KR20110119264A - Organic-inorganic hybrid electrolyte membrane, method for fabricating the same and fuel cell - Google Patents

Abstract

PURPOSE: An organic-inorganic hybrid electrolyte membrane is provided to prevent the leakage of inorganic particles in the operation of a fuel cell, to effectively reduce fuel penetration, to improve ion conductivity and to maintain excellent performance in a high temperature/low humidification condition. CONSTITUTION: An organic-inorganic hybrid electrolyte membrane comprises: a polymer(12) having an ion exchange group(10) and inorganic particles(16) which are chemically bonded with the polymer and have the ion exchange group. A method for preparing the organic-inorganic hybrid electrolyte membrane comprises the steps of: preparing an organic membrane containing the polymer having the ion exchange group; absorbing an inorganic particle precursor having the ion exchange group to the organic membrane; and bonding a polymer(14) having the ion exchange group with the inorganic particle precursor having the ion exchange group using a sol-gel reaction, and inorganic particle precursors having the ion exchange group.

Description

Organic-inorganic hybrid electrolyte membrane, method for fabricating the same and fuel cell

The present invention relates to an organic-inorganic composite electrolyte membrane, a method of manufacturing and application thereof, and more particularly, to an organic-inorganic composite electrolyte membrane containing an ion conductive polymer and an ion conductive inorganic particle, a method for manufacturing the same, and an application to a fuel cell. will be.

A fuel cell is an electrochemical device that directly converts chemical energy of a fuel into electrical energy through an electrochemical reaction, and is drawing attention as a future energy production device based on the advantages of high energy density and eco-friendliness. Among them, a polymer electrolyte fuel cell is a fuel cell using a polymer membrane having a hydrogen ion exchange characteristic as an electrolyte, and there is no risk of corrosion or evaporation due to an electrolyte, and it has advantages such as low operating temperature, high power density, and quick response characteristics. . In addition, methanol, ethanol, natural gas and the like can be reformed and used in addition to hydrogen, so that fuel can be easily transported and stored, and can be used as a power supply for transporting automobiles or a small power supply for electronic devices.

In the development of such a polymer electrolyte membrane, the target membrane has high hydrogen ion conductivity, low fuel permeability, high performance at high temperature, oxidative stability, and mechanical strength, and various kinds of composite membranes have been developed for this purpose. For example, efforts have been made to reduce fuel permeability of fuel cell membranes and to improve stability and performance at high temperatures by introducing inorganic materials into the polymer electrolyte membrane. However, since ordinary inorganic materials are incapable of carrying ions, it may be the cause of increasing the internal resistance of the fuel cell by reducing the hydrogen ion conductivity of the membrane. In addition, when the organic-inorganic composite membrane is introduced by the introduction of inorganic particles, phase separation may occur between the organic polymer and the inorganic particles, resulting in a heterogeneous membrane, and inorganic particles may leak during fuel cell operation.

The technical problem to be solved by the present invention is to provide an organic-inorganic composite electrolyte membrane having excellent performance and stability and a fuel cell using the same.

Another technical problem to be solved by the present invention is to provide a method for producing an organic-inorganic composite electrolyte membrane having cost-effective and improved physical properties.

One aspect of the present invention to achieve the above technical problem provides an organic-inorganic composite electrolyte membrane.

The organic-inorganic composite electrolyte membrane includes a polymer having an ion exchange group and inorganic particles chemically bonded to the polymer and having an ion exchange group.

Each ion exchange group of the polymer and the inorganic particles may be any one of a sulfonic acid group, a carboxyl group and a phosphoric acid group regardless of each other.

The polymer having an ion exchange group may be any one copolymer selected from the following first compound group and the following second compound group.

<1st compound group>

,

,

,

,

,

,

,

,

(Here, the ion exchange group possessed by the polymer is bonded to a benzene ring (at least one when the benzene ring is 2 or more) included in the compounds.)

<Second compound group>

,

,

,

,

,

,

,

,

(In the above compounds, * denotes an atom which forms a chemical bond with an inorganic particle having an ion exchange group.)

The inorganic particles having the ion exchange group may be silica in which a substituent represented by Formula 1 is bonded to a silicon atom.

<Formula 1>

(Wherein R ₁ is C1 to C5 alkylene or arylene and Q is an ion exchange group.)

Another aspect of the present invention to achieve the above technical problem provides a fuel cell.

The fuel cell includes an anode and a cathode disposed opposite and an electrolyte membrane positioned between the anode and the cathode, wherein the electrolyte membrane is the above-mentioned organic-inorganic composite electrolyte membrane.

Another aspect of the present invention to achieve the above technical problem provides a method for producing an organic-inorganic composite electrolyte membrane.

The method includes preparing an organic membrane containing a polymer having an ion exchange group, absorbing an inorganic particle precursor having an ion exchange group in the organic membrane, and using a sol-gel reaction with the polymer having the ion exchange group and the ion exchanger. Bonding between inorganic particle precursors having an inorganic particle precursor having an ion exchange group.

Each ion exchange group of the polymer and the inorganic particle precursor may be any one of a sulfonic acid group, a carboxyl group and a phosphoric acid group irrespective of each other.

The polymer having an ion exchange group may be any one copolymer selected from the following first compound group and the third compound group below.

<1st compound group>

,

,

,

,

,

,

,

,

(Here, the ion exchange group possessed by the polymer is bonded to a benzene ring (at least one when the benzene ring is 2 or more) included in the compounds.)

<Third compound group>

,

,

,

,

,

,

,

,

(In the above compounds, R is either hydrogen, methoxy group or ethoxy group.)

The inorganic particle precursor having the ion exchange group may be a compound represented by the following formula (3).

<Formula 3>

(Wherein R is any one of hydrogen, a methoxy group or an ethoxy group, R ₁ is C1-C5 alkylene or arylene, and Q is an ion exchange group.)

According to the present invention as described above, due to the chemical bonding of the ion conductive polymer and the ion conductive inorganic particles, it is possible to prevent the leakage of the inorganic particles during operation of the fuel cell. In addition, since the inorganic particles may be selectively positioned in the ion transport channel, the fuel permeability may be effectively reduced, and the ion conductivity may be reduced by improving the ion conductivity by providing ion conductivity to the inorganic particles. In addition, due to the high moisture retention of the ion conductive inorganic particles, it is possible to maintain excellent performance even under high temperature and low humidity conditions.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a schematic view showing an ion conductive polymer and an ion conductive inorganic particle included in an organic-inorganic composite electrolyte membrane according to an embodiment of the present invention.
FIG. 2 is a schematic view showing a case in which each ion exchange group of the polymer and the inorganic particles has a sulfonic acid group, and the ion conductive inorganic particles have ion conductive silica.
3 is a schematic view showing a fuel cell according to another embodiment of the present invention.
4 is a flowchart illustrating a method of manufacturing an organic-inorganic composite electrolyte membrane according to still another embodiment of the present invention.
FIG. 5 is a graph illustrating performance evaluation results of a direct methanol fuel cell in which an organic-inorganic composite electrolyte membrane and Nafion 115 prepared according to Preparation Example 1 were introduced into an electrolyte membrane, respectively.
FIG. 6 is a graph illustrating performance evaluation results of a polymer electrolyte fuel cell in which an organic-inorganic composite electrolyte membrane and Nafion 112 prepared according to Preparation Example 1 were respectively introduced into an electrolyte membrane.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the thicknesses of layers and regions are exaggerated for clarity. Like numbers refer to like elements throughout. In addition, in the following description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

Throughout this specification, a material having an "ion exchange group" is interpreted to have the same meaning as a "ion conductive" material.

The organic-inorganic composite electrolyte membrane according to the present embodiment includes a polymer having an ion exchange group and inorganic particles chemically bonded to the polymer and having an ion exchange group.

Each ion exchange group of the polymer and the inorganic particle means a functional group capable of transferring hydrogen ions through an ion transport channel of an electrolyte membrane, and may be any one of a sulfonic acid group, a carboxyl group, and a phosphoric acid group regardless of each other.

The polymer having the ion exchange group may be a non-fluorine-based polymer, for example, may be any one selected from the following first compound group and any copolymer selected from the following second compound group.

<1st compound group>

,

,

,

,

,

,

,

,

(Here, the ion exchange group possessed by the polymer is bonded to a benzene ring (at least one when the benzene ring is 2 or more) included in the compounds.)

<Second compound group>

,

,

,

,

,

,

,

,

(* In the compounds, * represents an atom that forms a chemical bond with the inorganic particles having an ion exchange group.)

The inorganic particles having the ion exchange group may be preferably silica (hereinafter referred to as “ionically conductive silica”) in which a substituent represented by the following Chemical Formula 1 is bonded to a silicon atom.

<Formula 1>

(Wherein R ₁ is C1 to C5 alkylene or arylene and Q is an ion exchange group.)

In the case where the ion conductive silica is used as the inorganic particle having the ion exchange group, the water retention in the electrolyte membrane can be improved by a large number of hydroxyl groups (OH) present in the silica, and thus ion transfer is easy even at high / low humid conditions. It can be done.

An example of the ion conductive polymer in which the ion conductive silica is chemically bonded may be represented by the following Chemical Formula 2.

<Formula 2>

(In the above formula, the portion enclosed by the dotted line represents ion conductive silica.)

1 is a schematic view showing the ion conductive polymer and the ion conductive inorganic particles contained in the organic-inorganic composite electrolyte membrane described above.

FIG. 2 is a schematic view showing a case in which each ion exchange group of the polymer and the inorganic particles has a sulfonic acid group, and the ion conductive inorganic particles have ion conductive silica.

Referring to FIG. 1, the ion conductive inorganic particles 16 are chemically bonded to the ion conductive polymer 14 and are positioned around the ion exchanger 10 of the ion conductive polymer 14.

In other words, according to the present embodiment, the ion conductive inorganic particles 16 are chemically bonded to the ion conductive polymer 14, so that the ion conductive inorganic particles without the local phase separation of the ion conductive polymer 14 and the ion conductive inorganic particles 16 are formed. 16 can be selectively positioned in the ion transfer channel, and the ion conductive inorganic particles 16 can be prevented from leaking during operation of the fuel cell. In addition, by imparting ion conductivity to the inorganic particles, it is possible to reduce the interval between the functional groups that serve as ion transfer, it is possible to improve the ion conductivity.

In addition, referring to FIG. 2, the hydroxy group present in the ion-conducting silica 16 can maintain high moisture retention at high temperatures, and maintains high ionic conductivity even at high temperatures because the bound water is present around the sulfonic acid group. Can be.

The organic-inorganic composite electrolyte membrane according to the present embodiment uses all kinds of fuel cells capable of using the polymer electrolyte membrane, for example, a polymer electrolyte membrane fuel cell (PEMFC) using methanol as a fuel, methanol or ethanol, and the like. Direct alcohol fuel cell (DAFC) and the like.

3 is a schematic view showing a fuel cell according to another embodiment of the present invention.

Referring to FIG. 3, the fuel cell 30 includes an anode 32 and a cathode 34 disposed opposite to each other, and an electrolyte membrane 36 interposed between the anode 32 and the cathode 34. The electrolyte membrane 36 is characterized in that the organic-inorganic composite electrolyte membrane described above.

For example, Scheme 1 below illustrates an electrochemical reaction of a direct methanol fuel cell using methanol fuel in a fuel cell according to the present embodiment.

<Scheme 1>

Anode: CH ₃ OH + H ₂ O → CO ₂ + 6H ⁺ + 6e ^- E ^o = 0.046 V

^{_{Cathode: 3 / 2O 2 + 6H +}} + 6e - → 3H 2 OE o = 1.23V

Total: CH ₃ OH + 3 / 2O ₂ → CO ₂ + 2H ₂ OE ^o = 1.18 V

As can be seen in Reaction Scheme 1, when fuel is injected into the anode 32 of the fuel cell 30, the fuel is oxidized by the electrochemical reaction in the anode 32, and electrons are generated. It is delivered to the cathode 34 through) to generate electrical energy. On the other hand, the electrons moved to the cathode 34 reduces oxygen to oxygen ions, and the oxygen ions react with the hydrogen ions moved to the cathode 34 through the electrolyte membrane 36 to generate water. At this time, the conductivity of hydrogen ions is affected by the distance between the ion exchange groups located along the polymer skeleton, and the narrower the distance, the greater the conductivity of the hydrogen ions. In addition, since the hydrogen ions alone do not pass through the electrolyte membrane 36 and must move with some water molecules, when the electrolyte membrane 36 lacks moisture, the hydrogen ions may not be properly transferred, thereby degrading battery efficiency. have.

As described above, in view of the characteristics required for the fuel cell electrolyte membrane, according to the present embodiment, as described above, the organic-inorganic composite electrolyte membrane including the ion conductive polymer to which the ion conductive inorganic particles are chemically bonded is used as the electrolyte membrane of the fuel cell. By using this, the gap between the ion exchangers can be reduced to improve the ion conductivity. In addition, in the case of using the ion conductive silica particles as the ion conductive inorganic particles may have improved ion conductivity by improving the water retention in the electrolyte membrane.

4 is a flowchart illustrating a method of manufacturing an organic-inorganic composite electrolyte membrane according to still another embodiment of the present invention.

Referring to FIG. 4, an organic membrane containing a polymer having an ion exchange group is prepared (S10).

The ion exchange group of the polymer may be any one of a sulfonic acid group, a carboxyl group and a phosphoric acid group.

The polymer having an ion exchange group may be any one copolymer selected from the following first compound group and the third compound group below.

<1st compound group>

,

,

,

,

,

,

,

,

Here, the ion exchange group of the polymer is bonded to the benzene ring (at least one when the benzene ring is 2 or more) included in each of the compounds.

<Third compound group>

,

,

,

,

,

,

,

,

(In the above compounds, R is either hydrogen, methoxy group or ethoxy group.)

The step of preparing an organic membrane containing the polymer having the ion exchange group is not particularly limited. For example, after absorbing a solution containing a monomer for forming a polymer into the porous support membrane, causing a polymerization reaction and the polymerization It can be carried out through the step of introducing an ion exchange group to the polymer formed by the reaction. In this case, the solution containing the monomer may further include a crosslinking agent. For example, when the monomer used is a styrene monomer, a vinyl monomer, or a mixture thereof, divinylbenzene, bis (vinyl phenyl) ethane, triallylyl Anallylate (triallylcyanurate) and the like. The porous support membrane may be a porous polyethylene membrane. However, the present invention is not limited thereto.

As another example, a process of first preparing a polymer having an ion exchange group, dissolving the prepared polymer in a suitable organic solvent such as DMF, NMP, etc. to prepare a polymer solution, and then casting the polymer solution on a glass substrate and drying it. Also through the step of preparing an organic membrane containing an ion exchange group can be performed.

An inorganic particle precursor having an ion exchange group is absorbed in the organic film (S12).

The inorganic particle precursor having the ion exchange group may be a compound represented by the following formula (3).

<Formula 3>

(Wherein R is any one of hydrogen, a methoxy group or an ethoxy group, R ₁ is C1-C5 alkylene or arylene, and Q is an ion exchange group.)

The ion exchange group of the inorganic particle precursor may be any one of a sulfonic acid group, a carboxyl group and a phosphoric acid group.

For example, when the ion exchange group is a sulfonic acid group, the ion conductive inorganic particle precursor is a thiol group such as 3-mercaptopropyltrimethoxylsilane, 4-mercaptobutyltriethoxylsilane, and the like. The thiol group may be prepared by oxidizing a sulfonic acid group using an oxidizing agent such as hydrogen peroxide. Thereafter, the hydrolysis reaction may be further coarse.

In addition, the process of absorbing the ion conductive inorganic particle precursor may be performed, for example, by immersing the organic membrane in a liquid ion conductive inorganic particle precursor. In addition, when a crosslinking agent such as tetraethylorthosilicate (TEOS) is added to the organic membrane in the process of absorbing the ion conductive inorganic particle precursor represented by Chemical Formula 3, the ion conductivity during the sol-gel reaction described later Formation of an inorganic particle can be made easier.

By using the sol-gel reaction between the polymer having the ion exchange group and the inorganic particle precursor having the ion exchange group, and between the inorganic particle precursor having the ion exchange group (S14).

In the sol-gel reaction process, a chemical bond of a polymer-inorganic particle is formed by a reaction between an ion conductive polymer and an ion conductive inorganic particle precursor, and an ion conductive inorganic particle is formed by a reaction between the ion conductive inorganic particle precursors. .

In this case, the formed ion conductive inorganic particles react with a compound belonging to the third compound group among the materials constituting the ion conductive polymer to form a chemical bond, for example, the chemical bond is an oxygen-silicon covalent bond (siloxane Combination).

Therefore, when controlling the content of the compound belonging to the third compound group of the material constituting the ion conductive polymer, it is possible to control the amount of inorganic particles chemically bonded to the polymer, the inorganic particles to be introduced according to the characteristics of the electrolyte membrane required The amount of can be easily controlled. In addition, since the ion-conductive inorganic particles may be selectively positioned along the ion transport channel of the electrolyte membrane, that is, through the skeleton of the ion-conducting polymer through the chemical bond, fuel permeability can be effectively reduced even with a small amount of inorganic material, thereby reducing manufacturing costs. can do. In addition, there is an advantage that can reduce the heterogeneity of the membrane may occur when the content of the inorganic particles increases.

Hereinafter, preferred examples are provided to aid the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited to the following experimental examples.

<Manufacture example 1>

With polymer Organic  Produce

A monomer solution was prepared by mixing 5 ml of styrene, 5 ml of vinyltrimethoxysilane, 0.1 ml of divinylbenzene, and 0.25 g of benzophenyloxide used as a radical polymerization initiator. Next, the monomer solution was absorbed into a porous polyethylene (PE) film, and then heat-polymerized at 80 ° C. for 8 hours to prepare an organic film containing a polymer.

Preparation of Ion Conductive Minerals (Inorganic Particle Precursors)

1 ml of 3-mercaptopropyltrimethoxylsilane was added to a mixed solution of 5 ml of hydrogen peroxide and 5 ml of ethanol, and then reacted with stirring for 5 hours at room temperature to form a thiol group of 3-mercaptopropyltrimethoxysilane ( thiol group) was oxidized to sulfonate group. Next, 1 ml of tetraethyl orthosilicate was added, followed by stirring for 30 minutes to prepare a liquid ion conductive inorganic material (inorganic particle precursor).

Polymer Sulfonation  And introduction of ion conductive minerals

In a mixed solution of 2 ml of chlorosulfonic acid and 98 ml of 1,2-dichloroehtane, the organic membrane containing the polymer prepared above was immersed, and then sulfonated at room temperature for 1 hour. Next, the reaction was stopped by washing the membrane with acetone and dried at room temperature. Subsequently, each was stored in 1N NaOH and 1N HCl for 1 day, and then washed with distilled water. After the sulfonation reaction was completed, the membrane was immersed in the previously prepared ion conductive inorganic solution for 10 minutes to absorb the inorganic material into the ion transfer channel. The membrane in which the ion conductive inorganic material was absorbed was dried at room temperature, and then heated at 80 ° C. for 5 hours to induce a sol-gel reaction. The absorption of inorganics and the sol-gel reaction were repeated three times. Finally, the prepared membrane was heated at 100 ° C. for 2 hours, stored in 1N HCl for 1 day, and then washed with distilled water to prepare an organic-inorganic composite electrolyte membrane.

Analysis Example 1 Analysis of Characteristics of Organic-Inorganic Composite Electrolyte Membrane

The physical properties of Nafion 115, a polymer membrane compatible with the organic-inorganic composite electrolyte membrane prepared according to Preparation Example 1, was measured and shown in Table 1 below.

Electrolyte membrane thickness
(Μm) Hydrogen ion conductivity
(S / cm) MeOH Permeability
(× 10 ⁵ cm ² / s) Nafion 115 152 0.083 19.9 Organic-Inorganic Composite Electrolyte Membrane 36 0.092 4.58

Referring to Table 1, it can be seen that the organic-inorganic composite electrolyte membrane prepared according to Preparation Example 1 has about 10.8% improved hydrogen ion conductivity and about 23.0% reduced methanol permeability compared to Nafion 115.

In addition, the organic-inorganic composite electrolyte membrane prepared in Preparation Example 1 and Nafion 115 were applied to a direct methanol fuel cell (DMFC) to evaluate their performance.

FIG. 5 is a graph illustrating performance evaluation results of a direct methanol fuel cell in which an organic-inorganic composite electrolyte membrane and Nafion 115 prepared according to Preparation Example 1 were introduced into an electrolyte membrane, respectively.

Referring to FIG. 5, it can be seen that the organic-inorganic composite electrolyte membrane prepared according to Preparation Example 1 exhibits an open circuit voltage (OCV) and a maximum power density similar to that of Nafion 115 despite a thin thickness. . Therefore, it can be seen that the organic-inorganic composite electrolyte membrane prepared according to Preparation Example 1 has excellent ion conductivity and methanol permeation reduction performance.

Analysis Example 2: Performance Evaluation at High Temperature / Low Humidity Conditions

Performance was evaluated by applying Nafion 112, a polymer membrane commercialized with the organic-inorganic composite electrolyte membrane prepared in Preparation Example 1, to a polymer electrolyte membrane fuel cell (PEMFC).

FIG. 6 is a graph illustrating performance evaluation results of a polymer electrolyte fuel cell in which an organic-inorganic composite electrolyte membrane and Nafion 112 prepared according to Preparation Example 1 were respectively introduced into an electrolyte membrane. 6 is a graph in which the humidification of the hydrogen electrode is 75% and the oxygen electrode is operated under unhumidified conditions.

When the fuel cell was operated at 80 ° C. and 100% humidification, the organic-inorganic composite electrolyte membrane exhibited similar performance to that of Nafion 112 (not shown). However, as shown in FIG. 6, the humidification of the hydrogen electrode was 75%. When the oxygen electrode was operated under a non-humidifying condition, the performance of Nafion 112 was greatly reduced, while the performance of the organic-inorganic composite electrolyte membrane was 100%. As a result, the organic-inorganic composite electrolyte membrane showed a maximum power density of about 51.3% higher than that of Nafion 112.

As described above, it can be seen that the organic-inorganic composite electrolyte membrane prepared according to the present example shows excellent performance in both direct methanol fuel cells and polymer electrolyte fuel cells, and especially compared to conventional commercial membranes under high temperature / low humidification conditions. It can be seen that it shows improved performance.

In the above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications and changes by those skilled in the art within the spirit and scope of the present invention. You can change it.

10: ion exchanger 12: polymer
14: ion conductive polymer 16: ion conductive inorganic particles
30: fuel cell 32: anode
34: cathode 36: electrolyte membrane
38: external circuit

Claims (9)

A polymer having an ion exchange group; And
An organic-inorganic composite electrolyte membrane chemically bonded to the polymer and comprising inorganic particles having ion exchange groups. The method of claim 1,
Each ion exchange group of the polymer and the inorganic particles is any one of a sulfonic acid group, a carboxyl group and a phosphoric acid group irrespective of each other. The method of claim 1,
The polymer having an ion exchange group is an organic-inorganic composite electrolyte membrane is any one selected from the following first compound group and any copolymer selected from the following second compound group:
<1st compound group>

,

,

,

,

Here, the ion exchange group of the polymer is bonded to the benzene ring (at least one when the benzene ring is 2 or more) included in the compounds.
<Second compound group>

,

,

,

,

In the above compounds, * denotes an atom which forms a chemical bond with an inorganic particle having an ion exchange group. The method of claim 1,
The inorganic particle having an ion exchange group is an organic-inorganic composite electrolyte membrane which is a silica in which a substituent represented by Formula 1 is bonded to a silicon atom:
<Formula 1>

Wherein R is C1-C5 alkylene or arylene and Q is an ion exchange group. An anode and a cathode disposed opposite;
An electrolyte membrane positioned between the anode and the cathode,
The electrolyte membrane is a fuel cell of the organic-inorganic composite electrolyte membrane of any one of claims 1 to 4. Preparing an organic membrane containing a polymer having an ion exchange group;
Absorbing an inorganic particle precursor having an ion exchange group in the organic membrane; And
A method for preparing an organic-inorganic composite electrolyte membrane comprising using a sol-gel reaction to bond between the polymer having the ion exchange group and the inorganic particle precursor having the ion exchange group, and the inorganic particle precursor having the ion exchange group. The method of claim 6,
Each ion exchange group of the polymer and the inorganic particle precursor is any one of a sulfonic acid group, a carboxyl group and a phosphoric acid group irrespective of each other. The method of claim 6,
The polymer having an ion exchange group is any one selected from the following first compound group and any one copolymer selected from the following third compound group organic-inorganic composite electrolyte membrane manufacturing method:
<1st compound group>

,

,

,

,

Here, the ion exchange group of the polymer is bonded to the benzene ring (at least one when the benzene ring is 2 or more) included in the compounds.
<Third compound group>

,

,

,

,

In the above compounds, R is either hydrogen, methoxy group or ethoxy group. The method of claim 6,
The inorganic particle precursor having an ion exchange group is a compound of the organic-inorganic composite electrolyte membrane which is a compound represented by the formula (2):
<Formula 3>

Wherein R is either hydrogen, methoxy or ethoxy, R ₁ is C1-C5 alkylene or arylene and Q is an ion exchange group.

Images