JP2005150005A - Ion conductor, its manufacturing method, and electrochemical device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ion conductor which can effectively prevent leakage of a fuel gas (or a liquid fuel) and an oxidizer, and to provide its manufacturing method and an electrochemical device. <P>SOLUTION: The ion conductor 4 contains an ion dissociating group in a region 7 inside the peripheral part 6 of a solid polymer membrane 5. The solid polymer membrane 5 sandwiched between a first catalyst electrode 2 and a second catalyst electrode 3 contains the ion dissociating group in the region 7 in contact with catalyst layers 1a, 1b. The electrochemical device has a multilayer structure formed of the first catalyst electrode 2, a second catalyst electrode 3, and the ion conductor 4 sandwiched between these electrodes. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an ion conductor, a method for producing the same, and an electrochemical device such as a fuel cell.

  A power generation body (hereinafter referred to as MEA (Membrane & Electrode assembly)) used in an electrochemical device such as a polymer electrolyte fuel cell is mainly Nafion (registered trademark) (perfluorosulfonic acid resin (manufactured by DoPont). Nafion (R), etc.))) and the like, and electrodes with catalyst layers formed on both surfaces of the electrolyte membrane (for example, see Patent Document 1 described later) .)

The above MEA can obtain electric power when protons (H ⁺ ) generated in the fuel electrode side catalyst layer react with oxygen gas as an oxidant on the oxygen electrode side catalyst layer. When (or fuel liquid) and oxygen gas coexist, the power generation capacity is significantly reduced. Therefore, the fuel and oxygen gas are separated.

  FIG. 5A is a schematic sectional view of a conventional MEA.

  The MEA 50 of the conventional example includes an electrolyte membrane 51 made of a sulfonated fluoropolymer such as Nafion (registered trademark) (perfluorosulfonic acid resin (Nafion (R) manufactured by DoPont)), and the like. It is comprised from the electrode layer (catalyst layer + diffusion layer) 52 formed in both surfaces.

  The solid polymer electrolyte membrane 51 includes an ion conducting region 53 sandwiched between the electrode layers 52 and a peripheral portion 55 sandwiched between the sealing materials 54. By sandwiching the peripheral portions 55 with the sealing material 54, The structure prevents the fuel gas (or fuel liquid) and oxygen gas (not shown) from being mixed. The sealing material 54 is made of a soft material such as O-ring.

Japanese Patent Laid-Open No. 3-208260 (page 3, lower right column, lines 1 to 16; FIG. 1)

  However, although conventional fluorine-based solid polymers such as Nafion that form electrolyte membranes are solid due to the proton conduction mechanism, proton-conducting performance is not achieved unless the fluorine-based solid polymer itself has sufficiently absorbed moisture. Does not work. Since the fluorine-based solid polymer has high water swellability, it is swollen by the water content and generated water during power generation, and fuel gas (or fuel liquid) and oxygen gas leak. This leak lowers the fuel efficiency and hinders the chemical reaction of the electrode, causing a reduction in output density.

  In addition, a hot press operation for forming an interface is performed at the time of manufacturing the MEA. Since the electrolyte membrane is suddenly contracted at the time of the hot press operation, as shown in FIG. In the portion 55, a fold 56 is generated. And the position of the sealing material 54 changes with generation | occurrence | production of this ridge 56, As a result, the isolation function of the fuel gas (or fuel liquid) and oxygen gas by a sealing material falls. As the isolation function decreases, the amount of fuel gas (or fuel liquid) leakage increases, and this leakage phenomenon reduces the output.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to effectively prevent leakage of fuel gas (or fuel liquid) and oxidant. And a manufacturing method thereof, and an electrochemical device.

  That is, the present invention relates to an ionic conductor containing an ion dissociable group in a region inside the periphery of the solid polymer membrane (preferably in the entire region).

  An ion conductor in which the solid polymer film sandwiched between the first catalyst electrode and the second catalyst electrode contains an ion dissociable group in a region in contact with the catalyst (preferably in the entire region). It is related to.

  Further, the present invention relates to a method for producing an ion conductor, which includes a step of introducing an ion dissociable group into a region inside the peripheral portion of the solid polymer membrane (desirably, the entire region).

  In addition, there is a step of introducing an ion dissociable group into a region of the solid polymer membrane sandwiched between the first catalyst electrode and the second catalyst electrode that is in contact with the catalyst (preferably, the entire region). This relates to a method for manufacturing a body.

  Furthermore, an electrochemical device having a laminated structure of a first catalyst electrode, a second catalyst electrode, and an ion conductive solid polymer film sandwiched between these electrodes, The present invention relates to an electrochemical device containing an ion dissociable group in a region inside the peripheral portion (preferably in the entire region).

  An electrochemical device having a laminated structure of a first catalyst electrode, a second catalyst electrode, and an ion conductive solid polymer film sandwiched between the electrodes, wherein the solid polymer film is The present invention relates to an electrochemical device containing an ion dissociable group in a region in contact with the catalyst (preferably in the entire region).

Here, the above “ion dissociable group” means a group from which ions such as protons (H ⁺ ) can be released by ionization, and “ion dissociation” means that ions such as protons from ions by ionization. This means leaving the group (the same applies hereinafter).

  The present inventor has intensively studied to prevent a decrease in output due to the leakage phenomenon of the fuel gas (or fuel liquid) and the oxidant as described above. As a result, the presence of an ion dissociable group such as a sulfonic acid group is caused by contraction of the membrane. It was found to cause expansion. Then, by introducing the ion dissociable group only in a region where the catalyst contacts in advance during the production of the ion conductor and limiting the ion conduction path such as protons, the above-described swelling and contraction of the ion conductor It has been found for the first time that the occurrence of a leak phenomenon of fuel gas (or fuel liquid) and oxidant can be reduced.

  That is, according to the present invention, the solid polymer membrane contains the ion dissociable group in a region inside the periphery thereof or is sandwiched between the first catalyst electrode and the second catalyst electrode. The solid polymer membrane contains the ion dissociable group in a region in contact with the catalyst, and the peripheral portion or the region not in contact with the catalyst does not have water swellability. Even when it is hydrated to activate its ion conduction performance, it does not swell and can maintain a high sealing function.

  In addition, for example, even when the above-described hot pressing operation is performed when manufacturing the laminated structure, wrinkles are generated in the peripheral portion or the region that is not in contact with the catalyst due to the rapid contraction of the ionic conductor as in the conventional example. Therefore, a decrease in output due to the above-described leakage phenomenon can be reduced.

  Therefore, energy efficiency and current density can be improved.

In the present invention, the ion dissociable group, particularly the proton dissociable group, includes —OH, —OSO ₃ H, —COOH, —SO ₃ H, —OPO (OH) ₂ , —C ₆ H ₄ —SO. _At least one of ₃ H can be mentioned, and —OPO (OH) ₂ , —SO ₃ H or —COOH is particularly preferable. When -OPO (OH) ₂ is used as the proton dissociable group, since there are two protons that can be dissociated per one proton dissociable group, high proton conductivity can be obtained, In addition, the chemical stability can be further improved. Further, when —SO ₃ H is used, higher proton conductivity can be obtained because of higher proton dissociation property.

  As the solid polymer film, it is preferable to use polyvinylidene fluoride, polytetrafluoroethylene or polyethylene. Although the thickness of the said solid polymer film is not specifically limited, For example, 10-200 micrometers is preferable, More preferably, it is 10-50 micrometers.

  Moreover, it is preferable that the ion dissociable group is introduced into the base polymer chain forming the solid polymer film as described above.

  In the method for producing an ionic conductor according to the present invention, it is preferable that a predetermined region of the solid polymer film is covered with a mask and the ion dissociable group is introduced through a non-mask portion of the mask. .

  Specifically, after covering a predetermined region of the solid polymer film with a mask and performing at least one of electron beam irradiation treatment, γ-ray irradiation treatment, and alkali hydroxide treatment, the solid polymer film It is desirable to introduce the ion dissociable group into Moreover, it is preferable that after the treatment, monomer molecules are bonded to the solid polymer film, and further, the ion dissociable group is introduced into the combined body.

  According to this, the solid polymer film located in the non-mask portion, that is, the region inside the peripheral portion (or the region in contact with the catalyst) is subjected to electron beam irradiation treatment, γ-ray irradiation treatment or alkali hydroxide treatment. And the reaction activity in the above-described region can be improved. The conditions such as the processing time are not particularly limited and can be selected as appropriate. Here, in the alkali hydroxide treatment, for example, when the solid polymer film coated with the mask is immersed in a high-concentration KOH methanol solution, the reaction of the solid polymer film in the non-mask portion at about 80 ° C. Activity is improved. However, this alkali hydroxide treatment can be applied only when a polymer composed mainly of polyvinylidene fluoride is used as the solid polymer film. Although the mask may be removed immediately after the treatment, the mask may be removed after the introduction of an ion dissociable group described later.

  As a method for introducing the ion dissociable group, graft polymerization is desirable. For example, when a sulfonic acid group is introduced as the ion dissociable group, it is desirable to perform graft polymerization using a monomer such as styrene or vinyl sulfonate after the treatment. Here, as described above, the reaction activity of the region subjected to the electron beam irradiation treatment, the γ-ray irradiation treatment or the alkali hydroxide treatment, that is, the region inside the peripheral part (or the region in contact with the catalyst) is improved. Therefore, the ion dissociable group can be selectively introduced into the same region.

  Hereinafter, the electrochemical device based on this invention is demonstrated concretely, referring drawings.

  The electrochemical device according to the present invention is preferably configured as a fuel cell as shown in FIG. Here, FIG. 1 is a schematic sectional view of an example of a fuel cell as an electrochemical device according to the present invention.

  As shown in FIG. 1, this fuel cell includes a negative electrode (fuel electrode or hydrogen electrode) 2 with a catalyst layer 1a, a positive electrode (oxygen electrode) 3 with a catalyst layer 1b, and both electrodes 2 facing each other. 3 is a laminated structure (hereinafter also referred to as MEA (Membrane & Electrode assembly)) with the ion conductor 4 of the present invention having proton conductivity sandwiched between the three.

  As shown in FIG. 1, the ion conductor 4 constituting the MEA is in a region 7 (or a region in contact with the catalyst layers 1 a and 1 b) 7 inside the peripheral portion 6 in the peripheral portion 6 of the solid polymer membrane 5. Contains ion dissociable groups.

  Further, the peripheral portion 6 of the solid polymer film 5 is fixed to the container 9 via, for example, a sealing material 8. That is, the container 9 is divided into a part on the negative electrode 2 side and a part on the positive electrode 3 side, and the sealing material 8 is disposed between these parts and the peripheral part 6 of the solid polymer film 5. It is preferable.

  As the material of the container 9, metal, carbon resin, or the like can be used, and its size can be selected as appropriate.

  Moreover, an O-ring etc. can be used as the sealing material 8, The size can be selected suitably.

  Hereinafter, an example of the manufacturing method of the ion conductor based on this invention is demonstrated with reference to FIG. In FIG. 2, left diagrams (a) to (d) are schematic sectional views showing an example of the manufacturing method according to the present invention in the order of steps, and right diagrams (a ′) to (d ′) correspond to the left diagrams. FIG.

  First, as shown in FIGS. 2A and 2A, a solid polymer film 5 is formed as an ion conductor substrate before introducing the ion dissociable group. As the solid polymer film 5, it is preferable to use polyvinylidene fluoride, polytetrafluoroethylene or polyethylene. Moreover, although the thickness of the solid polymer film 5 is not specifically limited, For example, 10-200 micrometers is preferable, More preferably, it is 10-50 micrometers.

  Next, as shown in FIGS. 2 (b) and 2 (b ′), a region (or a region in contact with the catalyst) inside the peripheral portion of the solid polymer film 5 is covered with a mask 10. As the mask 10, Teflon (registered trademark) (polytetrafluoroethylene (PTFE)) or the like can be used, and the thickness thereof may be arbitrary, but for example, 0.1 to 0.3 mm is preferable.

  Next, as shown in FIGS. 2C and 2C, the solid polymer film 5 on which the mask 10 is disposed is subjected to an electron beam irradiation process, a γ-ray irradiation process, or an alkali hydroxide process. As a result, the solid polymer film 5 located in the non-mask portion 11 of the mask 10, that is, the region 7 inside the peripheral portion 6 (or the region in contact with the catalyst) 7 is subjected to electron beam irradiation treatment, γ-ray irradiation treatment, or alkali hydroxide treatment. And the reaction activity of the region 7 can be improved. The conditions such as the processing time are not particularly limited and can be selected as appropriate. Here, in the alkali hydroxide treatment, for example, when the solid polymer film 5 with the mask 10 is immersed in a high-concentration KOH methanol solution, the reaction activity of the region 7 corresponding to the non-mask portion 11 is improved at about 80 ° C. To do. However, this alkali hydroxide treatment can be applied only when a polymer composed mainly of polyvinylidene fluoride is used as the solid polymer film 5. After the treatment, the mask 10 may be removed immediately, but the mask 10 may be removed after introduction of an ion dissociable group described later.

  Next, as shown in FIGS. 2D and 2D ′, the ion dissociable group is introduced into the base polymer chain forming the solid polymer film 5 as described above. Here, in FIG. 2C and FIG. 2C ′, the region where the electron beam irradiation treatment, the γ-ray irradiation treatment or the alkali hydroxide treatment has been performed, that is, the region inside the peripheral portion 6 (or the region in contact with the catalyst) 7. Therefore, the ion dissociable group can be selectively introduced into the same region. As a method for introducing the ion dissociable group, graft polymerization is desirable. For example, when a sulfonic acid group is introduced as the ion dissociable group, it is desirable to perform graft polymerization using a monomer such as styrene or vinyl sulfonate.

Examples of the ion dissociable group, particularly a proton dissociable group, include —OH, —OSO ₃ H, —COOH, —SO ₃ H, —OPO (OH) ₂ , and —C ₆ H ₄ —SO ₃ H. can include at least one, among them _{-OPO (OH) 2, -SO 3} H or -COOH are preferred. When -OPO (OH) ₂ is used as the proton dissociable group, since there are two protons that can be dissociated per one proton dissociable group, high proton conductivity can be obtained, In addition, the chemical stability can be further improved. Further, when —SO ₃ H is used, higher proton conductivity can be obtained because of higher proton dissociation property.

  As described above, the ion conductor 4 containing the ion dissociable group or the region between the first catalyst electrode and the second catalyst electrode in the region 7 inside the peripheral portion 6 of the solid polymer film 5. It is possible to easily manufacture the ion conductor 4 containing the ion dissociable group in the region 7 where the solid polymer film 5 sandwiched between the layers is in contact with the catalyst layers 1a and 1b.

  The ion conductor 4 according to the present invention produced as described above contains the ion dissociable group in the region 7 inside the peripheral portion 6 in the solid polymer film 5 or the first The solid polymer film 5 sandwiched between the catalyst electrode and the second catalyst electrode contains an ion dissociable group in the region 7 in contact with the catalyst layers 1a and 1b, and the peripheral portion 6 or the catalyst layers 1a and 1b Since the non-contact region does not have water swellability, it does not swell even when it is hydrated to activate ion conduction performance such as protons, and a high sealing function can be maintained.

  Further, for example, even when the above-described hot pressing operation is performed when manufacturing the laminated structure (MEA), wrinkles are not generated in the peripheral portion 6 due to the rapid contraction of the ion conductor 4 as in the conventional example. Therefore, it is possible to reduce a decrease in output due to a leak phenomenon.

  In FIG. 1, as a method for producing an MEA including the negative electrode 2 with the catalyst layer 1 a, the positive electrode 3 with the catalyst layer 1 b, and the ion conductor 4, for example, first, a gas-permeable current collector as the negative electrode 2 and the positive electrode 3 A solution in which the catalyst material is dispersed is applied on top to form catalyst layers 1a and 1b.

As the gas permeable current collector, any conventionally known one such as a carbon sheet can be used. The catalyst material is preferably fine particles such as platinum, and other electrode materials may be used as long as the target reaction proceeds. The added amount is 0.15 to 1.0 g / catalyst amount g, the area carrying density is 0.1 to 2.0 mg / cm ² (however, the weight of Pt or the like), and the catalyst particle size is 1 to 20 nm. It is good to do. Furthermore, the thickness of the gas permeable current collector and the catalyst layers 1a and 1b may be arbitrary.

  Then, by separately pressing the electrodes 2 and 3 with the catalyst layers 1a and 1b separately prepared on both surfaces of the ion conductor 4 prepared as described above, the ion conductor 4 and the electrodes 2 and 3 are pressed. An MEA comprising:

  In this fuel cell, when used, fuel such as hydrogen gas, methanol aqueous solution, dimethyl ether solution or the like is supplied on the negative electrode 2 side, and oxygen gas (air) is supplied on the positive electrode 3 side. When the fuel is supplied, hydrogen ions are generated. The hydrogen ions move to the positive electrode 3 side together with the hydrogen ions generated in the negative electrode 2 and the hydrogen ions generated in the solid polymer film 4, and are supplied to the positive electrode 3 side there. Reacts with oxygen (air), thereby extracting the desired electromotive force.

  In such a fuel cell, the solid polymer membrane 5 contains the ion dissociable group in the region 7 inside the peripheral portion 6 or is sandwiched between the first catalyst electrode and the second catalyst electrode. Since the polymer membrane 5 contains the ion dissociable group in the region 7 in contact with the catalyst layers 1a and 1b, for example, even when water is contained in order to activate ion conduction performance such as protons, the peripheral portion 6 is It does not swell and can maintain a high sealing function.

  Further, for example, even when the above-described hot pressing operation is performed when the MEA is manufactured, wrinkles are not generated in the peripheral portion 6 due to the rapid contraction of the ion conductor 4 as in the conventional example. Can be reduced.

  Therefore, energy efficiency and current density can be improved.

  Here, although the example which manufactures a fuel cell as the said electrochemical device was demonstrated above, you may manufacture the hydrogen production apparatus by the reaction mechanism opposite to a fuel cell as said electrochemical device besides this. . Moreover, it can utilize for the water electrolysis apparatus etc. which use the proton conductive solid electrolyte.

  Moreover, although the example which uses MEA independently was demonstrated above, in the electrochemical device based on this invention, the some of MEA may be laminated | stacked or juxtaposed. Moreover, it is good also as a structure which further laminated | stacked the structure which juxtaposed several of the said laminated structure. In these cases, there is an effect that a higher electromotive force can be easily obtained.

  Examples according to the present invention will be described below.

Example 1
First, a commercially available polytetrafluoroethylene (PTFE) sheet (manufactured by Wako Pure Chemical Industries, Ltd., thickness 50 μm) is cut out to 10 cm × 10 cm, and a 2.2 cm × 2.2 cm square square is formed on the center of this PTFE sheet. A SUS sheet (10 cm × 10 cm) that was hollowed out was placed.

  Next, an electron beam irradiation treatment was performed on the PTFE sheet with a mask produced as described above. As the electron beam irradiation conditions, irradiation was performed at a dose rate of 360 kG / h for 2 hours, and irradiation was performed in a total amount of 720 kGy. The irradiation atmosphere was performed in nitrogen.

  Next, the mask was removed from the PTFE sheet, styrene / divinylbenzene (DVB) was grafted at 60 ° C., and then boiled in a 6 M sulfuric acid aqueous solution. Thereby, the ionic conductor by which the sulfonic acid group was introduce | transduced into the area | region which irradiated the electron beam above was able to be manufactured.

Example 2
An ion conductor was produced in the same manner as in Example 1 except that a commercially available polyvinylidene fluoride (PVDF) sheet (manufactured by Kureha Chemical Co., Ltd., thickness: 50 μm) was used instead of the PTFE sheet.

Example 3
In Example 2, it was impregnated for 45 minutes in an NaOH 1M solution of ethanol / isopropanol (1: 1 vol%) heated to 80 ° C. without performing electron beam irradiation. The sulfonation reaction was carried out by reacting a mixture of styrene / tetrahydrofuran (THF) based on the document Xinping Qju et al., J. Electrochem. Soc 150 (7) A917-921 (2003), and then using concentrated sulfuric acid. The method of heating for 4 hours (70 degreeC) was employ | adopted.

Example 4
In Example 3, an ionic conductor was produced in the same manner as in Example 3 except for using treatment conditions and the like except that KOH was used instead of NaOH.

Comparative Example 1
Nafion (registered trademark) 112 (film thickness of 50 μm when dried) sold by DoPont was used as the ion conductor.

  The sealing properties shown below were measured for the ion conductors of Examples 1 to 3 and Comparative Example 1 produced as described above.

<Measurement of sealing properties>
The sealability was measured using an evaluation system configured as shown in FIG. That is, the measurement membrane 12 is incorporated in the container 13, nitrogen gas 15 of 1.0 atm is sealed in the A chamber 14 in contact with one side of the measurement membrane 12, and the B chamber 16 on the other side is evacuated by a rotary pump. State (10 ^-2 Torr). The volume in a vacuum state was 4 cc, and the degree of vacuum was recorded with a manometer 17 over time. The faster the degree of vacuum drop, the worse the sealing performance. As an index for estimating the decrease in the degree of vacuum, the degree of vacuum in the B chamber 16 after 60 seconds was used. However, after performing a pretreatment of passing pure water through the A chamber 14 side at room temperature for 1 minute and then drying with dry nitrogen for 10 hours so that the deterioration of the sealing performance is emphasized by the swelling and shrinkage of the film, The sealing property was measured. The results are shown in Table 1 below and FIG.

  As is apparent from Table 1 and FIG. 4, the electrochemical device according to the present invention contains the ion dissociable group in a region inside the periphery of the solid polymer film, or the first The solid polymer membrane sandwiched between the catalyst electrode and the second catalyst electrode contains an ion dissociable group in a region in contact with the catalyst, so that the peripheral portion does not swell and maintains a high sealing function. We were able to.

  Further, no wrinkles were generated in the peripheral portion due to abrupt contraction of the ionic conductor, and the leakage phenomenon was effectively reduced.

  On the other hand, in Comparative Example 1, the ion dissociable group was introduced into the entire membrane, and the entire water swellability was high. Therefore, the leakage property was reduced due to swelling shrinkage.

  While the present invention has been described with reference to the embodiments and examples, the above examples can be variously modified based on the technical idea of the present invention.

  For example, in the electrochemical device based on the present invention such as the fuel cell, the shape, configuration, material, and the like can be appropriately selected without departing from the present invention.

1 is a schematic cross-sectional view of an electrochemical device according to the present invention in an embodiment of the present invention. It is the schematic which shows an example of the manufacturing method of the ion conductor based on this invention in order of a process. It is a schematic sectional drawing of the system for a sealing performance in the Example of this invention. It is a graph which compares and shows the measurement result of sealing performance similarly. It is a partial expanded schematic sectional drawing of the electrochemical device by a prior art example.

Explanation of symbols

1a, 1b ... catalyst layer, 2 ... negative electrode, 3 ... positive electrode, 4 ... ionic conductor, 5 ... solid polymer membrane,
6 ... peripheral part, 7 ... area | region (or area | region which contact | connects a catalyst layer) inside a peripheral part, 8 ... sealing material,
9 ... Container, 10 ... Mask, 11 ... Non-mask part

Claims (18)

  An ionic conductor containing an ion dissociable group in a region inside the periphery of a solid polymer membrane.   An ionic conductor, wherein the solid polymer film sandwiched between the first catalyst electrode and the second catalyst electrode contains an ion dissociable group in a region in contact with the catalyst. The ionic dissociative group is -OH, an _{-OSO 3 H, -COOH, -SO 3} H, -OPO (OH) 2, at least one of -C ₆ H ₄ -SO ₃ H, claim 1 Or the ionic conductor described in 2.   The ionic conductor according to claim 1, wherein the solid polymer film is polyvinylidene fluoride, polytetrafluoroethylene, or polyethylene.   The ionic conductor according to claim 4, wherein the ion dissociable group is introduced into a base polymer chain forming the solid polymer film.   A method for producing an ionic conductor, comprising a step of introducing an ion dissociable group into a region inside a peripheral portion of a solid polymer membrane.   A method for producing an ionic conductor, comprising a step of introducing an ion dissociable group into a region in contact with a catalyst of a solid polymer film sandwiched between a first catalyst electrode and a second catalyst electrode.   The method for producing an ionic conductor according to claim 6 or 7, wherein a predetermined region of the solid polymer film is covered with a mask and the ion dissociable group is introduced through a non-mask portion of the mask. .   The ion-dissociable group is introduced into the solid polymer film after performing at least one of electron beam irradiation treatment, γ-ray irradiation treatment, and alkali hydroxide treatment. A method for producing an ionic conductor.   10. The method for producing an ionic conductor according to claim 9, wherein after the treatment, monomer molecules are bonded to the solid polymer film, and the ion dissociable group is further introduced into the combined body. -OH as the ionic dissociative group, -OSO ₃ H, used _{-COOH, -SO 3 H, -OPO (} OH) 2, at least one of -C ₆ H ₄ -SO ₃ H, claim 6 Or the manufacturing method of the ion conductor as described in 7.   The method for producing an ionic conductor according to claim 6 or 7, wherein polyvinylidene fluoride, polytetrafluoroethylene, or polyethylene is used as the solid polymer film.   An electrochemical device having a laminated structure of a first catalyst electrode, a second catalyst electrode, and an ion conductive solid polymer membrane sandwiched between these electrodes, the periphery of the solid polymer membrane An electrochemical device containing an ion dissociable group in a region inside the part.   An electrochemical device having a laminated structure of a first catalyst electrode, a second catalyst electrode, and an ion conductive solid polymer membrane sandwiched between these electrodes, wherein the solid polymer membrane comprises a catalyst An electrochemical device containing an ion dissociable group in a region in contact with the substrate. The ionic dissociative group is _{-OH, -OSO 3 H, -COOH,} -SO 3 H, -OPO (OH) 2, is at least one kind of -C ₆ H ₄ -SO ₃ H, claim 13 Or the electrochemical device as described in 14.   The electrochemical device according to claim 13 or 14, wherein the solid polymer film is polyvinylidene fluoride, polytetrafluoroethylene, or polyethylene.   The electrochemical device according to claim 16, wherein the ion dissociable group is introduced into a base polymer chain forming the solid polymer film.   The electrochemical device according to claim 13 or 14, wherein the electrochemical device is configured as a fuel cell.

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