KR20180003925A - Reinforced-Composite Electrolyte Membrane Comprising Porous Polymer Substrate And Manufacturing Method Thereof - Google Patents

Abstract

The present invention relates to a reinforced-composite electrolyte membrane impregnating an ionic conductive polymer by substituting the surface of a porous substrate and the inside of pores with an ionic functional group. If a reinforced-composite electrolyte membrane manufactured according to the present invention is applied to a fuel cell or a flow battery, high mechanical strength of a porous material is maintained and selective ion permeability of an electrolyte membrane is increased through introduction of ionic characters. Also, hydrogen ion conductivity and impregnation ratios (porosity) of an ionic resin are maximized so performance of a battery is improved.

Description

TECHNICAL FIELD [0001] The present invention relates to a reinforced-composite electrolyte membrane including a porous substrate and a method of manufacturing the same.

The present invention relates to a reinforced-composite electrolyte membrane in which an ion conductive polymer is impregnated into pores and the surface of the porous substrate is replaced with an ionic functional group.

Fuel cells and redox flow cells are being researched and developed as a next generation energy source because of their high energy efficiency and eco - friendly characteristics with low emission of pollutants.

Fuel cells are energy conversion devices that convert the chemical energy of a fuel directly into electrical energy. That is, a fuel cell uses a fuel gas and an oxidizing agent, and generates electricity using electrons generated during the oxidation-reduction reaction. The membrane electrode assembly (MEA) of a fuel cell is composed of a cathode, an anode, and an electrolyte membrane, that is, an ion conductive electrolyte membrane, as a portion where an electrochemical reaction of hydrogen and oxygen takes place.

Redox Flow Battery (Redox Flow Battery) is a system in which an active substance contained in an electrolyte is oxidized and reduced to be charged and discharged. An electrochemical storage device that stores chemical energy of an active substance directly as electric energy to be. The unit cell of the redox flow battery includes an electrode, an electrolyte, and an electrolyte membrane.

One of the key components of such a fuel cell and redox flow cell is a polymer electrolyte membrane (ion exchange membrane, electrolyte membrane) capable of cation exchange. The polymer electrolyte membrane is not a simple membrane such as a film but a polymer membrane having a function of separating a substance. Specifically, a polymer capable of cation exchange such as a fuel cell or a redox flow cell is used as an electrolyte membrane.

The electrolyte membrane applied to the fuel cell and the redox flow cell should be able to separate the anode / cathode, and it is absolutely necessary to have high selective ion permeability to prevent the movement of other active ions while transferring hydrogen ions. At present, an ionic conductive polymer (ion resin) such as Nafion is used as a material of an electrolyte membrane, but pure polymer is expensive, and because of its low mechanical strength and selective permeability, it is applied to an electrolyte membrane of a long- There is a limit to doing so.

In order to solve such a problem, an ionic polymer is impregnated into a porous substrate to form an electrolyte membrane in the form of a reinforcing membrane (hereinafter referred to as a reinforcing-composite electrolyte membrane). The reinforced-composite electrolyte membrane is provided with a porous substrate for imparting mechanical properties and dimensional stability. Since the porous substrate should maintain its mechanical durability while not deteriorating its performance, it is necessary to select a suitable material support having high porosity and excellent mechanical properties. In addition, since the ion conductivity of the membrane may be greatly changed depending on the method of impregnating the ion conductive polymer with the support and the kind of the ion conductive polymer, development of an effective method of impregnating the ion conductive polymer is required.

Korean Patent Laid-Open Publication No. 2014-0128894 "Fuel cell including polymer electrolyte membrane, membrane electrode assembly including a polymer electrolyte membrane and membrane electrode assembly"

Therefore, the inventors of the present invention have conducted various studies and have found that when the functional group of the porous substrate is replaced with an ionic functional group, an ionic interaction with the ionic polymer impregnated in the pores is induced to increase the affinity between the porous substrate and the ionic polymer And have completed the present invention.

Accordingly, an object of the present invention is to provide a reinforced-composite electrolyte membrane having improved processability by increasing the rate of impregnation of an ion conductive polymer, and a method for producing the same.

In order to accomplish the above object, the present invention provides a reinforced-composite electrolyte membrane comprising a hydrophilic porous substrate having a surface and pores replaced by ionic functional groups, and an ion conductive polymer impregnated in the porous substrate. In this case, the hydrophilic porous substrate may have a multi-layer structure in which a hydrophilic polymer is coated on the hydrophobic polymer.

The present invention also provides a method for preparing a porous substrate, comprising: i) preparing a porous substrate; Ii) coating the porous substrate with a polymer having a hydrophilic functional group; Iii) treating the hydrophilic porous substrate with a substance having an ionic functional group to replace the hydrophilic functional group with an ionic functional group; And iv) impregnating the porous substrate substituted with the ionic functional group with the ion conductive polymer.

The present invention also provides a fuel cell having the reinforced composite electrolyte membrane.

The present invention also provides a redox flow battery having the reinforced composite electrolyte membrane.

The application of the reinforced-composite electrolyte membrane prepared according to the present invention to a fuel cell or a flow battery increases the selective ion permeability of the electrolyte membrane through the introduction of ionic functional groups while maintaining the high mechanical strength of the porous substrate, The impregnation rate (processability) of the ionic resin is maximized, and the performance of the battery is improved.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of a reinforced-composite electrolyte membrane illustrating the replacement of the hydrophilic functional groups within the porous substrate pores of the present invention with ionic functional groups.
2 is an experimental schematic diagram for measuring the vanadium ion permeability of an electrolyte membrane according to Example 1 and Comparative Example 1 of the present invention.
3 is data of vanadium ion permeability data of an electrolyte membrane according to Example 1 and Comparative Example 1 of the present invention.

The present invention discloses a reinforced-composite electrolyte membrane comprising a hydrophilic porous substrate in which a surface and pores are substituted with an ionic functional group, and an ion conductive polymer impregnated in the porous substrate. Hereinafter, the present invention will be described in detail.

The reinforced-composite electrolyte membrane not only improves the mechanical strength, durability and selective permeability but also has an advantage in that the manufacturing cost is lower than that of the pure polymer. However, the conventional technology has a problem that it is difficult to completely impregnate the ionic polymer into the pores of nano size, and the ionic polymer is separated from the porous substrate when the battery is driven for a long time. In addition, there is a disadvantage in that the conductivity is reduced by the ratio of the porous substrate to the pure ionic polymer since the porous substrate itself has no ion transfer capability.

To compensate for these drawbacks, the porous substrate used in the reinforced-composite electrolyte membrane is mostly hydrophobic, so it is coated with a hydrophilic polymer such as polyvinyl alcohol (PVA). Here, the hydroxyl group (hydroxyl group, -OH) of the coated polyvinyl alcohol modifies the hydrophobic polymer to hydrophilicity to help impregnate the ion conductive polymer into the pores of the porous substrate. However, the porous material itself does not have ion transport capability, and the hydroxyl group of the coated polyvinyl alcohol does not play a large role in the hydrogen transfer due to the high pKa (10.67).

Accordingly, the present invention provides a porous substrate having a porous substrate with a hydrophilic functional group, such as a hydroxyl group or a peptide group, substituted with various ionic functional groups through a simple chemical reaction, The ionic conductivity and the ion permeability of the electrolyte membrane can be improved. The hydrophilic porous substrate may be a multi-layer structure in which a hydrophilic polymer is coated on a porous hydrophobic polymer substrate.

FIG. 1 is a schematic view of a reinforced-composite electrolyte membrane illustrating a hydrophilic functional group on the surface and pores of a porous substrate according to the present invention substituted with an ionic functional group. The hydrophilic polymer 12 is formed on the porous hydrophobic polymer 11, Layered reinforced composite electrolyte membrane 100. The hydrophilic functional group 13 of the hydrophilic polymer 12 is substituted with a hydrophobic functional group 14 through a chemical reaction.

More specifically, referring to FIG. 1, the hydrophobic polymer 11 constituting the hydrophilic porous substrate 10 may be made of, for example, polyethylene (PE), ethylene vinyl acetate copolymer (EVA), polypropylene (PP), polyimide , Polyamide (PA), polycarbonate (PC), polyacrylonitrile (PAN), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene terephthalate (PET), polyvinyldifluoroethylene at least one member selected from the group consisting of polyvinylidene fluoride, polyvinyldifluoroethylene, polyvinylchloride, polyvinylidene chloride, polyetherketone, polyetheretherketone (PEEK), and polyethylene ether nitrile .

The hydrophilic polymer 12 for modifying the porous substrate formed of the hydrophobic polymer 11 is preferably selected from a group of hydrocarbon-based polymers having a hydrophilic functional group 13 including a hydroxyl group, a peptide group, a halogen element and the like And may be selected from, for example, polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cellulose, polydodamine, chitosan.

The ionic functional group 14 substituting the hydrophilic functional group 13 of the hydrophilic modified porous substrate 10 may be a negative type, a positive type or an amphoteric functional group, and more specifically, At least one selected from a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and an amine group may be selected and coated on the surfaces and pores of the porous substrate.

For example, by introducing an anionic group represented by the following general formula (1), (2) or (3) to increase the ion exchange capacity (IEC value) by imparting hydrogen ion conductivity to the electrolyte membrane itself.

[Chemical Formula 1]

(2)

(3)

On the other hand, substitution with the cationic molecule represented by the following Chemical Formula 4, 5 or 6 induces electrostatic repulsion, thereby blocking the ion permeability of the positively charged vanadium when the flow battery is driven, thereby improving the selective permeability .

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

Further, when an ampholytic molecule having an anionic functional group and a cationic functional group simultaneously represented by the following general formulas (7) and (8) is introduced, the above-described improvement in conductivity and selective permeability can be simultaneously achieved.

(7)

[Chemical Formula 8]

(In the above formulas 7 and 8, n is an integer of 1 to 10)

According to one embodiment of the present invention, the higher the degree of substitution of the hydrophilic functional group (13) of the porous substrate (10) with the ionic functional group (14), the better the ion conductivity effect and the selective ion permeability effect of the present invention Glass, but may be substituted with 1 to 50% substitution, particularly 20 to 50%, in consideration of experimental conditions for substituting the functional groups of the polymer coated inside the pores of the porous substrate 10 in reality.

The porous substrate 10 in which the surfaces and pores formed therein are substituted with the ionic functional groups 14 can facilitate the impregnation of the ion conductive polymer 20 to improve the workability and the ionic polymer 14 and the surface- It is possible to induce an ionic interaction between the base material and the substrate to prevent the polymer from leaking from the electrolyte membrane and to increase the mechanical and physical strength.

According to one embodiment of the present invention, the thickness of the porous substrate 10 is not particularly limited, but is preferably in the range of 1 to 200 占 퐉, more preferably in the range of 5 to 100 占 퐉. If the thickness of the porous substrate is less than 1 탆, the mechanical properties can not be maintained. If the thickness exceeds 200 탆, the electrolyte membrane acts as a resistance layer, thereby deteriorating the performance of the battery.

According to one embodiment of the present invention, the pore size of the porous substrate 10 is not particularly limited, but is preferably 0.1 to 100 탆. If the pore size of the porous substrate is less than 0.1 탆, the electrolyte membrane acts as a resistance layer, and if it exceeds 100 탆, the mechanical properties can not be maintained.

According to one embodiment of the present invention, the porosity of the porous substrate 10 is not particularly limited, but is preferably in the range of 10 to 95%. When the porosity of the porous substrate is less than 10%, the electrolyte membrane acts as a resistive layer, and when it exceeds 95%, the mechanical properties can not be maintained.

According to an embodiment of the present invention, the porous substrate 10 may be in the form of a fiber or a membrane. In the case of a fiber form, it is a nonwoven fabric forming a porous web, and includes a spunbond or a meltblown form composed of long fibers.

The ion conductive polymer 20 impregnated into the porous substrate 10 may be filled in the pores of the porous substrate and may be ion-exchanged. The polymer is not particularly limited and may be any of those generally used in the art Can be used. For example, a hydrocarbon-based polymer, a partially fluorinated polymer, or a fluorinated polymer.

The ion conductive polymer 20 is not particularly limited as long as it is a polymer capable of ion exchange with cation conductivity or anion conductivity, and any of those known in the art can be used. For example, the polymer may be a fluorine-based polymer, a partially fluorinated polymer, or a hydrocarbon-based polymer, and more specifically, a perfluorosulfonic acid polymer, a hydrocarbon polymer, an aromatic sulfonic polymer, an aromatic ketone polymer, a polybenzimidazole polymer, a polystyrene polymer, Based polymer, polyimide-based polymer, polyvinylidene fluoride-based polymer, polyether sulfone-based polymer, polyphenylene sulfide-based polymer, polyphenylene oxide-based polymer, polyphosphazene-based polymer, polyethylene naphthalate- Based polymer, a polyester-based polymer, a doped polybenzimidazole-based polymer, a polyether ketone-based polymer, a polyphenylquinoxaline-based polymer, a polysulfone-based polymer, a sulfonated polyarylene ether-based polymer, a sulfonated polyether ketone- Sulfonated polyether ether ketone-based polymer, sulfonated polyol A single polymer or a mixture of two or more polymers selected from the group consisting of sulfonated polyimide polymers, sulfonated polyphosphazene-based polymers, sulfonated polystyrene-based polymers, and radiation-polymerized sulfonated low density polyethylene-g-polystyrene- Is a homo copolymer, an alternating copolymer, a random copolymer, a block copolymer, a multiblock copolymer or a graft copolymer. ≪ / RTI >

The thickness of the reinforced composite electrolyte membrane in which the ionic polymer 20 is impregnated into the pores of the porous substrate 10 according to the present invention may be 10 to 500 탆 and may be 5 to 200 탆 as required. A reinforced-composite electrolyte membrane having a thickness in the above range is preferable for maintaining mechanical properties without acting as a resistive layer.

I) preparing a porous substrate 10; Ii) coating the porous substrate (10) with a polymer having hydrophilic functional groups (13); Iii) treating the hydrophilic porous substrate with a substance having an ionic functional group (14) to replace the hydrophilic functional group (13) with an ionic functional group (14); And iv) impregnating the porous base material substituted with the ionic functional group 14 with the ion conductive polymer 20.

Stepwise, first, i) the porous substrate 10 is prepared. The types and physical properties of the porous substrate are as described above, and the porous substrate 10 may be a porous hydrophobic polymer substrate.

Next, ii) the porous substrate 10 is coated with a polymer having a hydrophilic functional group 13. When the surface and pores of the hydrophobic porous substrate 10 are coated with the hydrophilic polymer 12, the kind and physical properties of the hydrophilic polymer 12 are as described above.

There is no limitation on the method of coating the surface of the porous substrate 10 with the hydrophilic polymer 12 and the inside of the pore. In one embodiment, after the porous substrate 10 is treated with a base, the hydrophilic functional group 13 The branch may be modified to be hydrophilic by using a composition containing a substance and an oxidizing agent.

As a method of treating the porous substrate 10 with a base, for example, a base treatment may be performed by contacting the porous substrate 10 with a base under certain conditions. The method of contacting the porous substrate 10 with a base includes a method in which a porous substrate is immersed in a base liquid in which a base is dissolved or dispersed in a predetermined solvent or a method in which a base liquid is applied to a porous substrate 10 or coated and sprayed have. However, the surface treatment method of the porous substrate 10 according to the present invention is not limited thereto. Also, the base solution may be vaporized under certain conditions to contact the porous substrate 10 to perform the base treatment.

The base treatment may be carried out by, for example, contacting the solution with a base solution at 20 to 90 ° C for 5 minutes to 24 hours. At this time, the method of contacting the porous substrate 10 with the base solution may be, but not limited to, immersion, application, and spraying as described above. Further, the base in a vapor state and the porous base material can be brought into contact with each other and base treatment can proceed.

The base solution used may be prepared by dissolving in a suitable solvent. The solvent may be water, alcohol or a mixed solvent of water and alcohol, but is not particularly limited thereto. The concentration of the base solution may also preferably be 5 to 25%. When the base concentration is less than 5%, the base treatment of the porous substrate is insignificant and the dehydrogenation can proceed less. If the base concentration exceeds 25%, the mechanical strength of the porous substrate may be decreased and other properties may be deteriorated.

Next, iii) the hydrophilic porous substrate 10 is treated with a substance having an ionic functional group 14 to replace the hydrophilic functional group 13 with an ionic functional group 14. The kind and physical properties of the substance having the ionic functional group 14 are as described above.

For example, a hydrophilic porous substrate is fixed to a predetermined frame and immersed in distilled water at 30 to 50 ° C for 6 to 24 hours to prevent wrinkling during surface treatment. Subsequently, the porous substrate is immersed again in an aqueous solution containing the substance having the ionic functional group (14) to carry out the substitution reaction. At this time, the reaction conditions may be determined according to the kind of the substance having the ionic functional group (14), and the reaction is preferably carried out at 40 to 120 ° C for 12 to 48 hours. Thereafter, it is washed and dried to remove the remaining material.

Thereafter, iv) the ionic conductive polymer is impregnated into the porous substrate substituted with the ionic functional group. Specifically, when the mixture of the ion conductive polymer 20 and the solvent is filled in the pores of the porous substrate 10 and then dried, the solvent is removed, and only the ion conductive polymer 20 remains on the surface and pores of the porous substrate 10.

In this case, it is preferable that the solvent to be used has a solubility index similar to that of the ion conductive polymer (20) and a low boiling point. This is because the mixing can be made uniform and the solvent can then be easily removed. Specifically, a solvent such as N, N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF) acetone, tetrahydrofuran, methylene chloride, chloroform, dimethylformamide, N-methyl-2-pyrrolidone (NMP) Cyclohexane, water or a mixture thereof can be used as a solvent.

The impregnation of the ion conductive polymer 20 is preferably performed by casting the ion conductive polymer solution on a porous substrate substituted with an ionic functional group and performing a drying operation. The casting may include all of the casting methods commonly used in the art. Specifically, the casting method may be a coating using a comma coater, a spin coating, a dip coating, or a slot die coating.

The reinforced-composite electrolyte membrane in the above production method is preferably applicable to an electrolyte membrane for a flow cell or a fuel cell.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. These drawings may be embodied in various different forms as an embodiment for explaining the present invention, and are not limited thereto.

≪ Example 1 >

1. Hydrophilic coating of porous substrate

A polytetrafluoroethylene (PTFE) base material having a pore size of 450 nm and a thickness of 30 占 퐉 was prepared. The porous PTFE substrate was coated with polyvinyl alcohol (PVA).

2. Ionic substitution

The hydrophilized porous PTFE substrate was fixed to a 10 cm x 10 cm frame. The PTFE frame was immersed sufficiently in a D.I. water bath and maintained at 60 DEG C for 12 hours. An aqueous solution containing 30% by weight of ethanolamine (Ethanolamine, sigma-aldrich> 98%) was prepared. Then, the PTFE frame was placed and reacted with stirring at 80 ° C for one day. The PTFE frame was then rinsed several times with distilled water to remove residual ethanolamine and vacuum dried at room temperature for one day.

3. Ionic conductive polymer impregnation

An ion conductive polymer solution was prepared by diluting a perfluorinated polyether ketone (CF3 group) as a partially fluorinated polymer to 20 wt% in DMAc. The prepared ion conductive polymer solution was formed into a uniform thickness using a coater. And PTFE in which the surface and pore interior were substituted with the ionic functional groups fixed to the frame was placed thereon and allowed to stand for 1 hour so that the ion conductive polymer could be impregnated. And dried at room temperature for 2 hours and at 80 占 폚 for one day to evaporate the remaining solvent. The frame was removed using a cutter knife, and the ion conductive polymer solution was further formed on the opposite surface of the PTFE. And dried at 80 DEG C for 24 hours at 110 DEG C to evaporate the remaining solvent. The electrolyte membrane was treated with 1M H ₂ SO ₄ aqueous solution at 80 ° C for 12 hours with acid treatment and then with distilled water to prepare an electrolyte membrane.

≪ Comparative Example 1 &

The porous PTFE substrate used in Example 1 was subjected to the same processes as those in Step 3 without performing the surface treatment of Step 1 and Step 2 of Example 1 to prepare an electrolyte membrane.

<Experimental Example 1>

As shown in FIG. 2, a water tank containing 2M H ₂ SO ₄ solution in which 1M of VOSO ₄ was dissolved and 2M H ₂ SO ₄ solution in which 1M of MgSO ₄ was dissolved was used as the electrolyte membrane prepared in Example 1 and Comparative Example 1, And the transmittance of vanadium ion was calculated using the following equation (1). The results are shown in FIG.

[Equation 1]

(Where, V _B is the volume (L) of MgSO ₄ solution, C _A is a concentration of the increased vanadium ions after time (concentration of vanadium ions in enrichment side, mol / L) of MgSO ₄ solution in Equation (1) L is the thickness (m) of the electrolyte membrane used, A is the active area (m ² ) of the electrolyte membrane used, C _B is the concentration of vanadium ions in the MgSO ₄ solution, ) And D is the diffusion coefficients of vanadium ions (m ² / s)

Referring to FIG. 3, the results are summarized in Table 1 below. In Table 1, L is the thickness (cm) of the electrolyte membrane used, A is the active area (cm ² ) of the used electrolyte membrane, V _Mg is the volume of one solution (cm ³ ) Transmittance (cm ² / min).

Slope L A V _Mg P cm cm ² cm ³ cm ² / min Example 1 2.01E-07 0.015 7.69 190 7.44E-08 Comparative Example 1 3.76E-06 0.007 7.69 200 6.85E-07

As can be seen from FIG. 3 and Table 1, it can be seen that the permeability of vanadium in the electrolyte membrane of Example 1 was reduced to 1/10 of that of the electrolyte membrane of Comparative Example 1, It is expected that the cross-over phenomenon is reduced to prevent mixing of the electrolytic solution to improve the performance.

10. Porous substrate
11. Hydrophobic polymers
12. Hydrophilic polymer
13. Hydrophilic functional group
14. Ionic functional groups
20. Ionic Conducting Polymers
100. Reinforced-composite electrolyte membrane

Claims (15)

A hydrophilic porous substrate in which the surface and pore interior are replaced by ionic functional groups; And
And an ion conductive polymer impregnated into the porous substrate.
The method according to claim 1,
Wherein the ionic functional group is at least one selected from anionic, cationic, or amphoteric functional groups.
The method according to claim 1,
Wherein the ionic functional group is at least one selected from a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and an amine group.
The method according to claim 1,
Wherein the ionic functional group is at least one selected from functional groups corresponding to the following formulas (1) to (8).
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

(In the above formulas 7 and 8, n is an integer of 1 to 10)
The method according to claim 1,
Wherein the hydrophilic porous substrate has a multi-layer structure in which a hydrophilic polymer is coated on a porous hydrophobic polymer substrate.
6. The method of claim 5,
The hydrophobic polymer substrate may be made of polyethylene (PE), ethylene vinyl acetate copolymer (EVA), polypropylene (PP), polyimide (PI), polyamide (PA), polycarbonate (PC), polyacrylonitrile , Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene terephthalate (PET), polyvinyldifluoroethylene, polyvinylchloride, polyvinylidene chloride, A reinforced composite electrolyte membrane characterized by containing at least one member selected from the group consisting of polyetherketone, polyetheretherketone (PEEK), and polyethylene ether nitrile.
6. The method of claim 5,
Wherein the hydrophilic polymer is a hydrocarbon-based polymer having a hydrophilic functional group including a hydroxyl group, a peptide group or a halogen element.
8. The method of claim 7,
Wherein the hydrocarbon-based polymer is selected from polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cellulose, polydodamine, chitosan, and combinations thereof.
The method according to claim 1,
Wherein the substitution degree of the ionic functional group is 1 to 50%.
I) preparing a porous substrate;
Ii) coating the porous substrate with a polymer having a hydrophilic functional group;
Iii) treating the hydrophilic porous substrate with a substance having an ionic functional group to replace the hydrophilic functional group with an ionic functional group; And
And iv) impregnating the porous substrate substituted with the ionic functional group with the ion conductive polymer.
11. The method of claim 10,
Wherein the polymer having the hydrophilic functional group in step ii) is a hydrocarbon-based polymer having a hydrophilic functional group including a hydroxyl group, a peptide group or a halogen element.
12. The method of claim 11,
Wherein the hydrocarbon-based polymer is selected from polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cellulose, polydodamine, chitosan, and combinations thereof.
11. The method of claim 10,
In the step iii), the ionic functional group is at least one selected from the group consisting of a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and an amine group.
A fuel cell comprising the reinforced-composite electrolyte membrane according to any one of claims 1 to 10.
A redox flow battery having the reinforced-composite electrolyte membrane of any one of claims 1 to 10.

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