KR101074949B1 - Method for fabricating carbon-metal composites, method for fabricating electrode using the composites, and electrochemical capacitor and fuel cell having the electrode - Google Patents

Abstract

It provides a carbon-metal composite manufacturing method, an electrode manufacturing method using the composite, an electrochemical capacitor and a fuel cell having the electrode. The carbon-metal composite may be obtained by mixing a porous carbon precursor and a metal precursor to obtain a carbon-metal precursor mixed material, and then carbonizing the carbon-metal precursor mixed material.

Description

Method for fabricating carbon-metal composites, method for fabricating electrode using the composites, and electrochemical capacitor and fuel cell having the electrode}

The present invention relates to a carbon material and an electrode using the same, and more particularly, to a carbon-metal composite and an electrode of an electrochemical device using the same.

In order to solve environmental pollution problems such as rising and depletion of fossil fuels, air pollution and noise, attention has been focused on new electrochemical devices having high power and high energy density but not causing environmental problems.

New electrochemical devices include secondary batteries mainly used as power sources for portable electronic devices, fuel cells used as power sources or auxiliary power sources for electric vehicles, and electrochemical capacitors as energy storage media.

Currently, commercially available electrochemical devices, in particular, carbon particles such as carbon black are used as electrodes of secondary batteries, fuel cells, or electrochemical capacitors. The carbon particles are connected to each other by point contact with each other instead of having a large surface area in the form of particles, thereby increasing electrode resistance.

The problem to be solved by the present invention is to provide an electrode having a low surface area while having a low resistance.

Another problem to be solved by the present invention is to provide a secondary battery and an electrochemical capacitor including an electrode having a low reaction area and a low resistance with an electrolyte.

Another object of the present invention is to provide a fuel cell including an electrode having excellent fuel or air permeability and low resistance.

One aspect of the present invention to achieve the above object provides a method for producing a carbon-metal composite. First, a porous carbon precursor and a metal precursor are mixed to obtain a carbon-metal precursor mixed material. The carbon-metal precursor mixed material is carbonized to obtain a carbon-metal composite.

The carbon precursor may have the form of a linear structure or an airgel. The carbon precursor may be a pitch system, a synthetic polymer system, a plant system, or a mixed material including at least one of them. The metal precursor may be a metal, a metal oxide, a metal nitride, a metal sulfide, or a salt including at least one of them.

The carbon-metal precursor mixed material may be reacted with a reducing agent before the carbonization process, or the carbon-metal composite may be reacted with a reducing agent after the carbonization process. The carbon-metal composite may be activated.

Another aspect of the present invention to achieve the above object provides an electrode manufacturing method. First, a porous carbon precursor and a metal precursor are mixed to obtain a carbon-metal precursor mixed material. The carbon-metal precursor mixed material is carbonized to obtain a carbon-metal composite. The carbon-metal composite is used to form the electrode.

Another aspect of the present invention to achieve the above object provides an electrochemical capacitor. The electrochemical capacitor includes an anode, a cathode, and an electrolyte located between the anode and the cathode. At least one of the anode and the cathode may be an electrode manufactured by the above method.

Another aspect of the present invention to achieve the above object provides a fuel cell. The fuel cell includes an anode, a cathode, and an ion exchange membrane interposed between the electrodes. At least one of the electrodes may be an electrode manufactured by the above method.

According to the present invention, the carbon-metal composite is formed by using a carbon precursor which is a porous material, for example, a linear structure or airgel of a fibrous, rod, ribbon, tubular or wire type, so that the internal resistance is reduced due to the point contact. Unlike the large carbon particles, there is an advantage to lower the internal resistance. Furthermore, when the metal is used as a metal capable of serving as a catalyst in the electrochemical device, the reaction site may be increased. In addition, by mixing and carbonizing the carbon precursor and the metal precursor to form a carbon-metal composite, the metal may be physically and / or chemically bonded to the surface and the inside of the carbon support to further lower the resistance.

In addition, the ratio of the surface area to volume in the carbonization process can be greatly improved. Therefore, when the carbon-metal composite is used as an electrode of a secondary battery or an electrochemical capacitor, there is an advantage of increasing the reaction area with an electrolyte, and when used as an electrode of a fuel cell, fuel or There is an advantage to increase the air permeability.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to describe the present invention in more detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. In the figures, where a layer is said to be "on" another layer or substrate, it may be formed directly on the other layer or substrate, or a third layer may be interposed therebetween.

Carbon-metal composites

1 is a flow chart showing a carbon-metal composite manufacturing method (S10) according to an embodiment of the present invention.

Referring to FIG. 1, a carbon precursor is formed using a carbon material (S11).

The carbon material may be a pitch system, a synthetic polymer system, a plant system, or a mixed material including at least one of them. The pitch-based material may be coal, petroleum, heavy oil or a material obtained by decomposing them, and the synthetic polymer-based material may be phenol resin, polyacrylonitrile (PAN), polyvinylidene chloride (PVDC), or It may be at least one modified material, and the plant-based material may be cellulose, wood, sawdust, pulp, palm trees, or at least one modified material thereof.

The carbon precursor may be a fibrous, rod, ribbon, tubular, wire linear structure or aerogel as the porous material. The linear structure may have a nano size diameter. The porous carbon precursor has a large surface area and may have a high carbonization rate in the carbonization process described later. The airgel may also be formed in a form in which linear structures are connected to each other.

The carbon precursor in the form of the linear structure may be formed using a spinning method or a template method. The spinning can be wet spinning, dry spinning, melt spinning, or electrospinning. Wet spinning is a method in which a solution containing the carbonaceous material is extruded from a spinning nozzle into a coagulating solution and solidified by a chemical reaction or dehydration to form a fiber. Dry spinning is a method of obtaining fibers by evaporating a solvent while blowing a solution containing the carbonaceous material from the spinning nozzle into air or an inert gas. Melt spinning extrudes the carbon material melt from the spinning nozzle into air to cool and form the fibers. Electrospinning can be carried out by spinning a solution containing the carbon material through the spinning nozzle in a state where an electric field is applied between the spinning nozzle and the focusing body to stack the fibers on the focusing body. The focusing body may have a roller shape, and the nozzle may be a syringe pump.

The casting method is a method of forming a carbon precursor using a hard template or a soft template. The hard mold may be a porous alumina membrane. Specifically, the fiber or tube may be polymerized through chemical or electrical polymerization in the pores of the porous alumina membrane. The soft template may be Mobil Composition of Matter (MCM) -41, Santa Barbara (SBA) -3, or SBA-15, which is a material having one-dimensional pores.

The carbon precursor and the metal precursor are mixed to form a carbon-metal precursor mixed material (S12). In the carbon-metal precursor mixed material, the metal may be bound to the carbon precursor in an ionic state.

The metal precursor may be a metal, a metal oxide, a metal nitride, a metal sulfide, or a salt including at least one of them. The metal is lithium (Li), iron (Fe), zinc (Zn), cobalt (Co), copper (Cu), ruthenium (Ru), iridium (Ir), palladium (Pd), gold (Au), platinum (Pt), silver (Ag), nickel (Ni), sodium (Na), magnesium (Mg), titanium (Ti), aluminum (Al), manganese (Mn), molybdenum (Mo), vanadium (V) or these It may be an alloy containing at least one of.

The mixing of the carbon precursor and the metal precursor may include mixing the metal precursor in a solution in which the carbon precursor is dissolved or dispersed in an organic solvent, or impregnating the carbon precursor in a solution in which the metal precursor is dissolved or dispersed in an organic solvent. Can be done.

Carbonizing the carbon-metal precursor mixture material to prepare a carbon-metal composite (C _x M _y ) (S13). In the carbon-metal composite (C _x M _y ), a metal may be chemically and / or physically bonded to the surface or the inside of the carbon support.

The carbonization process thermally decomposes the carbon-metal precursor mixture material to escape oxygen, hydrogen, nitrogen, and the like, and causes carbon and metal to form a physical and / or chemical bond. Specifically, the carbonization process may be to heat-treat the carbon-metal precursor mixture material at 500 to 2500 ° C. for 0.5 to 24 hours in an inert gas atmosphere. As an example, in order to carbonize the carbon-metal precursor mixed material, heat treatment may be performed at 500 to 1000 ° C. for 1 to 4 hours, which is a temperature range in which carbonization may be efficiently performed. Meanwhile, in order to graphitize the carbon-metal precursor mixed material, the heat treatment temperature may be increased up to 2000 to 2500 ° C. The inert gas may be nitrogen (N ₂ ) or argon.

In order to reduce most of the metal which is reduced but not partially reduced in the carbonization process, the carbon-metal precursor mixed material is reacted with a reducing agent before the carbonization process or the carbon-metal composite (C _x M) after the carbonization process. _y ) can be reacted with a reducing agent. The reducing agent is an inorganic reducing agent such as sodium borohydride (NaBH ₄ ), hydrazine (hydrazine, NH ₂ NH ₂ ), organic reducing agents such as formaldehyde, acetaldehyde, hydrogen gas, or It may be a mixture of two or more of them.

The carbon-metal composite (C _x M _y ) can be activated to further increase the surface area. Examples of the activation treatment include gas activation using oxidizing gases such as water vapor and carbon dioxide, and chemical activation using calcium hydroxide (KOH), sodium hydroxide (NaOH), zinc chloride (ZnCl3), phosphoric acid (H3PO4), and the like. have.

The ratio of carbon (C) and metal (M) in the carbon-metal composite (C _x M _y ), ie, x / y, may be 1-30. To this end, the mixing ratio of the carbon precursor and the metal precursor may be adjusted in the carbon-metal precursor mixed material forming step (S12).

The carbon-metal composite (C _x M _y ) is formed using a carbon precursor that is a porous material, for example, a linear structure or aerogel of a fibrous, rod, ribbon, tubular, or wire type, and due to the point contact Unlike carbon particles with high resistance, there is an advantage that the internal resistance can be lowered. Furthermore, when the metal is used as a metal capable of performing a catalyst in the electrochemical device, the reaction site may be increased. In addition, by mixing and carbonizing the carbon precursor and the metal precursor to form a carbon-metal composite, the metal may be physically and / or chemically bonded to the surface and the inside of the carbon support to further lower the resistance.

In addition, the ratio of the surface area to volume in the carbonization process can be greatly improved. Therefore, when the carbon-metal composite material (C _x M _y ) is used as an electrode of a secondary battery or an electrochemical capacitor, there is an advantage of increasing the reaction area with an electrolyte, and when used as an electrode of a fuel cell The high porosity has the advantage of increasing the permeability of fuel or air.

Electrode Fabrication Using Carbon-Metal Composites

2 is a flowchart illustrating a method of manufacturing an electrode using a carbon-metal composite according to another embodiment of the present invention.

Referring to Figure 2, first to prepare a carbon-metal composite (S10). The manufacturing method of the carbon-metal composite may be substantially the same as the manufacturing method of the carbon-metal composite described with reference to FIG. 1.

An electrode is formed using the carbon-metal composite (S20).

Specifically, a slurry in which the carbon-metal composite is dispersed may be made, and the slurry may be coated on a substrate to form a carbon-metal composite film. Coating the slurry onto a substrate can be carried out using spray coating, roll coating, spin coating, screen coating, inkjet printing, wire coating, offset printing, or curtain coating. However, the process of forming the carbon-metal composite film using the slurry may be omitted in some cases.

A conductive material can be added to the slurry. The conductive material is at least one selected from the group consisting of carbon black, graphite, carbon fiber, carbon nanotube, graphene, and their respective derivatives. It may be more than a kind. The conductive material may be contained in an amount of 0.01 to 50% by weight based on the entire electrode, but may be appropriately adjusted depending on the characteristics of the electrode.

A binder can be added to the slurry. The binder is polytetrafluoroethylene (PTFE), polyvinylidene fluoride (Polyvinylidene) Fluoride, PVDF), Polyvinyl alcohol (PVA), Polybutadiene Rubber (PBR), Carboxy Methyl Cellulose (CMC), or modified polymers of any of these, It may be two or more co-polymers or mixtures of these. The binder is preferably about 0.01 to 20% by weight with respect to the entire electrode, the amount can be appropriately adjusted according to the characteristics of the electrode.

Functional additives may be added to the slurry. The functional additive can increase the mechanical, thermal and chemical stability of the electrode. The functional additive may be a stabilizer, filler, flame retardant, nucleating agent, lubricant, antiblocking agent and the like. Stabilizers have functions such as durability improvement, prevention of oxidation or deterioration of the polymer, and include hydroxybenzophenone series, Ni phenolate, hindered phenol, and organic phosphite esters. Fillers have a stiffness enhancing function, and include talc, cerite, glass fibers, piezoelectrics, carbon black, and carbon nanotubes (CNT). Flame retardants are flame retardant and include halogenated organic compounds, Mg / Al hydroxides, halogenated organic compounds, and ammonium polyphosphate. Nucleating agents have the ability to enhance stiffness and transparency through tuberculosis nucleation and polymer chain restraint, and include organophosphate partial metal salts and dibenzylidene sorbitol derivatives. The lubricant has a function of improving moldability, and includes alkanate amide, alkenate amide, fatty acid ester and the like. The antiblocking agent has a function of preventing film sticking and includes fine silica and the like.

The carbon-metal composite or the carbon-metal composite film may be optically treated. As a result, the physical and chemical stability of the electrode can be improved. However, the optical treatment may be omitted in some cases. The optical treatment may be UV treatment or electron beam treatment. To this end, a photocurable resin may be added when forming the carbon-metal composite material or in the slurry. The photocurable resin may be a reactive oligomer such as polyester, polyether, urethane, epoxy, silicone, fluorine, or the like. In addition, photoinitiators such as hydroxy dimethyl acetophenone, benzoin, benzoin ether, benzyl, benzyl ketal, methylene blue, cyanine, florescein and eosin, and reactive diluents, and other additives are added. can do.

The carbon-metal composite or the carbon-metal composite film may be compressed to form an electrode matrix. The electrode matrix can greatly increase mechanical strength and modulus due to compression. Specific methods of compression may be a roll pressing method, a press method, a vacuum molding method, or a heating method.

When the electrode matrix is used as an electrode of a fuel cell, the catalyst ink may be further impregnated into the electrode matrix. The catalyst ink may contain a catalyst, ionomer and dispersion solvent. The catalyst may be platinum or a platinum containing alloy. For example, Pt, Pt / Ru, Pt / Pd, Pt / Au, Pt / Ag, Pt / Ir, Pt / Rh, and Pt / Os. The ionomer may be a polymer including a fixed ion covalently attached to the side chain as an ion conductive material. The dispersion solvent may be distilled water or alcohol. The catalyst may be added in the form of a supported catalyst supported in the support. The support may be a carbon material.

Electrochemical capacitors

3 is a cross-sectional view showing an electrochemical capacitor according to another embodiment of the present invention.

Referring to FIG. 3, the electrochemical capacitor includes a first electrode 13, a second electrode 17, and a separator 15 interposed between these electrodes. An electrolyte solution is filled between the first electrode 13 and the separator 15 and between the second electrode 17 and the separator 15. One of the first electrode 15 and the second electrode 17 is a cathode and the other is an anode.

The separator 15 may be a film laminate containing polyethylene or polypropylene as an insulating porous body, or a fiber nonwoven fabric containing cellulose, polyester, or polypropylene.

The electrolyte solution may be aqueous or non-aqueous, but in order to increase the operating voltage of the capacitor, a non-aqueous electrolyte is preferable. The non-aqueous electrolyte solution includes an electrolyte and a medium, and the electrolyte may be lithium salt, copper salt or ammonium salt. The lithium salt is lithium perchloroate (LiClO ₄ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium trifluoromethane sulphonate (LiCF ₃ SO ₃ ), lithium hexafluoroacetate ( LiAsF ₆ ), or lithium trifluoromethanesulfonylimide (Li (CF ₃ SO ₂ ) ₂ N). The copper salt may be copper (I) thiocyanate, triflate copper (II) triflate, or the like. The ammonium salt is tetraethylammonium tetrafluoroborate (TEABF ₄ ), triethylmonomethylammonium tetrafluoroborate, tetraethylammonium hexafluorophosphate, N, N-diethyl-N-methyl-N- (2-meth Methoxyethyl) ammonium (DEME) salt. The medium is ethylene carbonate, propylene carbonate. Dimethyl carbonate, methylethyl carbonate, diethyl carbonate, acrylonitrile or γ-caprolactone.

When the first electric field is applied between the electrodes 15 and 17, the electrochemical capacitor is charged with the ions in the electrolyte solution moving along the electric field and adsorbed to the electrode surface, and between the electrodes 15 and 17. When a second electric field opposite to the first electric field is applied, ions adsorbed on the surfaces of the electrodes may be desorbed and discharged.

At least one of the first electrode 15 and the second electrode 17 may be an electrode formed using the carbon-metal composite described with reference to FIG. 2. As an example, both the first electrode 15 and the second electrode 17 may be electrodes formed using the carbon-metal composite described with reference to FIG. 2. As another example, any one of the first electrode 15 and the second electrode 17 is an electrode formed using the carbon-metal composite described with reference to FIG. 2, and the other is RuO ₂ , Ni (OH) Metal oxides such as ₂ , MnO ₂ , PbO _2, and the like.

The electrode formed using the carbon-metal composite has a large porosity and a very high ratio of surface area to volume. Therefore, there is an advantage that can increase the reaction area with the electrolyte. In addition, the metal is bonded to the surface and the inside of the carbon has the advantage of reducing the internal resistance of the electrode.

Secondary battery

A secondary battery according to another embodiment of the present invention includes a positive electrode including a positive electrode active material, a negative electrode which is an electrode formed using the carbon-metal composite described with reference to FIG. 2, a separator positioned between the positive electrode and the negative electrode, and an electrolyte. Include.

The cathode active material may be LiMO ₂ (where M is V, Cr, Co, or Ni) capable of deintercalation-intercalation of the lithium ion. The separator prevents physical contact between the positive electrode and the negative electrode and prevents movement of lithium ions. The separator has a microporous structure and may be a polyolefin film or a poly vinyl difluoride film. The electrolyte may be used as a medium for moving lithium ions, in an organic solution containing a lithium salt, or in a gelled form of such an electrolyte.

The negative electrode formed using the carbon-metal composite has a large porosity and a very high ratio of surface area to volume. Therefore, it may be advantageous for deintercalation-intercalation of lithium ions. In addition, the metal is bonded to the surface and the inside of the carbon has the advantage of reducing the internal resistance of the electrode.

Fuel cell

4 is a cross-sectional view showing a fuel cell according to another embodiment of the present invention.

Referring to FIG. 4, the fuel cell includes a first electrode 23, a second electrode 27, and an ion exchange membrane 25 positioned therebetween. The ion exchange membrane 25 may be a polymer electrolyte membrane such as a Nafion membrane. One of the first electrode 23 and the second electrode 27 is an anode and the other is a cathode.

Fuel may be diffused and introduced through an oxide electrode of the first electrode 23 and the second electrode 27, and air may be diffused and introduced through a reduction electrode. The fuel may be hydrogen or liquid fuel. The liquid fuel may be formic acid, methanol, ethanol, ethylene glycol, dimethyl ether, or methyl formate. The fuel may generate hydrogen ions and electrons as it is oxidized on a catalyst in the anode. The generated electrons may generate electrical energy while moving to the reduction electrode through an external circuit. In addition, the hydrogen ions may move to the reduction electrode through the ion exchange membrane 15. The air may meet the hydrogen ions in the cathode to generate water.

At least one of the first electrode 23 and the second electrode 27 may be an electrode formed using the carbon-metal composite described with reference to FIG. 2.

The electrode formed using the carbon-metal composite has a large porosity and a very high ratio of surface area to volume. High porosity can increase the permeability of fuel or air. In addition, the metal is bonded to the surface and the inside of the carbon has the advantage of reducing the internal resistance of the electrode.

Hereinafter, preferred examples are provided to aid the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited to the following experimental examples.

Examples of Carbon-Metal Composites

<Manufacture example 1>

1 g of cellulose diacetate was dissolved in 10 g of acetone to form a first solution. 4 g of Ca (SCN) ₂ 4H ₂ O was dissolved in 10 g of water to make a second solution. The first and second solutions were mixed with stirring to form a uniform transparent third solution. The third solution was cooled to form a gel phase, which was immersed in ethanol to remove unreacted ions, thereby preparing a cellulose airgel.

After the cellulose airgel 1g impregnation the litter platinum ions to _{Pt (NH 3) 4 Cl 2} · H 2 O aqueous solution of 300mM, then reducing the litter of the impregnating platinum ions into 100 mM NaBH ₄ aqueous solution of cellulose airgel-platinum composite material Was prepared.

The cellulose airgel-platinum composite material was placed in a tubular heating furnace and heat-treated at 450 ° C. under a nitrogen atmosphere to prepare a carbon airgel-platinum composite.

FIG. 5A is an SEM image showing cellulose aerogels prepared during the preparation of Example 1. FIG. 5B is an SEM image showing the cellulose aerogel-platinum composite prepared during the preparation of Example 1. FIG. 5C is a SEM photograph of the carbon aerogel-platinum composite prepared through Preparation Example 1. FIG.

5A, 5B and 5C, it can be seen that the cellulose aerogel and the cellulose aerogel-platinum composite have nanofiber phases. In FIG. 5C, the aggregation of platinum particles could not be found, indicating that they were evenly distributed on the surface and inside. Even after the carbonization is progressing, it can be seen that the platinum nanoparticles are uniformly dispersed on the carbon surface without aggregation.

<Manufacture example 2>

A carbon airgel-platinum composite was prepared in the same manner as in Preparation Example 1, except that the cellulose aerogel-platinum composite material was placed in a tubular heating furnace and heat-treated at 600 ° C. under a nitrogen atmosphere.

6A is a SEM image of the carbon airgel-platinum composite prepared through Preparation Example 2, and FIG. 6B is a TEM image of the carbon airgel-platinum composite prepared through Preparation Example 2. FIG.

6A and 6B, each line of the carbon aerogel-platinum composite is formed by cellulose aerogels agglomerated and carbonized, and it can be seen that platinum nanoparticles are evenly dispersed on the surface thereof. Even dispersibility is one of the important factors in the composite material, which can exhibit maximum efficiency in a small amount.

<Manufacture example 3>

1.5 g of polyacrylonitrile (PAN) was dissolved in 10 g of dimethylformaldehyde. This solution was electrospun through a syringe pump at a voltage of 10 kV at a rate of 0.2 microliters per minute to prepare PAN nanofibers.

10 mg of the PAN nanofibers were immersed in 20 mM Pt (NH ₃ ) ₄ Cl ₂ H ₂ O aqueous solution and then impregnated with platinum ions, followed by dipping in 100 mM NaBH ₄ aqueous solution to reduce the impregnated platinum ions. A composite material was obtained.

The PAN fiber-platinum nanocomposite was placed in a tubular heating furnace and subjected to a first heat treatment at 230 ° C. for 5 hours and a second heat treatment at 950 ° C. for 1 hour under a nitrogen atmosphere to obtain a carbon fiber-platinum nanocomposite.

7A is an SEM image showing the PAN nanofibers obtained during the preparation of Example 3, FIG. 7B is a SEM image of the PAN fiber-platinum nanocomposites obtained during the preparation of Example 3, and FIG. 7C is obtained through Preparation Example 3. SEM image of carbon fiber-platinum nanocomposite.

Referring to Figures 7a, 7b and 7c, it can be seen that the platinum particles in the PAN fiber-platinum nanocomposite material (Fig. 7b) is dispersed on the surface of the PAN fiber. In addition, in the carbon fiber-platinum nanocomposite (FIG. 7C), even after carbonization, the fiber shape is maintained, and the platinum particles are evenly coated on the carbon fiber surface. Uniform dispersion of the metal particles can exhibit great efficiency even in small amounts.

&Lt; Preparation Example 4 &

1.5 g of polyacrylonitrile (PAN) was dissolved in 10 g of dimethylformaldehyde. This solution was electrospun through a syringe pump at a voltage of 10 kV at a rate of 0.2 microliters per minute to prepare PAN nanofibers.

10 mg of the PAN nanofibers were immersed in 20 mM Pt (NH ₃ ) ₄ Cl ₂ H ₂ O aqueous solution and impregnated with platinum ions, which were then placed in a tubular heating furnace and heat-treated at 230 ° C. for 5 hours under nitrogen atmosphere, and then at 1 at 950 ° C. Carbon fiber-platinum nanocomposites were prepared by time-treatment.

8A is a SEM photograph showing the carbon fiber-platinum nanocomposite obtained through Preparation Example 4. FIG. 8B is a TEM photograph showing the surface of the carbon fiber-platinum nanocomposite obtained through Preparation Example 4. FIG. 8C is a TEM photograph showing a cross section of the carbon fiber-platinum nanocomposite obtained through Preparation Example 4. FIG.

8A, 8B, and 8C, it can be seen that many pores are formed on the surface of the carbon fiber. This is because the ionic platinum is produced by the reaction with the PAN fiber surface, it was possible to obtain a carbon fiber-platinum nanocomposite having a large surface area. In addition, it can be seen that the platinum particles are evenly distributed on the surface of the carbon fiber and the inside of the carbon fiber.

1 is a flow chart showing a carbon-metal composite manufacturing method (S10) according to an embodiment of the present invention.

2 is a flowchart illustrating a method of manufacturing an electrode using a carbon-metal composite according to another embodiment of the present invention.

3 is a cross-sectional view showing an electrochemical capacitor according to another embodiment of the present invention.

4 is a cross-sectional view showing a fuel cell according to another embodiment of the present invention.

FIG. 5A is an SEM image showing cellulose aerogels prepared during the preparation of Example 1. FIG.

5B is an SEM image showing the cellulose aerogel-platinum composite prepared during the preparation of Example 1. FIG.

5C is a SEM photograph of the carbon aerogel-platinum composite prepared through Preparation Example 1. FIG.

6A is an SEM image of a carbon airgel-platinum composite prepared through Preparation Example 2. FIG.

6B is a TEM image of a carbon airgel-platinum composite prepared through Preparation Example 2. FIG.

7A is an SEM image showing the PAN nanofibers obtained during the preparation of Example 3. FIG.

7B is an SEM image of the PAN fiber-platinum nanocomposite obtained during the preparation of Preparation Example 3. FIG.

7C is an SEM image of the carbon fiber-platinum nanocomposite obtained through Preparation Example 3. FIG.

8A is a SEM photograph showing the carbon fiber-platinum nanocomposite obtained through Preparation Example 4. FIG.

8B is a TEM photograph showing the surface of the carbon fiber-platinum nanocomposite obtained through Preparation Example 4. FIG.

8C is a TEM photograph showing a cross section of the carbon fiber-platinum nanocomposite obtained through Preparation Example 4. FIG.

Claims (9)

Mixing the porous carbon precursor and the metal precursor in the form of a linear structure or an airgel to obtain a carbon-metal precursor mixed material; Carbonizing the carbon-metal precursor mixture material to obtain a carbon-metal composite having fibrous carbon and metal particles contained on or in the surface of the fibrous carbon; And Reacting the carbon-metal precursor mixed material with a reducing agent before carbonizing the carbon-metal precursor mixed material, or reacting the carbon-metal composite with a reducing agent after carbonizing the carbon-metal precursor mixed material. Method of manufacturing carbon-metal composites. delete The method of claim 1, The porous carbon precursor having a form of the linear structure or aerogel is a pitch (pitch), synthetic polymers, plant-based, or a carbon-metal composite manufacturing method comprising at least one of them. The method of claim 1, The metal precursor is a metal, a metal oxide, a metal nitride, a metal nitride, a metal sulfide, or a salt containing at least one thereof. delete The method of claim 1, Carbon-metal composite manufacturing method further comprising the step of activating the carbon-metal composite. Preparing a carbon-metal composite using the method of any one of claims 1, 3, 4, and 6; And Electrode manufacturing method comprising the step of forming an electrode using the carbon-metal composite. delete delete

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