is a flow chart showing the step of preparing the porous substrate of FIG.

3 is a flow chart showing the detailed steps of the material coating step on the porous substrate of FIG.

4 shows a coated porous material according to one embodiment of the invention.

5 is a microstructure image of a porous carbon fiber according to an embodiment of the present invention (a is a carbon fiber whole image, b is an enlarged view of a, c is an enlarged view of b, d is an image after heat treatment).

6 is a scanning electron micrograph of the metal oxide coated porous carbon fiber according to the immersion coating concentration according to an embodiment of the present invention.

7 is a scanning electron microscope image after heat treatment of the metal oxide coated porous carbon fiber according to the immersion coating time according to an embodiment of the present invention.

8 is a photograph showing the production of a three-electrode system electrochemical cell according to an embodiment of the present invention.

9 is a graph showing the supercapacitor characteristics of the metal oxide coated porous carbon fiber according to the immersion coating time according to an embodiment of the present invention.

10 is a graph showing the cycle stability results of the hybrid supercapacitor according to the embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings will be described embodiments of the present invention; In describing the present invention, when it is determined that detailed descriptions of related known functions or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted. In addition, terms used in the present specification are terms used to properly express preferred embodiments of the present invention, which may vary according to user's or operator's intention or customs in the field to which the present invention belongs. Therefore, the definitions of the terms should be made based on the contents throughout the specification. Like reference numerals in the drawings denote like elements.

Throughout the specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding other components unless specifically stated otherwise.

As used throughout the specification, the term "polymer" means a large molecule having a molecular weight of 10,000 or more, and means a form in which the same unit is repeatedly repeated mainly by chemical bonding.

As used throughout the specification, the term "electrospinning" refers to a method of extracting nano or micro fibers by applying a high voltage electric field to a polymer material.

As used throughout the specification, the term "dip coating" refers to a coating method in which a coating material is dipped in a paint and then dried, and in the present invention, a porous substrate is composed of a metal, a metal oxide, a ceramic polymer, and a carbon material. It means a method of dipping for a predetermined time in a solution in which the precursor of at least one material selected from the dissolved.

Hereinafter, a method of manufacturing a coated porous material of the present invention, a coated porous material, and an electrode including the coated porous material will be described in detail with reference to Examples and drawings. However, the present invention is not limited to these embodiments and drawings.

Method for producing a coated porous material according to an embodiment of the present invention can produce an environmentally friendly coated porous material that is environmentally friendly and contains a large amount of mesopores. When used as an electrode material, the specific surface area is large, so that penetration of the electrolyte is easy, and the storage capacity can be improved.

1 is a flow chart showing the manufacturing process of the coated porous material according to an embodiment of the present invention. As shown in Figure 1, the method for producing a coated porous material according to an embodiment of the present invention, the step of preparing a porous substrate (S100) and the porous substrate, metal, metal oxide, ceramic polymer and carbon material It may include the step (S200) of coating at least one material selected from the group consisting of.

FIG. 2 is a flowchart showing detailed steps of manufacturing the porous substrate of FIG. 1. Referring to Figure 2, the detailed step of preparing a porous substrate according to an embodiment of the present invention, preparing a composite solution containing a polymer precursor (S110); Forming a porous substrate using the composite solution (S120); And heat treating the porous substrate (S130).

The preparing of the composite solution containing the polymer precursor (S110) may be to prepare a composite solution including at least one selected from the group consisting of starch and organic acids in a solvent.

The porous substrate may include a crystalline polymer and an amorphous polymer. The crystalline polymer and the amorphous polymer may include starch.

The complex solution may include at least one of starch and an organic acid. For example, it may be prepared by adding an organic acid to a starch solution prepared by dissolving starch in a solvent.

Starch, a natural polymer, has a crystalline and amorphous structure alternately stacked in nano size. In order to contain a large amount of mesopores in the carbon fiber after electrospinning and finally carbonized such starch, a gelatinization process of starch is required. Therefore, the starch may be a gelled starch solution which is subjected to gelation while heating at a temperature of 60 ° C. to 150 ° C. and cooling to room temperature.

The solvent may be used without limitation as long as the solvent can dissolve the crystalline polymer and the amorphous polymer, and the solvent may include an organic solvent or an inorganic solvent. For example, the solvent is chloroform (CHCl ₃ ), chlorobenzene, water, acetic acid, acetone, acetonitrile, aniline, benzene, benzonitrile, benzyl alcohol, bromobenzene, bromoform, 1-butanol, 2- Butanol, carbon disulfide, carbon tetrachloride, chlorobenzene, chloroform, cyclohexane, cyclohexanol, decalin, dibromethane, diethylene glycol, diethylene glycol ether, diethyl ether, diglyme, dimethoxymethine, N, N-dimethylformamide, ethanol, ethylamine, ethylbenzene, ethylene glycol ether, ethylene glycol, ethylene oxide, formaldehyde, formic acid, glycerol, heptane, hexane, iodobenzene, mesitylene, methanol, methoxybenzene, Methylamine, methylene bromide, methylene chloride, methylpyridine, morpholine, naphthalene, nitrobenzene, nitromethane, octane, pentane, pentyl alcohol, phenol, 1-propanol, 2-propanol , Pyridine, pyrrole, pyrrolidine, quinoline, 1,1,2,2-tetrachlorethane, tetrachloroethylene, tetrahydrofuran, tetrahydropyran, tetralin, tetramethylethylene diamine, thiophene, toluene, 1 , 2,4-trichlorobenzene, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, triethylamine, triethylene chloride ether, 1,3,5-trimethyl It may be one containing at least one selected from the group consisting of benzene, m-xylene, o-xylene, p-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene and 1,4-dichlorobenzene.

For example, starch as a biodegradable polymer raw material has been highlighted because of its excellent biodegradability, low price compared to other raw materials, abundant resources and easy supply. Starch has a big advantage in that it is a non-toxic natural raw material that can be supplied indefinitely as long as there is a green plant on the earth, compared to petroleum resources which are in danger of being depleted. Starch is insoluble in water and has a property of precipitation, but soluble starch can be prepared by steaming at high pressure or treating with dilute acid to cause some hydrolysis.

For example, the starch may include a polysaccharide to which a large amount of D-glucose (glucose) is condensed and connected. For example, the starch may be amylose, amylopectin, fructan, gellan, glucan, glycogen, pullulan, dextran, cellulose, met, xylan, lignin, araban, galactan, galacturonan, alginate-based Compounds, chitin, chitosan, glucurono xylan, arabinoxylan, xyloglucan, glucomannan, pectic acid, pectin, arabinogalactan, carrageenan, agar, glycosaminoglycan, gum arabic, traga It may include, but is not limited to, at least one polysaccharide selected from the group consisting of gacant gum, gati gum, karaya gum, locust bean gum, and galactomannan. Even if the starch is not mentioned, any polymer having a structure laminated in a crystalline and amorphous structure is applicable to the present invention.

Starches that can be used in the present invention are, for example, seeds, roots, stems, plants, including potatoes, sweet potatoes, corn, wheat, rice, cassava, tapioca, barley, sorghum, peas, meaning mixtures of amylose and amylopectin. The fruit may also mean an extractable polymer, but may not be limited thereto.

The polysaccharides are chemically modified, in particular by urea or urethane groups, or by hydrolysis, oxidation, esterification, etherification, sulphation, phosphate, amination, amidation or alkylation, or by some of these modifications. It can be chemically modified.

The starch may be from 0.01% to 50% by weight of the starch composite solution. When the starch is less than 0.01% by weight of the starch composite solution, the surface uniformity is lowered when the carbon fiber is formed, and electrical conductivity and ion conductivity are lowered. When the starch is more than 50% by weight, the energy density as an electrode may be reduced. .

The method of dissolving the starch may be used without limitation as long as the starch may be uniformly dispersed in the solvent. For example, the starch may be performed by ultrasonication or stirring.

In order to add viscosity to the solution in which the starch is dissolved, the viscosity improving polymer may be further added. Viscosity enhancing polymers added to add viscosity include, for example, polyviniyl alcohol, collagen, gelatin, chitosan, alginate, hyaluronic acid, Dextran, poly (lactic acid), polyglycolic acid (poly (glycolic acid): PGA), poly (lactic-co-glycolic acid): poly (lactic-co-glycolic acid): PLGA ], Poly-ε- (caprolactone) [poly (ε-carprolactone)], polyanhydride [poly (anhydrides)], polyorthoesters, polyethylene glycol [poly (ethyleneglycol)], polyurethane ), Polyacrylic acid, cellulose acetate, cellulose nitrate, regenerated cellulose, regernerated, perfluorosulfonic acid polymer, polyacrylonitrile, Polyetherimides, poly Polyethersulfones, polyethylene terephthalate, polyether, polyethylene, polyimides, polypropylene, polysiloxanes, polysulfones, polyvinylated It may include at least one selected from the group consisting of fluorine (polyvinylidenefluoride) and poly-N-isopropyl acrylamide (poly (N-isopropyl acrylamide)).

The viscosity improving polymer may be from 0.01% by weight to 50% by weight in the starch composite solution. If the viscosity-improving polymer is less than 0.01% by weight of the starch composite solution, the viscosity may be low, so that starch fibers may not be formed by the electrospinning method, and if it is more than 50% by weight, electrospinning may not be performed well.

The starch and the viscosity-improving polymer may be used by mixing in a ratio of 5: 5 to 8: 2.

The method of dissolving the viscosity improving polymer may be used without limitation as long as the viscosity improving polymer is uniformly dispersed in the solution. For example, the viscosity improving polymer may be performed by ultrasonication or stirring. Can be.

The organic acid may be added to favor heat resistance and porosity for high temperature heat treatment, and may improve the rate of carbonization. The organic acid may be P-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, alkylbenzenesulfonic acid, and P-aminobenzenesulfonic acid. It may include at least any one selected from the group consisting of (P-aminobenzenesulfonic acid).

The organic acid may be from 0.01% to 20% by weight of the starch composite solution. When the organic acid is less than 0.01% by weight of the starch composite solution, it is difficult to porous the carbon fiber, and when the organic acid is more than 20% by weight, the carbon fiber may be cut and formed, thereby lowering the yield of carbon fiber.

Forming a porous substrate using the composite solution (S120) may be by electrospinning. For example, the composite solution containing starch may be put in a syringe to apply a high voltage to spin through a spinning nozzle to produce felt in the form of microfibers.

The viscosity of the complex solution may be from 50 cp to 1,000 cp. If the viscosity of the complex solution is less than 50 cp starch fiber is difficult to spin, if more than 1,000 cp it is difficult to form a porous substrate.

The electrospinning, 1 kV to 100 kV, 1 kV to 90 kV, 1 kV to 80 kV, 1 kV to 70 kV, 1 kV to 60 kV, 1 kV to 50 kV, 1 kV to 40 kV, 1 kV to 30 kV, 1 kV to 20 kV, 1 kV to 15 kV, 5 kV to 100 kV, 5 kV to 90 kV, 5 kV to 80 kV, 5 kV to 70 kV, 5 kV to 60 kV, 5 kV to 50 kV , 5 kV to 40 kV, 5 kV to 30 kV, 5 kV to 25 kV, 5 kV to 20 kV, 5 kV to 15 kV, 5 kV to 10 kV, or 10 kV to 15 kV have. In addition, the distance between the electrospinning tip and the target in the electrospinning may be 5 cm to 100 cm.

In addition, after the electrospinning process may be carried out to remove the solvent (not shown). Removing the solvent may be performed by evaporation, vacuum, and heat treatment.

Heat-treating the porous substrate (S130) may be performed for 5 seconds to 48 hours at a temperature of 200 ℃ to 1,800 ℃. The porous substrate may be incompletely carbonized when the heat treatment temperature is less than 200 ° C. and the heat treatment time is less than 5 seconds, and the porous substrate may be deformed when the heat treatment temperature is greater than 1800 ° C. and the heat treatment time is more than 48 hours. . The heat treatment condition may include one selected from the group consisting of air, vacuum, nitrogen, argon, hydrogen, hydrogen dioxide, methane, ethylene, butane, propane, and combinations thereof. For example, the prepared porous substrate may be heat treated under an oxygen atmosphere and carbonized with vacuum or an inert gas at a temperature range of 200 ° C. to 1,400 ° C. to finally prepare a porous material. For example, starch by the gelatinization process of the starch may be electrospun and electrospun to finally convert the amorphous structure in the starch into mesopores through a carbonization process to form a large amount of mesopores in the carbon fiber. .

3 is a flow chart showing the detailed steps of the material coating step on the porous substrate of FIG. Referring to Figure 3, the detailed step of the material coating step (S200) on the porous substrate according to an embodiment of the present invention to form a coating solution by dissolving the precursor of the material in a solvent (S210); Forming a coated porous material by coating a material on the porous substrate using the coating solution (S220); And heat treating the coated porous material (S230).

Forming a coating solution by dissolving a precursor of a material in a solvent (S210), dissolving the precursor by dissolving the precursor of at least one material selected from the group consisting of metals, metal oxides, ceramic polymers and carbon materials in a solvent. To form an immersion coating solution.

The solvent may be used without limitation as long as it is a solvent capable of dissolving the metal oxide precursor, and may include an organic solvent or an inorganic solvent. For example, the solvent is chloroform (CHCl ₃ ), chlorobenzene, water, acetic acid, acetone, acetonitrile, aniline, benzene, benzonitrile, benzyl alcohol, bromobenzene, bromoform, 1-butanol, 2- Butanol, carbon disulfide, carbon tetrachloride, chlorobenzene, chloroform, cyclohexane, cyclohexanol, decalin, dibromethane, diethylene glycol, diethylene glycol ether, diethyl ether, diglyme, dimethoxymethine, N, N-dimethylformamide, ethanol, ethylamine, ethylbenzene, ethylene glycol ether, ethylene glycol, ethylene oxide, formaldehyde, formic acid, glycerol, heptane, hexane, iodobenzene, mesitylene, methanol, methoxybenzene, Methylamine, methylene bromide, methylene chloride, methylpyridine, morpholine, naphthalene, nitrobenzene, nitromethane, octane, pentane, pentyl alcohol, phenol, 1-propanol, 2-propanol , Pyridine, pyrrole, pyrrolidine, quinoline, 1,1,2,2-tetrachlorethane, tetrachloroethylene, tetrahydrofuran, tetrahydropyran, tetralin, tetramethylethylene diamine, thiophene, toluene, 1 , 2,4-trichlorobenzene, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, triethylamine, triethylene chloride ether, 1,3,5-trimethyl It may be one containing at least one selected from the group consisting of benzene, m-xylene, o-xylene, p-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene and 1,4-dichlorobenzene.

The metal may be any material as long as it has an electrical conductivity. For example, at least one selected from the group consisting of gold, silver, copper, nickel, palladium, platinum, iron, tungsten, molybdenum, zinc, and aluminum. The metal oxide precursor may include a precursor of a metal oxide for manufacturing a pseudocapacitor. The metal oxide precursor, in the group consisting of MnO ₂ , Fe ₃ O ₄ , Fe ₂ O ₃ , SnO ₂ , RuO ₂ , V ₂ O ₅ , NiO, IrO ₂ , Co ₂ O ₃ , Co ₃ O ₄ and CoO It may include at least any one selected from the group consisting of chlorides, nitrates, sulfates, hydroxides, acetates and isoprooxide of at least one metal oxide selected. For example, when Fe ₃ O ₄ is used as the metal oxide, precursors include FeCl ₂ , FeCl ₃ , FeCl ₃ 6H ₂ O, FeCl ₂ 4H ₂ O, Fe (ClO ₄ ) ₃ H ₂ O, Fe (NO _{_{_{3) 3, Fe (NO 3}}} ) 3 9H 2 O, Fe 2 (SO 4) 3, FeSO 4, FeSO 4 7H 2 O, (NH 4) 2Fe (SO 4) 2 6H 2 O, NH 4 Fe (SO ₄ ) ₂ 12H ₂ O, FeOOH, Fe (CO ₂ CH ₃ ) ₂ And may include, but are not limited to.

The ceramic polymer may be a ceramic embedded in the polymer. In this case, the polymer used may be a thermoplastic polymer having a property of softening when heat is applied. It may be a surface-part embedded ceramic polymer of a ceramic crystal in which only a part of ceramic is embedded in the polymer surface portion, or may be a ceramic crystal internally uniformly embedded ceramic polymer having a ceramic crystal coating surface layer.

The carbon material may include at least one selected from the group consisting of graphite, graphene, graphene oxide, graphite, carbon nanorods, carbon fibers, carbon nanotubes, carbon black, activated carbon, and fullerenes.

Dissolution method of the precursor of at least one material selected from the group consisting of the metal, metal oxide, ceramic polymer and carbon material, at least one selected from the group consisting of the metal, metal oxide, ceramic polymer and carbon material. As long as the precursor of the material can be uniformly dispersed in the solvent, it can be used without limitation, for example, may be performed by ultrasonication or stirring.

The concentration of the coating solution may include up to 0.001 M saturated state, for example, may be from 0.01 M to 2 M. As the concentration of the coating solution approaches the saturation state, the porosity of the substrate may be accelerated. It can be maintained in a stable state up to a high concentration through the diversification of at least one material selected from the group consisting of metals, metal oxides, ceramic polymers and carbon materials.

Forming a coated porous material by coating a material on the porous substrate using a coating liquid (S220) is immersed in the coating liquid to the porous substrate is selected from the group consisting of the metal, metal oxide, ceramic polymer and carbon material Coating at least one material to form a coated porous material.

The coating may include, for example, doping, immersion coating and deposition. The deposition may, for example, include sputtering.

Coating the porous substrate on the coating solution may be performed for 1 second to 48 hours. When the coating time is less than 1 second, the precursor of at least one material selected from the group consisting of metals, metal oxides, ceramic polymers, and carbon materials is not sufficiently coated on the porous substrate, and when the coating time is more than 48 hours, By blocking the structure, at least one material selected from the group consisting of metals, metal oxides, ceramic polymers, and carbon materials may interfere with the movement of the electrolyte and cause cutting of the porous material.

Heat-treating the coated porous material (S230), the precursor of at least one material selected from the group consisting of metal, metal oxide, ceramic polymer and carbon material coated on the porous material is a metal, metal oxide, ceramic Phase change to polymer and carbon material. The heat treatment may be performed for 5 seconds to 48 hours at a temperature of 200 ℃ to 1,800 ℃. The heat treatment condition may include one selected from the group consisting of air, vacuum, nitrogen, argon, hydrogen, hydrogen dioxide, methane, ethylene, butane, propane, and combinations thereof.

At least one material selected from the group consisting of the metal, the metal oxide, the ceramic polymer and the carbon material may be uniformly included in the porous substrate through a simple immersion coating method to be combined with the porous substrate. Accordingly, at least one material selected from the group consisting of metals, metal oxides, ceramic polymers, and carbon materials is coated on a porous substrate having a large specific surface area with a large amount of mesopores, thereby having a larger specific surface area. By forming more micropores on the surface of the porous substrate in the process of phase change through, it is possible to produce a coated porous material having a very large specific surface area.

The coated porous material according to an embodiment of the present invention is environmentally friendly and carbon fiber through electrospinning at least one material selected from the group consisting of metals, metal oxides, ceramic polymers and carbon materials and controlling the carbonization process At least one material selected from the group consisting of metals, metal oxides, ceramic polymers and carbon materials is coated on the porous material containing a large amount of average mesopores on the surface of the film to provide excellent electrochemical properties with high specific surface area and high storage capacity. In addition, it is possible to overcome the limitations of the activated carbon fiber containing a large amount of micropores, which is a structure that is difficult to penetrate the conventional electrolyte.

4 is a schematic diagram illustrating a coated porous material according to one embodiment of the present invention. Referring to Figure 4, the coated porous material 100 according to an embodiment of the present invention is a metal, metal on the surface of the porous substrate 110, the plurality of pores 112 formed on the surface and the inside of the porous substrate 110 At least one material 120 selected from the group consisting of an oxide, a ceramic polymer, and a carbon material is coated. The plurality of pores 112 allows easy penetration of oxygen and electrolyte. The material 120 is uniformly included in the porous substrate 110 through the immersion coating method according to the manufacturing method is coupled to the porous substrate 110.

The porous substrate 110 may include at least one selected from the group consisting of fibers, thin films, or bulk structures.

The carbon material includes at least one selected from the group consisting of graphite, graphene, graphene oxide, graphite, carbon nanorods, carbon fibers, carbon nanotubes, carbon black, activated carbon, and fullerene, and the coated At least one of the materials may be at least one selected from the group consisting of particles, fibers, and flakes.

The specific surface area of the porous substrate 110 may be 100 m ² / g to 2,000 m ² / g. In the process of the phase change through the heat treatment of the coated porous substrate precursor of at least one material selected from the group consisting of metals, metal oxides, ceramic polymers and carbon materials by the manufacturing method more fine on the surface of the porous substrate By forming pores and increasing the adsorption of at least one material selected from the group consisting of metals, metal oxides, ceramic polymers, and carbon materials by high specific surface area, it is possible to increase efficiency when used in hybrid supercapacitors.

The porous substrate 110 may be, for example, starch fiber. Electrospinning and carbonizing starch fibers can produce a porous carbon fiber containing a large amount of mesopores.

The pore 120 of the porous substrate 100 may have a size of 0.1 nm to 10,000 nm, and the pore volume per unit mass of the coated porous substrate 100 may be 0.01 cm ³ / g to 5 cm ³ / g. Can be. Such pores are, for example, pores produced when carbonized starch fibers, and can maintain the shape of the porous carbon fibers stably in the meso pore size range and pore volume range, and increase the specific surface area. It is possible to increase the adsorption of at least one material selected from the group consisting of metal oxides, ceramic polymers and carbon materials.

At least one material 120 selected from the group consisting of the metal, the metal oxide, the ceramic polymer, and the carbon material in the coated porous material 100 may include 0.01 wt% to 30 wt%. If the material is less than 0.01% by weight does not affect the performance of the porous material, the energy density as an electrode is reduced, if more than 30% by weight may not only decrease the mechanical properties of the porous material but also open the porous material Metal oxides can interfere with the transport of the electrolyte by blocking the structure.

The metal oxide coated porous carbon fiber of the present invention may be prepared by a method of manufacturing a coated porous material according to an embodiment of the present invention.

According to a third aspect, there is provided an electrode comprising the coated porous carbon fiber according to the second aspect.

The electrode according to an embodiment of the present invention may include at least one selected from the group consisting of an electrode for a hybrid supercapacitor, a secondary battery anode material, a fuel cell electrode, and a catalyst carrier.

For example, an electrode for a hybrid supercapacitor can exhibit a complex function of a pseudo capacitor and an electric double layer capacitor, and has both an energy density and a high power density suitable for application to a high capacity hybrid energy storage device. It has high specific surface area, high conductivity, and can be used as a high energy electrode material such as supercapacitor.

For example, when the electrode for a hybrid supercapacitor is coated with Co ₃ O ₄ as a metal oxide, and has an aqueous solution of 1 MH ₂ SO ₄ electrolyte, it may have a capacity of 130 F / g or more, and the initial charge and discharge efficiency is 90%. After the 5,000 charge and discharge cycles, the discharge capacity retention rate can be maintained at 90% or more. By using a metal oxide having high performance such as RuO ₂ , the storage capacity can be further improved.

In addition, the porous material of the present invention can be applied not only to electrode materials but also to various filter materials, and thus has great industrial applicability.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the technical spirit of the present invention is not limited or limited thereto.

[[ 실시예Example ]]

<전기방사법 및 열처리 공정을 이용한 다공성 <Porosity using electrospinning method and heat treatment process 탄소섬유의Carbon fiber 제조> Manufacture

2 g of corn starch was added to 40 ml of water and dissolved by magnetic stirring at a temperature of 80 ° C. on a hotplate. After 2 hours, 3.5 g of polyvinyl alcohol (PVA) was added to the above solution and further dissolved at a temperature of 120 ° C. for 2 hours. To this, 0.19 g of toluenesulfonic acid was added to accelerate the carbonization process in the later heat treatment process, and to facilitate the formation of a porous structure. The viscosity of the solution after completion of dissolution showed 580 cP. Electrospinning was used to prepare the solution into starch fibers. The electrospinning voltage was set to 18 kV and a 15 cm diameter drum collector was rotated at 500 rpm to collect starch fibers. The distance from the drum collector to the electrospinning tip was 15 cm and the solution was set to be fed at a rate of 5 μl / min. The starch fibers produced through the 48-hour electrospinning process were subjected to 250 ° C. 3 hours (stabilization heat treatment) in air, 1500 ° C. 1 hour (carbon heat treatment) in vacuum, 800 ° C. 30 minutes (activation heat treatment) in a CO ₂ atmosphere, and Porous carbon fibers were prepared by sequentially performing heat treatment at 250 ° C. for 1 hour (functionalized heat treatment) in air. 5 is a microstructure image of a porous carbon fiber according to an embodiment of the present invention (a is a carbon fiber whole image, b is an enlarged view of a, c is an enlarged view of b, d is an image after heat treatment).

<< 침지코팅법을Immersion coating method 통한 코발트 산화물 코팅 다공성 Cobalt Oxide Coating Porous Through 탄소섬유의Carbon fiber 제조> Manufacture

Immersion coating was performed to coat the cobalt oxide on the porous carbon fiber prepared above. In this example, cobalt (II) acetate tetrahydrate (Cobalt (II) acetate tetrahydrate (Co (C ₂ H ₄ O ₂ ) ₂ )) was used as the cobalt oxide precursor, and the immersion coating solution was 0.025 M, 0.1 M, 0.2, respectively. Prepared at M and 0.4 M concentration. 5 minutes were immersed in each immersion condition. Thereafter, the solvent was removed at 80 ° C. for 8 hours, and the cobalt oxide precursor was phase-changed to cobalt oxide at 450 ° C. for 2 hours, and then the microstructure was observed.

6 is a scanning electron micrograph of the metal oxide coated porous carbon fiber according to the immersion coating concentration according to an embodiment of the present invention. As shown in Figure 6, as the concentration of the immersion coating solution thickened from 0.025 M to 0.4 M, it can be seen that the fiber tends to change to porous. Through the scanning electron microscope is Co ₃ O can determine the coating whether or not ₄ but, microstructure analyzed by Co ₃ O ₄ coated with a pseudo capacitor (Co ₃ O in conventional electrical double-layer supercapacitor (porous carbon fiber) of _In addition to adding the function of ₄ ), it was confirmed that it affects the formation of porous fibers.

In addition, in order to observe the microstructure change of the fiber according to the immersion coating time, the concentration of the immersion coating solution is fixed to 0.2 M, and the porous carbon fibers are immersed for 5 minutes, 20 minutes, 1 hour and 2 hours, respectively, and then vacuumed as above. The solvent was removed at 80 ° C. for 8 hours, and the microstructure was observed after phase change of the cobalt oxide precursor to cobalt oxide at 450 ° C. for 2 hours.

7 is a scanning electron microscope image after heat treatment of the metal oxide coated porous carbon fiber according to the immersion coating time according to an embodiment of the present invention. Referring to FIG. 7, as in the case where the concentration of the immersion solution was diversified, the tendency of porosity tended to increase with time, and the microstructures were observed to be thinner and cut during 2 hours of immersion.

Table 1 below summarizes the specific surface area and the pure carbon nanofibers (comparative example) after the heat treatment according to the immersion time in the immersion coating solution of the present invention.

Referring to Table 1, as expected through the microstructure, it can be seen that the specific surface area is significantly improved compared to the uncoated porous carbon fiber through the coating of cobalt oxide. This is because the cobalt precursor is coated on the surface, and in the process of phase change through heat treatment, more micropores are formed on the surface of the porous carbon fiber, which may play a significant role in improving electrode performance.

<분석><Analysis>

The metal oxide-coated porous carbon fiber produced by the electrospinning method can be seen that it can be used as an electrode of the hybrid supercapacitor independently without adding a conductive material and a binder. 8 is a photograph showing the production of a three-electrode system electrochemical cell according to an embodiment of the present invention. A three-electrode electrochemical cell was prepared in the same manner as in FIG. 8 using the metal oxide-coated porous carbon fiber prepared above. Graphite rods (carbon rods) were used as counter electrodes, Ag / AgCl standard electrodes were used as reference electrodes, and measurement was performed using an aqueous electrolyte of 1 MH ₂ SO ₄ .

9 is a graph showing the supercapacitor characteristics of the metal oxide coated porous carbon fiber according to the immersion coating time according to an embodiment of the present invention. It is a graph measuring the specific capacitance of the electrode using a galvanostatic charge and discharge method. Referring to FIG. 9, the pure carbon nanofibers before the immersion coating showed a specific capacity of 35 F / g, whereas the embodiment of the present invention, which was immersed in a 0.2 M solution for 1 hour, performed 137 F / g. In addition, it was possible to obtain a specific storage capacity improved by about four times. This result can be expected to be not only the effect of the pseudocapacitor due to cobalt oxide, but also a synergistic effect due to the increase of pores generated during the phase change of the cobalt oxide precursor to cobalt oxide. The prepared cobalt oxide coated porous carbon fiber was confirmed to exhibit the performance of the hybrid supercapacitor.

10 is a graph showing the cycle stability results of the hybrid supercapacitor according to the embodiment of the present invention. The cycle stability of the hybrid supercapacitor manufactured through FIG. 10 was evaluated, and it was confirmed that the performance of 91% was maintained after 5,000 cycles. This is a high periodic stability that can not be seen in the pseudo capacitor, the hybrid supercapacitor manufactured through this result confirmed that the high periodic stability of the electric double layer supercapacitor and the high specific surface area of the pseudo capacitor.

As described above, the present invention has been described by way of limited embodiments and drawings, but the present invention is not limited to the above embodiments, and those skilled in the art to which the present invention pertains various modifications and variations from such descriptions. This is possible. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the claims below but also by the equivalents of the claims.

Claims

Preparing a porous substrate; And

Coating at least one material selected from the group consisting of a metal, a metal oxide, a ceramic polymer, and a carbon material on the porous substrate;

Including,

Wherein said porous substrate comprises a crystalline polymer and an amorphous polymer.
The method of claim 1,

Preparing the porous substrate,

Preparing a composite solution containing a polymer precursor;

Forming the porous substrate using the composite solution; And

Heat-treating the porous substrate;

Including, a method of producing a coated porous material.
The method of claim 2,

The composite solution, at least any one of starch and organic acid, method of producing a coated porous material.
The method of claim 2,

Forming the porous substrate using the composite solution is by electrospinning, the viscosity of the composite solution is 50 cp to 1,000 cp, the method of producing a coated porous material.
The method of claim 1,

Coating at least one material selected from the group consisting of metals, metal oxides, ceramic polymers and carbon materials on the porous substrate,

Dissolving a precursor of at least one material selected from the group consisting of a metal, a metal oxide, a ceramic polymer, and a carbon material in a solvent to form a coating solution;

Coating at least one material selected from the group consisting of metals, metal oxides, ceramic polymers, and carbon materials using the coating solution to form a coated porous material; And

Heat treating the coated porous material;

Including, a method of producing a coated porous material.
A porous substrate including a crystalline polymer and an amorphous polymer; And

A coated porous material comprising at least one material selected from the group consisting of metals, metal oxides, ceramic polymers and carbon materials, coated on the porous substrate.
The method of claim 6,

The porous substrate is coated, porous material comprising at least any one selected from the group consisting of fibers, thin films or bulk structures.
The method of claim 6,

The carbon material includes at least one selected from the group consisting of graphite, graphene, graphene oxide, graphite, carbon nanorods, carbon fibers, carbon nanotubes, carbon black, activated carbon, and fullerenes,

Wherein the coated at least one material comprises at least one selected from the group consisting of particles, fibers and flakes.
The method of claim 6,

The specific surface area of the porous substrate is 100 m 2 / g to 2,000 m 2 / g,

The pore volume per unit mass of the porous substrate is 0.01 cm 3 / g to 5 cm 3 / g, coated porous material.
The method of claim 6,

The pore size of the coated porous material is 0.1 nm to 10,000 nm, the coated porous material.
The method of claim 6,

The coated porous material of the coated porous material is 0.01% to 30% by weight.
An electrode comprising the coated porous material of claim 6.
An electrode comprising the coated porous material of claim 7.
An electrode comprising the coated porous material of claim 8.
An electrode comprising the coated porous material of claim 9.
An electrode comprising the coated porous material of claim 10.
An electrode comprising the coated porous material of claim 11.