KR100441066B1 - Mosaic Polymer Electrolyte Membranes and Method for Preparing the Same - Google Patents

Abstract

The present invention provides a fuel cell comprising an inert porous polymer membrane, an inert polymer resin impregnated in a portion not in direct contact with an electrode of the porous polymer membrane, and a hydrogen ion conductive polymer electrolyte resin impregnated in a portion in direct contact with an electrode of the porous polymer membrane. The present invention relates to a mosaic-type composite polymer electrolyte membrane.

In addition, the present invention uses an inert porous polymer membrane as a support for the polymer electrolyte, the portion of the porous membrane in direct contact with the electrode is impregnated with a hydrogen ion conductive resin, the other portion is reinforced composite by applying an inert polymer resin A method for producing a polymer electrolyte membrane, and a method for producing a gasket-electrolyte membrane integrated by forming a gasket on the outer portion of the reinforced composite polymer electrolyte membrane.

Since the composite polymer electrolyte membrane prepared in the present invention can minimize the use of the electrolyte, the manufacturing cost of the electrolyte membrane can be greatly reduced.

Description

Mosaic Composite Polymer Electrolyte Membrane and Method for Preparing the Same {Mosaic Polymer Electrolyte Membranes and Method for Preparing the Same}

The present invention relates to a reinforced composite polymer electrolyte membrane having a hydrogen ion conductivity, a method for producing the same, and a method for producing a composite polymer membrane in which the electrolyte membrane and the gasket are integrally formed.

More specifically, the present invention provides an inert porous polymer membrane, an inert polymer resin impregnated in a portion not in direct contact with an electrode of the porous polymer membrane, and a hydrogen ion conductive polymer electrolyte resin impregnated in a portion in direct contact with an electrode of the porous polymer membrane. It relates to a mosaic-type composite polymer electrolyte membrane for a fuel cell comprising a.

In addition, the present invention uses an inert porous polymer membrane as a support for the polymer electrolyte, the portion of the porous membrane in direct contact with the electrode is impregnated with a hydrogen ion conductive resin, the other portion is reinforced composite by applying an inert polymer resin A method for producing a polymer electrolyte membrane, and a method for producing a gasket-electrolyte membrane integrated by forming a gasket on the outer portion of the reinforced composite polymer electrolyte membrane.

A unit cell conceptual diagram of a polymer electrolyte membrane fuel cell (PEMFC) using a general polymer electrolyte membrane is shown in FIG. 1. In the unit cell, an anode 1 and a cathode 3 are positioned on both sides of the polymer electrolyte membrane 2, and a gas diffusion layer 4 serving as a current collector plate is located outside the anode, and a gas flow path is formed outside the anode cell. The separator or bipolar plate is formed, and the battery support plate (7, end plate) is located outside. Since the components of the fuel cell must be completely in close contact with each other, they are tightly tightened by using fasteners (8, tie bar) connecting both support plates. During cell operation, hydrogen or alcohol flows through the anode and oxygen flows through the cathode. In the fuel cell, since the reaction gases must not leak out or mix with each other, a gasket 5 is provided to prevent the outflow and mixing of the gases.

That is, in the fuel cell having the structure as described above, the polymer electrolyte membrane 2 must have hydrogen ion conductivity in order to move the hydrogen ions generated at the anode to the cathode, and function as an electrical insulator so that the anode and the cathode are not in contact with each other. It also serves as a gasket to prevent gas from leaking out. Therefore, high hydrogen ion conductivity, gas impermeability, and moderate mechanical strength are required for the polymer electrolyte membrane.

FIG. 2 illustrates a typical electrolyte membrane-electrode assembly (hereinafter referred to as MEA), which is manufactured by coating electrodes 10 on both sides of the electrolyte membrane 9.

Until now, Nafion (Nafion ^TM , a perfluoro sulfonic acid polymer, commercially available from Dupont) having high hydrogen ion conductivity has been used as a polymer electrolyte membrane. There is a disadvantage that the strength is weakened.

In order to solve this problem, U.S. Patent No. 5,635,041 impregnates a thin porous polytetrafluoroethylene (hereinafter referred to as PTFE) membrane with a hydrogen ion conductivity resin to improve hydrogen ion conductivity by about three times, and mechanical A polymer film excellent in strength and a method for producing the same have been proposed.

Specifically, the method described in the document consists of impregnating the polymer electrolyte resin in the pores of the porous membrane by applying a hydrogen ion conductive polymer electrolyte resin solution to the surface of the porous membrane of the PTFE system, as a hydrogen peroxide conductive polymer electrolyte Sulfonic acid resins or perfluorinated carboxylic acid resins and the like are used.

In addition, US Patent No. 6,156,451 proposes a method for preparing a hydrogen ion conductive composite membrane by impregnating an inert porous polymer membrane with a perfluoro sulfonyl halide or a perfluoro sulfonate polymer resin and then hydrolyzing the same.

However, since the ion conductive composite polymer electrolyte membrane of the prior art is a state in which a hydrogen ion conductive polymer electrolyte material is impregnated throughout the membrane, the membrane is greatly deformed upon absorption or drying of a solvent such as water, methanol, isopropanol, or the like. Difficult and less durable problems exist. In addition, there is a disadvantage in that the manufacturing cost is high because the amount of the hydrogen ion conductive polymer electrolyte material is still large. In addition, since a strong acidic polymer electrolyte material is also present in contact with the gasket, the constituent material of the gasket requires special physical properties, and in general, an expensive inert polymer is used.

Therefore, if the parts other than the contacting electrode are impregnated with a polymer material having no hydrogen ion conductivity and very low solvent absorption, the swelling caused by the solvent will be remarkably reduced, and the physical strength will be increased to increase durability when mounted in the fuel cell. Can be increased significantly. In addition, if an expensive hydrogen ion conductive polymer electrolyte is used only in a part of the composite membrane, the manufacturing cost becomes very low.

The present invention is to provide a reinforced composite polymer electrolyte membrane having a cheaper, more durable, and not harmful to battery components by solving the problems of the existing electrolyte membrane as described above.

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the composite polymer electrolyte membrane described above, and to provide a mosaic-type composite polymer electrolyte membrane having a high physical strength, a low manufacturing cost of the electrolyte membrane, and a high durability.

1 is a fuel cell configuration diagram.

2 is a schematic view showing a combination of an electrolyte membrane and an electrode.

3 is a schematic diagram illustrating an inert polymer film.

4 is a schematic diagram illustrating an inert porous polymer membrane.

5 is a schematic view showing a form impregnated with an inert film on a porous polymer membrane.

FIG. 6 is a schematic diagram illustrating a composite membrane in which an ion conductive polymer electrolyte is impregnated in an intermediate portion of FIG. 5; FIG.

7 is a schematic view showing a combination of a reinforced polymer film and an electrode.

8 is a schematic diagram showing a combination of an electrode and a reinforced polymer film having four electrodes formed on one surface thereof.

Figure 9 is a schematic diagram showing a composite membrane formed with protrusions serving as a gasket on the outer portion.

10 is a cross-sectional view of FIG. 8.

11 is a performance measurement graph of a unit cell produced using a composite electrolyte membrane.

<Explanation of symbols for the main parts of the drawings>

1: separator plate 2, 4: gasket,

3: electrode-electrolyte membrane assembly, 5: separator on the cathode side,

6: hydrogen inlet, 7: support plate,

8: fixed bolt, 9: hydrogen ion conductive electrolyte membrane,

10: electrode, 11: inert polymer film,

12: cut out portion of the inert polymer film,

13: porous membrane,

14: porous membrane impregnated with an inert polymer film,

15: impregnated with an ion conductive polymer resin,

16: electrode, 17 projection for gasket.

MEANS TO SOLVE THE PROBLEM In manufacturing a composite polymer membrane using an inert porous polymer membrane as a support body, the part which directly contacts an electrolyte membrane and an electrode is impregnated with a hydrogen ion conductive polymer electrolyte resin, and the other part is impregnated with an inert polymer. By manufacturing the electrolyte membrane, durability can be improved, solvent swelling can be minimized, and a mosaic type composite polymer electrolyte membrane can be manufactured at low manufacturing cost, and the electrolyte membrane and the gasket are fixed by fixing the projections serving as the gasket to the outside of the composite membrane. The present invention has been developed by developing a method that can solve the problem of manufacturing and installing additional gaskets by making them integral.

Therefore, in the present invention, a porous polymer membrane having no hydrogen ion conductivity is used as a support, and a step of blocking pores by impregnating a hydrogen ion conductive polymer electrolyte resin in an inner portion of the entire area of the support which is in direct contact with the electrode, impregnating the electrolyte resin. The remaining outer portion is not related to the method for producing a mosaic-type composite polymer electrolyte membrane comprising the step of applying an inert polymer and to a method for forming a projection serving as a gasket on the outer portion of the mosaic-type composite polymer electrolyte membrane.

According to one embodiment of the invention, the mosaic-type composite polymer electrolyte membrane, as shown in Figure 3, first to prepare an inert polymer film 11 of the same size as the porous membrane to a predetermined portion 12 in accordance with the electrode size Cut off. The polymer film is superimposed on the porous membrane 13 of FIG. 4, and the polymer film is compressed by pressing at a high temperature and high pressure to bond or impregnate the polymer film on the porous membrane as shown in FIG. 5. Next, a polymer electrolyte resin is applied to a portion 13 to which the polymer film is not applied, thereby completely blocking pores of the porous membrane 15, thereby preparing a reinforced composite electrolyte membrane. After the impregnation of the polymer electrolyte is completed, the prepared composite membrane is dried, treated with sulfuric acid at a concentration of 0.5 to 3 mol of 80 to 90 ℃, and then treated with ultra pure water of 90 ℃ again to prepare a reinforced composite electrolyte membrane. When the electrode 16 is manufactured by coating a catalyst material on both sides of the electrolyte-coated portion 15 in the composite electrolyte membrane, the preparation of the electrolyte membrane-electrode assembly as shown in FIG. 7 is completed.

FIG. 8 illustrates a combination of a polymer membrane and an electrode in which four electrodes are formed on a single electrolyte membrane, and since the space between the electrodes is filled with an inert polymer material 14, the four electrodes are ion conductive membranes. Are not connected to each other by This type of electrode is used to fabricate monopolar stacks.

When manufacturing the mosaic-type composite polymer membrane by the method described above, the method of treating the outer portion of the porous membrane with an inert polymer resin may be used one of the following various methods.

The first method is to use an inert polymer resin in the form of a film of 10 to 50 micrometers thick, to prepare an inert polymer film of the same size as the porous polymer membrane, and cut out the center portion of the film to the same size as the electrode size After that, as shown in FIG. 5, the polymer layer is superimposed on the porous polymer membrane and pressed in a hot press or calendering device to impregnate or adhere the molten polymer resin to the pores of the porous polymer membrane.

In the second method, the powder of inert polymer resin is dissolved in a solvent, and then, the resultant solution is thinly coated on a predetermined portion of the porous polymer membrane with a predetermined thickness and dried, and when the drying is completed, the supporting thin plates are stacked on the top and bottom of the porous polymer membrane. Afterwards, a high-pressure press or calendering device is used to melt the inert polymer resin to impregnate the pores of the porous membrane.

The third method is a method in which the inert polymer resin is melted at a high temperature or dissolved in a solution, and then impregnated into the porous polymer membrane by using a tape casting method, dipping method, spraying method, or brushing method.

As the inert polymer resin impregnated in the outer portion of the porous polymer membrane, there is no hydrogen ion conductivity and is electrochemically stable, and a powder or film of a polymer material having a melting point of 150 ° C. or more is used, and silicon, PTFE, polyvinylidene fluoride ( polyvinyliden fluoride (PVDF), polyethylene (polyethylene, PE), polysulfone (PS), polypropylene (PP), polyethylene terephthalate (PET), polyimide (PP) PI), polyethersulfone (hereinafter referred to as PES), or a material obtained by mixing two or more of these polymer resins, and among them, PVDF or PTFE is preferable.

The temperature during hot pressing using a hot press or calendering device is suitable near the melting temperature of the polymer resin, but is lower than the melting temperature of the inert polymer resin to prevent the inert polymer resin from penetrating into the electrolyte region. It is preferable to compress at. For example, in the case of polyvinylidene fluoride, it is suitable to compress in the range of 150-170 degreeC. The method of impregnating or adhering the inert polymer resin is selected from a high temperature compression method, a calendering method, a tape casting method, an immersion method, a brushing method, and the like, of which a calendering method and a high temperature compression method are suitable.

In order to prevent the polymer resin from penetrating into the electrolyte-impregnated part in the process of impregnating the inert polymer resin into the porous membrane, masking is performed using a Teflon paper or the like in the area of the porous membrane to be impregnated with the electrolyte. need. In addition, in order to prevent the composite membrane from curling after applying the polymer resin, it is preferable to impregnate or adhere the inert polymer resin to both surfaces of the porous membrane. For example, when a thin polymer resin film is superposed on both sides of the porous membrane and pressed at high temperature, a flat composite membrane is produced.

When the mosaic composite membrane is used, the electrolyte membrane and the gasket may be integrally formed, and thus the use may be performed without additional gaskets. To this end, thickening of the portion impregnated with the polymer resin on the outer side, or as shown in Figs. 9 and 10, the projection 17 having a height of 0.2 to 2.0 millimeters in height and 0.5 to 3.0 millimeters in width is applied to the outer portion 14 impregnated with the inert polymer. To form a gasket. Herein, materials of the protrusions may be PTFE, PVDF, PP, PE, PET, viton, silicone resin, or the like, and the protrusions may be formed on only one side or both sides of the membrane as shown in FIG. 10. Can be formed.

In the process of manufacturing the mosaic-type composite polymer electrolyte membrane, the following two methods may be used to impregnate the pores of the outer portion of the porous membrane using an inert polymer resin as described above, and then impregnate the hydrogen ion conductive polymer electrolyte. have.

First, using an electrolyte solution in which a hydrogen ion conductive polymer, perfluoro sulfonic acid (-SO ₃ H) or perfluoro sulfonate (-SO ₃ X, X = Na, K) is dissolved in a mixed solvent such as alcohol. Way. The electrolyte solution is impregnated into the electrolyte portion of the porous membrane and then dried, and the pores of the porous membrane are completely blocked by repeating the impregnation and drying process. When drying is complete, the solution is treated with hot sulfuric acid and ultrapure water. The method of impregnating the electrolyte solution is selected from the group of spraying, tape casting, dipping and the like, and preferably spraying or tape casting is used.

In a second method, the porous membrane is impregnated with perfluoro sulfonyl halide (-SO ₂ X, X = F, Cl), which is a precursor of perfluoro sulfonic acid. Perfluoro sulfonyl halide in powder or film form was superimposed on the porous membrane, and then impregnated by pressing at 50 to 300 atmospheres with a press or calender heated to 230 to 320 ° C., and impregnated perfluoro sulfonyl halogen A post-treatment process for converting the cargo into an ion conductive material is performed to prepare a reinforced composite electrolyte membrane. Alternatively, the perfluoro sulfonyl halide is melted at a high temperature, and then impregnated into the porous membrane using a tape casting method, a brushing method, or a dipping method. The post-treatment process is first performed by immersing a polymer membrane impregnated with sulfonyl halide in a concentrated alkali solution, preferably caustic soda solution (NaOH solution) or potassium hydroxide solution (KOH solution), at a temperature of about 60 to 120 ° C, followed by boiling. Substituted with sodium (Na) or potassium (K) group (-SO ₃ Na or -SO ₃ K), and then treated with sulfuric acid solution at 60 to 100 ° C. to replace alkali metal group with hydrogen group to perfluoro which is a hydrogen ion conductive material To sulfonic acid (-SO ₃ H).

In general, perfluorosulfonyl halides, which are precursors of perfluoro sulfonic acid, are present in a molten state at a temperature of 230 to 320 ° C., so that they can be directly impregnated into the porous membrane at the high temperature, and then impregnated perfluoro By converting the sulfonyl halide to perfluoro sulfonic acid, a polymer electrolyte membrane having hydrogen ion conductivity can be prepared simply. In addition, since the impregnation process is carried out at a high temperature, the bonding force between the porous membrane serving as the support and the electrolyte is increased to prevent the formation of pinholes and to improve the durability of the membrane. Perfluorosulfonyl halides are preferably perfluorosulfonyl fluoride or perfluorosulfonyl chloride.

In the case of using the method for producing a mosaic-type composite film using the perfluorosulfonyl halide described above, an electrolyte film may be further thinly formed on the composite film in order to completely prevent generation of pinholes. The first composite membrane formed is converted to the sulfonyl halide form electrolyte into the perfluoro sulfonic acid form using the post-treatment method specified above, and then an electrolyte resin film is further applied to the surface of the composite membrane. At this time, the thickness of the electrolyte film to be applied is preferably 2 to 50 ㎛. Coating of the electrolyte resin film may be carried out using a spray method, a brushing method, a dipping method, a screen printing method or a tape casting method.

The polymer electrolyte material used in preparing the mosaic composite membrane may be a perfluoro sulfonyl halide, a perfluoro sulfonic acid, a perfluoro carboxylic acid, a polystyrene sulfonic acid, a polystyrene carboxylic acid-based polymer electrolyte, or the The polymer material in the form in which hydrogen ions of sulfonic acid or carboxylic acid are substituted with ions such as sodium or potassium, or the polymer electrolyte is selected from a solution dissolved or dispersed at 2 to 50% by weight in a mixed solvent of alcohol and water.

The porous polymer membrane used to prepare the mosaic composite polymer electrolyte membrane is selected from the group of polytetrafluoroethylene, polyvinylidene fluoride, polyimide, polysulfone, polyethersulfone, polyethylene and polypropylene known in the art. Of these, polytetrafluoroethylene or polyvinylidene fluoride is preferred. The porous polymer membrane has a porosity of 30 to 90%, a pore size of 0.01 to 5.0 μm, and a thickness of 10 to 200 μm.

The final thickness of the mosaic composite polymer electrolyte membrane prepared by the above method is preferably 20 to 300 μm.

In order to form the projections for the gasket on the composite film, a band of an inert polymer having a shape as shown in FIGS. 9 and 10 is formed on the outer side of the composite film by using a mold manufactured in advance. The standard is 0.1 to 3.0 millimeters in height, 0.3 to 30 millimeters in width, and preferably 0.5 to 1.5 millimeters in height and 1-3 millimeters in width. As shown in FIG. 10, the gasket protrusion may be formed on only one surface of the composite film or both surfaces. As the material of the gasket protrusion, it is suitable to use a silicone resin, Viton resin, PVDF, PTFE, PP, PI, PS, PES, PE, PET or an inert polymer resin in which two or more thereof are mixed.

In order to improve the physical strength of the prepared composite polymer electrolyte membrane may be carried out a post-treatment step of heating for more than 1 hour in ultrapure water or steam of 80 to 150 ℃.

The following is a more detailed description of the method of the present invention through the following examples, the present invention is not limited by these examples.

Example 1 (Mosaic Film No. = MCF-01)

First, a small amount of non-conductive PVDF resin powder (Kynar) was heat-compressed at 170 ° C. and 100 atm in a press to produce a 40 μm-thick PVDF film, which was cut to a size of 10 cm × 10 cm. Further, through the same process, perfluorosulfonyl fluoride (PFSF) powder (Du Pont Co., Ltd.) was thermally compressed under a condition of 250 ° C. and 100 atm to prepare a PFSF film having a thickness of 40 μm. Next, as shown in Fig. 3, two inner 10 cm x 10 cm sized PVDF films were cut out by 5 cm x 5 cm, and then both sides of the porous PTFE membrane (thickness = 10 µm, size = 10 cm x 10 cm, Tetratec) Overlay on. The porous PTFE membrane overlaid with PVDF was heat-compressed for 5 minutes at a pressure of 100 atm in a heating press at 190 ° C., and then cooled slowly to prepare a porous Teflon membrane coated with PVDF.

PFSF film (5 cm x 5 cm size) as an electrolyte precursor on both sides of the central portion of the PVDF-Teflon membrane obtained through the above process, i.e., the central part (5 cm x 5 cm size) of the PVDF-coated porous Teflon membrane (13) (15) ) Was attached and then thermally compressed under a condition of 250 ° C. and 100 atm. After the above process, the pores are no longer present in the Teflon membrane coated with PVDF and PFSF.

Subsequently, the prepared composite membrane was placed in a 5 molar aqueous solution of sodium hydroxide at 90 ° C. and boiled for 3 hours to replace the fluoride group with sodium group, which was then added to a 90 ° C. sulfuric acid solution (2 molar concentration) and boiled for 2 hours to hydrogen ion conductivity. The preparation of the mosaic composite polymer electrolyte membrane was completed. The total thickness of the prepared membrane in the dry state was 73 μm (mosaic membrane number = MCF-01).

An electrolyte membrane-electrode assembly (hereinafter referred to as MEA) was prepared using the prepared mosaic composite membrane as an electrolyte membrane. At this time, the total amount of platinum and ruthenium metal was 3 mg / cm ² in the anode electrode, and the platinum content was 3 mg / cm ² in the cathode electrode, and the size of the electrode was 25 cm ² (5cm x 5cm, respectively). Was.

The prepared MEA was put into a mold as shown in FIG. 1 to make a unit cell, and then a DMFC performance experiment was performed. Performance test conditions are as follows. Aqueous solution of 2 mol concentration methanol was flowed to the anode at a rate of 5 cc / min, oxygen was flowed to the cathode at a rate of 250 cc / min, and the unit cell temperature was 90 ° C. Experimental results are shown in FIG. 11. The performance of the unit cell using the mosaic-type composite membrane was superior to that of the prior art unit cell using Nafion 115 (thickness = 127 μm, Du Pont) as the electrolyte membrane (using the same electrode in all experiments).

Example 2 (mosaic film number = MCA-01)

A mosaic composite electrolyte membrane was prepared in the same manner as in Example 1. However, perfluorosulfonyl fluoride was not used here as an electrolyte resin, but a perfluorosulfonic acid solution (20% Nafion solution, Du Pont) which was a hydrogen ion conductive material was used. As in Example 1, PVDF was hot pressed on the outer portion of the porous Teflon membrane, and then a 20% Nafion solution was sprayed on the central porous membrane portion, and the pores were sprayed sequentially on both sides of the porous membrane. It was completely preventable.

The prepared mosaic composite membrane was placed in distilled water at 90 ° C. and boiled for 2 hours to stabilize the electrolyte portion of the composite membrane. The final thickness of the dried composite membrane was 70 μm (mosaic membrane number = MCA-01). MEA was prepared in the same manner as in Example 1 using the prepared mosaic-type composite membrane, and the unit cell performance was measured using the prepared MEA. As shown in FIG. 11 (MCA-01), it showed superior performance compared to the conventional Nafion 115 membrane.

<Example 3> (mosaic film number = MCAG-01)

After the mosaic composite film was manufactured in the same manner as in Example 2, MEA was manufactured using the same electrode as in Example 1. Subsequently, a protrusion 17 serving as a gasket was formed in the outer portion of the MEA in the form as shown in FIG. 9. At this time, the protrusions were formed of PVDF, and the above-mentioned PVDF (Kynar) powder was placed in the same mold as the shape of the protrusions and placed on the MEA, and the dies were heated at 200 ° C. to melt the PVDF powder to form the protrusions. . Since protrusions are formed in the molten state at high temperature, the adhesion between the protrusions and the MEA, that is, the composite film, is perfectly achieved. The height of the produced projections was 0.6 mm and the width was 3 mm (mosaic membrane number = MCAG-01).

The unit cell performance was measured in the same manner as in Example 1 using the gasketed mosaic-shaped MEA. As shown in FIG. 11 (MCAG-01), the projection-formed MEA was completely airtight and showed high unit cell performance.

<Example 4>

The physical strengths of the mosaic composite membranes prepared in Examples 1 and 2 and the Nafion 115 membrane of the prior art were measured. Table 1 shows the tensile strength measurement of each electrolyte membrane.

As shown in the table, the membrane using PFSF (MCF-01) showed the best characteristics.

Tensile Strength of Various Electrolyte Membranes Electrolyte membrane number Tensile strength (kgf / cm) MCF-001 3.8 MCA-001 3.3 MCAG-001 3.1 Nafion 115 2.7

Comparative Example 1

Using a Nafion 115 (Du Pont) electrolyte membrane having a thickness of 127 μm made of pure perfluorosulfonic acid as the polymer electrolyte membrane, an MEA was prepared using the same electrode as in Example 1, and the unit cell was used. The performance was measured. Performance measurement conditions are the same as in Example 1, and the measurement results are shown in FIG.

When the composite polymer electrolyte membrane prepared according to the present invention is used in a fuel cell, high cell performance can be obtained, and gas leakage through the polymer electrolyte membrane is minimized even under high pressure operating conditions. In addition, since the inert polymer is impregnated in the outer portion of the composite electrolyte membrane, deformation of the electrolyte membrane due to moisture absorption or drying is minimized during the pretreatment of the electrolyte membrane or during preparation for use in a fuel cell, and thus easy handling. Damage to the electrolyte membrane is minimized during prolonged operation. When the composite electrolyte membrane is mounted on a fuel cell, the gasket is not damaged because a chemically inert polymer is present in a portion of the electrolyte membrane contacting the gasket, and the electrolyte membrane is not deformed during operation, thereby increasing durability. Since the inert polymer has a very low methanol absorption, no permeation of methanol can be made through the portion other than the electrode. Therefore, when directly used in a methanol fuel cell, it is possible to significantly reduce the methanol crossover to increase the cell performance.

In addition, the existing polymer electrolyte membrane wastes an expensive electrolyte material because the electrolyte exists in addition to the portion in contact with the electrode. However, since the composite polymer electrolyte membrane prepared in the present invention can minimize the use of the electrolyte, the manufacturing cost of the electrolyte membrane can be greatly reduced.

Claims (26)

Providing an inert porous polymer membrane, Impregnating an inert polymer resin having no hydrogen ion conductivity in a portion of the porous polymer membrane that is not in direct contact with an electrode to prevent pores of the porous membrane; The perfluorosulfonyl halide in the form of a film or fine powder is spread on a plurality of parts in direct contact with the electrode of the porous polymer membrane, and then compressed at a high temperature of 230 to 320 ° C. to form a composite polymer membrane, and the alkali is formed on the formed polymer membrane. Solution, sulfuric acid solution and ultrapure water in order to convert the perfluorosulfonyl halide to perfluorosulfonic acid to impregnate a hydrogen ion conductive polymer electrolyte resin in a plurality of portions in direct contact with the electrode in the porous polymer membrane. step, Treating the composite polymer membrane prepared above in order using a high temperature sulfuric acid solution and ultrapure water, and Forming a projection made of an inert polymer material having a gasket function on each of the inert polymer resins outside the plurality of portions in direct contact with the electrodes of the prepared mosaic-type composite electrolyte membrane A method of producing a mosaic-type composite polymer electrolyte membrane for a monopolar fuel cell, comprising a composite electrolyte membrane and a gasket integrally present. The method of claim 1, wherein the porous polymer membrane has a porosity of 30 to 90%, a pore size of 0.05 to 5.0 μm, and a thickness of 10 to 200 μm. 3. The porous polymer membrane according to claim 1 or 2, wherein the porous polymer membrane is made of porous polytetrafluoroethylene membrane, polypropylene membrane, polyethylene membrane, polyimide membrane, polysulfone membrane, polyether sulfone membrane and polyvinylidene fluoride membrane. Selected from the group. The method of claim 1, wherein the impregnating the inert polymer resin in the porous polymer membrane is a film, fine powder, melt or a polymer resin selected from PTFE, PVDF, PE, PP, PET, PI, PS, PES and mixtures thereof And impregnating the solution dissolved in the organic solvent into the porous polymer membrane by hot pressing, calendering, tape casting, brushing, dipping or spraying. delete delete delete The method of claim 1, wherein the hot pressing is performed at a pressure of 40 to 300 kgf / cm ² . The method according to claim 1 or 4, wherein the inert polymer resin and the polymer electrolyte resin are impregnated on both sides of the porous polymer membrane simultaneously or sequentially to prevent pinhole formation or the winding of the composite polymer membrane. The method of claim 1, wherein the electrolyte film selected from the group consisting of perfluoro sulfonic acid, perfluoro carboxylic acid, polystyrene sulfonic acid, and polystyrene carboxylic acid has a thickness of 2 to 50 µm on the surface of the impregnated electrolyte membrane. And spraying, brushing, dipping, tape casting or screen printing to remove the pinholes. The method according to claim 1 or 10, wherein the prepared composite polymer electrolyte membrane has a final thickness of 20 to 300 µm. delete The process according to claim 1, wherein the gasket functioning projection is selected from the group consisting of silicone resins, PVDF, PTFE, PP, PE, PET, Viton and mixtures of two or more thereof, which are inert polymer materials. The method of claim 1, wherein the protrusions formed in the integrated composite membrane have a height of 0.1 to 3 millimeters and a width of 0.1 to 30 millimeters. delete delete delete delete delete delete delete delete delete delete delete delete