KR101831297B1 - Method for Preparation of Porous Carbon Membranes - Google Patents

Abstract

The method for preparing a porous membrane according to the present invention comprises the steps of forming a polymer thin film by coating a solution of a polymer dissolved in a solvent on a substrate, forming a porous polymer thin film by phase transitions to the polymer thin film formed, Irradiating the porous polymer thin film with radiation to crosslink the porous polymer thin film, and carbonizing the crosslinked porous polymer thin film to produce a porous carbon membrane. According to the present invention, it is possible to manufacture conductive carbon materials of various shapes and sizes inexpensively and easily by forming a conductive porous carbon membrane using a cheap general-purpose polymer without a process of synthesizing a conductive material, and to provide an additive such as a cross- There is an advantage that the process is very simple and clean.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a porous carbon membrane,

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a porous carbon membrane, and more particularly, to a method for producing a porous carbon membrane using phase transformation and irradiation with a general-purpose polymer material.

The water industry, which targets domestic water and industrial water, has become a key industrial group in the 21st century that can solve the rapid industrialization of emerging and developing countries and the global water shortage. The global water market is estimated to be worth $ 556 billion by 2013 and is expected to grow to $ 689 billion by 2018.

Capacitive deionization (CDI) technology is a technology that adsorbs and removes ions using an electrochemical principle on electrodes with a high specific surface area. It operates at a relatively low potential and has very low energy consumption. It is a very environmentally friendly technology because it does not use harmful chemical reagents such as bases. These CDI technologies are widely required technologies in various industries such as ultrapure water production, boiler water production, cooling water production of power plant, removal of environmental pollutants in ground water, and desalination of seawater.

Carbon materials such as carbon nanofibers, carbon aerogels, mesoporous carbon, carbon nanotubes, graphene, and porous carbon spheres are being studied in a large amount. However, the carbon materials under study are difficult to manufacture, most of which are very expensive and have poor adsorption performance.

In the CDI technology, the first-generation electrode has a disadvantage in that the efficiency of desalination is too low because the porous electrode is used as it is. In order to solve this problem, an ion-selective ion exchange membrane combined with the surface of the electrode (second-generation electrode) has been developed, and the form of such a product is currently commercialized. Such an electrode form has the advantage of increasing the adsorption capacity, reducing the electrical resistance, and lowering the price.

It is known that the specific surface area of the porous activated carbon which is mainly used at present is greatly influenced by the pore size and that the specific surface area can be greatly increased by manufacturing the pores of the activated carbon particles to several nm or less. However, in the CDI process, these micropores have been reported to have little effect on increasing the electroadhesion capacity due to the superposition effect of the electric field. That is, there is a limit to increase the capacitance of the electrode using activated carbon having a high specific surface area. Therefore, it is necessary to develop a new electrode manufacturing method which can increase the adsorption capacity by controlling the surface structure of the electrode as well as studying the constituent materials of the electrode in order to develop a highly efficient electrode for electro-absorption.

As a conventional technique, the following Patent Document 1 discloses a method of forming nanopores by reacting a carbon precursor and an amphipathic block copolymer that is hydrogen-bonded to the carbon precursor to form nanopores, stabilizing the nanoporous structure by irradiating ultraviolet (UV) A step of thermally curing the thermosetting compound at a temperature 20 to 50 DEG C higher than the glass transition temperature (Tg) of the copolymer, and a step of carbonizing the thermosetting compound at 600 to 800 DEG C to obtain a carbon material having uniform pore diameter, And a method of manufacturing a porous carbon membrane material in which the nanopore structure is maintained during carbonization.

The above method requires a special amphiphilic block copolymer, has a limitation on the thickness of the thin film upon UV irradiation, and has a disadvantage that the material to be cured by UV is very limited. Further, there is a disadvantage that the pores are clogged due to the heat curing process after UV irradiation, and the energy consumption is large and the time is long.

Korean Patent No. 10-1425374

 Y. Liu, C. Nie. X. Liu, X. Xu, Z. Sun, L. Pan, RSC Advances, 5, 15205-15225 (2015)

In order to overcome the above problems, the inventors of the present invention discovered that a porous carbonaceous electrode material for CDI can be prepared from a relatively inexpensive precursor material while studying carbonaceous materials using radiation, and completed the present invention.

Accordingly, an object of the present invention is to provide a method for manufacturing a porous conductive carbon membrane at low cost and with ease by using phase transformation and irradiation with a general-purpose polymeric material.

According to an aspect of the present invention, there is provided a method of manufacturing a porous carbon membrane, comprising: forming a polymer thin film by coating a solution of a polymer dissolved in a solvent on a substrate; Preparing a porous polymer thin film by performing phase transformation on the formed polymer thin film; Irradiating the prepared porous polymer thin film with radiation to crosslink the porous polymer thin film; And carbonizing the cross-linked porous polymer thin film to produce a porous carbon membrane.

The polymer may be selected from the group consisting of polyacrylonitrile (PAN), polyvinylidene fluoride (PVdF), polyvinyl alcohol (PVA), polystyrene (PS), polysulfone PSF). ≪ / RTI >

The solvent may be at least one selected from the group consisting of dimethylformamide, dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone, toluene.

The polymer solution may further comprise at least one additive selected from the group consisting of polyethylene glycol, polyvinyl pyrrolidone, and dimethyl sulfone.

The phase transition may be performed by immersing the substrate coated with the polymer thin film in a non-solvent, and the solvent may be water, an alcohol, or a mixed solution thereof.

Further, the phase transition may further include performing a phase transition by steam induction before immersing in the non-solvent.

The substrate may be a non-conductive substrate, such as a silicon substrate, a glass substrate, or a quartz substrate.

The radiation is an ion beam, and the irradiation energy of the ion beam is 1 keV to 1 MeV, and the total ion dose can be adjusted to 1 × 10 ¹⁰ to 1 × 10 ¹⁹ ions / cm 2.

The radiation is an electron beam, and the irradiation energy of the electron beam is 1 keV to 10 MeV and the total electron beam irradiation dose can be adjusted to 1 × 10 ¹⁴ to 1 × 10 ²⁰ electrons / cm 2.

As described above, the method of manufacturing a porous carbon membrane using radiation according to the present invention can manufacture a porous conductive carbon membrane inexpensively and easily by using a cheap general-purpose polymer material without synthesizing the porous conductive carbon material, There is no need for a lot of thermal stabilization processes, no harmful additives such as crosslinking agents are required, and the process is very simple and clean.

In addition, according to the present invention, the carbon membrane manufactured according to the method of manufacturing a porous conductive carbon membrane using radiation can be used not only for an electrode for CDI, but also for various electronic devices such as organic light emitting devices, transistors, memory devices, It can also be used in various fields such as bio-electronic devices, solar cells, secondary batteries, fuel cells, and other energy devices.

1 is a schematic view illustrating a method of manufacturing a porous carbon membrane using phase transition and radiation according to an embodiment of the present invention.
2 is a photograph of the porous carbon membrane prepared in Example 1 and Comparative Example 1 of the present invention by scanning electron microscope.
FIG. 3 is a graph of spectroscopic spectrum of porous carbon membranes prepared according to an embodiment of the present invention using Fourier transform infrared spectroscopy (FT-IR).
4 is a graph showing a Raman spectroscopic spectrum of the porous carbon membranes prepared in Example 1. FIG.
FIG. 5 is a graph showing the conductivity of the porous carbon membranes prepared in Example 1 and Comparative Example 1. FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

Throughout this specification, the term "combination thereof" included in the expression of the machine form means one or more combinations or combinations selected from the group consisting of the constituents described in the expression of the machine form, And the like.

The present invention relates to a method for producing a porous carbon membrane, and more particularly, to a method for producing a porous carbon membrane using phase transformation and irradiation with a general-purpose polymer material.

Hereinafter, a method of manufacturing a porous carbon membrane according to the present invention will be described in detail with reference to the embodiments and examples and the drawings.

According to another aspect of the present invention, there is provided a method of fabricating a porous carbon membrane, comprising: coating a polymer solution on a substrate to form a polymer thin film; A step of immersing the coated polymer thin film in a non-solvent to form a porous polymer thin film; Crosslinking the polymer thin film by irradiating the prepared porous polymer thin film with radiation; And carbonizing the crosslinked porous polymer thin film to produce a porous carbon membrane (see FIG. 1).

First, according to one embodiment of the present invention, a polymer solution is spin-coated on a substrate to form a polymer thin film on a substrate.

In this case, the polymer used is a general purpose polymer which is generally available and is a polyacrylonitrile (PAN), a polyvinylidene fluoride (PVdF), a polyvinyl alcohol (PVA), a polystyrene , PS), and polysulfone (PSF). These polymers may be used singly or in combination of two or more.

The concentration of the polymer solution in the preparation of the polymer solution is preferably 0.1 to 20% by weight. The solvent used for preparing the polymer solution may include dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), and toluene.

When the polymer solution is prepared at a concentration of less than 0.1% by weight, the thin film may not be formed well. If the polymer solution is prepared at a concentration of more than 20% by weight, There is a possibility that a thick film is formed and radiation such as an electron beam or an ion beam can not pass through.

Meanwhile, the polymer solution may further include an additive to control the shape and size of the pores formed on the surface or inside of the carbon membrane to be produced.

The additive may be selected from the group consisting of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), dimethylsulfone (DMSO2), methyl cellosolve, glycerol, alkylene glycols having 1 to 10 carbon atoms, alkylene glycol repeating polyalkylene glycol containing the unit, LiCl, LiClO4, methanol, ethanol, isopropanol, acetone (acetone), phosphoric acid, propionic acid, acetic acid, silica (SiO _2), pyridine, and polyvinyl pyridine selected from the group consisting of: 1 More than two species of compounds. The additive may be used in an appropriate amount in consideration of specific physical properties and uses of the carbon membrane, size and distribution of pores to be produced, and may be included in the polymer resin composition in an amount of 0.1 to 90% by weight, for example.

The substrate may be a nonconductive substrate, preferably a silicon substrate, a glass substrate, or a quartz substrate, but is not limited thereto.

Then, the polymer thin film coated on the substrate is phase-transformed to produce a porous polymer thin film having a pore structure.

The phase transition is carried out by immersing the substrate coated with the polymer thin film in the non-solvent. The phase transition by the non-solvent is a method of forming pores by causing phase separation between a polymer and a solvent by appropriately using the temperature or nonsolvent of the polymer, and the characteristics of the porous thin film produced according to the phase separation conditions are determined.

The phase transition by the non-solvent is a step of immersing the polymer thin film coated on the substrate in the non-solvent to form the inner pores to produce the porous polymer thin film. The non-solvent which can be used here includes methanol, ethanol, propanol, isopropanol, water, glycols, or a mixture of two or more thereof.

On the other hand, the phase transition by vapor induction may be performed before the phase transition by the non-solvent, so that predetermined pores can be formed on the surface of the polymer thin film. The polymer resin composition applied on the substrate is exposed to humid air to expose the polymer resin composition coated on the substrate to air at a relative humidity of 10 to 100% Can be formed. The steam-induced phase transformation step may be performed at a relative humidity of 10% to 100%, preferably 50% to 100%. Further, the steam-induced phase change step may be carried out at a temperature of 0 to 300 ° C for 1 second to 10 minutes, and at a temperature of 0 to 50 ° C for a time of 5 minutes or less.

The non-solvent phase transition may include precipitating the result of the vapor-induced phase transition to a non-solvent having a temperature of 0 to 90 占 폚 for 10 minutes to 24 hours.

Next, the step of irradiating the crosslinked porous polymer thin film with crosslinking is performed. Specifically, the porous polymer thin film is irradiated with radiation such as an ion beam, an electron beam, or a gamma ray so that the polymer thin film can be crosslinked, thereby stabilizing the porous structure formed by the phase transition.

The irradiation with the radiation is preferably performed at room temperature to prevent thermal deformation and decomposition of the polymer, and is preferably performed in an inert atmosphere such as vacuum or nitrogen.

The radiation may be an ion beam, an electron beam, a gamma ray, a neutron beam, an X-ray or an ultraviolet ray.

When the ion beam is irradiated, gases such as hydrogen, helium, argon, neon, or xanthan gasses may be used alone or in combination as an injection gas, and the current density is preferably adjusted to 1 ㎂ / cm 2 or less. The ion beam irradiation energy can be applied at 1 keV to 1 MeV, and the total ion dose is preferably adjusted to 1 × 10 ¹⁰ to 1 × 10 ¹⁹ ions / cm 2. When the total ion irradiation dose is less than 1 x 10 < ¹⁰ > ions / cm < 2 >, the polymer is not sufficiently crosslinked and the carbonylation yield is very low. In the case of irradiation exceeding 1 x 10 ¹⁹ ions / Or decomposition occurs.

When the electron beam is irradiated, the energy of the electron beam is preferably 1 keV to 10 MeV and the dose of the total electron beam is preferably adjusted to 1 × 10 ¹⁴ to 1 × 10 ²⁰ electrons / cm 2. When the irradiation amount of the total electron beam is less than 1 × 10 ¹⁴ electrons / cm 2, there is a problem that the polymer is not sufficiently crosslinked and the carbonization yield is low. In the case of irradiation exceeding 1 × 10 ²⁰ electrons / cm 2, There is a problem that occurs.

When the gamma ray is irradiated, the irradiation amount of the total gamma ray is preferably adjusted to 50 to 10,000 kGy. When the total gamma irradiation dose is less than 50 kGy, there is a problem in that the polymer is not sufficiently crosslinked and the yield of the carbonization is low. In the case of irradiation exceeding 10,000 kGy, the polymer is thermally deformed or decomposed.

Finally, the crosslinked porous polymer thin film is carbonized to form a porous carbon membrane. At this stage, carbonization causes an aromatic hexagonal C = C bond appearing in the carbon-based materials, thereby imparting conductivity to the porous carbon membrane .

Specifically, the crosslinked porous polymer thin film may be carbonized in a heating furnace where an inert atmosphere of 800 ° C to 1400 ° C is maintained to form a porous carbon membrane. If the heating furnace is maintained at a temperature lower than 800 ° C, there is a problem that the carbonization reaction does not progress effectively and the electrical characteristics are reduced. When the heating furnace temperature is maintained higher than 1400 ° C, no further improvement in electrical characteristics is observed. In the carbonization reaction, the porous polymer thin film can be fully carbonized by being heated for 1 hour to 3 hours. Further, in order to further improve the carbonation reaction, the thermal stabilization step may be performed for 1 hour to 3 hours at a temperature range of 200 ° C to 400 ° C. During the carbonization reaction, nitrogen, helium, neon, argon or xenon may be used as an inert gas in order to maintain an inert atmosphere, and 2 to 5% of hydrogen may be used in order to improve the electrical characteristics.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[Example 1] Production of porous carbon membrane from polyacrylonitrile using ion beam

5 g of polyacrylonitrile (PAN) was dissolved in 95 g of DMF to prepare a 5 wt% PAN solution. The polyacrylonitrile solution prepared above was spin-coated on the substrate to form a polyacrylonitrile thin film.

The prepared polyacrylonitrile thin film was immersed in distilled water for 24 hours to generate a phase transition phenomenon to produce a porous polyacrylonitrile thin film having a pore structure. The prepared porous polyacrylonitrile thin film was washed with distilled water and then dried in a vacuum oven.

The following, the hydrogen (H +) ion beam to the thin film acrylonitrile, the dried porous polyacrylonitrile ^{1 × 10 15 ions / cm 2} , 5 × 10 15 ions / cm 2, 1 × 10 16 ions / cm 2 and 2 × 10 ¹⁶ ions / cm < ² > at an irradiation dose of 10 < 6 > / cm < ² > At this time, the ion beam apparatus used for the ion beam irradiation was a device capable of supplying ion beam energy of up to 300 keV.

Next, the ion beam irradiated porous polyacrylonitrile thin film was put into a tubular heating furnace, and carbonization reaction was performed at 1000 ° C for 1 hour while maintaining the nitrogen atmosphere. As a result of the carbonization reaction, a porous carbon membrane was obtained.

[Example 2] Production of porous carbon membrane from polysulfone using ion beam

A porous carbon membrane was prepared in the same manner as in Example 1 except that polysulfone was used instead of polyacrylonitrile.

[Example 3] Production of porous carbon membrane from polyacrylonitrile using electron beam

A porous carbon membrane was prepared in the same manner as in Example 1 except that the ion beam of Example 1 was irradiated with an electron beam at an irradiation dose of 500 kGy.

[Comparative Example 1] Production of porous carbon membrane using thermal stabilization method

Polyacrylonitrile was dissolved in DMF to prepare a 5% by weight polyacrylonitrile solution. The polyacrylonitrile solution prepared above was spin-coated on a silicon substrate to form a polyacrylonitrile thin film.

The polyacrylonitrile thin film thus formed was dipped in distilled water for 24 hours to induce a phase transition phenomenon, thereby preparing a porous polymer thin film having a pore structure. The prepared porous polymer thin film was washed with distilled water and dried in a vacuum oven.

Then, the dried porous polyacrylonitrile thin film was heat-treated at 250 to 300 ^° C for 4 hours in the air to stabilize the porous polyacrylonitrile thin film.

Next, the stabilized porous polyacrylonitrile thin film was put into a tubular heating furnace, and carbonization reaction was performed at 1000 ° C for 1 hour while maintaining the nitrogen atmosphere. As a result of the carbonization reaction, a porous carbon membrane was obtained.

The conditions of the above Examples and Comparative Examples are summarized in Table 1 below.

division
Type of polymer used Used radiation
Irradiation energy (keV)
Used radiation
Kinds
Radiation dose
Example 1
Polyacrylonitrile
150
Hydrogen (H ⁺ ) ion beam ² × 10 ¹⁵ ions / cm 2
^~
5 × 10 ¹⁵ ions / cm ²
Example 2
Polysulfone
150
Hydrogen (H ⁺ ) ion beam ² × 10 ¹⁵ ions / cm 2
^~
5 × 10 ¹⁵ ions / cm ²
Example 3
Polyacrylonitrile
30
Electron beam 1 x 10 ¹⁶ electrons / cm ^2
~
1 x 10 ¹⁸ electrons / cm ²
Comparative Example 1

Polyacrylonitrile
-
-
-

[Test Example 1] Morphological analysis of polyacrylonitrile with progress of the process

The porous carbon membrane formed by irradiating 5 × 10 ¹⁵ ions / cm ² of hydrogen ion beam in Example 1 was analyzed by a scanning electron microscope. The results are shown in FIG.

2 is a photograph of a porous carbon membrane prepared from PAN in Example 1 of the present invention and a carbon membrane prepared in Comparative Example 1 by a scanning electron microscope (manufacturer: JEOL, model name: JSM-6390).

2 (a) is a porous PAN film after phase transition, (b) is a porous PAN film irradiated with hydrogen ions, and (c) is a scanning electron micrograph )to be. The enlarged image in each photograph is a photograph taken at a magnification of 15,000 times.

From FIG. 2 (a), it can be seen that the porous PAN thin film is well formed by the phase transition, and that the porous PAN thin film is maintained well after the hydrogen ion irradiation from (b). From the final stage (c), it can be confirmed that the porous carbon membrane is well formed after carbonization.

From FIG. 2 (d), it can be seen that the phase-transformed porous PAN membrane clogged the pores during the thermal stabilization process. After the final carbonization, there was almost no such pores.

Based on the above results, it was found that the PAN crosslinking reaction effectively proceeded by ion beam irradiation, and the porous carbon membrane was well formed after carbonization, and it was confirmed that the porous thin film can be formed more effectively than the conventional thermal stabilization method.

[Test Example 2] Analysis of chemical structure before and after carbonization of an ion beam irradiated PAN thin film

In order to analyze the chemical structure of the porous carbon membrane formed by irradiating 5 × 10 ¹⁵ ions / cm 2 of ion beam in Example 1, a spectrum was measured with a Fourier transform infrared spectroscope (FT-IR, manufacturer: Varian, model name: 640-IR) And the results are shown in FIG.

FIG. 3 is a graph showing a spectroscopic spectrum of a porous carbon membrane manufactured according to the present invention using a Fourier transform infrared spectroscope. 3 (a) is an infrared spectroscopic spectrum of pure PAN, (b) is an ion beam irradiated PAN film, and (c) is an infrared spectroscopy spectrum of a carbonized thin film.

As shown in Figs. 3 (a) and 3 (b), in the case of the PAN thin film irradiated with an ion beam of 5 x 10 ¹⁵ ions / cm 2, the portion of the C = O peaks due to the formation of the crosslinked structure becomes wider Except for the same peak characteristics.

On the other hand, in the infrared spectroscopic spectrum after carbonization in FIG. 3 (c), it was confirmed that an aromatic hexagonal C = C bond characteristic peak appeared in carbon-based materials such as carbon nanotubes, graphite and graphene.

Based on the above results, it was confirmed that the crosslinking structure of PAN was effectively formed by ion beam irradiation, and it was proved that the aromatic hexagonal carbon structure was well formed through the carbonization reaction.

[Test Example 3] Analysis of aromatic hexagonal carbon structure of a porous carbon membrane formed by ion beam irradiation

Structural analysis was performed using a Raman spectrometer (manufacturer: Horiba jobin-Yvon, model name: LabRam HR) in order to confirm whether or not an aromatic hexagonal carbon structure of the porous carbon membrane formed in Example 1 was formed. Respectively.

4 (a) is a Raman spectroscopic spectrum of a porous carbon membrane prepared using ion beam irradiation and a carbon membrane prepared by a thermal stabilization method in Example 1. FIG.

As shown in Fig. 4 (a), the spectrum of the resulting carbon membrane is both 1580 cm ^- was confirmed that have a peak at ¹ and 1350 cm ^-1. These two peaks are known as peaks present in graphite materials having an aromatic hexagonal structure. Specifically, the G-peak at 1580 cm ^-1 means that a carbon structure showing conductivity is formed, and the D-peak at 1350 cm ^-1 is not a perfect crystal structure in the carbonization process but an amorphous Carbon structure is formed.

From the above results, it was confirmed that an aromatic hexagonal carbon structure was well formed in the porous carbon membrane.

4 (b) is a graph showing the ratio ( _{D D} / I _G ) of the sizes of D- and G-peaks in (a). As shown in Fig. _{4 (b), (I D} / I G) value was determine this value (I _D / I _G) of the carbon films prepared by ion beam irradiation is smaller, wherein the ion beam irradiated from these results Was superior to the thermal stabilization method.

[Test Example 4] Measurement of conductivity of a porous carbon membrane formed by ion beam irradiation

The conductivity of the porous carbon membrane formed in Example 1 was measured using a resistance meter (manufacturer: Advanced Instrument Technology, Model: SR-1000N), and the results are shown in FIG.

FIG. 5 is a graph comparing the conductivities of the porous carbon membranes formed in Example 1 and Comparative Example 1. FIG. As shown in FIG. 5, the conductivity of the carbon membrane prepared by the thermal stabilization method in Comparative Example 1 was 320 S / cm, while the porous carbon membranes formed according to Example 1 showed higher conductivity, Up to 430 S / cm.

Based on the above results, it was confirmed that the conductivity of the porous carbon membrane according to the present invention is improved.

The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (10)

Coating a polymer solution obtained by dissolving a polymer in a solvent on a substrate to form a polymer thin film;
Preparing a porous polymer thin film by performing phase transformation on the formed polymer thin film;
Irradiating the prepared porous polymer thin film with radiation at room temperature to crosslink the porous polymer thin film; And
And carbonizing the cross-linked porous polymer thin film to produce a porous carbon membrane,
The radiation is an ion beam,
Wherein the irradiation energy of the ion beam is 50 keV to 1 MeV, and the total ion dose is adjusted to 1 x 10 ¹⁴ to 1 x 10 ¹⁷ ions / cm 2. The method according to claim 1,
The polymer may be selected from the group consisting of polyacrylonitrile (PAN), polyvinylidene fluoride (PVdF), polyvinyl alcohol (PVA), polystyrene (PS), polysulfone (PSF) Wherein the porous carbon membrane is at least one selected from the group consisting of carbon nanotubes. The method according to claim 1,
Wherein the solvent is at least one selected from the group consisting of dimethylformamide, dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone and toluene. The method according to claim 1,
Wherein the polymer solution further comprises at least one additive selected from the group consisting of polyethylene glycol, polyvinyl pyrrolidone, and dimethyl sulfone. The method according to claim 1,
Wherein the phase transition is performed by immersing the substrate coated with the polymer thin film in a non-solvent. 6. The method of claim 5,
Wherein the non-solvent is water, an alcohol, or a mixed solution thereof. delete The method according to claim 1,
Wherein the substrate is a nonconductive substrate, which is a silicon substrate, a glass substrate, or a quartz substrate. delete delete

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