WO2017086609A1 - Porous carbon structure using intrinsically microporous polymer, and battery electrode including same - Google Patents

Abstract

The present invention relates to a porous carbon structure which uses an intrinsically microporous polymer, a method for manufacturing same, and to a battery electrode using same. More particularly, the present invention relates to a method for manufacturing a porous carbon structure, the method comprising: a homogeneous solution preparation step for dissolving an intrinsically microporous polymer in a good solvent; a precursor preparation step for using the homogeneous solution to prepare a precursor; a porous structure formation step for using the precursor to form a porous structure through non-solvent induced phase separation; and a carbonization step for carbonizing the porous structure. The present invention also relates to a porous carbon structure, manufactured through such methods, having a cross section with an asymmetrical porous structure, and a battery electrode using same.

Description

Porous carbon structure using intrinsic microporous polymer and battery electrode including same

The present invention relates to a porous carbon structure using an intrinsic microporosity polymer, a manufacturing method thereof, and a battery electrode using the same.

More specifically, the step of preparing a homogeneous polymer solution dissolving the intrinsic microporous polymer in a good solvent; A porous structure forming step of forming a porous structure from the polymer homogeneous solution through non-solvent induced phase separation (NIPS); And a carbonization step of carbonizing the porous structure, while having an asymmetric macro-pore structure and an intrinsic microporous polymer carbonized in the cross section prepared through the method. The present invention relates to a porous carbon structure including a formed meso-pore structure and an intrinsic micro-pore structure, and a battery electrode including the same.

This application claims priority based on Korean Patent Application No. 10-2015-0162284 filed on November 19, 2015, and all the contents disclosed in the specification and drawings of the application are incorporated in this application.

In general, the porous carbon material has a high surface area and structural characteristics, and thus is widely used in energy fields such as fuel cells, batteries, and supercapacitors such as catalyst carriers, electrode materials, and electric double layer materials. In the related art, Korean Patent No. 10-0927718 describes a technique for a porous carbon structure that can be used as an electrode catalyst for a fuel cell, and Korean Patent No. 10-1092327 describes a porous structure used as a thermoelectric material. A technique for carbon nanotube film is disclosed.

Polymers of intrinsic microporosity (PIMs) are polymers that have chemically microporous properties in their molecules and are widely used in sensors, gas separation membranes, and the like, and are used in porous carbon structures and methods for manufacturing the same. It is described in Korean Patent Registration No. 10-1485867 and Korean Patent Publication No. 2015-0034972. However, when the porous carbon material is used as an electrochemical catalyst and an electrode material, the carbon of macropores should be produced in the form of a carbon material having a two-dimensional structure or a carbon structure having a three-dimensional structure using a binder. Structural structures are facing limitations in various fields such as limited use, film forming contact area, dispersion, and electrical resistance. In particular, the polymer binder generally used in the slurry process, which is a conventional electrode manufacturing method, must be improved as one factor that hinders the performance of the electrode.

An object of the present invention is to provide a three-dimensional carbon structure having a further improved porosity, a method of manufacturing the same and a battery electrode using the same.

More specifically, by using an intrinsic microporosity polymer to form a porous structure having an asymmetric macro-pore structure in the cross-section and carbonization of the meso pores formed by carbonization of the intrinsic microporous polymer It is to provide a three-dimensional carbon structure having a more improved porosity, characterized in that it comprises a -pore) structure and an intrinsic micro-pore structure and a carbon electrode for a battery manufactured using the same.

In addition, the present invention is to improve the performance of the electrode by producing a porous carbon electrode without a polymer binder generally used in the slurry process which is a conventional electrode manufacturing method.

In the present invention, in order to solve the above problems, the step of preparing a homogeneous polymer solution dissolving the intrinsic microporous polymer in a good solvent; A porous structure forming step of forming a porous structure through non-solvent induced phase separation from the polymer homogeneous solution; And a carbonization step of carbonizing the porous structure.

In the method of manufacturing a porous carbon structure according to the present invention, the intrinsic microporous polymer may be a polymer having a chemical structure of the formula (1).

<Formula 1>

(In Formula 1, X is selected from the group consisting of X1, X2, X3 and X4, and Y is selected from the group consisting of Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8, Y9 and Y10. .)

In addition, in the method of manufacturing a porous carbon structure according to the present invention, the intrinsic microporous polymer may be a polymer having a chemical structure of the formula (2).

<Formula 2>

(In Formula 2, Z is selected from the group consisting of Z1, Z2, Z3, Z4, and Z5.)

In the method of manufacturing a porous carbon structure according to the present invention, the porous structure forming step may include a non-solvent contact step of contacting the polymer uniform solution with the non-solvent.

In the method of manufacturing a porous carbon structure according to the present invention, the forming of the porous structure may include a precursor manufacturing step of preparing a precursor using a polymer homogeneous solution and a nonsolvent contacting step of contacting the precursor with a nonsolvent. .

In the method for producing a porous carbon structure according to the present invention, the good solvent and non-solvent may be a single solvent or a mixed solvent.

In the method of manufacturing a porous carbon structure according to the present invention, the precursor may be any one of gel-like particles, fibers, films or three-dimensional shapes in which both good solvents are not removed.

In the method for producing a porous carbon structure according to the present invention, the porous structure may include an asymmetric macro-pore structure in the cross section.

In addition, the porous carbon structure according to the present invention is prepared according to the manufacturing method, an asymmetric macro-pore structure in the cross-section, the meso-pore structure (meso-pore) structure and intrinsic formed while the intrinsic microporous polymer is carbonized It may include an intrinsic micro-pore structure.

In addition, an asymmetric macro-pore structure, a meso-pore structure and an intrinsic micro-pore structure formed while the intrinsic microporous polymer is carbonized in the cross section according to the present invention. Porous carbon structure is a battery electrode, the effect is very excellent.

Non-solvent induced phase separation using the intrinsic microporous polymer according to the present invention can produce a carbon structure having a three-dimensional porous structure.

The porous carbon structure using the intrinsic microporous polymer according to the present invention has an asymmetric macropore structure in the cross section, a meso-pore structure and an intrinsic micropore formed while the intrinsic microporous polymer is carbonized. micro-pore) structure.

In addition, the battery electrode using a porous carbon structure according to the present invention has a very large specific capacitance, so has a very excellent performance as a battery electrode.

1 is a photograph of an intrinsic microporous polymer membrane prepared by non-solvent induction phase separation according to an embodiment of the present invention and an electrode prepared by carbonizing it.

FIG. 2 is a scanning electron microscope (SEM) photograph showing a dense membrane cross section of an intrinsic microporous polymer membrane and an intrinsic microporous polymer membrane prepared by non-solvent induced phase separation according to an embodiment of the present invention.

3 is a scanning electron microscope (SEM) photograph of the surface and cross-section of an electrode prepared by carbonizing an intrinsic microporous polymer membrane prepared by non-solvent induction phase separation according to an embodiment of the present invention.

Figure 4 is a scanning electron microscope showing the surface change of the electrode prepared by carbonizing the intrinsic microporous polymer membrane prepared by non-solvent induced phase separation method according to the content of tetrahydrofuran (THF) in the mixed solvent according to an embodiment of the present invention (SEM) picture.

Figure 5 is a graph showing the BET measurement results of the electrode prepared by carbonizing the intrinsic microporous polymer membrane prepared by another non-solvent induction phase separation method in an embodiment of the present invention.

FIG. 6 is a graph illustrating CV measurement results of an electrode manufactured by carbonizing an intrinsic microporous polymer membrane prepared by non-solvent induction phase separation according to an embodiment of the present invention, and an electrode having a compact carbonized structure.

7 is a graph showing the results of CV measurement according to the scanning speed of the electrode prepared by carbonizing the intrinsic microporous polymer membrane prepared by the non-solvent induction phase separation method according to an embodiment of the present invention.

FIG. 8 is a graph illustrating CV measurement results of an electrode manufactured by carbonizing an intrinsic microporous polymer membrane prepared by non-solvent induced phase separation according to THF content according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail. However, embodiments according to the present invention may be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below, the embodiments of the present invention are average in the art It is provided to those skilled in the art to more fully explain the present invention.

In the present invention, in order to solve the above problems, the step of preparing a homogeneous polymer solution dissolving the intrinsic microporous polymer in a good solvent; A porous structure forming step of forming a porous structure through non-solvent induced phase separation from the polymer homogeneous solution; And a carbonization step of carbonizing the porous structure.

In the method of manufacturing a porous carbon structure according to the present invention, the intrinsic microporous polymer may be a polymer having a chemical structure of the formula (1).

<Formula 1>

(In Formula 1, X is selected from the group consisting of X1, X2, X3 and X4, and Y is selected from the group consisting of Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8, Y9 and Y10. .)

In the method of preparing a porous carbon structure according to the present invention, the intrinsic microporous polymer of Chemical Formula 1 may be a polymer prepared through Scheme 1 below.

<Scheme 1>

(X in Scheme 1 is selected from the group consisting of X1, X2, X3 and X4, Y is selected from the group consisting of Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8, Y9 and Y10. .)

Tables 1 and 2 below describe combinations of monomers X and Y necessary for the preparation of more preferred intrinsic microporous polymers according to the present invention.

Polymer 1	Polymer 2	Polymer 3	Polymer 4	Polymer 5	Polymer 6	Polymer 7	Polymer 8	Polymer 9	Polymer 10
X1 + Y1	X1 + Y2	X1 + Y3	X2 + Y1	X2 + Y2	X3 + Y2	X1 + Y4	X4 + Y4	X1 + Y5	X4 + Y5

Polymer 11	Polymer 12	Polymer 13	Polymer 14	Polymer 15
X1 + Y6	X1 + Y7	X1 + Y8	X1 + Y9	X1 + Y10

In the method of manufacturing a porous carbon structure according to the present invention, the intrinsic microporous polymer may be a polymer having a chemical structure of the formula (2).

<Formula 2>

(In Formula 2, Z is selected from the group consisting of Z1, Z2, Z3, X4 and Z5.)

In the method of preparing a porous carbon structure according to the present invention, the intrinsic microporous polymer of Chemical Formula 2 may be prepared through the following Scheme 2. That is, various functional groups may be provided through chemical modification of the nitrile group (-CN) in the repeating unit structure of the polymer 1 of Table 1 above.

<Scheme 2>

In addition, in the method of manufacturing a porous carbon structure according to the present invention, the intrinsic microporous polymer may be a polymer having a chemical structure of the formula (3).

<Formula 3>

In Formula 3, X is

,

,

,

,

,

,,

,

,

,

,

,

,

,

,

,

And

It is selected from the group consisting of.

In the method of manufacturing a porous carbon structure according to the present invention, the porous structure forming step may include a non-solvent contact step of contacting the polymer uniform solution with the non-solvent.

In the method for producing a porous carbon structure according to the present invention, the good solvent and non-solvent may be a single solvent or a mixed solvent.

In the method for producing a porous carbon structure according to the present invention, the good solvent may be a single solvent or a mixed solvent. The good solvent of the intrinsic microporous polymer according to the present invention is tetrahydrofuran (THF), chloroform (CHCl ₃ ), meta-cresol (m-cresol), dichlorobenzene, N-methyl-2-pyrrolidone (NMP), dimethyl Sulfoxide (DMSO), dimethylacetamide (DMAc), dimethylformamide (MDF), methyl ethyl ketone (MEK), acetone, triethyl phosphate (TEP), dichloromethane (DCM), triethyl glycol (TEG) , Caprolactam, butyrolactone, cyclohexane, toluene, dioxane, butyl acetate (n-BA), methyl chloride, hexafluoroisopropanol (HFIP), chlorobenzene, etc. Ethanol, lithium chloride (LiCl), polyvinylpyrrolidone (PVP), diethyl glycol (DEG), butanol (1-butanol), ethyl acetate (AA), Naproxen, methanol, calcium chloride (CaCl ₂ ), Single solvent or mixed solvent selected from the group consisting of glycerol Can. The good solvent according to the present invention is preferably tetrahydrofuran (THF), chloroform (CHCl ₃ ), meta-cresol, dichlorobenzene and a mixed solvent thereof.

As a more specific example, the good solvent of the polymer 1 shown in Table 1 is more preferably a mixed solvent of tetrahydrofuran (THF) and chloroform (CHCl ₃ ), and more preferably the good solvent of the polymers 2 to 6 is tetrahydrofuran (FHF). The good solvent of the polymers 7 to 9 is more preferably chloroform (CHCl ₃ ), and the good solvent of the polymer 10 is more preferably meta-cresol.

In the method for producing a porous carbon structure according to the present invention, the non-solvent is cyclohexanone, isophorone, γ-butyrolactone, methylyi, which are alcohols such as methanol, ethanol, isopropyl alcohol, and poor solvents. It may be one or more mixtures selected from the group consisting of pediatric milk ketone, dimethyl phthalate, propylene glycol methyl ether, propylene carbonate, acetone, water, and glycerol triacetate. More preferably, the nonsolvent is an alcohol such as methanol, ethanol or isopropyl alcohol.

Next, a precursor manufacturing step of preparing a precursor using the uniform solution will be described.

In the method of manufacturing a porous carbon structure according to the present invention, the forming of the porous structure may include a precursor manufacturing step of preparing a precursor using a polymer homogeneous solution and a nonsolvent contacting step of contacting the precursor with a nonsolvent. .

In the method of manufacturing a porous carbon structure according to the present invention, the precursor may be any one of gel-like particles, fibers, films or three-dimensional shapes in which both good solvents are not removed.

The homogeneous solution of the intrinsic microporous polymer dissolved in the good solvent may be molded into any desired form. For example, a known molding method using a solution may be used, and the shape to be molded is not limited. The shape of the molding can be formed into a porous structure through the non-solvent induced phase separation method in the form of gel particles, fibrous, film and three-dimensional form of them are all possible. The three-dimensional precursor is more preferably in a state in which both good solvents are not removed.

In the case of particles in the form of the precursor, the uniform solution may be prepared to have a variety of sizes from several nm to several cm while having a variety of forms, such as full sphere, hemispherical, etc. through various spray methods, precipitation methods. In the case of fibrous precursor, it can be produced in various lengths without limitation and various widths from several nm to several cm through the spinning method, printing method, etc. used in the manufacture of various fibers including electrospinning. Through film forming methods such as a blade (doctor blade), printing, etc., it can be manufactured with a thickness of several um to several cm without limit. In addition, in the case of a three-dimensional structure, a microporous polymer solution may be introduced onto a three-dimensional substrate made of various materials such as a metal net, or stacked with particles having insoluble properties in a used solvent in a three-dimensional structure and then introduced into the polymer solution. In addition, it may include the case where the homogeneous solution is prepared in the form of a precipitate by adding an excessive amount to the non-solvent.

Next, the porous structure forming step of forming the porous structure through the non-solvent induced phase separation method will be described.

Non-solvent Induced Phase Separation (NIPS) is a process in which the solvent is extracted by contacting the polymer solution with the non-solvent and causes phase separation. It is to use. When the polymer solution formed by dissolving the polymer in a suitable solvent is molded and then immersed in a coagulation bath containing a non-solvent, the solvent in the polymer solution is extracted, the polymer forms a matrix, and the solvent is removed to form pores. By using such a non-solvent induced phase separation method, the precursor is non-solvent induced by immersing the gel-like particles, fibers, films, and polymerized three-dimensional precursors thereof in a state in which all of the good solvents according to the present invention are not removed. The porous structure is formed by phase separation.

The porous structure according to the non-solvent induced phase separation method according to the present invention can be manufactured in various forms, including symmetric cellular structure, bicontinuous type structure, asymmetric cellular structure, and nodular ( It can be produced in the form of nodular, finger structure (finger type) or a three-dimensional porous structure of the hydrogel (hydrogel) form. In the present invention, since the porous structure will be used as an electrode, a structure in the form of a hydrogel having a three-dimensional porous structure is most preferable.

The porous structure according to the method of manufacturing a porous carbon structure according to the present invention may be an asymmetric porous structure thereof. More specifically, the gel-like particles, fibers, films, and polymerized three-dimensional precursors thereof, in which both good solvents are not removed by non-solvent induced phase separation, are contacted with the non-solvent when immersed in the non-solvent. From the start of the solidification of the polymer, the mixture of the good solvent and the non-solvent can form a porous structure of the porous structure of the cross-section of the asymmetric porous structure in the form of fine pores toward the inside toward the inside from the large pores. Representatively, the form may comprise a sponge like structure. Finger-like or sponge-like structures can be prepared from nonsolvent-induced phase separation and, when properly mixed with solvents, also form sponge-like structures. can do.

Meanwhile, in the present invention, the formation of the porous structure from the non-solvent induced phase separation method is mainly described. However, the phase separation method is not limited to the non-solvent induced phase separation method (NIPS), but the vapor-induced phase separation method (VIPS), Various phase separation methods such as reaction-induced phase separation (RIPS) and thermal induced phase separation (TIPS) may be used to prepare porous structures having the same or similar structure.

Finally, the carbonization step of carbonizing the porous structure will be described. The porous carbon structure according to the present invention is a carbonized intrinsic microporous polymer precursor having a porous structure through a phase separation method. The carbonization of the porous structure used in the present invention is performed at high temperature in the presence of high purity hydrogen, nitrogen, or a mixed gas thereof. It can be carried out by heating using. In addition, some of the active gas such as carbon dioxide or oxygen may be used to increase the carbonization effect. Heating temperature and time can be variously adjusted.

In the method for producing a porous carbon structure according to the present invention, the porous structure may include an asymmetric macro-pore structure in the cross section.

In addition, the porous carbon structure according to the present invention is prepared according to the manufacturing method, an asymmetric macro-pore structure in the cross-section, the meso-pore structure (meso-pore) structure and intrinsic formed while the intrinsic microporous polymer is carbonized It may include an intrinsic micro-pore structure.

In addition, an asymmetric macro-pore structure, a meso-pore structure and an intrinsic micro-pore structure formed while the intrinsic microporous polymer is carbonized in the cross section according to the present invention. The carbon structure is a battery electrode, and the effect is very excellent.

Electrode prepared from the non-solvent induced phase separation method of the present invention is a macro-pore, meso-pore, micro-pore appropriately formed to exhibit a three-dimensional porous structure characteristics Therefore, it is easy to access the electrolyte ions into the electrode, and as a result, it is possible to accumulate a lot of charges, which is excellent as a battery electrode.

The porous structure electrode manufactured as described above has a high electrical conductivity and excellent stability because it is a monolith type electrode that does not use a binder for electrode production, which causes resistance increase and affects electrochemical stability.

The porous structure electrode of the present invention can be used as an electrode for a supercapacitor using an aqueous system and an electrolyte, and can exhibit high capacitance and high output.

The porous structure electrode of the present invention may be utilized as an electrode of various secondary batteries such as lithium ion battery, sodium ion battery, lithium sulfur battery, sodium sulfur battery, and lithium air battery.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings and examples.

1. Preparation of intrinsic microporous polymer: Preparation of polymer 1

3,3,3 ', 3'-tetramethyl-1,1'-spirobisindane (TTSBI), which is X1, and 2,3,5,6, which are Y1, among the various intrinsic pore polymers of the present invention described in Table 1 and Table 2 A method for preparing Polymer 1 consisting of a combination of -tetrafluoroterephthalonitrile (TFTPN) will be described. TTSBI and TFTPN were reacted under the following conditions.

First, a two-necked 500 ml round bottom flask connected with a reflux condenser was used, followed by drying in an oven to remove moisture in the reactor and then flowing nitrogen before adding the sample. To the reactor was placed TTSBI (X1, 10.21 g, 30 mmol), TFTPN (Y1, 6.00 g, 30 mmol) and potassium carbonate (8.29 g, 60 mmol, DMF 210 mL. The mixture was placed in an oil bath preheated to 55 ° C. After the reaction was completed, the reaction was completed for 72 hours, and after completion of the reaction, 300 mL of THF was poured into the reaction to remove the oligomer, and then precipitated. The supernatant containing the oligomer was removed, and the precipitate was returned. It was dissolved in 300 mL THF, after which the polymer solution was poured into water, reprecipitated and filtered, and then dried in a vacuum dryer at 60 ° C. for 24 hours, after which the polymer was reprecipitated, filtered, and dried. It was obtained 1. GPC (Gel permeation chromatography) measurement result was measured with a value of M _n = 55,000 PDI (Polydispersity index) = 1.7.

2. Preparation of Polymer Membrane:

2.1 Comparative Example: Preparation of Dense Polymeric Membranes

The dense polymer membrane used as a comparative example uses dichlorobenzene as a solvent, uniformly dissolves the polymer powder (polymer 1, 1 g of the actual amount used) by 4 wt% of solid contents, and removes the doctor blade. Cast to a thickness of 300 um and dried at 80 ^° C. under a nitrogen atmosphere to produce a dense membrane.

Example: Preparation of Membrane by Non-solvent Induces Phase Separation (NIPS)

Polymer powder (polymer 1, 1 g) was dissolved in a mixed solvent (dichlorobenzene / THF) to make a homogeneous solution. At this time, a homogeneous solution was prepared under the same conditions as a dense membrane at 4 wt% of solid contents. The homogeneous solution was cast to a thickness of 300 um using a doctor blade and simultaneously precipitated in a non-solvent to prepare a porous precursor. At this time. As the non-solvent used, methanol at room temperature was used. In addition, a porous precursor was prepared by varying the mass ratio of THF in the mixed solvent under the same conditions as described above.

3. Carbonization stage

Carbonization of the porous structure used in the present invention is a high-purity hydrogen (H ₂₎ in a condition that excludes any carbon dioxide and oxygen (CO ₂ or O ₂ ) Into the furnace (furnace) at 100cc / min and the temperature was raised to 1100 ^o C to carbonize the porous precursor and dense membrane for about 30 minutes to 3 hours to prepare a carbonized three-dimensional porous structure electrode.

4. Property analysis

4.1 Porosity Measurement: Pore textural properties (BET)

The specific surface area, pore size, and pore volume of the carbonized electrode with actual three-dimensional porous structure were confirmed by BET analysis using N ₂ gas at 77 K. The pore size was measured using the Horvath-Kawazoe plot, and mesopores and macropores below 300 nm were measured using BET.

4.2 Electrical Characterization of Electrodes

The electrochemical properties of the carbonized porous electrode prepared from the phase separation method according to the present invention were confirmed. Carbonized porous electrodes and dense membranes were used as the electrodes, and the electrolytes were measured from a 3-electrode method (half-cell test) using an aqueous electrolyte (1.0 MH ₂ SO ₄ aqueous solution). At this time, the temperature conditions were all analyzed at room temperature.

Figure 1 (a) shows the intrinsic microporous polymer membrane prepared by non-solvent induction phase separation method according to an embodiment of the present invention, Figure 1 (b) shows an electrode prepared by carbonizing it. No cracking was observed in the carbonized porous structure electrode, and it was confirmed that the electrode could be used as a monolith type electrode without any polymer binder.

Figure 2 (a) is a scanning electron microscope (SEM) photograph showing a cross-section of the dense membrane of the intrinsic microporous polymer membrane, Figure 2 (b) is a cross-sectional view of the intrinsic microporous polymer membrane prepared by non-solvent induced phase separation method. . As shown in Figure 2 (a) of the intrinsic microporous polymer membrane prepared by a general film casting method can be seen that the cross section of the film is a dense structure, while the intrinsic micromachine produced by the non-solvent induced phase separation method It can be seen that the cross section of the porous polymer membrane is a sponge-like structure of micropores.

When the structure as shown in FIG. 2 is used as an actual electrode, the porous structure showing the sponge-like structure of micropores may improve the electrochemical properties by facilitating the movement of electrolyte ions relative to the dense membrane.

Figure 3 (a) is a scanning electron microscope (SEM) photograph of the surface of the electrode prepared by carbonizing the intrinsic microporous polymer membrane (cNPIM-8) prepared by a non-solvent induction phase separation method according to an embodiment of the present invention, Figure 3 (b) shows a scanning electron microscope (SEM) picture of the cross section of the electrode. The dense membrane without the non-solvent induced phase separation shows a dense membrane even after carbonization, and the porous structure showing the sponge structure characteristics of the microporous prepared from the non-solvent induced phase separation method also has no crushing or breaking of chain-chain after carbonization. It showed a microporous sponge structure.

Figure 4 is a scanning electron microscope showing the surface change of the electrode prepared by carbonizing the intrinsic microporous polymer membrane prepared by non-solvent induced phase separation method according to the content of tetrahydrofuran (THF) in the mixed solvent according to an embodiment of the present invention (SEM) picture.

4 is a result of preparing a porous precursor by varying the weight ratio of THF used in dichlorobenzene / tetrahydrofuran (THF) as a mixed solvent. Figure 4 (a) (cNPIM-3) is dichlorobenzene / THF = 7: 3 (weight ratio), Figure 4 (b) (cNPIM-5) is dichlorobenzene / THF = 5: 5 (weight ratio), Figure 4 (c) ( cNPIM-7) is dichlorobenzene / THF = 3: 7 (weight ratio), Figure 4 (d) (cNPIM-8) is a scanning electron micrograph of the porous precursor prepared by dichlorobenzene / THF = 2: 8 (weight ratio). As the content ratio of THF used as the mixed solvent increases, the pore size increases.

Figure 5 is a graph showing the BET measurement results of the electrode prepared by carbonizing the intrinsic microporous polymer membrane prepared by non-solvent induction phase separation method according to an embodiment of the present invention. cNPIM-0 is the data of dense membrane and cNPIM-7 is the electrode of 80% carbonization. Table 3 shows the results of measuring the specific surface area of the carbonized electrode having a porous structure according to the present invention. Dense film (cNPIM-0) is 2086.7 m ² / g, the carbonized porous electrode (cNPIM-7) was characterized by a very high specific surface area of 2101.1 m ² / g. Also, macro-pores, meso-pores, and micro-pores were observed in the carbonized porous electrode compared to the dense membrane.

	Surface area (m 2 / g)	Pore volume (cm 3 / g)	Total volume in pore (cm 3 / g)	Micropore size (nm)
cNPIM-0 (dense)	2086.7	0.75	0.78	0.72
cNPIM-7 (carbonization-80%)	2101.1	0.72	0.9	0.75

FIG. 6 is a graph showing CV measurement results of an electrode manufactured by carbonizing an intrinsic microporous polymer membrane prepared by a non-solvent induced phase separation method and an electrode in the form of a carbonized dense membrane according to an embodiment of the present invention. As a result of CV measurement, the porous electrode according to the present invention showed a larger current value than the electrode having a compact form. This is a result of the carbonized porous electrode having a porous structure has easy access of the electrolyte ions because it contains pores of various sizes.

  7 is a graph showing the results of CV measurement according to the scanning speed of the electrode prepared by carbonizing the intrinsic microporous polymer membrane prepared by the non-solvent induction phase separation method according to an embodiment of the present invention, Figure 8 is an embodiment of the present invention It is a graph showing the CV measurement results of the electrode prepared by carbonizing the intrinsic microporous polymer membrane prepared by non-solvent induced phase separation according to the THF content change according to the example.

As a result of CV measurement, the porous electrode according to the present invention showed very stable capacitor behavior by showing a CV graph of a nearly rectangular shape. That is, it could be confirmed that it is suitable for use as an electrode material for EDLC. In addition, in the case of an electrode manufactured by changing the THF content of the mixed solvent, the current value of CV increased as the THF content increased. That is, the specific capacitance of the electrode was increased because the pore size in the electrode was increased as the THF content was increased as shown in the SEM result of FIG. 4. In particular, in the case of Fig. 4 (d) and Fig. 6 (d) cNPIM-8 (THF content ratio of the porous precursor prepared from the phase separation method 8) when the current density is 100 mA / g, 405.8 F / g showed a very large specific capacitance, which means that the electrode prepared from the phase separation method has the proper formation of macro-pore, meso-pore, and micro-pore, resulting in three-dimensional porosity. It is interpreted that this is because it shows structural characteristics, thereby facilitating accessibility of electrolyte ions into the electrode and consequently allowing a large amount of charge accumulation.

As described above, the method for preparing a porous carbon structure using the non-solvent induced phase separation method of the intrinsic microporous polymer of the present invention and the porous carbon structure prepared according to the present invention have a three-dimensional porous structure having an asymmetric cross section. Battery electrode using the porous carbon structure according to it has a very large specific capacitance, it can be seen that has a very excellent performance as a battery electrode.

The non-solvent induced phase separation method using the intrinsic microporous polymer according to the present invention has a very large specific capacitance when manufacturing a carbon structure having a three-dimensional porous structure and a battery electrode using the same, and thus, a battery electrode manufacturing technology and a battery-related industry Very versatile, the porous structure electrode of the present invention can be used as an electrode of various secondary batteries, such as lithium ion battery, sodium ion battery, lithium sulfur battery, sodium sulfur battery, lithium air battery.

Claims (10)

1. Preparing a homogeneous polymer solution for dissolving the intrinsic microporous polymer in a good solvent;

   A porous structure forming step of forming a porous structure through non-solvent induced phase separation from the polymer homogeneous solution; And

   And a carbonization step of carbonizing the porous structure.
2. The method according to claim 1,

   The intrinsic microporous polymer has a chemical structure represented by the following Chemical Formula 1

   <Formula 1>

   

   (In Formula 1, X is selected from the group consisting of X1, X2, X3 and X4, and Y is selected from the group consisting of Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8, Y9 and Y10. .)

   

   
3. The method according to claim 1,

   The intrinsic microporous polymer has a chemical structure of Formula 2 below

   <Formula 2>

   

   (In Formula 2, Z is selected from the group consisting of Z1, Z2, Z3, Z4, and Z5.)

   
4. The method according to claim 1,

   The porous structure forming step comprises a non-solvent contact step of contacting the polymer homogeneous solution with the non-solvent.
5. The method according to claim 1,

   The porous structure forming step comprises a precursor manufacturing step of producing a precursor using a homogeneous polymer solution and a non-solvent contact step of contacting the precursor with the non-solvent.
6. The method according to claim 1,

   The good solvent and the non-solvent is a method for producing a porous carbon structure, characterized in that the single solvent or mixed solvent.
7. The method according to claim 3,

   The precursor is a method for producing a porous carbon structure, characterized in that any one of the gel-like particles, fibers, films or three-dimensional shape, all of the good solvent is not removed.
8. The method according to claim 1,

   The porous structure is a method of producing a porous carbon structure, characterized in that it comprises an asymmetric macro-pore structure in the cross section.
9. It is manufactured by the manufacturing method of any one of claims 1 to 6,

   Porous carbon characterized by including an asymmetric macro-pore structure in cross section, a meso-pore structure formed by carbonization of an intrinsic microporous polymer, and an intrinsic micro-pore structure Structure.
10. A battery electrode comprising the porous carbon structure according to claim 7.

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