KR101110366B1 - Manufacturing method of carbon nikel composite aerogel and supercapacitor electrode - Google Patents

Abstract

The present invention, the step of adding and stirring magnesium acetate to a mixed solution of formaldehyde and resorcinol, and the formaldehyde and resorcinol hydrolysis condensation reaction by the magnesium acetate at a temperature of 25 ~ 90 ℃ to form a chain Forming a gelled composition, wherein the chain and the chain are combined to form a cluster, and the cluster and the cluster are combined to form a network, and solvent-substituting the gelled composition with acetone or methanol; Aging the substituted composition to reinforce the network structure in the gel; solvent-substituting the solvent contained in the aged composition with liquid carbon dioxide; and drying the solvent-substituted composition with carbon dioxide by making carbon dioxide supercritical. Forming an RF airgel, and with respect to the RF airgel A method of manufacturing a carbon nickel composite airgel, comprising the steps of: synthesizing a carbon airgel by carrying out a oxidization process and supporting the carbon airgel in a nickel solution containing a nickel precursor and synthesizing a carbon nickel composite airgel; and a supercapacitor electrode using the same It relates to a manufacturing method of. According to the present invention, a gel can be formed in a short time, has a pore size and pore structure suitable for an electrode material for a supercapacitor, can be easily dried without destroying the pore structure formed inside the airgel, and nickel inside the pores. By introducing a metal, the electrode resistance can be lowered, the capacitance can be improved by the pseudo capacitor effect, and a carbon nickel composite airgel having a high specific surface area can be produced.

Carbon Aerogels, Carbon Nickel Composite Aerogels, Supercapacitors, Resorcinol, Formaldehyde

Description

Manufacturing method of carbon nickel composite airgel and manufacturing method of supercapacitor electrode using same {Manufacturing method of carbon nikel composite aerogel and supercapacitor electrode}

The present invention relates to a method for producing a carbon nickel composite airgel, and more particularly, a gel can be formed in a short time, has a pore size and a pore structure suitable for an electrode material for a supercapacitor, and has a pore structure formed inside the airgel. It can be easily dried without breaking, and by introducing nickel metal into the pores, the electrode resistance can be lowered, and the capacitance can be improved by the pseudo capacitor effect, and the manufacturing method of carbon nickel composite airgel having high specific surface area and the same The manufacturing method of the used supercapacitor electrode is related.

Supercapacitors, electrical storage devices, are often used to provide low power in the event of a power failure. There is no dielectric material that is inherent to conventional capacitors, and unlike a battery, it does not use a chemical reaction during charging and discharging. It can be used in small home appliances such as mobile phones and digital cameras, and in recent years, large and large sized supercapacitors have been made.

Supercapacitors have high instantaneous power and can be charged quickly in a few tens of seconds. As such, when mounted in an automobile, it can be used as a complement to main energy devices such as engines and fuel cells.

In recent years, various studies have been made on carbon aerogels as materials for electrodes of such supercapacitors. Carbon aerogels (CA) are new mesoporous materials with large specific surface areas, large pore volumes, high electrical conductivity and adjustable pore structure.

Although the carbon aerogels have various applications such as electrodes for supercapacitors, rechargeable batteries, catalyst support and gas absorbents, the process is still simple. Carbon aerogels with satisfactory wide and uniform specific surface areas and high storage capacities have not been developed.

In addition, since the carbon airgel has a nanoporous structure composed of numerous pores of uniform size, the pore structure is easily broken partially due to volume shrinkage during drying, thereby ensuring a uniform specific surface area and a uniform storage capacity. There was a problem that was not.

An object of the present invention is to form a gel in a short time, has a pore size and pore structure suitable for the electrode material for the supercapacitor, can be dried easily without breaking the pore structure formed inside the airgel, nickel inside the pores By introducing a metal, it is possible to lower the electrode resistance, improve the capacitance by the pseudo capacitor effect, and provide a method of manufacturing a carbon nickel composite airgel having a high specific surface area.

It is also an object of the present invention to provide a method of manufacturing a supercapacitor having low electrode resistance, high specific surface area and accumulation capacity.

The present invention, the step of adding and stirring magnesium acetate to a mixed solution of formaldehyde and resorcinol, and the formaldehyde and resorcinol hydrolysis condensation reaction by the magnesium acetate at a temperature of 25 ~ 90 ℃ to form a chain Forming a gelled composition, wherein the chain and the chain are combined to form a cluster, and the cluster and the cluster are combined to form a network, and solvent-substituting the gelled composition with acetone or methanol; Aging the substituted composition to reinforce the network structure in the gel, solvent-substituting the solvent contained in the aged composition with liquid carbon dioxide, and making the carbon dioxide supercritical so that the solvent-substituted composition is Drying to form an RF airgel, and with respect to the RF airgel Subjected to drawing process to the step and carried on the nickel solution to the carbon airgel comprises a nickel precursor to synthesize carbon aerogels proposes a method of producing a carbon-nickel composite airgel comprising the steps of synthesizing a carbon-nickel composite airgel.

The synthesizing of the carbon nickel composite airgel may include: supporting the carbon airgel in a reaction vessel containing the nickel solution; and first heat treating the carbon airgel supported on the nickel solution at a temperature of 60 to 120 ° C. Forming nickel in the pores of the carbon airgel and the second heat treatment to a temperature range of 600 ~ 1000 ℃ in the reducing gas, inert gas or reducing gas and inert gas atmosphere.

The nickel precursor is nickel acetate tetrahydrate, the nickel solution is a solution containing the nickel precursor, isopropyl alcohol and dimethylamine, the nickel precursor is contained 0.1 to 1 molar concentration in the nickel solution, the dimethylamine is It is preferable that 0.1-4 mol is contained in the said nickel solution, and 8-20 mol is contained in the said nickel solution.

The mixed solution of formaldehyde and the resorcinol is a solution obtained by mixing the formaldehyde and the resorcinol in distilled water so as to have a concentration of 1 to 10 M, and the mixed solution of the formaldehyde and the resorcinol to the The molar ratio of the content of socinol to that of magnesium acetate It is preferable to add so that it may become 50-500.

Preferably, the mixed solution of formaldehyde and resorcinol is a solution in which the formaldehyde and the resorcinol are mixed in a ratio of 1: 1 to 4: 1 in a molar ratio.

It is preferable that the said aging is carried out in the container which carried the gelled composition in acetone and sealed at the temperature range of 25-90 degreeC.

The drying is preferably maintained by drying at a temperature and pressure equal to or higher than 31 ° C. and 73 bar at which carbon dioxide is supercritical.

It is preferable that the said carbonization process is performed in a reducing gas, an inert gas, or a reducing gas and inert gas atmosphere in the temperature range of 600-1000 degreeC.

In addition, the present invention comprises the steps of pulverizing the carbon nickel composite airgel prepared by the method of claim 1 to powder, 90 to 98% by weight of the carbon nickel composite airgel pulverized into powder, 1 to 5% by weight of the conductive binder, Forming a paste by mixing 1 to 5% by weight of acetylene black in a solvent and applying the paste to a titanium, nickel, aluminum foil, plate or mesh to a thickness of 50 ~ 200㎛ supercapacitor comprising a step The manufacturing method of an electrode is shown.

According to the method for preparing a carbon nickel composite airgel according to the present invention, a gel can be formed in a short time by copolymerizing formaldehyde and resorcinol using magnesium acetate, and desired pores are controlled by controlling the content of magnesium acetate. It has the advantage that it can be adjusted to have a size and pore structure, and can be dried easily without destroying the pore structure formed inside the gel by drying with supercritical carbon dioxide, and the electrode resistance is lowered by introducing nickel metal into the pore. In addition, the carbon capacitor composite airgel having a large and uniform specific surface area which can be used as an electrode material for a supercapacitor can be manufactured by improving the capacitance by the pseudo capacitor effect.

The supercapacitor electrode manufactured according to the present invention has a low electrode resistance by introducing nickel metal into the pores, improves capacitance by the pseudo capacitor effect, and has a high specific surface area.

The carbon nickel composite aerogel of the present invention is not only an electrode material for a supercapacitor, but also a material for a rechargeable battery for automobiles, an electrode material for a fuel cell, a catalyst support, using a large specific surface area and a high capacitance. It may be variously applied to a gas adsorbent, a material for deionized water purification, a secondary battery, and the like.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided to those skilled in the art to fully understand the present invention, and may be modified in various forms, and the scope of the present invention is limited to the embodiments described below. It doesn't happen.

Carbon nickel composite aerogels (CA / Ni) are the pores of carbon airgels, a new porous material with a large specific surface area, large pore volume, high electrical conductivity and an adjustable pore structure. It is a substance formed by complexing nickel in it. Most of the pores of the carbon aerogels have mesopore size. Herein, the mesopore means a pore having a size of 20 to 500 ～. In addition, the micropores (micropore) refers to pores smaller than mesopores, that is, less than 20 microns, and the macropores (pores of macropore) refers to pores larger than the mesopores, that is, more than 500 microns. Carbon nickel composite airgel is a carbon airgel loaded in a nickel solution and heat-treated to fill the pores of the carbon airgel.

Since the charge stored in an electric double layer capacitor depends mainly on the surface area, a carbon nickel composite airgel having a large surface area can be mainly used as an electrode material of a supercapacitor. The amount of charge stored is also related to the pore size and pore structure. Electrolyte ions cannot penetrate the micropores completely, which means they have a small surface area to store charge. The carbon nickel composite airgel may be applied to not only an electrode for a supercapacitor, but also a rechargeable battery, a catalyst support, a gas absorbent, and the like.

Carbon nickel composite airgel according to a preferred embodiment of the present invention is a resorcinol-formaldehyde, phenol-furfural, phenol-resorcinol-formaldehyde through a sol-gel process Or by pyrolysis of organic airgel based on melamine-formaldehyde and complexation of nickel.

For example, an organic aerogel may be synthesized according to a hydrolysis-condensation reaction of formaldehyde and resorcinol. More specifically, an organic airgel may be synthesized by copolymerizing a catalyst of magnesium acetate and a resorcinol-formaldehyde mixture diluted in water. When forming the gel structure, the concentration of magnesium acetate as a catalyst is very important, because as the amount of magnesium acetate increases, the density decreases and the BET surface area increases. This affects the capacitance of the carbon nickel composite airgel.

Resorcinol and formaldehyde are condensed with polymer cluster crosslinks to form a wet gel structure. The gel structure can be dried using supercritical carbon dioxide to avoid destruction of the pore structure. This supercritical drying process makes it possible to maintain the pore structure of the gel structure without interfacial tension due to the absence of the gas-liquid interface.

The carbon nickel composite airgel of the present invention may be derived from pyrolysis of nickel and the resorcinol-formaldehyde airgel in an inert atmosphere. The carbon nickel composite airgel thus obtained has a high specific surface area per unit mass of about 300 to 520 m 2 / g, a low density of about 0.2 to 1.0 g / cm 3, an excellent electrical conductivity of about 5 to 50 S / cm, and a carbon purity of 99.5% or more. It can be used even without a special binder.

Hereinafter, a method of manufacturing a carbon nickel composite airgel according to a preferred embodiment of the present invention will be described.

Formaldehyde, resorcinol, and magnesium acetate (Mg (Ac) ₂ ) are added to a reaction vessel (eg, a beaker) containing distilled water, and for a predetermined time (for example, 1 hour to 48 hours). Agitation at room temperature (eg, 10-30 ° C.). For example, 23.9 g (0.29 mol) of formaldehyde and 16.1 g (0.145 mol) of resorcinol are added to 60 ml of distilled water and mixed to a concentration of 4.35 mol, and then 0.625 g (0.0029 mol) of magnesium acetate is preferably added. At this time, the concentration of magnesium acetate added is very important because, as the amount of magnesium acetate increases, the density decreases and the BET surface area increases, thereby affecting the capacitance of the carbon airgel. Considering this, magnesium acetate should have a concentration range of 0.063 to 0.625 g (0.00029 to 0.0029 moles).

The mixing ratio (molar ratio) of the formaldehyde and the resorcinol is 1: 1 to 4: 1 (a ratio of 1 to 4: 1 by the molar ratio of formaldehyde to resorcinol), preferably adjusted to 2: 1 When the molar ratio is out of the above range, that is, when the resorcinol is higher than the blending ratio, the springback effect does not occur sufficiently, so that the thickness of the finished carbon nickel composite airgel is reduced, resulting in a small porosity and high thermal conductivity. If the formaldehyde is higher than the blending ratio, there is a problem that the reactivity with resorcinol is lowered and the cost of the raw material is increased. Therefore, when combining formaldehyde and resorcinol in the above mixing ratio, there is an advantage in that it is possible to prepare a carbon nickel composite airgel of the most economical and optimal performance.

The stirred and mixed solution is gelated after a certain time. That is, if the mixed solution is left at a temperature higher than room temperature (for example, 40 to 90 ° C.) for a predetermined time (for example, 12 to 72 hours), hydrolysis-condensation of formaldehyde and resorcinol is performed. Gelation occurs by a hydrolysis-condensation reaction. Resorcinol and formaldehyde can be condensed with polymer cluster crosslinks to form a gel structure to obtain a gelled composition. Resorcinol and formaldehyde form a chain by a catalyst, magnesium acetate, a chain (chain) and clusters (chains), and clusters and clusters combine to form a network of aerogels.

The gelling composition is subjected to a solvent substitution process with a solvent such as acetone and methanol. It is preferable that acetone, methanol, etc. are used for the said solvent substitution. By performing the solvent substitution as described above, distilled water is substituted with a solvent such as acetone on the surface of the gel to lower the surface tension of the pores formed on the surface of the gel and thereby to prepare a carbon nickel composite airgel without cracking even after heat treatment at normal pressure. It becomes possible. The solvent substitution process can be carried out by supporting the solvent at 60 ~ 70 ℃.

Aging of the solvent substituted composition strengthens the network structure inside the gel. The aging is a method for completely chemical change by leaving the material at a suitable temperature for a long time, it is preferable to perform the aging of the solvent-substituted composition at a temperature of 60 ~ 70 ℃ for a certain time (for example 6 to 48 hours). In addition, since the moisture inside the gel is substituted with a solvent and the gel solid network is strengthened, the strength of the gel is enhanced.

The aged composition in gel form can be dried in a supercritical drying process using supercritical carbon dioxide to avoid breakage of the pore structure. This supercritical drying process makes it possible to maintain the pore structure of the aged composition in gel form without interfacial tension due to the absence of a gas-liquid interface.

Carbon dioxide (CO ₂ ) is a gaseous state at room temperature and atmospheric pressure, but if it exceeds the limit of a certain temperature and high pressure called the supercritical point (e.g., no evaporation process occurs), gas and liquid cannot be distinguished, that is, a critical state, Carbon dioxide in this critical state is called supercritical carbon dioxide fluid. Supercritical carbon dioxide has a molecular density close to a liquid, but has a low viscosity, close to a gas, and can be usefully used in a drying process of an aged composition due to its fast diffusion and high thermal conductivity.

This supercritical drying process using supercritical carbon dioxide involves placing the aged composition in a supercritical drying reactor, then filling the liquid CO ₂ with a pump and substituting CO ₂ for a solvent such as acetone in the aged composition. Performing a solvent replacement process, and then raising the temperature to a constant temperature (e.g., 40 ° C) at a constant temperature increase rate (e.g. bar) for a period of time (eg 16 hours) in the supercritical state of carbon dioxide. In general, carbon dioxide is supercritical at a temperature of 31 ° C. and a pressure of 73 bar. The carbon dioxide may be maintained at a constant temperature and a constant pressure at which the carbon dioxide becomes a supercritical state for a predetermined time (for example, 2 to 24 hours, preferably 16 hours), and then gradually depressurized to complete the supercritical drying process. The above-described supercritical drying process is a low temperature supercritical drying process that performs drying in a low temperature supercritical state, and has advantages in that it is safe and consumes less energy than a process performed in a high temperature supercritical state. In addition, since a volatile solvent such as acetone is used for the preparation of the carbon nickel composite airgel, it is preferable to use a low temperature supercritical process that is safer than a high temperature supercritical process.

15 is a view schematically showing a supercritical drying apparatus. A method of drying using the supercritical drying apparatus 100 will be described in more detail with reference to FIG. 15.

The aged composition is placed in the supercritical drying reactor 110, and carbon dioxide (CO ₂ ) is supplied from the carbon dioxide supply tank 120 to the supercritical drying reactor 110 by a pump 130. The solvent in the aged composition is replaced by CO ₂ by the liquid carbon dioxide supplied to the supercritical drying reactor 110. At this time, the temperature of the supercritical drying reactor 110 is room temperature (10 ~ 30 ℃), the pressure of the supercritical drying reactor 110 is 60 ~ 100 bar when the efficiency of the solvent replacement is good. The carbon dioxide to be supplied is liquid carbon dioxide and can be easily substituted with a solvent in the aged composition in the supercritical drying reactor 110. When the solvent is sufficiently substituted with carbon dioxide, the solvent is changed into a supercritical state. It is preferable to discharge to the drain 140.

Using a heating means (not shown), the temperature inside the supercritical drying reactor 110 is raised to a constant temperature (eg, 40 ° C.) and a constant pressure (100 bar or 100 kgf / cm 2) so that the carbon dioxide becomes a supercritical state. The dried composition is made and held in a supercritical state for a period of time (eg, 6-24 hours). In this case, the carbon dioxide is pumped by the pump 130 and the carbon dioxide, which is in a supercritical state of a predetermined temperature and a high pressure, may be supplied to the supercritical drying reactor 110 through the heat exchanger 150.

When the supercritical drying process is completed, the pressure inside the supercritical drying reactor 110 is gradually lowered by making the pressure lower than the critical state through opening and closing of the valve V3. The supercritical carbon dioxide is gasified to carbon dioxide due to the pressure lower than the critical state, and the gasified carbon dioxide (CO ₂ ) is transferred to the gas supply tank 120 to be recycled or discharged to the outside. Unexplained V1, V2 and V4 refer to valves.

When the CO ₂ supercritical drying process is performed, the porous RF airgel may be dried to have pores having nano-sized pores having a size of 1 nm or more and less than 1 μm.

A carbonization process is performed on the dried RF airgel. The carbonization process may be performed in an inert gas, reducing gas or inert gas and reducing gas atmosphere. The inert gas may be nitrogen (N ₂ ) gas, argon (Ar) gas, helium (He) gas, or the like, and the reducing gas may be hydrogen (H ₂ ) gas, carbon dioxide (CO ₂ ) gas, or the like. It is preferable to perform the said carbonization process in the temperature range of 600 degreeC-1000 degreeC (preferably temperature of about 800 degreeC). When the carbonization process is performed at a temperature of 600 ° C. or less, the carbonization is not performed well and the carbonization time is long. When the carbonization process is performed at a temperature exceeding 1000 ° C., the RF airgel agglomerates to produce fine particles. It is difficult to obtain carbon airgel electrodes with pores. The carbonization process converts the RF airgel into a carbon airgel.

Hereinafter, the carbonization process will be described in more detail. The temperature is continuously increased to a desired carbonization temperature (eg, 800 ° C.) at a first temperature (eg, room temperature), maintained at a carbonization temperature for a predetermined time (eg, 3 to 5 hours), and then cooled to room temperature. . At this time, the temperature increase rate is in the range of 1 to 20 ° C / min. In general, if the temperature increase rate is too slow, it is difficult to obtain a carbon airgel having a desired fine pore size due to the large growth rate of the particles. The cooling of the furnace may be caused to cool down in a natural state by shutting off the furnace power source, or may be cooled by arbitrarily setting a temperature drop rate (for example, 5 to 15 ° C./min). At this time, the magnesium acetate used as a catalyst is composed of an organic component, so it will be burned away when the temperature of 300 ~ 400 ℃, the carbonization temperature is made at a temperature higher than the burning temperature of the organic component, the magnesium acetate component when the carbonization process is completed Is removed and only the carbon component remains.

In order to complex the carbon airgel and nickel by introducing nickel metal into the pores of the carbon airgel, the carbon airgel is supported on a nickel solution including a nickel precursor to synthesize a carbon nickel composite airgel.

In the synthesis of the carbon nickel composite airgel, the carbon airgel is supported in a reaction vessel containing a nickel solution, and the carbon airgel is dried by first heat treatment (drying) the carbon airgel supported on the nickel solution at a temperature of 60 to 120 ° C. After the nickel is formed in the pores, the second heat treatment may be included in a reducing gas, an inert gas or a reducing gas and an inert gas atmosphere in a temperature range of 600 ~ 1000 ℃.

The nickel precursor may be nickel acetate tetrahydrate (Ni (CH ₃ COO) ₂ 4H ₂ O), and the nickel solution may be a solution containing the nickel precursor, dimethylamine ((CH ₃ ) ₂ NH), and isopropyl alcohol. have. The nickel precursor is contained in the nickel solution in a concentration of 0.1 to 1 mole, the dimethylamine is contained in the nickel solution 0.1 to 4 moles, the isopropyl alcohol is preferably contained in the nickel solution 8 to 20 moles.

The process for synthesizing the carbon nickel composite airgel in which nickel is formed in the pores of the carbon airgel will be described in more detail. For example, nickel (Ni), which is a mixed solution of 0.5 mol of nickel acetate tetrahydrate, 2 mol of dimethylamine and 16 mol of isopropyl alcohol, is described. Immerse the solution in nickel solution into the carbon airgel. When the nickel solution is infiltrated into the carbon airgel, the first heat treatment is performed at a predetermined temperature (eg, 100 ° C.), and then nickel (Ni) is formed in the pores of the carbon airgel. By the first heat treatment, a solvent component such as isopropyl alcohol is volatilized to disappear. It is preferable to repeat the process of dipping the carbon airgel in the nickel solution and the first heat treatment process to form nickel (Ni) in the pores of the carbon airgel. In the nitrogen (N ₂ ) gas atmosphere, the carbon nickel composite airgel may be prepared by performing a first heat treatment at a temperature in the range of 600 ° C. to 1000 ° C. (preferably about 800 ° C.).

The supercapacitor electrode (carbon nickel composite airgel electrode) may be manufactured using the carbon nickel composite airgel thus prepared. First, the carbon nickel composite airgel is pulverized into a powder using a process such as ball milling, and pulverized into a powder. 90 to 98% by weight of the prepared carbon nickel composite airgel, 1 to 5% by weight of the conductive binder, and 1 to 5% by weight of acetylene black are mixed with a solvent to form a paste, and then the paste is titanium, nickel, aluminum foil, plate or mesh. A supercapacitor electrode can be formed by applying to 50 to 200 micrometer thickness etc. to a back. The application may use a doctor blade or roll coating. In order to reinforce the adhesive strength of the carbon nickel composite airgel at the time of the coating may be press-compression while heating using a hot plate.

Hereinafter, the present invention will be described in detail by examples. The following examples are merely illustrative of the present invention, but the content of the present invention is not limited to the following examples.

≪ Example 1 >

23.9 g of formaldehyde and 16.1 g of resorcinol were added to 60 ml of distilled water in the reaction vessel and mixed to a concentration of 4.35 M, followed by 0.625 g (CA50), 0.312 g (CA100), 0.156 g (CA200), and 0.063 of magnesium acetate. g (CA500) was added respectively to obtain a mixed solution.

The mixed solution was stirred at 25 ° C. for 24 hours.

The stirred solution was allowed to stand for 24 hours at 60 ° C. higher than room temperature to cause gelation by hydrolysis-condensation reaction of formaldehyde and resorcinol. . At this time, since the contraction occurs when the solvent evaporates, the reaction vessel is sealed to allow the reaction between formaldehyde and resorcinol.

Solvent substitution of the gelled composition with acetone at 60 ℃ was carried out for 24 hours. The solvent was substituted with liquid carbon dioxide at a pressure of 80 bar at 25 ° C. using a supercritical drying apparatus, and RF aerogels were prepared through CO ₂ supercritical drying at 40 ° C. and 100 bar for 16 hours.

Carbonization process was performed on the dried RF airgel to obtain a carbon airgel. The carbonization process was performed at a temperature of 800 ° C. for 3 hours in a nitrogen (N ₂ ) gas atmosphere.

<Example 2>

The carbon airgel prepared in Example 1 was a mixed solution of 65.5 ml of isopropyl alcohol, 7.1 ml of nickel acetate tetrahydrate (Ni (CH ₃ COO) ₂ 4H ₂ O), and 27.4 ml of dimethylamine ((CH ₃ ) ₂ NH). After dipping in the nickel solution, the carbon airgel is impregnated with the nickel solution, it is dried at 100 ° C. (first heat treatment), and the carbon airgel is again immersed in the nickel solution and dried at 100 ° C. three times. Dip the solution. A carbon nickel composite airgel is prepared by performing a second heat treatment at a temperature of 800 ° C. in a nitrogen (N ₂ ) gas atmosphere.

<Example 3>

The carbon nickel composite airgel prepared in Example 2 was ground in a mortar and then milled for 14 hours using zirconia balls to be pulverized into particles having a particle size of 110 μm, followed by 90 wt% of the carbon nickel composite airgel and PTFE as a conductive binder. 5% by weight of polytetrafluoroethylene) and 5% by weight of acetylene black were mixed, and a paste was prepared by adding isopropyl alcohol. The carbon nickel composite airgel paste was roll milled to be mixed well and then applied to each of titanium plate, nickel mesh, nickel foil, and etched aluminum foil to a thickness of 150 μm. The coating was performed by a doctor blade or a roll coating, and was pressure-bonded by heating using a hot plate to enhance adhesion of the carbon nickel composite airgel using graphite bonds. The formed supercapacitor electrode was supported for 24 hours in sulfuric acid at 2M concentration to activate the electrode. Subsequently, the full-cell electrode test uses the same supercapacitor electrode for charging and discharging in the range of 0 to 1 V using Chronopotentiometry under a constant current in the range of 1 to 5 mA / cm 2 in 2M sulfuric acid solution. The test was performed to calculate the filling capacity. Cyclic voltammetry was then performed at a scan speed of 1 to 100 mV / s in the range of 0 to 1 V.

The present invention is described in more detail with reference to the following experimental examples, which do not limit the present invention. Hereinafter, RF50, RF100, RF200 and RF500 refers to the ratio of the content of resorcinol and magnesium acetate added when manufacturing the RF airgel, CA50, CA100, CA200 and CA500 is added when preparing the carbon airgel It means the ratio of the content of resorcinol and the content of magnesium acetate. For example, '50' in RF50 or CA50 represents the molar ratio of magnesium acetate based on resorcinol and the content of resorcinol and formaldehyde is 40. CA50 / Ni, CA100 / Ni, CA200 / Ni, and CA500 / Ni refer to a composite carbon nickel airgel formed by forming nickel in the pores of the carbon airgel.

FIG. 1 shows Fourier Transfrom (FT) Infrared Ray (IR) spectral curves of an RF airgel prepared according to Example 1. FIG. In the RF airgel, OH and CH ₂ stretching mode is 3385㎝ ^- appeared in the ^first and 2935㎝ ^-1. The aromatic C = C stretching absorption band appears at 1605 cm ⁻¹ , which is thought to be related to the double bond of resorcinol. The bands of 1218 cm ^-1 and 1085 cm ^-1 are due to CH ₂ -O-CH ₂ , and it appears that lesosinol and formaldehyde were formed by multiple condensation reactions. Resorcinol and formaldehyde form a chain by magnesium acetate as a catalyst, and the chain and the cluster to which the chain is coupled, and the cluster and the cluster are combined to form an airgel network.

2 shows an infrared spectral curve obtained by Fourier transforming a carbon nickel composite airgel in which nickel was formed in pores of the carbon airgel after heat treatment at 100 ° C. in a carbon airgel prepared according to Example 1, in a nickel solution according to Example 2, Curves with varying amounts of magnesium acetate are shown. In the carbon airgel pores nickel is formed, the stretching mode of the OH appears in 3437㎝ ^-1, Fourier transform infrared spectroscopy data (FT-IR data) will not appear is changed according to the amount of catalyst, COO ^- stretching mode of the 1576 It appears in ㎝ ^-1 and 1404㎝ ^-1, have originated from nickel acetate tetrahydrate high rate of nickel solution. After carbonization, the aromatic stretching mode of C = C disappeared at 1605 cm ^-1 .

3 shows a Fourier transform infrared spectral curve of the supercapacitor electrode (carbon nickel composite airgel electrode) prepared according to Example 3 after the evaluation of electrical properties, and shows a curve according to the change of magnesium acetate amount. The nickel complex of carbon airgel stretch mode of OH appears in 3382㎝ ^-1, bands of CH ₂ is shown in 1630㎝ ^-1. The Fourier transformed infrared spectroscopy data (FT-IR data) shows that the smaller the amount of the catalyst, the larger the peak of OH. When a small amount of the catalyst is added, the amount of adsorption of water is increased. 1245cm ^-1 and 1085cm ^-1 are the CO stretching mode and 635cm ^-1 and 868cm ^-1 are the SO stretching mode due to the electrolyte of 2M H ₂ SO ₄ . After carbonization, the aromatic stretching mode of C = C disappeared at 1605 cm ^-1 .

4A shows Raman spectral peaks scattered by a laser of 532 nm for a carbon aerogel prepared according to Example 1. FIG. At 1342 cm ^-1 and 1586 cm ^-1 , peaks attributable to carbon appear, the first being attributable to the D-band and the defective graphite peak, and the second at G-bad. The peaks represent graphite. The D band of the CA50 is wide and the intensity of the G band is slightly higher than that of the other samples. This is thought to be because graphite bonds are more developed than samples of other carbon aerogels.

FIG. 4b shows Raman spectral peaks scattered by a laser of 532 nm for a carbon nickel composite airgel prepared according to Example 2, similar to the Raman spectral peak shown in FIG. 4a but with samples CA200 / Ni and CA500 / Ni G bands appear sharper than CA200 and CA500 of FIG. 4A and are shifted by -14 cm ^-1 . This indicates that graphite was developed through nickel complexation.

5 is for the carbon nickel composite airgel prepared according to Example 2, it shows an X-ray diffraction (XRD) pattern according to the magnesium acetate catalyst ratio. When looking at the peak of CA50 / Ni, unlike other samples, no graphite peak pattern is observed, and the higher the amount of catalyst, the better the graphite peak is thought to be because nickel nanocrystals contribute to the graphite formation through nickel complexation.

FIG. 6 shows a supercapacitor electrode prepared according to Example 3, and shows an X-ray diffraction (XRD) pattern after 24 hours in 2M H ₂ SO ₄ electrolyte. Nickel was oxidized in the CA50 / Ni-CA500 / Ni due to the 2M H ₂ SO ₄ electrolyte resulting in a nickel oxide peak.

FIG. 7 illustrates a supercapacitor electrode manufactured according to Example 3, and shows an X-ray diffraction (XRD) pattern after electric property evaluation. After charging / discharging electrical characteristics of CA50 / Ni, CA100 / Ni, and CA500 / Ni, SO ₄ ^-2 and carbon in 2M H ₂ SO ₄ electrolyte reacted to produce sulfur in carbon airgel pores. The 2M H ₂ SO ₄ electrolyte at / Ni causes nickel to oxidize to form nickel oxide.

The specific surface area of the carbon nickel composite airgel (CA / Ni) was measured by nitrogen adsorption / desorption method using the Brunauer-Emmett-Teller (BET) equation. As shown in FIG. 8a, different molar ratios of magnesium acetate showed different characteristics. FIG. 8A is a graph illustrating nitrogen adsorption and desorption results for the carbon airgel prepared according to Example 1, where 'Ads' represents a case of nitrogen adsorption and 'Des' represents a case of nitrogen desorption.

The specific surface area of the carbon nickel composite airgel was calculated by the BET model. As shown in FIG. 8A, the shape of the hysteresis loop was changed according to the amount of catalyst, that is, the R ratio (mol of resorcinol / mol of catalyst). Another trend was shown. In the case of CA50 / Ni, typical I-V (current-voltage) type characteristics were shown, which means that it is a porous body composed of mesopores. The adsorption curve of CA50 / Ni increases at a constant rate until the relative pressure (relative pressure) reaches 0.8, then suddenly increases the amount of adsorption, and then at the lower relative pressure, the amount of desorption increases and then decreases at a constant rate. At this time, the maximum adsorption amount of CA50 / Ni was 432 cm 3 / g, 373 cm 3 / g for CA100 / Ni, 281 cm 3 / g for CA 200 / Ni, and 133 cm 3 / g for CA 500 / Ni. The maximum adsorption amount shows that CA50 / Ni is composed of the most mesopores. That is, it can be seen that the mesoporosity is the highest when the R ratio (mol of Resorcinol / mol of catalyst) is the lowest value, that is, the amount of catalyst is the highest.

Figure 8b shows the pore size distribution of the carbon nickel composite airgel prepared according to Example 2. The pore size of CA50 / Ni was 22-65 nm, CA100 / Ni was 17-46 nm, CA200 / Ni was 15-28 nm, and CA500 / Ni was 1.9-4.3 nm. In the case of CA50 / Ni and CA100 / Ni, the pore size was about the same as the size of several tens of nanometers. As shown in the electron microscope microstructure shown in FIG. 9D, in the case of CA500 / Ni, it is composed of macropores composed of very large pores, and the size of the carbon particles is also larger than 1 μm. Table 1 analyzes the pore characteristics according to the R ratio of the carbon nickel composite airgel.

CA50 / Ni CA100 / Ni CA200 / Ni CA500 / Ni BET (m ² / g) 513 508 361 352 Pore volume
(cc / g)
V meso 0.489 0.398 0.308 0.06 V micro 0.176 0.171 0.122 0.146 V macro 1.865 2.301 1.764 1.992 Pore size 284.7 291.6 283.6 41.34 Density (g / cc) 0.298 0.310 0.320 0.320

For BET specific surface area, CA50 / Ni was the largest with 513㎡ / g, followed by CA100 / Ni with 508㎡ / g, followed by CA200 / Ni with 361㎡ / g and CA500 / Ni with 352㎡ The value of / g is shown. In the pore volume (volume), the largest mesopore volume of CA50 / Ni was 0.49 cc / g, and CA100 / Ni was low at 0.40 cc / g, and gradually decreased. In the case of micropores, CA50 / Ni was 0.17cc / g, and CA100 / Ni was almost the same level. CA200 / Ni and CA500 / Ni showed slightly lower values of 0.12 ~ 0.15cc / g. In the case of macropores, CA50 / Ni and CA100 / Ni showed values of 1.9∼2.3cc / g, while CA200 / Ni and CA500 / Ni showed similar values of 1.8∼2.0g / cc. In the case of the density value, CA50 / Ni showed a tendency to increase gradually at 0.298 g / cm 3, and CA500 / Ni showed the highest value at 0.320 g / cm 3.

9a to 9d show a scanning electron microscope (Scanning Electron Microscope; SEM) photograph of the carbon nickel composite airgel (CA / Ni) prepared according to Example 2. In the case of CA50 / Ni, CA100 / Ni, and CA200 / Ni, it can be seen that the particles are composed of 10 nm size, and show a microstructure in which clusters of nanoparticles are connected to each other. However, in the case of CA500 / Ni it can be seen that the particle size is composed of large particles of 1㎛ or more. Therefore, it can be seen that CA500 / Ni consists of micropores or macropores.

10A to 10D show Transmission Electron Microscope (TEM) images of carbon nickel composite airgels (CA / Ni) prepared according to Example 2. FIG. Looking at the transmission electron micrograph of Figure 10 it can be observed in more detail the microstructure of the carbon nickel composite airgel. It can be seen that CA50 / Ni is composed of a network of particles having a size of 10 nm at several nanometers. As R ratio increases, the size of carbon particles and the size of nickel nanoparticles are gradually increased. In the case of CA100 / Ni and CA200 / Ni, it can be observed that the particle size is 10-20 nm. In the case of CA500 / Ni, sheets of micron size are connected to each other, and macropores exist between them. Seems to do. The size of the nickel nanoparticles increases as the R ratio increases, and it can be observed that CA50 / Ni and CA100 / Ni are 25-90 nm in size, and that CA / 200Ni and CA500 / Ni are 20-150 nm in size. Can be.

Table 2 shows the component content of the carbon nickel composite airgel according to the R ratio of the carbon nickel composite airgel.

EDX CA / Ni After cyclic voltammetry measurement Sample CA50 / Ni CA100 / Ni CA200 / Ni CA500 / Ni CA50Ni / CV CA100Ni / CV CA200Ni / CV CA500Ni /
CV C 94.52% 83.13% 85.6% 43.56% 82.11% 70.28% 76.32% 60.71% Ni 2.85% 7.46% 7.54% 33.77% 4.53% 9.29% 17.19% 35.91% O 2.63% 9.41% 6.86% 22.67% 8.93% 9.26% 6.31% 2.62% S 0 % 0 % 0 % 0 % 4.43% 11.17% 0.18% 0.76%

In the case of EDX of FE-SEM, the carbon content tends to decrease from CA50 / Ni to CA500 / Ni, and the nickel content increases. This is because as the R increases, the pores of the carbon nickel composite aerogel are larger, so that nickel is formed in the CA500 / Ni sample having larger pores when supported in the nickel solution. After electric property evaluation (CV), the carbon content tends to decrease from CA50Ni / CV to CA500Ni / CV, and the nickel content tends to increase. CANi / CV samples were subjected to electrical characterization on 2M H2SO ₄ electrolyte, which is believed to result in sulfur formation.

A charge / discharge curve at a 3.14 mA constant current with respect to the half cell of the supercapacitor electrode prepared according to Example 3 is shown in FIG. 11. In the charge-discharge cycling test of FIG. 11, 2M sulfuric acid (H ₂ SO ₄ ) is used as an electrolyte to circulate in a half-cell that is a three-electrode cell. It was made by cyclic voltametry (CV), and Ag / AgCl was used as the reference electrode for the supercapacitor electrode (carbon nickel composite airgel electrode), and the graphite sheet was used as the counter electrode. It is the value measured using. A current of 1 mA per unit area (cm 2) was applied to the reference electrode. During charging, a constant charge current of 3.14 mA was applied to the ELDC until a 1.0 V full-charge voltage was accumulated. During discharge, the ELDC was discharged at a positive discharge current of 3.14 mA through an electronic load.

The voltage change such as charge and discharge of the supercapacitor electrode (carbon nickel composite airgel electrode) was performed in two stages, and showed an inflection point at about 0.5V. While it is not clear, the surface of the carbon nickel composite aerogel (CA / Ni) surface occurs during the half-cell in charge and discharge, and the half-cell test is related to the nominal 1 V but the actual voltage of about 1.3 V. The charge capacity of the supercapacitor of the half-cell is shown. The CA50 / Ni has a value of 136.5 F / g, which is 1.4 times larger than the 9500 F / g of CA500 / Ni. It can be seen that. This can not be explained only by the difference in specific surface area, but the specific surface area of CA50 / Ni is about 513 m 2 / g, and in the case of CA500 / Ni, it is 1.5 times as large as 352 m 2 / g, which is related to storage capacity. In addition to the specific surface area, the pore volume seems to play a large role, which is 0.49 cm 3 / g for CA50 / Ni and 0.06 cm 3 / g for CA500 / Ni.

FIG. 12 is a graph illustrating cycle voltammetry characteristics of a supercapacitor electrode (carbon nickel composite airgel electrode) at a scan rate of 1 μs / s in a half cell. In FIG. 12, it can be seen that an oxide peak appears at 0.45 to 0.55 V and a reduction peak appears at 0.35 to 0.45 V. As the R ratio decreases, the area of the CV hysteresis curve increases, and the oxidation peak is 0.55 V. The reduction peak is lowered to 0.35V. The electrochemical characteristics of the half cell are summarized in Table 3.

CA50 / Ni CA100 / Ni CA200 / Ni CA500 / Ni Capacitance (F / g) 136.4 99.4 76.8 38.5 (F / cc) 58.2 38.2 30.3 19.0 Energy density (Wh / kg) 19.0 13.8 10.7 4.3 Power Density (W / kg) 142.2 162.0 165.3 89.4 ESR
10 kHz 0.1534 0.1565 0.1455 0.1582 1 kHz 0.2532 0.2640 0.2915 0.2947

In order to know the actual charge capacity of the supercapacitor, the constant current charge / discharge characteristics of the full cell were evaluated as shown in FIG. 13. The charge-discharge cycling test of FIG. 13 uses a 2M sulfuric acid (H ₂ SO ₄ ) as an electrolyte and a circulating voltage in a full cell that is a two-electrode cell. It was made using a cyclic voltametry (CV) and measured using a graphite sheet as a counter electrode. A current of 1 mA per unit area (cm 2) was applied to the reference electrode. During charging, a constant charge current of 3.14 mA was applied to the ELDC until a 1.0 V full-charge voltage was accumulated. During discharge, the ELDC was discharged at a positive discharge current of 3.14 mA through an electronic load.

In FIG. 14, the cyclic voltage current characteristics of the full cell were evaluated. FIG. 14 is a graph measuring cycle voltammetry characteristics of a carbon nickel composite airgel at a scan rate of 1 μs / s in a full cell.

The discharge capacity of the CA50 / Ni supercapacitor was 29F / g for the full cell, 25.1F / g for the CA100 / Ni, 15.0F / g for the CA200 / Ni, and 7.5F / for the CA500 / Ni. had a value of g. As shown in FIG. 13, unlike the half-cell, the charge and discharge curves show some curves, but are constantly charged and then discharged. The capacity of CA50 / Ni is 29F / g, which is about 3.9 times higher than 7.5F / g of CA500 / Ni, which is composed of mesopores about 7 times higher than CA500 / Ni. This is because the specific surface area is also high. The cyclic voltammetry shows that the redox peak is less likely to be seen in the half cell, and the smaller the R ratio of the carbon nickel composite airgel (CA / Ni), i.e., the greater the amount of catalyst, the larger the area of the curve. Can be. The electrochemical characteristics of the full cell are summarized in Table 4.

CA50 / Ni CA100 / Ni CA200 / Ni CA500 / Ni Capacitance
(F / g) 29.0 25.1 15.0 7.5 (F / cc) 11.5 10.0 6.4 3.9 Energy density (Wh / kg) 4.0 3.4 1.6 1.0 Power Density (W / kg) 79.0 78.2 46.8 47.6 ESR
10 kHz 0.0776 0.0857 0.1115 0.1272 1 kHz 0.1896 0.1826 0.2613 0.3684

As described above, it can be seen that the R ratio, that is, the amount of the magnesium acetate catalyst greatly affects the pore structure of the carbon nickel composite airgel, which is the final supercapacitor material. The smaller the R ratio, the smaller the size of the carbon particles, and the pores of the carbon nickel composite airgel formed through the network structure of the carbon particles are mesopores and the volume of the pores increases. In the case of the carbon nickel composite airgel, the larger the R ratio, the larger the size of the carbon particles. In particular, in the case of CA500 / Ni, the size of the particles increases in microns, so that the pores are either micropores or macropores. In the case of micropores, it decreased slightly as R ratio increased, but showed the same level of micropore volume. In case of macropores, CA50 / Ni is the largest at 2.301cm3 / g, and CA100 / Ni, CA200 / Ni and CA500 / Ni Showed nearly similar values. The electrochemical analysis showed that the smallest proportion of R, ie, the highest amount of catalyst, had a microstructure consisting of nanometer-sized carbon particles and mesopores, thereby having the largest specific surface area and mesopore volume. Able to know. Therefore, CA50 / Ni showed the highest charging capacity. In the case of full cell, CA50 / Ni had a value of 29F / g, and CA500 / Ni was 7.5F / g, and CA50 / Ni was about four times larger. You can see what you have.

As mentioned above, although preferred embodiment of this invention was described in detail, this invention is not limited to the said embodiment, A various deformation | transformation by a person of ordinary skill in the art within the scope of the technical idea of this invention is carried out. This is possible.

1 is a graph showing a Fourier transform infrared (IR) spectroscopy curve of an RF airgel prepared according to Example 1. FIG.

2 is a graph showing an infrared spectral curve obtained by Fourier transforming a carbon nickel composite airgel in which nickel was formed in pores of a carbon airgel after heat treatment at 100 ° C. in a carbon airgel prepared according to Example 1 in a nickel solution according to Example 2; to be.

3 is a graph showing a Fourier transform infrared spectral curve of a supercapacitor electrode prepared according to Example 3 after evaluation of electrical characteristics.

4A is a graph showing Raman spectral peaks scattered by a laser of 532 nm for a carbon aerogel prepared according to Example 1. FIG.

4B is a graph showing Raman spectral peaks scattered by a laser of 532 nm for a carbon nickel composite airgel prepared according to Example 2. FIG.

Figure 5 shows the X-ray diffraction (XRD) pattern according to the magnesium acetate catalyst ratio for the carbon nickel composite airgel prepared according to Example 2.

6 shows a supercapacitor electrode prepared according to Example 3, and shows an X-ray diffraction (XRD) pattern after 24 hours in 2M H ₂ SO ₄ electrolyte.

FIG. 7 shows the X-ray diffraction (XRD) pattern of the supercapacitor electrode manufactured according to Example 3 after evaluation of electrical characteristics.

Figure 8a is a graph showing the nitrogen adsorption and desorption results for the carbon airgel prepared according to Example 1.

Figure 8b is a graph showing the pore size distribution of the carbon nickel composite airgel prepared according to Example 2.

9a to 9d show scanning electron microscope (SEM) photographs of carbon nickel composite airgels prepared according to Example 2. FIG.

10A to 10D show transmission electron microscope (TEM) photographs of carbon nickel composite airgels prepared according to Example 2. FIG.

FIG. 11 is a graph showing charge and discharge curves at 3.14 mA constant current with respect to a half cell of a supercapacitor electrode manufactured according to Example 3. FIG.

FIG. 12 is a graph illustrating cycle voltammetry characteristics of a supercapacitor electrode (carbon nickel composite airgel electrode) at a scan rate of 1 μs / s in a half cell.

13 is a graph showing the constant current charge and discharge characteristics of a full cell.

14 is a graph illustrating the cyclic voltammogram characteristics of a full cell.

15 is a view schematically showing a CO ₂ supercritical drying apparatus.

<Explanation of symbols for the main parts of the drawings>

110: supercritical drying reactor 120: carbon dioxide feed tank

130: pump 140: sump

150: heat exchanger

Claims (9)

Stirring by adding magnesium acetate to a mixed solution of formaldehyde and resorcinol; Formaldehyde and resorcinol hydrolysis condensation reaction with the magnesium acetate at a temperature of 25 ~ 90 ℃ to form a chain, the chain and the chain is combined to form a cluster, the cluster and the cluster is combined to form a network Synthesizing the gelled composition; Solvent substitution of the gelled composition with acetone or methanol; Aging the solvent substituted composition to strengthen the network structure within the gel; Solvent-substituting the solvent contained in the aged composition with liquid carbon dioxide; Making carbon dioxide into a supercritical state to dry the solvent-substituted composition with carbon dioxide to form an RF airgel; Performing a carbonization process on the RF airgel to synthesize carbon airgel; And A method of manufacturing a carbon nickel composite airgel, comprising: synthesizing a carbon nickel composite airgel by supporting the carbon airgel in a nickel solution including a nickel precursor. The method of claim 1, wherein synthesizing the carbon nickel composite airgel comprises: Supporting the carbon airgel in a reaction vessel containing the nickel solution; Forming nickel in pores of the carbon airgel by first heat treating the carbon airgel supported on the nickel solution at a temperature of 60 to 120 ° C .; And  A method for producing a carbon nickel composite airgel comprising a second heat treatment in a reducing gas, an inert gas or a reducing gas and an inert gas atmosphere at a temperature in the range of 600 to 1000 ° C. The method of claim 2, wherein the nickel precursor is nickel acetate tetrahydrate, the nickel solution is a solution containing the nickel precursor, isopropyl alcohol and dimethylamine, the nickel precursor contains 0.1 to 1 molar concentration in the nickel solution And the dimethylamine is contained in the nickel solution in an amount of 0.1 to 4 moles, and the isopropyl alcohol is contained in the nickel solution in an amount of 8 to 20 moles. The method of claim 1, wherein the mixed solution of formaldehyde and resorcinol is a solution of mixing the formaldehyde and the resorcinol in distilled water to a concentration of 1 to 10 M, wherein the formaldehyde and the resorcinol The molar ratio of the content of resorcinol and the content of magnesium acetate in the mixed solution of Method for producing a carbon nickel composite airgel, characterized in that added to 50 to 500. The carbon nickel composite airgel of claim 1, wherein the mixed solution of formaldehyde and resorcinol is a mixture of the formaldehyde and the resorcinol in a ratio of 1: 1 to 4: 1 in a molar ratio. Manufacturing method. The method of claim 1, wherein the aging is A method for producing a carbon nickel composite airgel, characterized in that the gelled composition is supported in acetone and sealed in a container sealed at a temperature in the range of 25 to 90 ° C. The method of claim 1, wherein the drying, A method for producing a carbon nickel composite airgel, characterized in that the carbon dioxide is maintained at a temperature equal to or higher than 31 ° C. and a pressure of 73 bar at a supercritical state for a predetermined time and dried. The method of claim 1, The carbonization process is a method for producing a carbon nickel composite airgel, characterized in that the reducing gas, inert gas or reducing gas and inert gas atmosphere in the temperature range of 600 ~ 1000 ℃. Pulverizing the carbon nickel composite airgel prepared by the method of claim 1 into a powder; 90 to 98% by weight of a carbon nickel composite airgel pulverized into powder, 1 to 5% by weight of a conductive binder, and 1 to 5% by weight of acetylene black in a solvent to form a paste; And The method of manufacturing a supercapacitor electrode comprising the step of forming an electrode by applying the paste to a titanium, nickel, aluminum foil, plate or mesh 50 ~ 200㎛ thickness.

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