KR20160059285A - Proton exchange membrane, preparation method thereof and microbial fuel cell having the same - Google Patents

Abstract

The present invention relates to a cation exchange membrane for microbial fuel cells, a production method thereof, and a microbial fuel cell comprising the same. The cation exchange membrane of the present invention includes: a nanofiber membrane formed in a nanofiber web by electrospinning a fiber-moldable polymeric material and having a three-dimensional micropore which has the diameter less than 1 μm; a porous base material laminated on one side or both sides of the nanofiber membrane so as to supporting the nanofiber membrane; an ion-conductive material filled in the nanofiber membrane or both the nanofiber membrane and the porous base material, thereby increasing durability and performance.

Description

TECHNICAL FIELD [0001] The present invention relates to a cation exchange membrane for a microbial fuel cell, a method for producing the same, and a microbial fuel cell comprising the same. ≪ Desc / Clms Page number 1 >

The present invention relates to a cation exchange membrane for an inorganic porous type microbial fuel cell utilizing a nanofiber-based multi-layer composite membrane as a support, a method for producing the same, and a microbial fuel cell having the same.

Generally, a microbial fuel cell has a proton exchange membrane between an anode and a cathode to generate an oxidation reaction of an electrochemically active microorganism through an organic substance (fuel) supplied to a cathode. The hydrogen ions and the electrons are transferred to the anode part through the exchange membrane and the outer conductor, respectively, and the oxygen and the transferred electrons supplied to the anode part are subjected to reduction reaction to obtain electrical energy and water.

The microbial fuel cell is capable of continuously generating electric current through such a series of microorganisms and electrochemical reaction when an organic material that can use microorganisms is supplied to the cathode portion of the anaerobic tank from the outside, and it can utilize a wide range of raw materials such as wastewater .

The cation exchange membrane of the microbial fuel cell needs to separate the solution of the cathode (oxidizing electrode) and the anode (reducing electrode) and to transfer hydrogen ions to the reducing electrode. It is a structure that can not move ions or substances other than hydrogen ions (H ⁺ ) in the water environment, and plays a role of reducing the loss of the substrate from the oxidizing electrode to the reducing electrode and preventing the oxygen of the reducing electrode from flowing into the oxidizing electrode, It should act to increase efficiency.

Such a membrane can be classified into a composite membrane composed of a polymer single membrane using a hydrogen ion conductor such as a fluorine system or a hydrocarbon system and an organic / inorganic material or a porous support complexed with the polymer material. In the case of a single membrane, Nafion of DuPont, which is a fluorine-based polymer, is most widely used, but it is expensive, has low mechanical stability, is thick and has a large internal resistance. In addition, the effect of hydrogen ion exchange membrane for microbial fuel cell in underwater environment is unknown, and there is a disadvantage that it must be pretreated using acid or heat before use.

In order to overcome the drawbacks of the single membrane such as Nafion, a composite membrane in the form of a pore filling membrane impregnated with a hydrogen ion conductor material on a porous support is excellent in terms of mechanical strength and form stability, .

Conventional microbial fuel cells are disclosed in Korean Patent Registration No. 10-1190397 (Oct. 05, 2012), and include an anode electrode and a cathode electrode positioned opposite to each other, and a cation exchange membrane disposed between the anode electrode and the cathode electrode. The cation exchange membrane includes a porous support containing a hydrocarbon-based material, and an ion conductor filled in the pores of the porous support, the ion conductor including a hydrocarbon-based material, The hydrocarbon-based material contained in the porous support is selected from the group consisting of nylon, polyimide, polybenzoxazole, polyethyleneterephtalate (PET), polyethylene (PE), and polypropylene (PP) The hydrocarbon-based material contained in the ion conductor may be sulfonated polyimide (S-PI), sulfonated polyarylethersulfone (S-PAES), SP (PPSA), sulfonated polybenzimidazole (S-PBI), sulfonated polysulfone (S-PSU), sulfonate polystyrene sulfonated polystyrene (S-PS), and sulfonated polyphosphazene, wherein the cation exchange membrane comprises a porous support in an amount of 40 to 95% by weight, Is contained in an amount of 5 to 60% by weight, and the porous support has a thickness of 20 to 50 탆 and has a plurality of pores having a diameter of 1 to 50 탆 formed through the thickness of the porous support.

However, such a conventional porous support has a disadvantage in that the pore size is irregular in shape from several to several tens of micrometers, and the two-dimensional closed pore structure (2-D closed pore) from the surface to the back surface is not more than 60% .

Patent Document 1: Korean Patent Publication No. 10-1190397 (October 05, 2012)

Accordingly, an object of the present invention is to provide a nanofiber-based cation exchange membrane having a high specific surface area for a microbial fuel cell in an underwater environment, a method for producing the same, and a microbial fuel cell having the same.

It is another object of the present invention to provide a cation exchange membrane capable of preventing hydrogen ion exchange and other ions or substances from being transferred to a microbial fuel cell, a method for producing the same, and a microbial fuel cell having the same.

It is another object of the present invention to provide a nanofiber membrane having a hydrogen ion exchange function capable of rapidly absorbing and transferring hydrogen ions generated at the cathode portion by imparting a hydrophilization function through surface modification such as plasma or corona treatment to the surface of the nanofiber membrane A method for producing the same, and a microbial fuel cell having the same.

Another object of the present invention is to provide a cation exchange membrane having a nanofiber-based high-strength cation exchange membrane capable of improving durability and performance characteristics, a method for producing the cation exchange membrane, and a microbial fuel cell having the same.

In order to achieve the above object, the cation exchange membrane of the present invention comprises: a nanofiber membrane formed by electrospinning a fibrous polymeric material to form a nanofiber web and having three-dimensional micropores of less than 1 mu m in diameter; A porous substrate for supporting the nanofiber membrane, and an ion conductor material filled in the nanofiber membrane or the nanofiber membrane and the porous substrate.

The cation exchange membrane of the present invention comprises a porous substrate, a nanofiber membrane formed of nanofiber webs formed on both sides of the porous substrate by electrospinning the fibrous polymeric material and having three-dimensional micropores having a diameter of less than 1 탆, , An ion conductor material filling the nanofiber membrane or the nanofiber membrane and the porous substrate.

The nanofiber membrane is produced by dissolving a fiber-forming polymer in a solvent to prepare a spinning solution, electrospinning the spinning solution to form nanofibers having a fiber diameter of less than 1 탆, integrating the nanofibers, It can be formed into a fibrous web.

The amount (basis weight) of the nanofibers that are radiated to form the nanofiber membrane may be set in the range of 0.5 to 20 gsm (gram per square meter) based on the total amount of the spinning solution.

The nanofiber membranes may be formed in a multilayer structure in which a plurality of nanofiber membranes are laminated, and the nanofiber membranes may be formed by fusing the nanofibers by thermal compression or laminating.

The ionic conductor material is a polymer resin having a cation-exchange group, and includes poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), a copolymer of tetrafluoroethylene and fluorovinyl ether including a sulfonic acid group, Sulfated polyether ketone, and mixtures thereof may be used.

The porous substrate may be a nonwoven fabric or a woven fabric.

The method of laminating the nanofiber membrane and the porous substrate may be heat-sealed between the nanofiber membrane and the porous substrate by any one of laminating, calendering, hot plate calendering, ultrasonic bonding, and embossing.

The surface of the nanofiber membrane may be hydrophilized to maximize the exchange rate of hydrogen ions generated in the cathode portion.

A method for producing a cation exchange membrane according to the present invention comprises the steps of: preparing a spinning liquid by mixing a fiber-forming polymer material and a solvent at a predetermined ratio; and electrospunning the spinning solution to form nanofibers having a diameter of less than 1 탆, Forming a nanofiber membrane having micropores on the surface of the nanofiber membrane and the porous substrate; laminating the nanofiber membrane and the porous substrate; and filling the nanofiber membrane or nanofiber membrane and the porous substrate with the ion conductor material .

As described above, the microbial fuel cell of the present invention can improve the performance by integrating nanofibers having a high specific surface area of less than 1 mu m in diameter produced by electrospinning and having a nanofiber membrane having three-dimensional micropores.

In addition, the microbial fuel cell of the present invention is capable of hydrogen ion exchange in a microbial fuel cell while preventing other ions or substances from being transferred.

In addition, the microbial fuel cell of the present invention has a function of imparting a hydrophilization function to the surface of a nanofiber membrane through surface modification such as plasma or corona treatment, and thus can perform rapid hydrogen ion exchange and hydrogen ion exchange Function.

Also, the microbial fuel cell of the present invention can provide a nanofiber-based high-strength cation exchange membrane to improve durability and performance characteristics.

1 is a configuration diagram of a microbial fuel cell according to the present invention.
2 is a cross-sectional view of a cation exchange membrane according to the first embodiment of the present invention.
3 is a cross-sectional view of a cation exchange membrane provided with a nanofiber membrane having a multilayer structure of the present invention.
4 is a cross-sectional view of a cation exchange membrane according to a second embodiment of the present invention.
5 is a cross-sectional view of a cation exchange membrane according to a third embodiment of the present invention.
6 is a process flow chart showing a process for producing a cation exchange membrane according to the present invention.
FIGS. 7A and 7B are scanning electron microscope (SEM) photographs showing the surface of the PVC nanofibers according to the present invention, respectively enlarged 1,000 times and 10,000 times.
8A and 8B are scanning electron microscope (SEM) photographs showing the surface of PVDF nanofibers enlarged 500 times and 10,000 times, respectively, according to the present invention.
9 shows a scanning electron microscope (SEM) photograph showing the surface of a composite nanofiber obtained by blending electroluminescence of PVC / TPU at 50/50 wt.% According to the present invention.
10 is a scanning electron microscope (SEM) photograph of a cross section of a nanofiber composite membrane in which a PVDF nanofiber web and a PET nonwoven fabric are complexed according to the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The sizes and shapes of the components shown in the drawings may be exaggerated for clarity and convenience. In addition, terms defined in consideration of the configuration and operation of the present invention may be changed according to the intention or custom of the user, the operator. Definitions of these terms should be based on the content of this specification.

1 is a configuration diagram of a microbial fuel cell according to the present invention.

1, the microbial fuel cell according to the present invention includes an anode 10 and a cathode 20 positioned opposite to each other, and a cathode 20 disposed between the cathode 10 and the anode 20 And a proton exchange membrane 30 located in the proton exchange membrane.

As shown in FIG. 2, the cation exchange membrane 30 according to the first embodiment is made of a fiber-forming polymer material and is electrospun and integrated by nanofibers having a diameter of less than 1 탆 to form nano- A porous substrate 34 that is laminated on one side of the nanofiber membrane 32 and supports the nanofiber membrane 32; a nanofiber membrane 32 or nanofiber membrane 32; And an ion conductor material filled in the substrate.

The porous base material 34 is made of a nonwoven fabric or a woven fabric so as to reinforce the physical properties of the nanofiber membrane 32 as a strength reinforcing layer for supporting the nanofiber membrane 32, It is possible to use.

The ionic conductor material is a polymer resin having a cation-exchange group, and includes poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), a copolymer of tetrafluoroethylene and fluorovinyl ether containing a sulfonic acid group, Sulfated polyether ketone, and mixtures thereof.

The nanofiber membrane 32 is prepared by dissolving a fiber-forming polymer in a solvent to prepare a spinning solution, then spinning the spinning solution to form nanofibers having a fiber diameter of less than 1 占 퐉 and integrating the nanofibers to form micropores Nanofibers are formed in web form.

Here, the solvent is selected from the group consisting of dimethylformamide (DMF), dimethylacetamide (DMAc), tetrahydrofuran (THF), methylene chloride (MC), formic acid, acetone, alcohol, a solvent such as chloroform, water, or dimethyl sulfoxide (DMSO) may be used alone or in combination.

The average pore size of the nanofiber membrane 32 is preferably 0.2 to 1.0 mu m.

The amount (basis weight) of the nanofibers emitted to form the nanofiber membrane 32 is preferably set in the range of 0.5 to 20 gsm (gram per square meter).

The polymer material can be a natural polymer or a synthetic polymer material alone or in combination, and is a polymer material capable of forming nanofibers by electrospinning. As a material capable of being used as a proton exchange membrane for a microbial fuel cell electrochemically, There is no. Moreover, nanofiber membranes can be made by mixing ionic conductor materials to impart ionic conductivity.

When forming the nanofiber membrane 32, two or more kinds of fiber-forming macromolecule materials may be blended to perform electrospinning. The solvent may be selected from those having compatibility with the polymer material to be used, Or a mixture of two or more thereof.

Electrospinning to produce the nanofiber membrane 32 may be selected from electrospinning, electrospray, electrobrown spinning, centrifugal electrospinning, flash-electrospinning, -less radiation, top-down, top-down, etc., and can be appropriately adopted from among these processes.

Here, the nanofiber membranes 32 may be formed in a multilayer structure by laminating a plurality of nanofiber membranes 32. 3, the nanofiber membrane 32 may include a first nanofiber membrane 32a and a second nanofiber membrane 32b stacked on the first nanofiber membrane 32a, And a third nanofiber membrane 32c stacked on the second nanofiber membrane 32b.

When the nanofiber membrane 32 has a multi-layer structure, after the nanofiber web is formed, the fusion between the nanofiber and the nanofiber is induced by the thermocompression or laminating method, The conductor material is impregnated to form a cation exchange membrane of an inorganic porous type.

The porous base material 34 is laminated on one side or both sides of the nanofiber membrane 32 to improve the physical properties of the nanofiber and to maintain the proton exchange property for a long period of time.

The cation exchange membrane can be manufactured by impregnating the ion conductor material only with the nanofiber membrane 32 and by laminating the nanofiber membrane 32 filled with the ion conductor material and the porous substrate 34 together.

After the nanofiber membrane 32 and the porous substrate 34 are joined together, an ion conductor material may be impregnated to produce a cation exchange membrane.

The laminating of the nanofiber membrane 32 and the porous substrate 34 is a method of compositing the nanofiber membrane 32 with the porous substrate 34 using thermal fusing or the like and includes laminating, calendering, hot plate calendering, , Embossing or the like can be applied, and there is no particular limitation as long as the nanofiber membrane 32 is not peeled off.

In the process of filling the ion conductor material in the pores of the nanofiber membrane 32, a supporting process of impregnating the nanofiber membrane 32 with the ion conductor solution may be used. However, the process of laminating, spraying, electrospray, screen printing, doctor blade, gravure coating, and the like.

The surface of the nanofiber membrane 32 is provided with a hydrophilization function through surface modification such as plasma or corona treatment to maximize the hydrogen ion exchange rate in a form capable of rapidly absorbing and transferring hydrogen ions generated in the cathode portion .

As shown in FIG. 4, the cation exchange membrane 40 according to the second embodiment is composed of a fiber-forming polymeric material, and is electrospun and integrated by nanofibers having a diameter of less than 1 탆 to form nano- A first porous substrate 42 that is laminated on one side of the nanofiber membrane 46 and supports the nanofiber membrane 46; a second porous substrate 42 that is laminated on the other side of the nanofiber membrane 46, And a second porous substrate 44 that supports the fibrous membrane 32.

The cation exchange membrane 40 according to the second embodiment is formed by stacking the first porous substrate 42 and the second porous substrate 44 on both sides of the nanofiber membrane 46 to improve the supporting force of the nanofiber membrane 46 .

5, the cation exchange membrane 50 according to the third embodiment comprises a porous substrate 52, a porous substrate 52 laminated on one side of the porous substrate 52 and made of a fiber-forming polymer material, A first nanofiber membrane 54, which is integrated by nanofibers having a diameter of less than 1 mu m and has three-dimensional micropores, a second nanofiber membrane 54 that is laminated on the other side of the porous substrate 52 and is formed of a fiber- And a second nanofiber membrane 56 having three-dimensional micropores integrated by nanofibers having a diameter of less than 1 mu m.

The cation exchange membrane 50 according to the third embodiment can stack a plurality of nanofiber membranes by stacking a first nanofiber membrane 54 and a second nanofiber membrane 56 on both sides of the porous substrate 52 .

Hereinafter, a method for producing a cation exchange membrane will be described.

6 is a block diagram illustrating a method for preparing a cation exchange membrane according to an embodiment of the present invention.

First, a fiber-forming polymer material and a solvent are mixed at a predetermined ratio to prepare a spinning solution (S10). As the polymer substance, a natural polymer or a synthetic polymer substance may be used singly or as a mixture, and the ion conductive material may be mixed to impart ion conductivity.

The content (basis weight) of the nanofiber is set in the range of 0.5 to 20 gsm (gram per square meter).

If the content (basis weight) of nanofibers is less than 0.5 gsm, there is a problem in handling due to an excessively thin film. If the nanofiber content is over 20 gsm, there is no problem in use, but the process cost is increased due to material cost and production speed. The thickness of the microbial fuel cell increases and the internal resistance of the microbial fuel cell ultimately decreases, thereby decreasing the efficiency of the fuel cell system. Therefore, the amount of the polymer substance dissolved in the solvent is determined in consideration of the basis weight of the obtained nanofiber.

Then, the spinning solution is electrospun to form nanofibers having a diameter of less than 1 占 퐉, and the nanofibers are integrated to form a nanofiber membrane having micropores (S20). That is, the prepared spinning solution is introduced into a metering pump ) Is transferred to a nozzle pack provided with a spinning nozzle, and a voltage is applied to the spinning nozzle using a high voltage generator to perform electrospinning to produce a nanofiber. The nanofibers thus produced are collected in a collector to form a nanofiber membrane in the form of a nanofiber web.

Then, the nanofiber membrane 32 and the porous substrate 34 are joined together (S30). The nanofiber membrane 32 and the porous substrate 34 are laminated by heat fusion, and methods such as laminating, calendering, hot plate calendering, ultrasonic bonding, and embossing can be applied.

Here, the porous substrate may be laminated on one side or both sides of the nanofiber membrane, and the nanofiber membrane may be laminated on both sides of the porous substrate.

Then, the ion conductor material is filled only in the nanofiber membrane 32, or both the nanofiber membrane 32 and the porous substrate 34 (S40). At this time, the ion conductor material may be impregnated only in the nanofiber membrane 32, and the ion conductive material may be impregnated after the nanofiber membrane 32 and the porous substrate 34 are combined.

Then, after the ion conductor solution is filled, the organic solvent in the ion conductor solution is removed, and the ion conductor is filled in the pores of the nanofiber membrane so as to be an inorganic porous type (S50). Here, the step of removing the organic solvent may be a step of drying using hot air.

The surface of the nanofiber membrane 32 is subjected to hydrophilization treatment through surface modification such as plasma or corona treatment to maximize the hydrogen ion exchange rate in a form capable of rapid absorption and transfer of hydrogen ions generated in the cathode portion (S60 ).

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by these examples.

(Example 1)

Polyvinylchloride (PVC) as a fiber-forming macromolecular material is added to a mixed solvent of DMAc (dimethylacetamide) / THF (tetrahydrofuran) (mixing ratio is 4/6 in wt.%) To be 15 wt. To prepare a spinning solution.

The spinning solution thus prepared was transferred to a spinning nozzle pack to be subjected to electrospinning at an applied voltage of 20 kV, a distance of 20 cm between the spinning nozzle and the collector, and a discharge rate of 0.05 cc / ghole per minute at a temperature of 30 ° C. and a relative humidity of 60% To obtain PVC nanofibers having an average fiber diameter of less than 1 占 퐉. The thus produced PVC nanofibers were thermally fused to each other through rollers heated to 70 ° C.

7A and 7B are SEM micrographs of the PVC nanofiber membrane. As shown in FIG. 7B, it can be confirmed that the fusion of the fibers occurred due to the thermal fusion of the surface of the PVC nanofibers.

(Example 2)

Polyvinylidene fluoride (PVDF) was used as a fiber-forming polymeric material in a mixed solvent of DMAc (dimethylacetamide) / acetone (mixing ratio is 7/3 wt.%) At 15wt. % To prepare a spinning solution.

The spinning solution thus prepared was transferred to a spinning nozzle pack and subjected to electrospinning at an applied voltage of 25 kV, a distance of 20 cm between the spinneret and the collector, 0.05 cc / ghole per minute of discharge rate, a temperature of 30 ° C. and a relative humidity of 60% To obtain a PVDF nanofiber web having an average fiber diameter of 400 nm. The PVDF nanofiber web thus prepared was thermally fused with fibers through a roller heated to 150 ° C. FIG. 8 is a photograph of the PVDF nanofiber web obtained by enlarging it to a size of 500 times and a magnification of 10,000 times by a scanning electron microscope photograph.

(Example 3)

Polyvinylchloride (PVC) and thermoplastic polyurethane (TPU) were mixed with 50:50 wt. %, And the mixture was mixed in a mixed solvent of DMAc (dimethylacetamide) / THF (tetrahydrofuran) (mixing ratio is 4/6 in wt.%) So that the total amount of the spinning solution is 15 wt.%.

 The spinning solution thus prepared was electrospun in the same manner as in Example 1 to obtain PVC / TPU blended nanofibers, and the obtained nanofibers were thermally fused under the same conditions as in Example 1 to prevent lint. As a result, a PVC / TPU blend nanofiber membrane having an average diameter of about 1 탆 or less was obtained. Figure 9 shows a scanning electron microscope (SEM) photograph of the surface of a PVC / TPU blend nanofiber membrane.

(Example 4)

The PVDF nanofiber web prepared in Example 2 was laminated with a PET nonwoven fabric to obtain a two-layered composite membrane. A scanning electron microscope (SEM) photograph of the cross section of the thus obtained composite membrane is shown in FIG. 10, and it can be confirmed that the nanofiber membrane is laminated on the nonwoven fabric.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be construed as limited to the embodiments set forth herein. Various changes and modifications may be made by those skilled in the art.

10: cathode part 20: anode part
30: cation exchange membrane 32: nanofiber membrane
34: porous substrate 32a: first nanofiber membrane
32b: second nanofiber membrane 32c: third nanofiber membrane

Claims (15)

A nanofiber membrane formed into a nanofiber web shape by electrospinning a fiber-forming polymeric material and having three-dimensional micropores having a diameter of less than 1 mu m;
A porous substrate laminated on one side or both sides of the nanofiber membrane to support the nanofiber membrane; And
A cation exchange membrane for a microbial fuel cell comprising the nanofiber membrane or an ion conductor material filled in both the nanofiber membrane and the porous substrate. A porous substrate;
A nanofiber membrane that is formed on both sides of the porous substrate and is formed into a nanofiber web by electrospinning the fiber-forming polymeric material and has three-dimensional micropores having a diameter of less than 1 mu m; And
A cation exchange membrane for a microbial fuel cell comprising the nanofiber membrane or an ion conductor material filled in both the nanofiber membrane and the porous substrate. 3. The method according to claim 1 or 2,
Wherein the nanofiber membrane is formed as a nanofiber web having micropores integrated by electrospinning of a spinning solution in which a fiber-forming polymer is dissolved in a solvent. The method of claim 3,
Wherein a nanofiber content (basis weight) of the nanofiber membrane is 0.5 to 20 gsm (gram per square meter). 3. The method according to claim 1 or 2,
Wherein the nanofiber membrane is formed as a multilayer structure in which a plurality of nanofiber membranes are stacked,
And the nanofiber membranes are formed by fusing the nanofibers by thermal compression or laminating. 3. The method according to claim 1 or 2,
The ionic conductor material is a polymer resin having a cation-exchange group, and includes poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), a copolymer of tetrafluoroethylene and fluorovinyl ether including a sulfonic acid group, A sulfated polyether ketone, and a mixture thereof. The cation exchange membrane for microbial fuel cells according to claim 1, 3. The method according to claim 1 or 2,
Wherein the porous substrate is a nonwoven fabric or a woven fabric. 3. The method according to claim 1 or 2,
Wherein the nanofiber membrane and the porous substrate are thermally fused between the nanofiber membrane and the porous substrate by any one of laminating, calendering, hot plate calendering, ultrasonic bonding, and embossing. 3. The method according to claim 1 or 2,
Wherein the surface of the nanofiber membrane is hydrophilized so as to maximize the exchange rate of generated hydrogen ions in the cathode portion. Preparing a spinning solution by mixing the fiber-forming polymeric material and a solvent;
Electrospinning the spinning solution to form nanofibers having a diameter of less than 1 占 퐉 and integrating the nanofibers to form nanofiber membranes having micropores;
Laminating the nanofiber membrane with a porous substrate; And
And filling the nanofiber membrane, or both the nanofiber membrane and the porous substrate, with an ion conductor material. 11. The method of claim 10,
Further comprising laminating a plurality of said nanofiber membranes,
Wherein the step of laminating a plurality of the nanofiber membranes comprises fusing the nanofibers by a thermocompression bonding or a laminating method. 11. The method of claim 10,
Wherein the step of laminating the nanofiber membrane with the porous substrate comprises thermally fusing the nanofiber membrane and the porous substrate by any one of laminating, calendering, hot plate calendering, ultrasonic bonding, and embossing. Exchange membrane manufacturing method. 11. The method of claim 10,
Wherein the step of filling the ion conductor material is any one of a supporting process, laminating process, spraying process, electrospray process, screen printing process, and doctor blade process. 11. The method of claim 10,
Further comprising the step of subjecting the surface of the nanofiber membrane to a plasma or corona treatment to thereby impart a hydrophilization function to the nanofiber membrane. A cathode portion;
A cathode portion disposed to face the cathode portion; And
And a cation exchange membrane according to any one of claims 1 to 9, which is located between the cathode portion and the anode portion.

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