JP5266766B2 - Resin film structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To suppress the dimensional change in the expansion direction and shrinkage direction that occurs in wet and dry cycles in the fuel cell operation in a reinforced electrolyte membrane 10A used in the fuel cell for example. <P>SOLUTION: A ceramic porous body-containing layer or a glass electrolyte powder-containing layer (a second reinforcement) is arranged on both surfaces of a PTFE expanded porous membrane (a first reinforcement). The whole of a laminate is wrapped with electrolyte resin 3. The first reinforcement suppresses expansion of the membrane and the second reinforcement suppresses shrinkage of the membrane. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a resin-made membrane structure, and particularly, but not exclusively, relates to a membrane structure of a solid polymer electrolyte membrane used in a fuel cell.

  A solid polymer fuel cell is known as one form of the fuel cell. The polymer electrolyte fuel cell has a lower operating temperature (about -30 ° C to 120 ° C) than other types of fuel cells, and is expected to be a power source for automobiles because of its low cost and compactness. ing.

  As shown in FIG. 3, the polymer electrolyte fuel cell A includes a membrane electrode assembly (MEA) B as a main component, which includes an anode-side separator 20 including a fuel (hydrogen) gas flow path 21, and One fuel cell A called a single cell is formed by being sandwiched by a cathode-side separate 30 having an air (oxygen) flow path 31. In the membrane electrode assembly B, an anode side electrode 15a composed of an anode side catalyst layer 13a and a gas diffusion layer 14a is laminated on one side of a solid polymer electrolyte membrane 10 which is an ion exchange membrane, and the cathode side is placed on the other side. The cathode side electrode 15b composed of the catalyst layer 13b and the gas diffusion layer 14b is laminated.

  In the polymer electrolyte fuel cell, as the electrolyte membrane, a thin film of perfluorosulfonic acid polymer (USA, DuPont, Nafion membrane) which is a fluorine-based electrolyte resin (ion exchange resin) is mainly used. Moreover, since a sufficient strength cannot be obtained with a thin film of an electrolyte resin alone, a stretched porous reinforcing film (for example, a porous thin film obtained by stretching PTFE or polyolefin resin) is impregnated with an electrolyte resin dissolved in a solvent. A dried reinforced membrane electrolyte membrane is used (see Patent Documents 1 and 2, etc.).

JP 2004-059752 A JP 2005-285757 A

  The electrolyte resin used in the polymer electrolyte fuel cell is a resin having a characteristic of swelling due to moisture absorption, and the electrolyte membrane swells due to moisture absorption. In the conventional reinforced membrane type electrolyte membrane, the porous reinforced membrane obtained by stretching PTFE or polyolefin resin has a strong resistance in the tensile direction, suppresses the swelling behavior due to moisture absorption of the electrolyte resin, and the dimension in the expansion direction of the electrolyte membrane. It effectively prevents changes from occurring. However, the conventional porous reinforcing membrane has low resistance to the shrinkage direction, and when the electrolyte resin is dried after moisture absorption, wrinkles due to shrinkage may be generated in the electrolyte membrane. That is, it cannot be said that the conventional porous reinforcing membrane functions as a reinforcing membrane in the shrinking direction.

  The shrinkage of the electrolyte membrane occurs even when heat processing is performed in the manufacturing process for joining the catalyst layer to the electrolyte membrane, and the catalyst layer may be peeled off. In addition, even after being assembled into a battery as a membrane electrode assembly of a fuel cell, the electrolyte membrane experiences a cycle of dryness and humidity depending on the operating environment of the fuel cell, so that the electrolyte membrane also contracts and damages the electrolyte membrane. The problem that the life as a fuel cell becomes short may also occur.

  In addition, the above inconvenience is not limited to the electrolyte resin membrane used in the polymer electrolyte fuel cell, and has a function of swelling due to moisture absorption and a function of being contained in the resin and suppressing swelling of the resin. In the resin film made of the first reinforcing material (reinforcing film), the same occurs.

  The present invention has been made in view of the circumstances as described above, and is a first strengthening resin that has a property of swelling due to moisture absorption and a function that is contained in the resin and suppresses swelling of the resin. An object of the present invention is to obtain a film structure that can suppress a dimensional change in the shrinkage direction of a film in a resin film made of a material.

  The resin film structure according to the present invention is a resin film made of a resin having a property of swelling due to moisture absorption and a first reinforcing material that is included in the resin and has a function of suppressing the swelling of the resin. The resin film has a structure further including a second reinforcing material having a function of suppressing shrinkage of the resin adjacent to the first reinforcing material, and the first and second reinforcing materials. The reinforcing material is impregnated with the resin.

  In the membrane structure according to the present invention, the first reinforcing material has tensile strength and suppresses resin swelling, and the second reinforcing material has shrinkage resistance and suppresses resin shrinkage. It is possible to appropriately cope with the dimensional change of the membrane due to both expansion and contraction.

  Specific examples of the membrane having a resin membrane structure according to the present invention include a solid polymer electrolyte membrane used in a polymer electrolyte fuel cell and an ion exchange membrane used in salt electrolysis. When the resin membrane is a solid polymer electrolyte membrane, examples of the first reinforcing material include a PTFE stretched porous membrane or a polyolefin resin stretched porous membrane, and the second reinforcing material. Examples of the material include a porous ceramic body-containing layer or a glass electrolyte powder-containing layer.

When the second reinforcing material is a ceramic porous body, the porosity is preferably about 30 to 60%. If the porosity is less than 30%, there is an inconvenience of a decrease in proton conduction, and if the porosity is more than 60%, there is an inconvenience of a significant decrease in the strength of the ceramic porous body. As an example of the ceramic porous body having such a porosity, TiO ₂ powder can be mentioned. In the case of TiO ₂ powder, the average particle size is preferably about 1 to 3 μm.

When the second reinforcing material is a glass electrolyte powder, specific examples thereof include SiO ₂ —P ₂ O 5, PbO—SrO—P ₂ O ₅ , PbO—SrO—BaO—P ₂ O ₅ , SiO ₂ —ZrO. A powder such as _2- P ₂ O ₅ can be mentioned. It is known that such materials have proton conductivity. These materials may be used alone or in combination of two or more materials. In any case, the average particle size is preferably 2 to 3 μm.

  By providing the film structure according to the present invention, it is possible to suppress a dimensional change in both expansion and contraction of the film in a film mainly composed of a resin having a characteristic of swelling due to moisture absorption. When the membrane is an electrolyte membrane, it can be an electrolyte membrane that is more excellent in dimensional stability than before, and a fuel cell with a long life can be obtained when it is used as a membrane electrode assembly of a fuel cell.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic diagram showing two modes when the membrane structure according to the present invention is a membrane structure of a reinforced membrane type electrolyte membrane of a fuel cell, and FIG. 2 shows a membrane structure of a conventional reinforced membrane type electrolyte membrane. It is a schematic diagram which shows.

A reinforcing membrane type electrolyte membrane 10A shown in FIG. 1A has ceramic porous body layers (second reinforcing materials) 2 and 2 disposed on both sides of a PTFE stretched porous membrane (first reinforcing material) 1, The whole is enclosed in the electrolyte resin 3. The electrolyte resin 3 is impregnated into the porous bodies of both the PTFE stretched porous membrane 1 and the ceramic porous body layers 2 and 2. An example of the ceramic porous body is TiO ₂ porous powder. The electrolyte resin may be an electrolyte tree used in a conventional fuel cell, for example, Nafion (trade name) manufactured by DuPont.

Instead of the ceramic porous body layers 2 and 2, a glass electrolyte powder-containing layer may be disposed. Examples of the glass electrolyte powder include SiO ₂ —P ₂ O ₅ , PbO—SrO—P ₂ O ₅ , PbO—SrO—BaO—P ₂ O ₅ , SiO ₂ —ZrO ₂ having an average particle diameter of about 2 to 3 μm. -P ₂ O _5, powder such as may be exemplified.

  In the reinforced membrane electrolyte membrane 10B shown in FIG. 1B, the PTFE stretched porous membranes 1 and 1 are disposed on both surfaces of the ceramic porous body layer 2, and the whole is encapsulated in the electrolyte resin 3. Also here, the electrolyte resin 3 is impregnated into the porous bodies of both the ceramic porous body layer 2 and the PTFE stretched porous membranes 1 and 1. Here, instead of the ceramic porous body layer 2, a glass electrolyte powder-containing layer may be disposed. The materials for the ceramic porous body and the glass electrolyte powder are the same as those shown in FIG.

  As described above, in the resin-made film structure, the PTFE stretched porous film 1 is resistant to pulling, and the ceramic porous body layer (or glass electrolyte powder-containing layer) 2 is resistant to shrinkage. Therefore, by combining the two, it is possible to obtain the structures 10A and 10B that are resistant to pulling and shrinking. By including two reinforcing membranes, the ionic conductivity is lower than that of the polymer solid electrolyte alone, but in the case of a ceramic porous layer, the performance as an electrolyte membrane can be achieved by impregnating the porous body with an electrolyte resin. In the case of the glass electrolyte powder-containing layer, the reinforcing material itself has ionic conductivity, so that the performance of the entire electrolyte membrane can be secured.

  FIG. 2 schematically shows a conventionally known reinforced membrane electrolyte membrane 10. In the reinforcing membrane type electrolyte membrane 10, only the PTFE stretched porous membrane (first reinforcing material) 1 is included in the electrolyte resin 3. Again, the electrolyte resin 3 is impregnated in the pores of the PTFE stretched porous membrane 1.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
[Example 1]
1) Bead extrusion from PTFE fine powder, PTFE tape of 9mm thickness and 50mm x 50mm size manufactured by the usual method of roll rolling is set in a multiaxial stretching machine, heated and stretched 30 times, thickness A 0.010 mm porous membrane was obtained.
2) Titanium alkoxide (Ti (OC ₂ H ₅ ) ₄ ) was introduced into ethanol and hydrolyzed at 25 ° C. for 1 hour to form amorphous TiO ₂ . This solution was heat-treated at 400 ° C. for 1 hour to obtain a TiO ₂ porous body, and pulverized with a ball mill to prepare a TiO ₂ porous body powder having an average particle diameter of 2 μm. The porosity of the TiO ₂ porous material powder was 40%.
3) On both surfaces of the porous membrane obtained in 1), the porous powder obtained in 2) was slurried with water + ethanol, applied and dried, and the electrolyte polymer precursor polymer was applied on both sides of the composite membrane. A thin film prepared by extruding a polymer chain end of —SO ₂ F and a polymer NE111F manufactured by DuPont with a thickness of 12 μm using an extrusion molding machine was attached.
4) The membrane was impregnated at a pressure of 5 kg / cm ^{2 in} a 230 ° C. vacuum environment to obtain a membrane.
5) The membrane was hydrolyzed with a mixed solution of a 1 mol / L sodium hydroxide aqueous solution and an alcohol, and then the polymer chain end was converted to an acid form (—SO ₃ H) with a 1 mol / L sulfuric acid aqueous solution.
7) Washed with ion-exchanged pure water and then dried to obtain a reinforced electrolyte membrane having a structure shown in FIG. 1A having a thickness of about 30 μm.

[Example 2]
1) A porous membrane similar to that in Example 1 was produced.
2) PbO—SrO—BaO—P ₂ O ₅ , which is a glass material having proton conductivity, was pulverized with a ball mill to produce a glass electrolyte powder having an average particle diameter of 2 to 3 μm.
3) On both surfaces of the porous membrane obtained in 1), the glass electrolyte powder obtained in 2) was slurried with water + ethanol, dried, and the electrolyte resin precursor on both sides of the composite porous membrane. A thin film in which a molecule (polymer chain end is —SO ₂ F, polymer NE111F manufactured by DuPont) with a thickness of 12 μm was attached using an extrusion molding machine.
4) The membrane was impregnated at a pressure of 5 kg / cm ^{2 in} a 230 ° C. vacuum environment to obtain a membrane.
5) The membrane was hydrolyzed with a mixed solution of a 1 mol / L sodium hydroxide aqueous solution and an alcohol, and then the polymer chain end was converted to an acid form (—SO ₃ H) with a 1 mol / L sulfuric acid aqueous solution.
7) Washed with ion-exchanged pure water and then dried to obtain a reinforced electrolyte membrane having a structure shown in FIG. 1A having a thickness of about 30 μm.

[Comparative Example 1]
1) A PTFE tape with a thickness of 18 mm and 50 mm x 50 mm produced by bead extrusion from PTFE fine powder and rolled by the usual method is set in a multiaxial stretching machine, heated to 30 times, and stretched. A 0.020 mm porous membrane was obtained.
2) A thin film obtained by forming an electrolyte resin precursor polymer (polymer end is —SO ₂ F, polymer NE111F manufactured by DuPont) to a thickness of 12 μm on both sides of the porous membrane obtained in 1) with an extrusion molding machine. Was pasted.
3) The membrane was impregnated at a pressure of 5 kg / cm ^{2 in} a 230 ° C. vacuum environment to obtain a membrane.
4) After the membrane was hydrolyzed with a mixed solution of 1 mol / L sodium hydroxide aqueous solution and alcohol, the end of the polymer chain was converted to acid form (—SO ₃ H) with 1 mol / L sulfuric acid aqueous solution.
5) After washing with ion-exchanged pure water and drying, an electrolyte membrane having the structure shown in FIG. 2 was obtained.

[Evaluation Test 1]
The electrolyte membranes obtained in Examples 1 and 2 and the comparative example were impregnated in hot water at 90 ° C. for 2 hours to swell the membrane with water, and the membrane was further dried in air in an 80 ° C. drying oven for 2 hours. When drying and shrinking, the dimensions of each film were measured to evaluate the dimensional stability of each film. The results are shown in Table 1. Furthermore, the ionic conductivity of the electrolyte membranes obtained in Examples 1 and 2 and the comparative example was measured. The results are also shown in Table 1.

  The dimensional stability indicates an average dimensional change rate in the MD direction and the TD direction with reference to the initial dimension.

  Ion conductivity measurement was performed as follows. The saturated water-containing sample is cut into a 1 cm × 1.5 cm strip and the thickness t of the sample is measured. And it mounts | wears with the 2 terminal type conductivity measuring cell which measures the conductivity of a sample in-plane direction. The resistance (Ω) is measured by an AC impedance method (frequency: 0.01 Hz to 1 MHz, applied voltage: 10 mV) with ion-exchanged water attached to the sample at room temperature (25 ° C.). Ionic conductivity σ was derived from the obtained resistance value R by the following equation.

Formula · σ = L / (R × t × W)
Here, σ: ion conductivity (S / cm), L: film length (cm), R: resistance (Ω), t: film thickness (cm), W: film width (cm)

[Evaluation]
From the result of the evaluation test 1, the reinforced electrolyte membrane of the present example has a drastic improvement in shrinkage during drying, while the ionic conductivity and the swelling rate when containing water are substantially the same as the electrolyte membrane of the comparative example. According to the present invention, it can be seen that a reinforced membrane electrolyte membrane having more excellent dimensional stability can be obtained. By using this electrolyte membrane, it is possible to avoid a decrease in manufacturing yield due to generation of soot due to dimensional changes during the manufacture of the fuel cell, and to suppress deterioration due to the wet and dry cycle during fuel cell operation, providing a fuel cell with excellent durability can do.

The schematic diagram which shows two aspects in case the membrane structure by this invention is a membrane structure of the reinforced membrane type electrolyte membrane of a fuel cell. The schematic diagram which shows the membrane structure of the conventional reinforcement membrane type electrolyte membrane. The figure for demonstrating a polymer electrolyte fuel cell.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10A, 10B ... Reinforcing membrane type electrolyte membrane, 1 ... PTFE stretched porous membrane (first reinforcing material), 2 ... Ceramic porous body layer or glass electrolyte powder containing layer (second reinforcing material), 3 ... Electrolyte resin

Claims (3)

A resin having a property of swelling due to moisture absorption, a first reinforcing material layer encapsulated in the resin and having a function of suppressing the swelling of the resin, and the first reinforcing material layer encapsulated in the resin And a second reinforcing material layer having a function of suppressing shrinkage of the resin, and a film structure impregnated with the resin is provided in the first and second reinforcing material layers. A solid polymer electrolyte membrane ,
The first reinforcing material layer is a PTFE stretched porous membrane, and the second reinforcing material layer is made of a ceramic porous material layer having a porosity in the range of 30 to 60% or a glass electrolyte powder. A solid polymer electrolyte membrane characterized by being a layer. It said second reinforcement layer is a solid polymer electrolyte membrane according to claim 1 is a layer consisting of a powder of the ceramic porous body, a solid high polymer, wherein the ceramic porous body is characterized in that it is a TiO ₂ Electrolyte membrane. 2. The solid polymer electrolyte membrane according to claim 1, wherein the second reinforcing material layer is a layer made of a glass electrolyte powder, wherein the glass electrolyte powder comprises SiO ₂ —P ₂ O ₅ , PbO—SrO. _{-P 2 O 5, PbO-SrO} -BaO-P 2 O 5, the solid polymer electrolyte membrane, which is a one of a powder of _{SiO 2 -ZrO 2 -P 2 O 5} .

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