KR102350937B1 - Electrode having porous carbon including inorganic nanoparticles, supercapacitor comprising the electrode, and method of manufacturing the same - Google Patents

Abstract

The present invention relates to a porous carbon electrode containing inorganic nanoparticles, a supercapacitor including the electrode, and a method for manufacturing the same, wherein the porous carbon electrode containing inorganic nanoparticles includes a) mixing a carbon precursor and a nitrogen-containing compound preparing a solution; b) phase separation by adding a non-solvent to the prepared mixed solution; c) drying and carbonizing the phase-separated mixed solution to obtain a nitrogen-doped porous carbon body; and d) forming inorganic nanoparticles on the nitrogen-doped porous carbon body; It may be prepared from, and the inorganic nanoparticles may be metal nanoparticles or metal hydroxide nanoparticles.

Description

Electrode having porous carbon including inorganic nanoparticles, supercapacitor comprising the electrode, and method of manufacturing the same

The present invention relates to a porous carbon electrode containing inorganic nanoparticles, a supercapacitor including the electrode, and a method for manufacturing the same.

Hybrid vehicles and electric devices that require high output are gradually adopting supercapacitors as an efficient energy storage system. Supercapacitors can provide not only high capacity but also high power density and long lifetime.

The performance of a supercapacitor is determined by the electrode and electrolyte, and in particular, the main performance such as capacitance is mostly determined by the electrode material. As such an electrode material, porous carbon is mainly used. Since porous carbon has high electrical conductivity and a large surface area, it is widely used as an electrode material for supercapacitors that exhibits capacity through physical adsorption and desorption of ions.

However, porous carbon-based supercapacitors have relatively limited energy density due to the special storage mechanism in which charge/discharge is performed on the surface of the electric double layer, and thus replace conventional batteries such as Li-ion batteries, NiMH batteries and NiZn batteries. can't do it

Recently, a supercapacitor using nickel hydroxide (Ni(OH) _{2 ) capable of realizing high energy density has been studied.} The stacked nanostructured nickel hydroxide has a wide interlayer spacing between the lattices, so there are many advantages in which ions can be stored. However, since nickel hydroxide has low conductivity, there is a disadvantage in that charge traps frequently occur under conditions such as high current density.

Accordingly, the development of electrode materials exhibiting high energy density and electrochemical performance is required.

KR 10-1537953 B1 (2015.07.14)

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrode for a supercapacitor and a method for manufacturing the same having excellent stability with high energy density and high power density.

the present invention

a) preparing a mixed solution by mixing a carbon precursor and a nitrogen-containing compound;

b) phase separation by adding a non-solvent to the prepared mixed solution;

c) drying and carbonizing the phase-separated mixed solution to obtain a nitrogen-doped porous carbon body; and

d) forming inorganic nanoparticles on the nitrogen-doped porous carbon body;

It provides a method for manufacturing a porous carbon electrode containing inorganic nanoparticles, wherein the inorganic nanoparticles are metal nanoparticles or metal hydroxide nanoparticles.

In one embodiment according to the present invention, in step d), the inorganic nanoparticles may be formed on a nitrogen-doped porous carbon body using electrochemical deposition.

In one embodiment according to the present invention, the carbon precursor may be a nitrogen-containing polymer.

In one embodiment according to the present invention, the nitrogen-containing polymer may be polyamic acid.

In one embodiment according to the present invention, the nitrogen-containing compound may be a hydrocarbon-based compound having an atomic ratio of carbon:nitrogen of 1:1 to 1:5.

In one embodiment according to the present invention, the mixed solution phase-separated in step b) may have a porous polymer structure in which a polymer-rich phase forms a continuous phase.

In one embodiment according to the present invention, the inorganic nanoparticles are nickel (Ni), cobalt (Co), iron (Fe), nickel hydroxide (Ni(OH) ₂ ), cobalt hydroxide (Co(OH) ₂ ) and It may be one or a combination of two or more selected from the group consisting of iron hydroxide (Fe(OH) _{3 ).}

The present invention also relates to a nitrogen-doped porous carbon body; and

Including inorganic nanoparticles applied to the porous carbon body,

The inorganic nanoparticles provide a porous carbon electrode containing inorganic nanoparticles that are metal nanoparticles or metal hydroxide nanoparticles.

In one embodiment according to the present invention, the porous carbon body may have an average pore size of 2 to 10㎛.

In one embodiment according to the present invention, the inorganic nanoparticles-containing porous carbon body electrode may contain 1 to 25 parts by weight of inorganic nanoparticles based on 100 parts by weight of the porous carbon body.

The present invention also provides a supercapacitor including an inorganic nanoparticle-containing porous carbon body electrode according to an embodiment of the present invention.

The porous carbon electrode containing inorganic nanoparticles according to the method of the present invention has the advantage of exhibiting excellent electrochemical properties and oxidation/reduction reversibility as well as high capacity.

Even if the effects are not explicitly mentioned in the present invention, the effects described in the specification expected by the technical features of the present invention and the inherent effects thereof are treated as if they were described in the specification of the present invention.

1 is a view showing a manufacturing process of an inorganic nano-particle-containing porous carbon electrode according to the present invention.
2 is a view showing a scanning electron microscope image of the surface of the inorganic nano-particle-containing porous carbon body electrode according to the present invention.
3 is a view showing a scanning electron microscope image of a porous carbon body electrode containing inorganic nanoparticles according to an embodiment of the present invention.
4 is a view showing an X-ray photoelectron spectroscopy (XPS) analysis result of an inorganic nanoparticle-containing porous carbon electrode according to an embodiment of the present invention.
5 to 10 are diagrams showing cyclic voltammetry (CV) curves according to the scan speed of the inorganic nanoparticle-containing porous carbon electrode according to an embodiment of the present invention.
11 to 16 are diagrams showing cyclic voltammetry curves according to the scan speed of a supercapacitor including an inorganic nanoparticle-containing porous carbon electrode according to an embodiment of the present invention.

Unless otherwise defined in technical terms and scientific terms used in this specification, those of ordinary skill in the art to which this invention belongs have the meanings commonly understood, and in the following description and accompanying drawings, the subject matter of the present invention Descriptions of known functions and configurations that may unnecessarily obscure will be omitted.

Also, the singular form used herein may be intended to include the plural form as well, unless the context specifically dictates otherwise.

In addition, in the present specification, the unit used without special mention is based on the weight, for example, the unit of % or ratio means weight % or weight ratio, and the weight % means any one component of the entire composition unless otherwise defined. It means the weight % occupied in the composition.

In addition, the numerical range used herein includes the lower limit and upper limit and all values within the range, increments logically derived from the form and width of the defined range, all values defined therein, and the upper limit of the numerical range defined in different forms. and all possible combinations of lower limits. Unless otherwise defined in the specification of the present invention, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.

As used herein, the term 'comprising' is an open-ended description having an equivalent meaning to expressions such as 'comprising', 'containing', 'having' or 'characterized', and elements not listed in addition; Materials or processes are not excluded.

In addition, as used herein, the term 'substantially' means that other elements, materials, or processes not listed together with the specified element, material or process are unacceptable for at least one basic and novel technical idea of the invention. It means that it can be present in an amount or degree that does not significantly affect it.

The present invention comprises the steps of: a) preparing a mixed solution by mixing a carbon precursor and a nitrogen-containing compound; b) phase separation by adding a non-solvent to the prepared mixed solution; c) drying and carbonizing the phase-separated mixed solution to obtain a nitrogen-doped porous carbon body; and d) forming inorganic nanoparticles on the nitrogen-doped porous carbon body, wherein the inorganic nanoparticles are metal nanoparticles or metal hydroxide nanoparticles. provides

The inorganic nanoparticle-containing porous carbon body electrode according to the present invention is a porous carbon body based on a macro-pore structure formed through non-solvent induced phase separation, which is doped with nitrogen and formed with inorganic nanoparticles, and has high conductivity and high conductivity. It can exhibit excellent oxidation/reduction reaction reversibility as well as porosity and specific surface area, thereby exhibiting excellent electrochemical properties and high capacity.

The macro-pore structure may be an asymmetric macro-pore structure.

Referring to FIG. 1 , the method for manufacturing the inorganic nanoparticle-containing porous carbon body electrode is largely comprised of steps (1) preparing a nitrogen-doped porous carbon body and step (2) to the nitrogen-doped porous carbon body. It can be divided into a step of manufacturing a porous carbon electrode containing inorganic nanoparticles by depositing inorganic nanoparticles.

Specifically, step a) of step (1) is a step of preparing a mixed solution containing a carbon precursor and a nitrogen-containing compound by mixing a carbon precursor and a nitrogen-containing compound, wherein the carbon precursor and nitrogen The containing compound may be mixed in a molar ratio of 1:0.25 to 1:2, preferably 1:0.5 to 1:2. Specifically, in the mixed solution, the carbon precursor may be present in a concentration of 5 to 20 wt%, preferably 8 to 18 wt%, and the nitrogen-containing compound is 1 to 20 wt%, preferably 1 to 15 wt% may be present at a concentration of In the above range, the carbon precursor and the nitrogen-containing compound can be mixed sufficiently well, and furthermore, the porous carbon body can be uniformly doped with a sufficient amount of nitrogen atoms.

In addition, the mixed solution may use an organic solvent as a solvent, and any solvent capable of uniformly dissolving the carbon precursor and the nitrogen-containing compound may be used without limitation. Specific examples, dioxane, m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), tetrahydrofuran ( THF) and at least one of ethyl acetate may be selected, but the present invention is not limited thereto.

In one embodiment according to the present invention, the carbon precursor may be a nitrogen-containing polymer, specifically, any one or a combination of two selected from a nitrogen-containing aromatic polymer and a nitrogen-containing alicyclic polymer. Preferably, the nitrogen-containing polymer may be one selected from polyamic acid, polypyrrole and polyaniline. The molecular weight of the nitrogen-containing polymer may be 5,000 to 1,000,000 g/mol as a weight average molecular weight, but this is only an example and is not limited thereto.

In one embodiment of the present invention, the nitrogen-containing compound is preferably a compound containing a plurality of nitrogen atoms in one molecule. The nitrogen-containing compound may be a hydrocarbon-based compound having an atomic ratio of carbon and nitrogen of 1:1 to 1:5, and specifically, melamine, urea, thiourea, cysteine (L- Cystein), cyanuric acid (Cyanuric acid), dicyandiamide (Dicyandiamide), and may be at least one selected from the group consisting of cyanamide (Cyanamide).

Step a) of step (1) may further include applying the mixed solution on a substrate after preparing the mixed solution. The substrate is not limited as long as it is a substrate that does not dissolve in a solvent included in the mixed solution, and a known substrate may be used. In the step of applying on the substrate, a known application means may be used without limitation, and for example, a method of forming a film with a doctor blade after casting a mixed solution on the substrate or a method of spin coating, but is not limited thereto.

In a non-limiting example, through the spin coating process, the mixed solution including the carbon precursor and the nitrogen-containing compound may be uniformly applied to a thickness of 10 to 50 μm, through which the nitrogen-doped porous carbon Steps b) and c) for preparing the sieve can be performed more efficiently. The spin coating may be performed at a rotation speed of 500 to 2000 rpm, but is not limited thereto.

Next, in step b), a nonsolvent is added to the spin-coated mixed solution to induce phase separation into a polymer-rich phase and a polymer-poor phase. The phase-separated mixed solution may have a porous polymer structure in which the polymer-rich phase forms a continuous phase, and specifically, a polymer layer with small pores or an active layer is formed on the surface, and a finger shape ( It may have a porous structure including finger-like macropores, that is, an asymmetric structure including a supported layer. The porosity of the porous polymer structure may be adjusted according to the amount of the non-solvent. Specifically, the volume ratio of the non-solvent and the solvent in step a) may be 30:1 to 300:1, and in the above range, phase separation of the mixed solution may occur more easily, and the polymer may form a continuous phase It is possible to obtain a polymer structure having high porosity and porosity.

In the last step c), the phase-separated mixed solution is dried and carbonized to obtain a nitrogen-doped porous carbon body. The drying may be performed for 12 to 48 hours at a temperature range of 20 to 120° C., and the solvent and non-solvent included in the phase-separated mixed solution may be removed through drying. Of course, the limited temperature and time are not limited thereto as only an example for removing the solvent and the non-solvent.

After the drying is completed, a curing process may be additionally performed. Specifically, the curing process can be carried out in three stages, specifically, in the first stage at 140 to 170 ° C for 2 to 4 hours, in the second stage at 170 to 220 ° C for 0.5 to 2 hours, in the third stage 220 to 280 It can be carried out through heat treatment at ℃ for 0.5 to 2 hours.

After the drying and curing are completed, a porous polymer structure is obtained, and then carbonization may be performed. The carbonization may be a heat treatment at 200 to 1000 ℃, preferably at 250 to 900 ℃ for 5 to 12 hours. Specifically, the carbonization process is carried out by charging the porous polymer structure into a carbonization furnace, gradually increasing the temperature in an inert gas nitrogen or argon atmosphere, and maintaining the temperature at 200 to 1000 for 5 to 12 hours. may be, but this is only an example and is not limited thereto.

After carbonization is completed, it can be naturally cooled to room temperature, and through this, a nitrogen-doped porous carbon body having a high specific surface area and porosity can be obtained. At this time, the atomic ratio of carbon and nitrogen is 10:1 to 25:1, preferably may be 13:1 to 20:1. Specifically, by the asymmetric porous polymer structure, a relatively high concentration of nitrogen is doped on the surface, and a relatively low concentration of nitrogen is doped on the inside by macropores, so that the nitrogen content increases from the inside of the carbon body toward the surface. A concentration gradient can be shown.

In the nitrogen-doped porous carbon body prepared in step (1), inorganic nanoparticles may be subsequently applied to the nitrogen-doped porous carbon body through step (2), and the inorganic nanoparticles are coated with nitrogen doping The porous carbon body can be preferably used for the purpose of the electrode. Specifically, an electrochemical vapor deposition method may be used to apply the inorganic nanoparticles to the nitrogen-doped porous carbon body in step (2), and the inorganic nanoparticles are applied to the nitrogen-doped porous carbon body through electrochemical deposition. may be forming. More specifically, inorganic nanoparticles may be uniformly deposited through electrochemical deposition on the surface and pores of the nitrogen-doped porous carbon body.

The electrochemical deposition is a process of depositing inorganic nanoparticles on a nitrogen-doped porous carbon body by applying electric energy from the outside, and may be performed using a three-electrode system. The three-electrode system may be a system including a working electrode, a counter electrode, a reference electrode, and an electrolyte. The working electrode uses the nitrogen-doped porous carbon body prepared in step 1), the counter electrode uses a platinum electrode, the reference electrode uses an Ag/AgCl electrode or an SCE electrode, and the electrolyte is deposited A solution containing the desired metal precursor compound may be used. Specifically, the metal precursor compound may be a precursor compound including one or more metals selected from the group consisting of nickel (Ni), cobalt (Co) and iron (Fe), and the concentration of the metal precursor compound in the electrolyte may be 0.1M to 0.5M. Specifically, as shown in FIG. 2 , it can be confirmed that inorganic nanoparticles are deposited at a high density on the surface of the porous carbon body by the electrochemical deposition. More specifically, the inorganic nanoparticles include nickel (Ni), cobalt (Co), iron (Fe), nickel hydroxide (Ni(OH) ₂ ), cobalt hydroxide (Co(OH) ₂ ) and iron hydroxide (Fe(OH) ₃ ) may be one or a combination of two or more selected from the group consisting of.

The average particle size of the inorganic nanoparticles produced by reducing the metal precursor may have an average particle size of 0.5 to 20 nm, preferably 1 to 10 nm, and uniformly deposited not only on the surface of the nitrogen-doped porous carbon body, but also inside the pores it is preferable to have Specifically, due to the above-described asymmetric porous structure, a concentration gradient in which the content of the inorganic nanoparticles increases from the inside to the surface of the nitrogen-doped porous carbon body may be exhibited. In addition, the nitrogen-doped porous carbon body may have an average pore size of 1 to 100 μm, specifically 2 to 10 μm in the pore size distribution, and a specific surface area of 200 to 600 m ² /g, preferably 250 to 500 m ² /g. In the above range, the ratio of the inactive region of the porous carbon electrode containing inorganic nanoparticles can be reduced, and excellent mechanical stability can be exhibited.

The electrochemical deposition may be performed by applying a voltage of -500 to -1500 mV. In the above range, not only nano-sized inorganic nanoparticles can be more uniformly deposited on the nitrogen-doped porous carbon body, but also more inorganic nanoparticles can be formed on the nitrogen-doped porous carbon body, so that oxidation/reduction Reversibility can be improved.

The present invention also relates to a nitrogen-doped porous carbon body; and inorganic nanoparticles applied to the porous carbon body, wherein the inorganic nanoparticles are metal nanoparticles or metal hydroxide nanoparticles. Specifically, the porous carbon electrode may have an asymmetric macropore structure, and specifically, a dense layer may be formed on the surface, and a macroporous structure may be formed under the porous carbon electrode. Due to the asymmetric structure, a concentration gradient in which the content of nitrogen and inorganic nanoparticles increases from the inside of the carbon electrode toward the surface may be exhibited.

The inorganic nanoparticle-containing porous carbon body electrode can provide more reaction space due to the high specific surface area and high porosity of the porous carbon body, and shorten the ion transport path to improve the accessibility of the electrolyte. At the same time, the inorganic nanoparticle-containing porous carbon electrode may exhibit excellent oxidation/reduction reversibility and, further, high capacity by containing inorganic nanoparticles by electrochemical deposition. Specifically, through cyclic voltammetry analysis of the inorganic nanoparticle-containing porous carbon electrode, remarkably improved electrochemical properties and oxidation/reduction reversibility can be confirmed.

The porous carbon body may have an average pore size of 2 to 10 μm, and a specific surface area of ^{250 to 500 m 2 /g.} In addition, the inorganic nanoparticles-containing porous carbon body electrode may contain 1 to 25 parts by weight of inorganic nanoparticles, preferably 2 to 20 parts by weight, based on 100 parts by weight of the porous carbon body. In the above range, it is possible to provide more reaction space and at the same time maintain high electrical conductivity.

The present invention also provides a supercapacitor comprising an inorganic nanoparticle-containing porous carbon body electrode.

A supercapacitor according to an embodiment of the present invention uses an inorganic nanoparticle-containing porous carbon electrode as a positive electrode and a negative electrode, and a separator is disposed between the positive electrode and the negative electrode to prevent a short circuit between the positive electrode and the negative electrode, The positive electrode, the separator, and the negative electrode may be impregnated in the electrolyte, and may further include a current collector on the outside of the positive electrode and the negative electrode.

The electrolyte is a salt having the same structure as ^{A +} B ^{- , A +} is Li ⁺ , Na ⁺ , K ⁺ and the like, and contains one or more ions selected from alkali metal cations and hydrogen ions, B ^- is PF ₆ ^- , BF ₄ ^- , Cl ^- , Br ^- , I ^- , ClO ₄ ^- , AsF ₆ ^- , CH ₃ CO ₂ ^- , CF ₃ SO ₃ ^- , N(CF ₃ SO ₂ ) ₂ ^- , C(CF ₂ SO ₂ ) ₃ - , SO ₃ ^{2 - It} may include one or more ions selected from anions such as 2-. Preferably, it may be selected from _{an acid-based electrolyte containing H 2} SO ₄ , an alkali-based electrolyte containing KOH, and _{a neutral electrolyte containing Na 2} SO ₄ , but is not limited thereto.

The injection of the electrolyte may be performed at an appropriate stage during the battery manufacturing process according to the manufacturing process and required physical properties of the final product, and the electrolyte may be impregnated with the positive electrode and the negative electrode in a glove box in an argon gas atmosphere.

The current collector is not limited as long as it is chemically and electrochemically resistant to corrosion, and as a non-limiting example, stainless steel, aluminum, titanium or tantalum may be used. Considering the characteristics and price of the supercapacitor, stainless steel or aluminum is particularly preferable as the current collector.

The separator according to an embodiment of the present invention is not limited as long as it has a conventionally known material and configuration. Non-limiting examples thereof include a polyethylene porous membrane, polypropylene fibers or glass fibers, and nonwoven fabrics of cellulose fibers.

Hereinafter, the present invention will be described in detail with reference to Examples, but these are for describing the present invention in more detail, and the scope of the present invention is not limited by the Examples below.

Electrode Fabrication :

Pyromellitic Dianhydride (PMDA) and 4,4′-oxydianiline (ODA) were mixed in an N-methyl-2-pyrrolidone (NMP) solvent in a molar ratio of 1:1 to synthesize polyamic acid, a carbon precursor. At this time, the content of the polyamic acid in the solution was 12% by weight. Melamine as a nitrogen-containing compound was added to the polyamic acid solution to prepare a mixed solution, and at this time, the total number of moles of PMDA/ODA constituting the polyamic acid and the mole ratio of melamine were adjusted to be 1:2. After reacting the mixed solution in a nitrogen atmosphere for 24 hours, the mixed solution was spin-coated on a glass plate, and then phase-separated by supporting it in an acetone solution. The phase-separated mixed solution was sequentially heat treated at 160 °C for 3 hours, 200 °C for 1 hour, and 250 °C for 1 hour to prepare a nitrogen-doped porous polymer. Thereafter, the polymer was heated to 290 °C under argon atmosphere, heated to 450 °C under general atmosphere, and then heated again to 900 °C under argon atmosphere, maintained at the temperature for 30 minutes, and heat treated to form a nitrogen-doped porous carbon body was prepared.

Next, a working electrode is used as the nitrogen-doped porous carbon body, a counter electrode is used as a platinum electrode, an Ag/AgCl electrode is used as a reference electrode, and a Ni precursor Ni(SO ₃ NH ₂ ) ₂ concentration is used as an electrolyte. A Ni-containing porous carbon electrode was prepared through an electrochemical deposition process of 300 mC at a voltage of -900 to -1000 mV using a 0.2M solution in water.

The prepared Ni-containing porous carbon electrode was imaged through a scanning electron microscope and EDS (Energy Dispersive Spectrometry) analysis was performed, and the results are shown in FIG. 3 .

As can be seen in FIG. 3 , it was confirmed that pores of μm unit were formed in the Ni-containing porous carbon electrode, and it was confirmed that the Ni particles were deposited in 3.13 wt%.

A Ni-containing porous carbon electrode was prepared in the same manner as in Example 1, except that thiourea was used instead of melamine as the nitrogen compound.

A Co-containing porous carbon electrode was prepared in the same manner as _{in Example 1, except that CoCl 2} as a Co precursor was used instead of the Ni precursor.

A Co-containing porous carbon electrode was prepared in the same manner as in Example 3, except that thiourea was used instead of melamine as the nitrogen compound.

In Example 1, instead of the Ni precursor, Ni and Co precursors, NiSO ₄ and CoCl _{2 ,} were used as an electrolyte in a 50:50 molar ratio, and the electrochemical deposition was performed at 80 mC instead of 300 mC. Ni(OH) ₂ and Co(OH) ₂ containing porous carbon electrode was prepared.

XPS analysis was performed on the prepared Ni(OH) ₂ and Co(OH) ₂ containing porous carbon electrode, and the results are shown in FIG. 4 .

As can be seen in FIG. 4 , it can _{be confirmed that the hydroxides Ni(OH) 2} and Co(OH) ₂ of Ni and Co are deposited through electrodeposition.

A porous carbon electrode containing _{Ni(OH) 2} and Co(OH) ₂ was prepared in the same manner as in Example 5, except that thiourea was used instead of melamine as the nitrogen compound.

(Examples 7 to 10)

In Example 1 instead of the Ni precursor, Fe precursor (FeSO ₄ ) (Example 7), Ni precursor mixture of Ni and Fe precursor mixture in a 50:50 weight ratio instead of Ni precursor (Example 8), Ni precursor 50:50 instead of mixed An electrode was prepared in the same manner except for using a precursor mixture of Co and Fe (Example 9) and a precursor mixture of Ni:Co:Fe mixed in a weight ratio of 30:35:35 (Example 10) instead of Ni (Example 10). Table 1 below shows the results of EDS analysis for the used electrodes.

EDS weight% Example 1 Ni 3.13% Example 3 Co 1.92% Example 5 Ni 9.16% Co 1.74% Example 7 Fe 10.80% Example 8 Ni 0.97% Fe 0.40% Example 9 Co 1.62% Fe 2.13% Example 10 Ni 3.97% Co 1.08% Fe 0.22%

Test Example 1: Electrode analysis

The electrodes prepared according to Examples 1 to 6 were dispersed in a solvent in which distilled water: isopropanol: Nafion was mixed in a ratio of 1: 3: 0.1 at a concentration of 5 g/L, and then GCE (glassy carbon electrode, d = 5 mm, S = 0.20 cm ² ) After dropping 0.02 mg on the electrode, it was dried and used as a working electrode. Pt wire as the counter electrode and Hg/HgO electrode as the reference electrode were used. Within the 6M KOH electrolyte and 0~0.5V voltage range, the scan speed was increased to 10mV and 20~200mV at 20mV intervals, and the cyclic voltage current according to the scan speed The analysis was performed, and the results are shown in FIGS. 5 to 10, and the specific results are shown in Table 2 below. Specifically, FIG. 5 is a view showing the results for Example 1, FIG. 6 is Example 2, FIG. 7 is Example 3, FIG. 8 is Example 4, FIG. 9 is Example 5 and FIG. 10 is Example 6 to be.

Capacity to weight (F/g) Example 1 38.0 Example 2 17.4 Example 3 27.3 Example 4 17.3 Example 5 72.0 Example 6 115.5

As can be seen in Table 2, it can be seen that the Ni and Co-containing porous carbon electrode prepared in Examples 5 and 6 showed the highest capacity.

Test Example 2: Supercapacitor Analysis:

The electrodes prepared according to Examples 1 to 6 were dispersed in a solvent in which distilled water: isopropanol: Nafion was mixed in a ratio of 1: 3: 0.1 at a concentration of 5 g/L, and then 0.1 mg was dropped on a stainless steel plate and dried to have a diameter of 0.8 A circular shape of cm size was used as an anode, and a porous carbon body was combined with a stainless steel plate of the same size and used as a cathode. . Next, the cyclic voltammetry analysis was performed according to the scan speed while increasing the scan speed to 10 mV and 20 to 200 mV within the voltage range of 0 to 1.2 V at intervals of 20 mV, and the results are shown in FIGS. 11 to 16 , and specific results The values are shown in Table 3 below. Specifically, FIG. 11 is a view showing the results for Example 1, FIG. 12 is Example 2, FIG. 13 is Example 3, FIG. 14 is Example 4, FIG. 15 is Example 5 and FIG. 16 is Example 6 to be.

Capacity to weight (F/g) Example 1 87.5 Example 2 127.0 Example 3 65.2 Example 4 101.0 Example 5 104.9 Example 6 111.1

As can be seen in Table 3, it can be seen that the supercapacitor using the Ni-containing porous carbon electrode prepared in Example 2 showed the highest capacity.

Claims (11)

a) preparing a mixed solution by mixing a carbon precursor and a nitrogen-containing compound;
b) phase separation by adding a non-solvent to the prepared mixed solution;
c) drying and carbonizing the phase-separated mixed solution to obtain a nitrogen-doped porous carbon body; and
d) forming inorganic nanoparticles on the nitrogen-doped porous carbon body;
includes,
The inorganic nanoparticles are metal nanoparticles or metal hydroxide nanoparticles,
The inorganic nanoparticles are deposited on the surface and inside the pores of the nitrogen-doped porous carbon body,
A method of manufacturing an inorganic nanoparticle-containing porous carbon body electrode having a concentration gradient in which the content of the inorganic nanoparticles increases from the inside of the nitrogen-doped porous carbon body toward the surface. According to claim 1,
In step d), the inorganic nanoparticles are formed on a nitrogen-doped porous carbon body using electrochemical deposition. According to claim 1,
The method for producing a porous carbon electrode containing inorganic nanoparticles, wherein the carbon precursor is a nitrogen-containing polymer. 4. The method of claim 3,
The nitrogen-containing polymer is a method for producing an inorganic nano-particle-containing porous carbon body electrode of polyamic acid. According to claim 1,
The method for producing a porous carbon electrode containing inorganic nanoparticles, wherein the nitrogen-containing compound is a hydrocarbon-based compound having an atomic ratio of carbon:nitrogen of 1:1 to 1:5. According to claim 1,
The method for producing a porous carbon electrode containing inorganic nanoparticles in which the phase-separated mixed solution in step b) has a porous polymer structure in which a polymer-rich phase forms a continuous phase. According to claim 1,
The inorganic nanoparticles include nickel (Ni), cobalt (Co), iron (Fe), nickel hydroxide (Ni(OH) ₂ ), cobalt hydroxide (Co(OH) ₂ ) and iron hydroxide (Fe(OH) ₃ ). A method for producing a porous carbon electrode containing inorganic nanoparticles, which is one or a combination of two or more selected from the group. Nitrogen-doped porous carbon body; and
Including inorganic nanoparticles applied to the porous carbon body,
The inorganic nanoparticles are metal nanoparticles or metal hydroxide nanoparticles,
The inorganic nanoparticles are deposited on the surface and inside the pores of the nitrogen-doped porous carbon body,
An inorganic nanoparticle-containing porous carbon body electrode having a concentration gradient in which the content of the inorganic nanoparticles increases from the inside of the nitrogen-doped porous carbon body toward the surface. 9. The method of claim 8,
The porous carbon body is a porous carbon body electrode containing inorganic nanoparticles having an average pore size of 2 to 10㎛. 9. The method of claim 8,
The inorganic nanoparticle-containing porous carbon body electrode is an inorganic nanoparticle-containing porous carbon body electrode comprising 1 to 25 parts by weight of inorganic nanoparticles based on 100 parts by weight of the porous carbon body. A supercapacitor comprising an inorganic nanoparticle-containing porous carbon body electrode according to any one of claims 8 to 10.

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