KR20120134236A - Electrolyte membrane for fuel cell and method of manufacturing the same - Google Patents

Abstract

PURPOSE: An electrolyte membrane for a fuel cell is provided to have excellent ion conductivity by having optimum pore property and to have excellent ion conductivity-maintaining rate by easily absorbing moisture even under low moisture. CONSTITUTION: An electrolyte membrane comprises a porous nanoweb which comprises a hydrocarbon-based polymer which is insoluble to organic solvent, and an ion conductor which is filled into the pore of the porous nanoweb and comprises a hydrocarbon-based polymer(10) which is soluble to organic solvent. The porous nanoweb comprises absorptive fiber(20) in which absorptive material are dispersed. The absorptive material comprises absorptive inorganic particles. The absorptive inorganic particle comprises at least one selected from alkaline earth metal oxide, metal oxide, sulphate, and silicon oxide.

Description

Electrolyte Membrane for Fuel Cell and Method for Manufacturing the Same {Electrolyte Membrane for Fuel Cell and Method of manufacturing the same}

The present invention relates to an electrolyte membrane, and more particularly, to an electrolyte membrane used for a fuel cell.

A fuel cell is a battery that converts chemical energy generated by oxidation of a fuel into electrical energy directly, and has been in the spotlight as a next-generation energy source due to its high energy efficiency and eco-friendly features with low emission of pollutants.

A fuel cell generally has a structure in which an anode and a cathode are formed on both sides of an electrolyte membrane, and such a structure is called a membrane electrode assembly (MEA).

The fuel cells may be classified into alkali electrolyte fuel cells and polymer electrolyte fuel cells (PEMFC) according to the type of electrolyte membrane. Among them, polymer electrolyte fuel cells have a low operating temperature of less than 100 ° C and a solid electrolyte. It has been spotlighted as a portable, automotive, and home power supply because of the advantages of eliminating the water leakage problem, fast start and response characteristics, and excellent durability.

Representative examples of such a polymer electrolyte fuel cell may include a hydrogen ion exchange membrane fuel cell (PEMFC) using hydrogen gas as a fuel.

Summarizing the reaction occurring in the polymer electrolyte fuel cell, first, when a fuel such as hydrogen gas is supplied to the anode, hydrogen ions (H ⁺ ) and electrons (e ⁻ ) are generated by the oxidation of hydrogen at the anode. The generated hydrogen ions (H ⁺ ) are transferred to the cathode via the electrolyte membrane, and the generated electrons (e ⁻ ) are transferred to the cathode via an external circuit. Oxygen is supplied from the reduction electrode, and oxygen is combined with hydrogen ions (H ⁺ ) and electrons (e ⁻ ) to generate water by reduction of oxygen.

Since the electrolyte membrane is a passage through which hydrogen ions (H ⁺ ) generated from the anode are transferred to the cathode, the conductivity of the hydrogen ions (H ⁺ ) should be excellent. In addition, the electrolyte membrane must have excellent separation ability to separate hydrogen gas supplied to the anode and oxygen supplied to the cathode, and also have excellent mechanical strength, dimensional stability, chemical resistance, and the like. characteristics such as low loss) are required.

Currently used electrolyte membranes are perfluorosulfonic acid resins (trade name: Nafion) (hereinafter referred to as Nafion resins) as fluorine resins. However, the Nafion resin has a weak mechanical strength, so that when used for a long time, pinholes are generated, thereby lowering energy conversion efficiency. In order to reinforce the mechanical strength, there are attempts to increase the film thickness of Nafion resin, but in this case, there is a problem in that the resistance loss is increased and the amount of expensive materials is increased, thereby reducing economic efficiency.

In order to solve this problem, a reinforced composite membrane in which an ion conductor is impregnated with a hydrocarbon-based porous nanoweb has been developed.

However, such a reinforced composite membrane has a problem that the ion conductivity drops sharply when the humidification is not performed smoothly, that is, in a low humidity state.

The present invention is to solve the above problems, the porous nano-web serving as the support of the electrolyte membrane has a low ion conductivity as it has the optimum pore characteristics by including a fiber in which the hygroscopic material is uniformly distributed therein It is an object of the present invention to provide an electrolyte membrane for a fuel cell having excellent ion conductivity retention rate and a method of manufacturing the same, as moisture is smoothly absorbed even under humidity.

As one aspect for achieving the above object, the present invention, a porous nano-web comprising a hydrocarbon-based polymer insoluble in the organic solvent; And an ion conductor filled in pores of the porous nanoweb and containing a hydrocarbon-based polymer soluble in an organic solvent, wherein the porous nanoweb includes hygroscopic fibers, and a hygroscopic material is dispersed in the hygroscopic fibers. An electrolyte membrane is provided.

As another aspect, the present invention, a process for producing a spinning solution containing a hygroscopic material; Spinning the spinning solution to produce a porous nanoweb; Preparing an ion conductor solution by dissolving an ion conductor including a hydrocarbon-based polymer in an organic solvent; And filling the ion conductor solution in the pores of the porous nanoweb, and then removing the organic solvent.

The present invention has the following effects.

First, since the electrolyte membrane according to the present invention can adsorb moisture uniformly as a whole, it has excellent ion conductivity retention as it has high ion conductivity even in a low humidity state.

Secondly, the electrolyte membrane according to the present invention may have excellent ion conductivity as it includes a porous nanoweb having optimal pore characteristics by providing a hygroscopic material without using a binder.

Third, the electrolyte membrane according to the present invention can have excellent productivity because it is prepared by adding a hygroscopic material to the spinning solution.

1 is a cross-sectional view of a nanoweb according to an embodiment of the present invention.
2 and 3 are cross-sectional views of a nanoweb according to another embodiment of the present invention.
4 is a graph of ion conductivity according to humidity according to the shape of an electrolyte membrane.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. Therefore, the present invention encompasses all changes and modifications that come within the scope of the invention as defined in the appended claims and equivalents thereof.

Hereinafter, the present invention will be described in detail with reference to the drawings.

The electrolyte membrane according to the present invention includes a porous nanoweb, and an ion conductor filled in the pores of the porous nanoweb.

The electrolyte membrane according to the present invention comprises a porous nanoweb, and an ion conductor filled in the pores of the porous nanoweb.

The porous nanoweb serves as a support to improve the mechanical stability of the electrolyte membrane and to improve the shape stability by inhibiting volume expansion by moisture. The porous nanoweb may include a hydrocarbon-based polymer which is advantageous in terms of cost, and in particular, may include a hydrocarbon-based polymer that is insoluble in an organic solvent in order to easily fill an ion conductor in pores of the porous nanoweb. That is, when the porous nanoweb is dissolved in an organic solvent, when the ion conductor solution is filled in the pores of the porous nanoweb, the porous nanoweb may be dissolved, thereby lowering mechanical properties and performance of the electrolyte membrane.

Hydrocarbon-based polymers that satisfy these requirements include nylon, polyimide (PI), polybenzoxazole (PBO), polyethylene terephtalate (PET), polyethylene (PE), polypropylene (PP), copolymers thereof, or mixtures thereof. It is not necessarily limited thereto. Here, the term "insoluble" means a property that is insoluble in an organic solvent such as NMP, DMF, DMA, or DMSO at room temperature.

As such, when the electrolyte membrane including the porous nanoweb serving as a support is used for the membrane of the fuel cell, the electrolyte membrane has a good ion conductivity in a high humidity environment, but may cause a problem that the ion conductivity rapidly drops in a low humidity environment.

To solve this problem, the porous nanoweb includes a hygroscopic material that can easily absorb moisture. Such hygroscopic materials may be included in various forms in the porous nanoweb.

For example, the hygroscopic material may be imparted to the porous nanoweb in a coated form. That is, the porous nanoweb coated with the hygroscopic material may be manufactured by impregnating and drying the porous nanoweb in a solution including the hygroscopic material. However, when the hygroscopic material is coated on the porous nanoweb, the hygroscopic material is present only on the surface of the fiber constituting the porous nanoweb and the hygroscopic material does not exist inside the fiber. This can lead to a sharp drop in ionic conductivity at low humidity. In addition, when the hygroscopic material is coated on the porous nanoweb, the hygroscopic material may be easily detached from the nanoweb, so durability may be degraded, and the ion conductivity may be lowered because the hygroscopic material blocks pores of the nanoweb.

On the other hand, the hygroscopic material may be given in the form of evenly dispersed inside the fibers forming the porous nanoweb. For example, the hygroscopic material may be evenly dispersed in the fiber, or there may be a porous nanoweb including the fiber made of the hygroscopic material. As such, when the hygroscopic material is evenly dispersed throughout the porous nanoweb, moisture can be efficiently absorbed, thereby preventing a sharp drop in ion conductivity even at low humidity.

1 is a cross-sectional view of a porous nanoweb according to an embodiment of the present invention. As shown in FIG. 1, the hygroscopic material may be dispersed in a particle state inside the fiber.

In addition, the hygroscopic material may be mixed with the other hydrocarbon-based polymer evenly mixed.

2 is a cross-sectional view of a porous nanoweb according to another embodiment of the present invention. As shown in Figure 2, the hygroscopic material is located on one side of the mono-filament (mono-filament) and the other hydrocarbon-based polymer is located on the other side of the short fiber, that is, it may be a porous nano-web including a composite fiber.

In addition, the hygroscopic material is located in the sheath (sheath) of the outer side of the short fiber and the other hydrocarbon-based polymer may be a porous nanoweb including a composite fiber located in the core (core) of the short fiber.

3 is a cross-sectional view of a porous nanoweb according to another embodiment of the present invention. As shown in FIG. 3, the nanofiber may include a porous nanoweb including mixed fibers in which short fibers made of the hygroscopic material and short fibers made of other hydrocarbon polymers are evenly mixed.

The hygroscopic material may include inorganic particles. The inorganic particles may include alkaline earth metal oxides, metal oxides, silicon oxides, or sulfates. As such inorganic particles, CaO, BaO, SrO, TiO ₂ , or SiO ₂ may be used.

The hygroscopic material may include a hygroscopic polymer including a hydrophilic group. Such hygroscopic polymers include polyurethane, polyvinyl alcohol (PVA), polyethylene oxide (PEO), polypropylene oxide (PPO), polymethylene oxide (PMO), polyethylene oxide methacrylate, polyethylene oxide acrylate, polyethylene oxide dimethacryl At least one polymer or a copolymer thereof selected from the group consisting of latex, polyethylene oxide diacrylate and polyhydroxyethylmethylacrylate (PHEMA).

The porous nanoweb has a plurality of pores that are connected in three dimensions, the pores are formed uniformly as a whole, the ion conductors filled in the pores can be uniformly distributed, and thus the ion conductivity of the electrolyte membrane becomes uniform throughout It is preferable to be able.

The pores formed in the porous nanoweb may be formed within a diameter range of 0.05 to 30㎛, if the pores are formed less than 0.05㎛ ionic conductivity of the electrolyte membrane may drop sharply, if the pores exceed 30㎛ The mechanical strength and morphological stability of the membrane may be poor. In addition, the pores may preferably have a diameter of 0.5 to 20 ㎛, more preferably may have a diameter of 1.0 to 15 ㎛.

The porous nanoweb is made of a predetermined fiber, the thickness of the fiber may range from 0.005 to 30㎛. If the thickness of the fiber is less than 0.005㎛ the mechanical strength of the porous nanoweb may be lowered, and if the thickness of the fiber exceeds 30㎛ may not be easy to control the porosity of the porous nanoweb. In addition, the thickness of the fiber may be preferably in the range of 0.005 to 5㎛.

The ion conductor performs a function of conducting hydrogen ions, which is a main function of the polymer electrolyte membrane, and can use a hydrocarbon-based polymer having excellent ion conductivity and advantageous in terms of price, and as described above, the pores of the porous nanoweb. In order to easily fill the ion conductor in the inside, a hydrocarbon-based polymer soluble in an organic solvent may be included. Hydrocarbon-based polymers that can be used for ion conductors satisfying these requirements include sulfonated polyimide (S-PI), sulfonated polyarylethersulfone (S-PAES), sulfonated polyetheretherketone (S-PEEK), and perfluorosulfonic acid resin (Perfluorosulfonic resin). acid; PFSA), sulfonated polybenzimidazole (S-PBI), sulfonated polysulfone (S-PSU), sulfonated polystyrene (S-PS), sulfonate polyphosphazene (sulfonated polyphosphazene) or mixtures thereof, but is not necessarily limited thereto. Here, the "soluble" with respect to the organic solvent means the characteristic of melting at room temperature.

The ion conductor is filled in the pores of the porous nanoweb, the adhesion between the ion conductor and the porous nanoweb may be degraded when the operating conditions such as temperature or humidity during fuel cell operation is changed, in the case of the present invention Since both the ion conductor and the porous nanoweb are composed of hydrocarbon-based polymers, the adhesion between the two is basically excellent. In addition, the hydrocarbon-based polymer included in the ion conductor and the hydrocarbon-based polymer included in the porous nanoweb may be composed of the same material, and specifically, S-PI (sulfonated polyimide) is used as the ion conductor and the porous nanoweb When the hydrocarbon-based polymer included in the ion conductor is formed of sulfonated material of the hydrocarbon-based polymer included in the porous nanoweb, such as using PI (Polyimide), the adhesion between the ion conductor and the porous nanoweb will be excellent. Can be.

The electrolyte membrane configured as above may have an ion conductivity retention of 50 to 90%. That is, the electrolyte membrane may exhibit a moderate decrease without significantly lowering the ionic conductivity as it contains sufficient moisture even at low humidity, thereby exhibiting excellent fuel performance even with a sudden change in the humidity environment.

4 is a graph of ion conductivity according to humidity according to the shape of an electrolyte membrane. 4A is a graph of ionic conductivity for each relative humidity of an electrolyte membrane including a nanoweb composed of fibers in which a hygroscopic polymer is mixed with a hydrocarbon-based polymer. 4B is a graph of ionic conductivity for each relative humidity of an electrolyte membrane coated with a hygroscopic polymer on a nanoweb made of a hydrocarbon-based polymer. 4C is a graph of ion conductivity for each relative humidity of an electrolyte membrane in which a nanoweb made of a hydrocarbon-based polymer is filled with an ion conductor.

As shown in FIG. 4, the electrolyte membrane including the nanoweb in which the hygroscopic material is evenly dispersed in the fiber has a higher ion conductivity than other electrolyte membranes at the same relative humidity because the nanoweb does not change pore characteristics by the hygroscopic material. By efficiently adsorbing moisture, excellent ion conductivity can be maintained even at low humidity.

On the other hand, the electrolyte membrane coated with the hygroscopic material on the surface of the fiber has a relatively low ion conductivity because the hygroscopic material coated prevents the pores of the nanoweb, and thus the ion conductivity is relatively low. The conductivity is greatly reduced.

On the other hand, the electrolyte membrane that does not contain the hygroscopic material is relatively low in the ion conductivity as the moisture is not absorbed smoothly, the ion conductivity is sharply dropped at low humidity.

In the present invention, since both the porous nanoweb and the ion conductor constituting the polymer electrolyte membrane use a hydrocarbon-based polymer, the adhesion between the two is excellent, so the durability is excellent, and in addition to the conventional expensive Nafion resin or Teflon resin Since it uses a relatively inexpensive hydrocarbon-based polymer without using such, there is an advantage in terms of price in mass production.

Hereinafter, a method of manufacturing a polymer electrolyte membrane according to an embodiment of the present invention will be described. However, detailed description of the same parts as described above will be omitted.

First, a porous nanoweb composed of a fiber having a hygroscopic material dispersed therein and a hydrocarbon-based polymer insoluble to an organic solvent, and an ion conductor containing a hydrocarbon-based polymer soluble in an organic solvent are dissolved in an organic solvent. Prepare a solution.

There is no particular process sequence between the preparation of the porous nanoweb and the preparation of the ion conductor solution.

Since the porous nanoweb is mainly made of a hydrocarbon-based polymer that is insoluble in an organic solvent, the porous nanoweb may be prepared without dissolving in an organic solvent or may be prepared through a predetermined reaction after forming a porous precursor.

First, the method of manufacturing without melt | dissolving in an organic solvent is demonstrated.

For example, a porous nanoweb as shown in FIG. 1 may be manufactured by spinning a spinning polymer obtained by melting a hydrocarbon-based polymer and then mixing a hygroscopic material together.

Alternatively, the first spinning solution is melted to form a first spinning solution, the hygroscopic material is melted to form a second spinning solution, and then the first spinning solution and the second spinning solution are formed through the same hole using the same spinneret. Composite spinning can produce a porous nanoweb as shown in FIG.

Alternatively, the first spinning solution is melted to form a first spinning solution, the hygroscopic material is melted to make a second spinning solution, and then the first spinning solution and the second spinning solution are discharged through the respective holes using the same spinning cap. Spinning may be performed to produce a porous nanoweb as shown in FIG.

Next, a method for dissolving in an organic solvent and producing it will be described.

First, the precursor is dissolved in a spinning solvent to prepare a spinning solution to which a hygroscopic material is added. Subsequently, after the spinning solution is electrospun to form a porous precursor, the porous precursor is post-treated to prepare a porous nanoweb as shown in FIG. 1 which is insoluble in an organic solvent.

Alternatively, the precursor is dissolved in a spinning solvent to prepare a first spinning solution, and a hygroscopic material is dissolved in a spinning solvent to prepare a second spinning solution, and then the first spinning solution and the second spinning solution are the same using the same spinneret. After complex electrospinning through a detention hole to form a porous precursor, the porous precursor is post-treated to prepare a porous nanoweb as shown in FIG. 2 which is insoluble in an organic solvent.

Alternatively, the precursor is dissolved in a spinning solvent to prepare a first spinning solution, a hygroscopic material is dissolved in a spinning solvent to prepare a second spinning solution, and then the first spinning solution and the second spinning solution are each prepared using the same spinning cap. After electrospinning each through a hole to form a porous precursor, the porous precursor is post-treated to prepare a porous nanoweb as shown in FIG. 3 which is insoluble in an organic solvent.

Here, in the electrospinning process, when a spinning liquid is injected into a syringe to which a sprayed jet nozzle is connected and a high voltage of 1 to 1,000 kV is applied to the nozzle at room temperature to 100 ° C, the injected spinning liquid is discharged and the filament is released. After forming, the filament is spun onto a collector having a releasing film and then the release film is removed to form a porous nanoweb.

The post-treatment of the porous precursor is a process of converting a porous precursor soluble in an organic solvent into a porous nanoweb insoluble in the organic solvent, and may be performed by a heat treatment method or a chemical method. For example, a porous nanoweb insoluble in an organic solvent may be prepared by heat treating a porous precursor soluble in an organic solvent using a hot press set at high temperature and high pressure.

The porous nanoweb insoluble in the organic solvent may include polyimide or polybenzoxazole.

N-methyl-2-pyrrolidinone (NMP), dimethylformamide (DMF), or dimethyl acetamide (DMA) may be used as the organic solvent. It is not necessarily limited thereto.

Next, the ion conductor solution is filled in the pores of the porous nanoweb.

The process of filling the ion conductor solution into the pores of the porous nanoweb may use a supporting process, but is not necessarily limited thereto, and may use various methods known in the art, such as a spraying process, a screen printing process, and a doctor blade process. Can be.

When using the supporting process, it is preferable to perform the supporting process 2 to 5 times at room temperature for 5 to 30 minutes.

After the ion conductor solution is filled, the organic solvent in the ion conductor solution is removed to fill the pores of the porous nanoweb. The process of removing the organic solvent may be a process of drying for 2 to 5 hours at a temperature of 60 ~ 150 ℃.

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples. However, the following examples are only intended to help the understanding of the present invention, and the scope of the present invention should not be limited.

Example  One

A spinning solution prepared by dissolving 15% by weight of polyamic acid and 5% by weight of silicon dioxide in a tetrahydrofuran (THF) spinning solvent was electrospun at a temperature of 25 ° C. and a voltage of 30 mA to form a porous precursor. After the heat treatment for 5 hours in an oven at 350 ℃ to prepare a hygroscopic porous nano-web.

S-PEEK (sulfonated polyetheretherketone) was melted in N-methyl-2-pyrrolidinone (NMP) to prepare a 10 wt% ion conductor solution.

The hygroscopic porous nanoweb was supported on the ion conductor solution at room temperature. Specifically, the immersion process was performed three times at room temperature for 20 minutes, and a reduced pressure atmosphere was applied for 1 hour to remove fine bubbles. Thereafter, the mixture was dried in a hot air oven maintained at 80 ° C. for 3 hours to remove NMP, thereby preparing an electrolyte membrane.

Example  2

20 wt% of polyamic acid was dissolved in tetrahydrofuran spinning solvent to prepare a first spinning solution, and 15 wt% of polyvinyl alcohol was dissolved in water to prepare a second spinning solution. The second spinning solution was supplied to the spinneret and electrospun in a state where a temperature of 25 ° C. and a voltage of 30 kW were applied through different prison holes to form a porous precursor, followed by heat treatment in an oven at 200 ° C. for 10 hours. Composite porous nanowebs were prepared.

In Example 1 described above, an electrolyte membrane was prepared in the same manner as in Example 1 except for using the composite porous nanoweb instead of the hygroscopic porous nanoweb.

Example  3

A spinning solution prepared by dissolving 15% by weight of polyamic acid in a tetrahydrofuran spinning solvent was electrospun at a temperature of 25 ° C. and a voltage of 30 mA to form a porous precursor, followed by 5 hours in an oven at 350 ° C. Heat treatment to prepare a porous nanoweb.

Polyvinyl alcohol, a hygroscopic material, was dissolved in water to prepare a hygroscopic solution of 10% by weight.

The porous nanoweb was immersed in the hygroscopic solution and dried to prepare a hygroscopic porous nanoweb coated with 5% by volume of polyvinyl alcohol.

In Example 1 described above, an electrolyte membrane was prepared in the same manner as in Example 1 except for using the hygroscopic porous nanoweb coated with polyvinyl alcohol.

Example 4

20 wt% of polyamic acid was dissolved in tetrahydrofuran spinning solvent to prepare a first spinning solution, and 10 wt% of silicon dioxide was dissolved in tetrahydrofuran spinning solvent to prepare a second spinning solution. The liquid and the second spinning solution were supplied to a spinneret to electrospin at a temperature of 25 ° C. and a voltage of 30 kW through different prison holes to form a porous precursor, followed by 10 hours in an oven at 200 ° C. Heat treatment to prepare a hygroscopic composite porous nanoweb.

An electrolyte membrane was prepared in the same manner as in Example 1 except for using the composite porous nanoweb instead of the hygroscopic porous nanoweb.

Comparative example  One

In Example 1 described above, an electrolyte membrane was prepared in the same manner as in Example 1 except for using the spinning solution to which silicon dioxide was not added.

Physical properties of the electrolyte membranes prepared by Examples and Comparative Examples are shown in Table 1 below, measured by the following method.

Hydrogen ion conductivity (S / cm)

Conductance of the electrolyte membranes prepared according to Examples and Comparative Examples was measured by a constant current four terminal method. Specifically, after stabilizing for 30 minutes under a relative humidity of 50% or 100% humidity in a state of immersion in distilled water at a temperature of 80 ° C., a constant AC current is applied to both ends of the electrolyte membrane to measure the difference in the AC potential generated at the center of the hydrogen ion. The conductivity was obtained, and the results are shown in Table 1 below.

Ion conductivity retention rate (%)

Hydrogen ion conductivity (S100) at 100% humidity measured by the above-described method and hydrogen ion conductivity (S50) at 50% relative humidity measured by changing only relative humidity to 50% of the above-described method The ion conductivity retention (%) was measured through the equation.

Ion Conductivity Retention Rate (%) = (S50 / S100) × 100

division S100
Hydrogen ion conductivity (S / cm) S50
Hydrogen ion conductivity (S / cm) Ion Conductivity Retention Rate
(%) Example 1 0.0572 0.0412 72 Example 2 0.2210 0.1901 86 Example 3 0.2019 0.1716 85 Example 4 0.1020 0.0561 55 Comparative Example 1 0.1260 0.0010 0.79

10: hydrocarbon-based polymer 20: hygroscopic material
A: electrolyte membrane containing hygroscopic fiber B: coated electrolyte membrane
C: Electrolyte Membrane without hygroscopic material

Claims (14)

Porous nano web comprising a hydrocarbon-based polymer insoluble in the organic solvent; And
Filled in the pores of the porous nano-web, comprising an ion conductor containing a hydrocarbon-based polymer soluble in organic solvents,
The porous nano web includes a hygroscopic fiber,
An electrolyte membrane, wherein a hygroscopic material is dispersed in the hygroscopic fiber. The method of claim 1,
The hygroscopic material is an electrolyte membrane, characterized in that it comprises hygroscopic inorganic particles. The method of claim 2,
The hygroscopic inorganic particles include at least one of alkaline earth metal oxides, metal oxides, sulfates, and silicon oxides. The method of claim 3,
The hygroscopic inorganic particles include at least one of CaO, BaO, SrO, TiO ₂ , and SiO ₂ . The method of claim 1,
The hygroscopic material comprises an hygroscopic polymer having a hydrophilic group. The method of claim 5,
The hygroscopic polymer is polyurethane, polyvinyl alcohol (PVA), polyethylene oxide (PEO), polypropylene oxide (PPO), polymethylene oxide (PMO), polyethylene oxide methacrylate, polyethylene oxide acrylate, polyethylene oxide dimethacryl An electrolyte membrane comprising at least one polymer or a copolymer thereof selected from the group consisting of latex, polyethylene oxide diacrylate and polyhydroxyethylmethylacrylate (PHEMA). The method of claim 1,
Hydrocarbon-based polymers included in the nanoweb, an electrolyte membrane including nylon, polyimide (PI), polybenzoxazole (PBO), polyethylene terephtalate (PET), polyethylene (PE), polypropylene (PP), copolymers thereof, or mixtures thereof . The method of claim 1,
Hydrocarbon-based polymers contained in the ion conductor, S-PI (sulfonated polyimide), S-PAES (sulfonated polyarylethersulfone), S-PEEK (sulfonated polyetheretherketone), perfluoro sulfonic acid resin (Perfluorosulfonic acid; PFSA), sulfonate poly Benzimidazole (S-PBI), sulfonated polysulfone (S-PSU), sulfonated polystyrene (S-PS), sulfonated polyphosphazene or mixtures thereof Electrolyte membrane containing. The method of claim 1,
The electrolyte membrane is an electrolyte membrane, characterized in that the ion conductivity retention of 50 to 90%. Preparing a spinning solution containing a hygroscopic material;
Spinning the spinning solution to produce a porous nanoweb;
Preparing an ion conductor solution by dissolving an ion conductor including a hydrocarbon-based polymer in an organic solvent; And
After filling the ion conductor solution into the pores of the porous nano-web, the method of manufacturing an electrolyte membrane comprising the step of removing the organic solvent. The method of claim 10,
The process of preparing the spinning solution includes the step of adding the hygroscopic material to the hydrocarbon-based polymer. The method of claim 10,
The step of producing the spinning solution, the step of preparing a first spinning solution containing a hydrocarbon-based polymer; And manufacturing a second spinning solution containing a hygroscopic material,
The manufacturing method of the porous nanoweb, the method of producing an electrolyte membrane comprising the step of simultaneously spinning the first spinning liquid and the second spinning liquid through each of the hole in the spinneret. The method of claim 10,
The spinning solution manufacturing process includes a step of melting a hydrocarbon precursor soluble in an organic solvent in a spinning solvent,
The process of manufacturing the porous nanoweb,
Electrospinning the spinning solution to form a porous precursor; And
And post-treating the porous precursor to produce a porous nanoweb that is insoluble in an organic solvent. 14. The method according to any one of claims 10 to 13,
The hygroscopic material is a method for producing an electrolyte membrane containing inorganic particles or hygroscopic polymer.

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