JP2007294431A - Solid electrolyte film and its manufacturing method, manufacturing facility, electrode membrane assembly, and fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To continuously manufacture a solid electrolyte film superior in proton conductivity. <P>SOLUTION: In a casting membrane forming process 63, dope containing a solid electrolyte is casted into a casting band from a casting die. A casting membrane 61 is formed on the casting band. The casting membrane 61 is dried in a casting membrane drying process 66a. The casting film 61 and a poor solvent of the solid electrolyte are made to be contacted in a contact solvent process 66b. The self-supporting characteristics of the casting film 61 manifests itself in a short time in a self-supporting characteristics manifestation process 66. The casting membrane 61 is scraped off from the casting band 93 as a precursor film 67. The precursor membrane 67 is immersed into water. After drying the precursor membrane 67, proton substitution is carried out, and a hydrogen substitution membrane 75 is obtained. By washing the hydrogen substitution membrane 75 in water and drying it, the solid electrolyte membrane 79 is obtained. By carrying out the self-supporting characteristics manifestation process 66 before a solvent substitution process 70, the time for manufacturing of the solid electrolyte membrane 79 can be shortened. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a solid electrolyte film, and a method for producing the same, a production facility, an electrode membrane composite, and a fuel cell, and more particularly, a solid electrolyte film having proton conductivity and used in a fuel cell, and a method for producing the same. The present invention relates to equipment, an electrode membrane composite, and a fuel cell.

  Fuel cells are attracting attention as next-generation power generation means that can improve environmental pollution and energy problems. The fuel cell has a plurality of stacked fuel cells (also referred to as electrode membrane composite (MEA)), and these fuel cells are electrically connected in series. The fuel cell has an anode electrode and a cathode electrode connected by an external circuit, and a solid electrolyte film sandwiched between these electrodes. A typical process in which the fuel cell generates an electromotive force is as follows. First, when a hydrogen atom-containing substance is supplied to the cathode electrode, the hydrogen atoms become protons in the cathode electrode. Next, this proton passes through the solid electrolyte film and combines with oxygen at the anode electrode, so that an electromotive force can be generated between the two electrodes of the fuel cell.

  Recently, solid electrolyte films (referred to as organic polymer type films) formed of polymers have attracted attention among solid electrolytes. Since this organic polymer film has the characteristics that the operating temperature is low and it can be reduced in size and weight, it is expected to be used for a fuel cell for home use or in-vehicle use. Therefore, the organic polymer type film is required to have characteristics such as high proton conductivity, excellent heat resistance, and uniformity of these characteristics.

  By the way, as a method for forming a polymer into a film, there are a melt film forming method and a solution film forming method as well known. The former can produce a film without using a solvent, but there are problems that the polymer is modified by heating and impurities in the raw polymer remain in the film as they are. On the other hand, although the latter has problems in equipment such as solution production equipment and solvent recovery equipment, the temperature during heating may be low, and it is possible to remove impurities in the polymer in the solution production process. There is. Furthermore, the latter also has an advantage that a film excellent in flatness and smoothness can be produced as compared with the former film.

  The outline of the solution casting method will be described below. First, a dope containing an organic compound as a raw material and a solvent is cast on a support to form a cast film. A cast film having self-supporting properties is peeled off from the support and dried by a drying means to form a film.

Therefore, first, as a method for producing an organic polymer film excellent in quality and heat resistance, for example, in Patent Document 1, there is a method of immersing a polyvinylidene fluoride resin in a liquid in which an electrolyte and a plasticizer are mixed. Proposed. Patent Document 2 proposes a method for producing a proton conducting membrane by synthesizing an inorganic compound in a solution containing an aromatic polymer material having a sulfonic acid group and removing the solvent. Yes. In this method, silicon oxide, phosphoric acid derivatives and the like are added to improve pores. In Patent Document 3, a method for producing an ion exchange membrane by adding a metal oxide precursor to a solution containing an ion exchange resin, casting a liquid obtained by subjecting the precursor to hydrolysis and polycondensation reaction, and the like. Has been proposed. In Patent Document 4, a film having proton conductivity is produced by a solution casting method, that is, a solution casting method, and this film is immersed in an organic compound aqueous solution that is soluble in water and has a boiling point of 100 ° C. or more. A method for producing a proton conducting membrane by equilibrium swelling and evaporating water by heating has been proposed. In Patent Document 5, a method of obtaining a solid electrolyte film by dissolving a compound mainly composed of polybenzimidazole having an anionic ionic group in an alcohol solvent having a boiling point of 90 ° C. or higher containing tetraalkylammonium hydroxide. Has been proposed. In Patent Document 6, a coating solution containing (a) a polymer having an ion conductive component, (b) a water-soluble inorganic compound or a water-soluble organic compound having a molecular weight of less than 1000, and (c) an organic solvent is applied to a substrate. There has been proposed a method for producing a proton conducting membrane by removing the organic solvent (c) to form a dry coating film and then removing the water-soluble compound (b).
JP-A-9-320617 JP 2001-307752 A JP 2002-231270 A JP 2004-79378 A JP 2004-131530 A JP-A-2005-146018

  By the way, when manufacturing a solid electrolyte film by a solution casting method, a cast film is dried and the organic solvent remaining on the cast film is evaporated. A compound that can be a solvent for a solid electrolyte generally has a high boiling point. In addition, this solvent is often a basic organic compound having a large polarity and easily acting with protons. When a film in which this basic organic compound remains is used as a solid electrolyte film, the basic organic compound prevents protons from passing through the solid electrolyte film, and the proton conductivity of the solid electrolyte film decreases, which is sufficient for a fuel cell. The electromotive force cannot be demonstrated. Therefore, it is necessary to remove the organic solvent remaining in the film in the solid electrolyte film manufacturing process. However, complete removal of the high boiling point solvent is not easy, and it takes 20 hours or more to completely remove the solvent. In particular, the present situation is that the drying time of the cast film occupies most of the time required for the production process of the solid electrolyte film. As described above, in the method for producing a solid electrolyte film by the solution casting method, shortening of the production time is a big problem, which is a big obstacle for mass production.

  As a method for shortening the drying time of the casting membrane, it is conceivable to reduce the degree of drying of the casting membrane in the casting membrane drying step, or to dry the casting membrane rapidly. In the former case, since the casting film does not have sufficient self-supporting property, it becomes difficult to peel off the casting film in the peeling process. Even if the cast film can be peeled off as a wet film, the wet film is deformed by its own weight and cannot be transported to the next step. When manufacturing a solid electrolyte film in an on-line system in which each process is performed continuously, the casting film drying process not only improves the workability of stripping the casting film, but also allows the wet film to withstand its own weight. It is necessary to develop support in the casting membrane. On the other hand, in the latter case, when the cast film is dried rapidly, local pinholes due to non-uniform drying are generated in the cast film. A solid electrolyte film produced from a cast film having pinholes cannot exhibit sufficient performance as a solid electrolyte film.

  In Patent Document 1, the solution casting method is denied, and the problem that impurities contained in the raw material remain in the film is not solved. The methods of Patent Documents 2 to 5 are all manufacturing methods on a small scale, and are not considered methods for mass production. And the method of patent document 2 has the problem that dispersion | distribution of the composite_body | complex which consists of a polymer and an inorganic compound is difficult. The method of Patent Document 3 has a problem that the film forming process is complicated. Patent Document 4 has a problem that pores are generated in the film by immersing the film in water, and a uniform film cannot be obtained, and a method for solving this problem is not described. Further, although it is described that various kinds of solid electrolyte films can be produced by the solution casting method, there is no description of a specific method. Patent document 5 limits the raw material to be used, and does not describe that it can be manufactured using other materials having excellent performance. Patent Document 6 does not solve the difficulty of removing the high-boiling organic solvent by drying.

  As a result of intensive studies, the present inventor has found that the drying time of the cast film can be shortened by contact between the poor solvent of the solid electrolyte and the cast film. Furthermore, it discovered that the time which removes the solvent contained in a wet film can be shortened by performing solvent substitution to the wet film obtained from the cast film which the poor solvent contacted. According to the present invention, it is possible to reduce the manufacturing time of the solid electrolyte film while maintaining the performance of the manufactured solid electrolyte film.

  The method for producing a solid electrolyte film of the present invention includes a first step in which a dope in which a solid electrolyte is dissolved in an organic solvent is cast on a support traveling from a casting die to form a casting film; A second step of bringing the cast film into contact with a contact poor solvent that is a poor solvent for the solid electrolyte to develop self-supporting property in the cast film; and the casting film having self-supporting property as a wet film It has the 3rd process stripped off from the said support body, and the 4th process which dries the said wet film and makes it a solid electrolyte film, It is characterized by the above-mentioned.

  The organic solvent is preferably a mixture containing a first compound that is a good solvent for a solid electrolyte and a second compound that is a poor solvent, and the contact poor solvent is water and a compound that is a good solvent for the solid electrolyte. It is preferable that it is either one of these aqueous solutions.

The contact time between the cast film and the contact poor solvent is determined according to at least one of the hardness of the cast film that changes due to the contact and the weight of the first compound in the cast film that changes due to the contact. It is preferable that the elastic modulus of the wet film in the third step is 6 × 10 ⁵ Pa or more.

  It is preferable to have the 5th process which makes the said wet film and the liquid compatible with the said organic solvent contact. The liquid is preferably either water or an aqueous solution of an organic compound. Furthermore, the contact time between the wet film and the liquid is preferably 10 minutes or less.

  It is preferable to have a sixth step of drying the cast film before the second step.

  The first compound is preferably dimethyl sulfoxide, and the second compound is preferably an alcohol (however, having 1 to 5 carbon atoms). It is preferable to have an acid contact step in which the wet film is brought into contact with the proton donor acid solution while transporting the wet film, and a washing step of washing with the washing liquid before the fourth step, wherein the acid is ionized when ionized. It is more preferable that the anion formula weight is 40 or more and 1000 or less.

  The solid electrolyte is preferably a hydrocarbon polymer. The hydrocarbon polymer is preferably an aromatic polymer. Furthermore, the aromatic polymer is preferably a copolymer composed of structural units represented by the general formulas (I) to (III) of Chemical Formula 3.

（ただし、Ｘは水素原子を除くカチオン種、ＹはＳＯ_２ 、Ｚは化４の（Ｉ）または（II）に示す構造であり、ｎとｍとは０．１≦ｎ／（ｍ＋ｎ）≦０．５を満たす。）

(However, X is a cation species excluding a hydrogen atom, Y is SO ₂ , Z is a structure shown in Chemical Formula (I) or (II), and n and m are 0.1 ≦ n / (m + n) ≦ 0.5 is satisfied.)

  The production facility for a solid electrolyte film of the present invention is formed by casting a cast film on a support that travels a dope in which the solid electrolyte is dissolved in an organic solvent, thereby forming a cast film on the support. An apparatus, a solvent contact device for bringing the casting membrane into contact with a poor contact solvent that is a poor solvent for the solid electrolyte, and causing the casting membrane to exhibit self-supporting property, and the casting membrane having self-supporting property A wet stripping device, a liquid contact device for bringing the wet film into contact with a liquid compatible with the organic solvent, and a drying device for drying the wet film into a solid electrolyte film. It is characterized by that.

  The production facility includes an acid contact device in which an acid solution as a proton donor is accommodated and guide means for guiding the wet film in the acid solution is disposed between the liquid contact device and the drying device. It is preferable to prepare in between.

  The solid electrolyte film of the present invention is manufactured by the method for manufacturing a solid electrolyte film.

  The electrode membrane composite of the present invention comprises the solid electrolyte film, an anode electrode that is provided in close contact with one surface of the solid electrolyte film, and generates protons from a hydrogen-containing substance supplied from the outside, A cathode electrode that is provided in close contact with the other surface of the solid electrolyte film and synthesizes water from the proton that has passed through the solid electrolyte film and a gas supplied from the outside.

  The fuel cell of the present invention is provided with the electrode membrane composite, a first current collector that is provided in contact with the anode electrode of the electrode membrane composite, and transfers electrons between the anode electrode and the outside, And a second current collector that transfers electrons between the cathode electrode of the electrode film composite and the outside.

  According to the method for producing a solid electrolyte film of the present invention, a first step in which a dope in which a solid electrolyte is dissolved in an organic solvent is cast on a support traveling from a casting die to form a casting film; A second step of bringing the casting film into contact with a poor contact solvent that is a poor solvent for the solid electrolyte to develop self-supporting property in the casting film; and moistening the casting film having self-supporting property Since it has the 3rd process peeled off from the said support body as a film, and the 4th process which dries the said wet film and makes it a solid electrolyte film, shortening the time which a 2nd process and a 4th process require As a result, the time required for manufacturing the solid electrolyte film can be shortened. That is, it can be said that the method for producing a solid electrolyte film of the present invention is a production method suitable for mass production. When an electrode membrane composite using this solid electrolyte film is used in a fuel cell, the fuel cell exhibits an excellent electromotive force.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described here. First, the raw material of the solid electrolyte film of the present invention will be described, and then the method for producing the solid electrolyte film will be described.

〔material〕
The dope includes a polymer as a solid electrolyte and a solvent that dissolves the polymer as its components. The solid electrolyte component is preferably a hydrocarbon polymer, more preferably an aromatic polymer among hydrocarbon polymers, more preferably a polymer having a cationic species among aromatic polymers, and particularly preferably a compound represented by Chemical Formula 3. . The cationic species can be divided into H (hydrogen atom) and other than H, and any of them may be used in the present invention. However, when the compound shown in Chemical formula 3 is used, H is more than X is H. More preferred is a cationic species other than When X is a cationic species other than H, it is preferable to perform proton substitution after the film formation step or after film formation. That is, a polymer in which X in Chemical Formula 3 is a cationic species other than proton can be said to be a proton-accepting polymer. In the case of proton substitution, in order to clarify the explanation of the polymer before proton substitution and the polymer after substitution, the former is called a precursor and the latter is called a solid electrolyte.

  In the present specification, proton substitution refers to substitution of a cation species other than a hydrogen atom in a polymer with a hydrogen atom. The cationic species means an atom or an atomic group that generates a cation when ionized. This cationic species need not be monovalent. Moreover, in this specification, unless otherwise indicated, a cation refers to a cation.

  In the case of producing a film made of a precursor (hereinafter referred to as a precursor film), a dope containing the precursor shown in Chemical Formula 3 is produced, and this dope is cast on a support to be formed on the support. The cast film is peeled off to obtain a precursor film. And this precursor film is proton-substituted, and the film (henceforth a solid electrolyte film) which consists of solid electrolyte is manufactured by substituting X of the substance shown to Chemical formula 3 contained in a precursor film for a hydrogen atom. be able to.

  Moreover, the precursor film which consists of a compound shown to Chemical formula 3 makes the moisture absorption expansion coefficient and proton conductivity of the solid electrolyte film manufactured by proton substitution compatible. When n / (m + n) <0.1 in the compound shown in Chemical Formula 3, there are few proton acceptors in the precursor film, and a proton conduction path, so-called proton channel is sufficiently formed in the solid electrolyte film. There are times when you can't. For this reason, the solid electrolyte film may not exhibit proton conductivity sufficient for practical use. On the other hand, when n / (m + n)> 0.5 in the compound shown in Chemical Formula 3, the water absorption of the solid electrolyte film is increased, so that the expansion coefficient due to water absorption, that is, the water absorption expansion coefficient is increased. The solid electrolyte film tends to deteriorate.

  In addition, even if it manufactures a film with a cationic seed | species without replacing X in the compound shown in Chemical formula 3 with H (hydrogen atom), the film has a function as a solid electrolyte film. Therefore, it can be used as a solid electrolyte film without proton substitution. However, the proton conductivity tends to increase as the ratio of X substituted with H (hereinafter referred to as proton substitution rate) increases. In that sense, X is particularly preferably H when used in a fuel cell. That is, it is preferable that the proton substitution rate is high in proton substitution for producing a solid electrolyte film from a precursor film.

  Preferred cations in the compound shown in Chemical Formula 3 are preferably alkali metal cations, alkaline earth metal cations, and ammonium cations, and examples include calcium ions, barium ions, quaternary ammonium ions, lithium ions, sodium ions, and potassium ions. .

As solid electrolyte, what has the following various performance is preferable. The proton conductivity is preferably 0.005 S / cm or more, and more preferably 0.01 S / cm or more, for example, at 25 ° C. and a relative humidity of 70%. Furthermore, the proton conductivity after being immersed in a 50% methanol aqueous solution at 18 ° C. for one day is preferably 0.003 S / cm or more, more preferably 0.008 S / cm or more, and particularly with respect to that before immersion. The rate of decrease in proton conductivity after immersion is preferably within 20%. The methanol diffusion coefficient is preferably 4 × 10 ⁻⁷ cm ² / s or less, and particularly preferably 2 × 10 ⁻⁷ cm ² / s or less.

  As for strength, those having an elastic modulus of 10 MPa or more are preferred, and those having a modulus of 20 MPa or more are particularly preferred. The method for measuring the elastic modulus is described in detail in paragraph [0138] of JP-A-2005-104148, and the above value of the elastic modulus is a value obtained by a tensile tester manufactured by Toyo Baldwin. Therefore, when obtaining the elastic modulus using another test method or tester, it is preferable to obtain the correlation with the value obtained by the test method or tester in advance.

  As for durability, it is preferable that each change rate of weight, ion exchange capacity, and methanol diffusion coefficient is 20% or less before and after a time-lapse test immersed in a 64 wt% methanol aqueous solution at a constant temperature, and 15% The following are particularly preferred. Further, before and after the time-lapse test in hydrogen peroxide, the rate of change in weight, ion exchange capacity, and methanol diffusion coefficient is preferably 20% or less, and particularly preferably 10% or less. Further, in a 64 wt% aqueous methanol solution, the volume swelling rate at a constant temperature is preferably 10% or less, and particularly preferably 5% or less.

  Further, those having a stable water absorption and water content are preferred. Moreover, it is preferable that it is so small that solubility is substantially negligible with respect to alcohols, water, and a mixed solvent of alcohol and water. Further, it is preferable that the weight loss and the shape change when immersed in the liquid are small enough to be substantially ignored.

  The proton conducting performance of the solid electrolyte film is expressed by a so-called index which is a ratio between proton conductivity and methanol permeability coefficient. And it can be said that the larger the index in a certain direction, the higher the proton conducting performance in that direction. In the thickness direction of the solid electrolyte film, the proton conductivity is proportional to the thickness, and the methanol permeability coefficient is inversely proportional to the thickness. Therefore, the proton conductivity of the solid electrolyte film can be controlled by changing the thickness. In a solid electrolyte film used for a fuel cell, an anode electrode is provided on one side and a cathode electrode is provided on the other side. Therefore, the index in the thickness direction of the solid electrolyte film is larger than the index in the other direction. Is preferred. The thickness of the solid electrolyte film is preferably 10 to 300 μm. For example, in the case of a solid electrolyte having both a high proton conductivity and a methanol diffusion coefficient, it is particularly preferable to produce a film having a thickness of 50 to 200 μm, and a solid having a low proton conductivity and a low methanol diffusion coefficient. In the case of an electrolyte, it is particularly preferable to produce a film so that the thickness is 20 to 100 μm.

  The heat resistant temperature is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and particularly preferably 300 ° C. or higher. The heat-resistant temperature here means a temperature when heating is performed at a heating rate of 1 ° C./min and weight loss reaches 5%. Note that this weight reduction is calculated excluding the amount of evaporation such as moisture.

Furthermore, the present invention is particularly effective when a solid electrolyte having a maximum power density of 10 mW / cm ² or more is used as a film by a conventional method for a fuel cell.

  By using the polymer which is the precursor of the above solid electrolyte, a dope suitable for the production of the precursor film can be produced. Moreover, the solid electrolyte film suitable as a fuel cell can be manufactured by carrying out proton substitution using this precursor film. The dope suitable for producing the precursor film is, for example, a dope having a relatively low viscosity and easily removing foreign matters by filtration.

  The polymer as a component of the dope may be a polymer having a proton donating group that is a solid electrolyte. The polymer having a proton donating group is not particularly limited, and a polymer having an acid residue and known as a proton conducting material can be used. Among them, preferred polymers include, for example, addition polymerization polymer compounds having sulfonic acid in the side chain, side chain phosphate group poly (meth) acrylate, sulfonated polyether ether ketone obtained by sulfonation of polyether ether ketone, and sulfonated polybenz. Examples thereof include imidazole, sulfonated polysulfone obtained by sulfonated polysulfone, and sulfonated products of heat-resistant aromatic polymer compounds. Examples of the addition polymerization polymer compound having sulfonic acid in the side chain include perfluorosulfonic acid represented by Nafion (registered trademark), sulfonated polystyrene, sulfonated polyacrylonitrile styrene, sulfonated polyacrylonitrile butadiene styrene, and the like. Examples of the sulfonated product of the heat resistant aromatic polymer include sulfonated polyimide.

  Preferable examples of perfluorosulfonic acid include substances described in, for example, JP-A-4-366137, JP-A-6-231777, and JP-A-6-342665. Is particularly preferred. However, in Chemical formula 5, m is 100 to 10000, 200 to 5000 is preferable, and 500 to 2000 is more preferable. And n is 0.5-100, and 5-13.5 is especially preferable. Moreover, x is substantially equivalent to m, and y is substantially equivalent to n.

  Preferable examples of sulfonated polystyrene, sulfonated polyacrylonitrile styrene, and sulfonated polyacrylonitrile butadiene styrene include compounds described in JP-A-5-174856 and JP-A-6-1111834, and substances shown in Chemical formula 6 below. Can be mentioned.

  Examples of the sulfonated product of the heat-resistant aromatic polymer include, for example, JP-A-6-49302, JP-A-2004-10777, JP-A-2004-345997, JP-A-2005-15541, JP-A-2005-15541. JP 2002-110174 A, JP 2003-100317 A, JP 2003-55457 A, JP 9345818 A, JP 2003-257451 A, JP 2000-510511 A, JP 2002-105200 A. Substances described in the publication are mentioned, and among them, a substance that is a copolymer composed of each structural unit represented by the following general formulas (I) to (III) of Chemical Formula 7, Chemical Formula 8, and Chemical Formula 9 is particularly preferable. It is mentioned as a thing.

（ただし、Ｘは水素原子、ＹはＳＯ_２ 、Ｚは化４の（Ｉ）または（II）に示す構造であり、ｎとｍとは０．１≦ｎ／（ｍ＋ｎ）≦０．５を満たす。）

(However, X is a hydrogen atom, Y is SO ₂ , Z is a structure shown in Chemical Formula (I) or (II), and n and m are 0.1 ≦ n / (m + n) ≦ 0.5) Fulfill.)

  In addition, the solid electrolyte film made of the compounds shown in Chemical Formulas 5 to 9 achieves both the hygroscopic expansion coefficient and the proton conductivity. When n / (m + n) <0.1 in the substance shown in Chemical formula 9, a proton conduction path, so-called proton channel, may not be formed sufficiently. For this reason, the solid electrolyte film may not exhibit proton conductivity sufficient for practical use. On the other hand, when n / (m + n)> 0.5 in the substance shown in Chemical Formula 9, the water absorption of the solid electrolyte film is increased, so that the expansion coefficient due to water absorption, that is, the water absorption expansion coefficient is increased. The solid electrolyte film tends to deteriorate.

  The sulfonation reaction in the process of obtaining the compounds shown in Chemical Formulas 5 to 9 can be carried out according to various synthetic methods in known literature. As the sulfonating agent, sulfuric acid (concentrated sulfuric acid), fuming sulfuric acid, gaseous or liquid sulfur trioxide, sulfur trioxide complex, amidosulfuric acid, chlorosulfonic acid and the like can be used. As the solvent, hydrocarbons (benzene, toluene, nitrobenzene, chlorobenzene, dioxetane, etc.), alkyl halides (methylene chloride, chloroform, dichloroethane, carbon tetrachloride, etc.) and the like can be used. The reaction temperature may be determined in the range of −20 ° C. to 200 ° C. according to the activity of the sulfonating agent. As another method, a mercapto group, a disulfide group, and a sulfinic acid group can be introduced into the monomer in advance, and a sulfonated product can be synthesized by an oxidation reaction with an oxidizing agent. At this time, hydrogen peroxide, nitric acid, bromine water, hypochlorite, hypobromite, potassium permanganate, chromic acid, etc. can be used as the oxidizing agent, and water, acetic acid, Propionic acid or the like can be used. The reaction temperature in this method may be determined in the range of room temperature (for example, 25 ° C.) to 200 ° C. according to the activity of the oxidizing agent. As yet another method, a sulfonated compound may be synthesized by introducing a halogenoalkyl group into the monomer in advance and performing a substitution reaction with sulfite, bisulfite, or the like. In this case, water, alcohols, amides, sulfoxides, sulfones and the like can be used as the solvent. The reaction temperature may be determined in the range of room temperature (for example, 25 ° C.) to 200 ° C. In addition, the solvent in the above sulfonation reaction may be a mixture in which two or more kinds of substances are mixed.

In the reaction step to the sulfonated product, an alkyl sulfonating agent may be used. As a general method, there is a Friedel-Crafts reaction using sulfone and AlCl ₃ (Journal of Applied Polymer Science, Vol. 36, 1753-1767, 1988). When an alkyl sulfonating agent is used to perform the Friedel-Crafts reaction, hydrocarbons (benzene, toluene, nitrobenzene, acetophenone, chlorobenzene, trichlorobenzene, etc.), alkyl halides (methylene chloride, chloroform, dichloroethane, Carbon chloride, trichloroethane, dichloroethane, tetrachloroethane, etc.) can be used. The reaction temperature may be determined in the range of room temperature to 200 ° C. Note that the solvent in the reaction may be a mixture of two or more substances.

  The solvent component of the dope is not particularly limited as long as it dissolves the polymer as the solid electrolyte described above, and an organic compound is preferable. In the case of using a precursor as a dope raw material, any material that dissolves the precursor may be used. Examples include aromatic hydrocarbons (eg, benzene, toluene, etc.), halogenated hydrocarbons (eg, dichloromethane, chlorobenzene, etc.), alcohols (eg, methanol, ethanol, n-propanol, n-butanol, diethylene glycol, etc.), Ketones (eg, acetone, methyl ethyl ketone, etc.), esters (eg, methyl acetate, ethyl acetate, propyl acetate, etc.), ethers (eg, tetrahydrofuran, methyl cellosolve, etc.), and nitrogen-containing compounds (N-methylpyrrolidone (NMP)) N, N-dimethylformamide (DMF), N, N′-dimethylacetamide (DMAc) and the like), dimethyl sulfoxide (DMSO) and the like.

  The dope solvent may be a mixture of a plurality of compounds. When the solvent is a mixture, it is preferable to use a mixture of a compound that is a good solvent and a compound that is a poor solvent of the solid electrolyte component of the dope. Whether a certain liquid compound is a good solvent or a poor solvent for a solid electrolyte is determined by mixing the solvent and the polymer so that the solid electrolyte is 5% by weight of the total weight, and by the presence or absence of insoluble matter. can do. In addition, what is necessary is just to determine whether it is a good solvent or a poor solvent with respect to a precursor, when using a precursor as a raw material of dope. A good solvent for the solid electrolyte, that is, a substance that dissolves the solid electrolyte has a relatively high boiling point among the compounds generally used as the solvent, while the poor solvent has a boiling point among the compounds generally used as the solvent. Is the relatively low one. Therefore, by using a mixture containing a compound that is a poor solvent and a compound that is a good solvent as the solvent for the dope, the efficiency and effect of removing the solvent in the film production process can be enhanced. Can be greatly improved.

  When the dope solvent is a mixture of a compound that is a poor solvent for a solid electrolyte and a compound that is a good solvent, the former is referred to as a poor solvent component and the latter is referred to as a good solvent component. The weight ratio of the poor solvent component is preferably as large as possible, specifically 10% or more and less than 100%. More preferably, (weight of good solvent component) :( weight of poor solvent component) is preferably 90:10 to 10:90. As the weight ratio of the poor solvent component increases, the ratio of the low-boiling substance in the total weight of the solvent increases, and therefore, the drying efficiency and the drying effect in the manufacturing process of the solid electrolyte film can be further improved.

  As the good solvent component, DMF, DMAc, DMSO, and NMP are preferable. Among them, DMSO is particularly preferable in terms of safety and relatively low boiling point. As the poor solvent component, a so-called lower alcohol having 1 to 5 carbon atoms, methyl acetate, and acetone are preferable. Among them, a lower alcohol having 1 to 3 carbon atoms is more preferable, and when DMSO is used as a good solvent. Methyl alcohol is particularly preferred from the viewpoint of the most excellent compatibility with it.

  In order to improve various properties of the solid electrolyte film, an additive can be added to the dope. Examples of the additive include an antioxidant, fibers, fine particles, a water absorbing agent, a plasticizer, and a compatibilizer. The addition rate of these additives is preferably in the range of 1% by weight to 30% by weight when the total solid content in the dope is 100% by weight. However, the addition rate and the type of substance do not adversely affect proton conductivity. The additive will be specifically described below.

  Antioxidants include (hindered) phenolic, monovalent or divalent sulfur, trivalent phosphorus, benzophenone, benzotriazole, hindered amine, cyanoacrylate, salicylate, oxalic acid anilide These compounds are listed as preferred examples. Specific examples thereof include compounds described in JP-A-8-53614, JP-A-10-101873, JP-A-11-114430, and JP-A-2003-151346.

  Preferred examples of the fibers include perfluorocarbon fibers, cellulose fibers, glass fibers, polyethylene fibers, and the like, and specifically, JP-A-10-31815, JP-A-2000-231938, JP-A-2001-307545. And fibers described in JP-A Nos. 2003-317748, 2004-63430, and 2004-107461.

  Examples of the fine particles include titanium oxide, zirconium oxide, and the like. Specific examples include various fine particles described in JP-A Nos. 2003-178777 and 2004-217931.

  Water-absorbing agents, that is, hydrophilic substances include cross-linked polyacrylate, starch-acrylate, poval, polyacrylonitrile, carboxymethylcellulose, polyvinylpyrrolidone, polyglycol dialkyl ether, polyglycol dialkyl ester, synthetic zeolite, titania gel, zirconia gel And yttria gel are preferable examples. Specific examples include water absorbing agents described in JP-A Nos. 7-135033, 8-20716, and 9351857.

  Preferred examples of the plasticizer include phosphate ester compounds, chlorinated paraffins, alkylnaphthalene compounds, sulfone alkylamide compounds, oligoethers, and aromatic nitriles. Examples thereof include plasticizers described in JP-A Nos. 288916 and 2003-317539.

  As the compatibilizer for dissolving the solid electrolyte in the solvent, those having a boiling point or sublimation point of 250 ° C. or higher are preferable, and those having a boiling point of 300 ° C. or higher are more preferable.

  The dope may further contain various polymers different from the solid electrolyte for the purpose of (1) increasing the mechanical strength of the film and (2) increasing the acid concentration in the solid electrolyte film.

  Among the above objects, a polymer having a molecular weight of about 10,000 to 1,000,000 and having good compatibility with the precursor is suitable for (1). For example, perfluorinated polymers, polystyrene, polyethylene glycol, polyoxetane, polyether ketone, polyether sulfone, and polymers containing two or more polymer repeating units are preferred. Moreover, it is preferable to contain these substances in dope so that it may become the range of 1-30 weight% with respect to the total weight when it is set as a film. In addition, you may improve compatibility with a precursor by using a compatibilizer. As the compatibilizer, those having a boiling point or sublimation point of 250 ° C. or higher are preferable, and those having a boiling point of 300 ° C. or higher are more preferable.

  Among the above objects, (2) is preferably a polymer having a proton acid site. Examples of such a polymer include perfluorosulfonic acid polymers such as Nafion (registered trademark), sulfonated polyetheretherketone having a phosphate group in the side chain, sulfonated polyethersulfone, sulfonated polysulfone, and sulfonated polybenzimidazole. Examples thereof include sulfonated products of heat-resistant aromatic polymer compounds such as Moreover, it is preferable to contain these substances in dope so that it may become the range of 1-30 weight% with respect to the total weight when it is set as a film.

  Furthermore, when the obtained solid electrolyte film is used in a fuel cell, an active metal catalyst that promotes the redox reaction between the anode fuel and the cathode fuel may be added to the dope. As a result, the fuel that has permeated into the solid electrolyte film from one electrode is consumed in the solid electrolyte without reaching the other electrode, so that the crossover phenomenon can be prevented. The active metal catalyst is not particularly limited as long as it functions as an electrode catalyst, but platinum or an alloy based on platinum is particularly suitable.

[Dope production]
Below, dope used for manufacture of the film of this invention is demonstrated. FIG. 1 shows a dope manufacturing facility according to the present invention. However, the present invention is not limited to the dope manufacturing apparatus and method shown here. Hereinafter, a method for producing a dope using a precursor will be described as an example. In addition, it replaces with the precursor 12a, and also when manufacturing dope using a solid electrolyte, it can carry out by the method similar to the following.

  The dope manufacturing facility 10 includes a solvent tank 11 for storing an organic solvent 11a, a hopper 12 for supplying a precursor 12a, an additive tank 15 for storing an additive, an organic solvent 11a, and a precursor. 12a and the mixing tank 17 which mixes an additive, and sets it as the liquid mixture 16, the heating apparatus 18 for heating the liquid mixture 16, and the temperature regulator 21 for adjusting the temperature of the heated liquid mixture 16; In order to filter the dope 24 whose concentration has been adjusted, a first filtering device 22 that filters the mixed solution 16 that has exited the temperature regulator 21 to form a dope 24, a flash device 26 for adjusting the concentration of the dope 24, and the like. The second filtration device 27 is provided. Further, the dope manufacturing facility 10 is provided with a recovery device 28 for recovering the solvent that evaporates in the flash device 26 and a regeneration device 29 for regenerating the recovered solvent. The dope manufacturing facility 10 is connected to a film manufacturing facility 33 via a stock tank 32. In addition, although the valves 36-38 for adjusting the amount of liquid feeding and the pumps 41 and 42 for liquid feeding are provided in the dope manufacturing equipment 10, about the increase / decrease in the position and number where these are arrange | positioned It is changed appropriately.

  The process of manufacturing the dope 24 using the dope manufacturing facility 10 will be described below. By opening the valve 37, the organic solvent 11 a is sent from the solvent tank 11 to the mixing tank 17. Next, the precursor 12 a is sent from the hopper 12 to the mixing tank 17. At this time, the precursor 12a may be continuously fed to the mixing tank 17 by a sending unit that continuously measures and feeds, or the mixing tank 17 is fed by a sending unit that measures and sends a predetermined amount. May be sent intermittently. In addition, the required amount of the additive solution is sent from the additive tank 15 to the mixing tank 17 by opening and closing the valve 36. The solvent used for the additive solution is preferably the same compound as the polymer solvent from the viewpoint of compatibility in the dope.

  In addition to the method of sending the additive as a solution, for example, when the additive is liquid at room temperature, the additive can be fed into the mixing tank 17 in the liquid state. Further, when the additive is solid, a method of feeding into the mixing tank 17 using a hopper or the like is also possible. When a plurality of types of additives are added, a solution in which a plurality of types of additives are dissolved can be placed in the additive tank 15. Alternatively, it is also possible to use a plurality of additive tanks and put a solution in which the additive is dissolved in each of them and send them to the mixing tank 17 through independent pipes.

  In the above description, the order of putting in the mixing tank 17 is the organic solvent 11a, the precursor 12a, and the additive, but is not limited to this order. For example, after sending the precursor 12a to the mixing tank 17, a preferable amount of the organic solvent 11a can be sent. Further, the additive is not necessarily limited to mixing the precursor 12a and the organic solvent 11a in the mixing tank 17, and may be mixed in a mixture of the precursor 12a and the organic solvent 11a by an in-line mixing method or the like in a later step. Good.

  The mixing tank 17 encloses the outer surface thereof, a jacket 46 supplied with a heat transfer medium between the mixing tank 17, a first stirrer 48 rotated by a motor 47, and a second stirrer 52 rotated by a motor 51, It has. The mixing tank 17 supplies the heat transfer medium to the inside of the jacket 46 and circulates it to adjust the temperature inside. The internal temperature of the mixing tank 17 is preferably in the range of −10 ° C. to 55 ° C. By appropriately selecting and using the types of the first stirrer 48 and the second stirrer 52, the mixed liquid 16 in which the precursor 12a is swollen with the organic solvent 11a is obtained. The first stirrer 48 preferably has an anchor blade, and the second stirrer 52 is preferably a dissolver type eccentric stirrer.

  Next, the liquid mixture 16 is sent to the heating device 18 by the pump 41. The heating device 18 is preferably a jacketed tube having a tube body (not shown) and a jacket (not shown) for passing a heat transfer medium between the tube body, and further, the mixed liquid 16 is added. It is preferable to have a pressurizing part (not shown) for pressing. By using such a heating device 18, the solid content in the mixed solution 16 can be effectively and efficiently dissolved under heating conditions or pressure heating conditions. Hereinafter, this method of dissolving the solid component in the organic solvent 11a by heating is referred to as a heating dissolution method. In the heating dissolution method, it is preferable to heat the mixed solution 16 so as to be 60 ° C to 250 ° C.

  Note that the solid component may be dissolved in the organic solvent 11a by a cooling dissolution method instead of the heating dissolution method. The cooling dissolution method is a method of proceeding dissolution while cooling the mixed solution 16 so that the temperature of the mixed solution 16 is maintained or lower. In the cooling dissolution method, the mixed solution 16 is preferably cooled to a temperature of −100 ° C. to −10 ° C. The precursor 12a can be sufficiently dissolved in the organic solvent 11a by the heating dissolution method or the cooling dissolution method as described above.

  After the liquid mixture 16 is brought to about room temperature by the temperature controller 21, it is filtered by the first filtration device 22 to remove foreign matters such as impurities and aggregates, thereby obtaining a dope 24. The filter used in the first filtration device 22 preferably has an average pore diameter of 10 μm or less. However, when the pore diameter is too small, the time required for filtering the dope becomes long. Therefore, the average pore diameter of the filter may be appropriately selected in consideration of the manufacturing time and the like.

  The dope 24 after filtration is sent to the stock tank 32 by the valve 38 and temporarily stored, and then used for film production.

  By the way, as described above, the method in which the solid component is once swollen and then dissolved to form a solution increases the time required for the dope production as the concentration of the precursor 12a in the solution increases. May be problematic in terms. In such a case, it is preferable to once make a dope having a concentration lower than the target concentration and then carry out a concentration step to achieve the target concentration. For example, the dope 24 filtered by the first filtration device 22 is sent to the flash device 26 by the valve 38, and the dope 24 is concentrated by evaporating a part of the organic solvent 11 a of the dope 24 by the flash device 26. it can. The concentrated dope 24 is extracted from the flash device 26 by the pump 42 and sent to the second filtration device 27. The temperature of the dope 24 during filtration is preferably 0 ° C to 200 ° C. The dope 24 from which foreign matter has been removed by the second filtration device 27 is sent to the stock tank 32 and once stored, and then used for film production. In addition, since the concentrated dope 24 may contain bubbles, it is preferable to perform a bubble removal process before sending it to the second filtration device 27. As the bubble removal method, for example, various known methods such as an ultrasonic irradiation method for irradiating the dope 24 with ultrasonic waves are applied.

  Further, the solvent gas generated by the flash evaporation in the flash device 26 is condensed by the recovery device 28 having a condenser (not shown) and recovered as a liquid. The recovered solvent is regenerated and reused as a solvent for dope production by the regenerator 29. Such recovery and recycling have an advantage in terms of manufacturing cost, and since the manufacturing process of the dope 24 is performed in a closed system, there is an effect of preventing adverse effects on the human body and the environment.

  In addition, when impurities such as coarse particles or foreign matters are contained in the dope 24, when the dope 24 is used as a solid electrolyte film, the proton conductivity of the solid electrolyte film decreases, or the solid electrolyte film itself May deteriorate. Therefore, it is preferable to filter the dope 24 by using a filtering device at least once in the course of manufacturing the dope 24. The filtration aperture of the filtration device is preferably 10 μm or less. In addition, the installation number and installation location of the filtration apparatus in the dope manufacturing facility 10 and the frequency | count of filtering dope are not specifically limited, What is necessary is just to determine as needed.

  By the above manufacturing method, the dope 24 in which the concentration of the precursor 12a is 5% by weight or more and 50% by weight or less with respect to the total weight can be manufactured. More preferably, the concentration of the precursor 12a of the dope 24 is in the range of 10 wt% to 40 wt% with respect to the total weight. Further, the concentration of the additive is preferably in the range of 1% by weight to 30% by weight when the entire solid content in the dope is 100% by weight. In the dope 24, whether the solid content is dissolved in the organic solvent 11a can be confirmed by illuminating the filtered dope 24 with a fluorescent lamp.

[Solid electrolyte film manufacturing process]
Next, the manufacturing method of the solid electrolyte film of this invention is demonstrated. In FIG. 2, the flow of the solid electrolyte film manufacturing process 60 which concerns on this invention is shown. In FIG. 2, only the flow of steps when using a dope containing a polymer that is a precursor of a solid electrolyte as shown in Chemical Formula 3 will be briefly described, and details of each step will be described with reference to FIG. .

  The solid electrolyte film manufacturing process 60 includes a casting film forming process 63 for forming a casting film 61 from a dope on the support, and a self-supporting property for causing the casting film 61 formed on the support to exhibit self-supporting properties. An expression step 66, a peeling step 68 that peels off the casting film 61 from the support to form a wet film (hereinafter referred to as a precursor film) 67, and a solvent replacement step in which the precursor film 67 and the replacement solvent are brought into contact with each other. 70, a draining step 71 for removing the liquid adhering to the precursor film 67 that has undergone the solvent substitution step 70, a precursor film drying step 72 for drying the precursor film 67 that has undergone the draining step 71, and a precursor substitution by proton substitution. A proton substitution step 76 using the body film 67 as the hydrogen substitution film 75, a water washing step 77 for washing the hydrogen substitution film 75, and drying the hydrogen substitution film 75 after washing. And a hydrogen substitution film drying step 78 of the solid electrolyte film 79 Te.

  In the cast film forming step 63, the dope is cast on the support to form the cast film 61. The support is wound around the drive roller and travels endlessly. The casting film 61 moves as the support travels until it is stripped off as a precursor film 67 in a stripping step 68 described later.

  The cast film 61 immediately after formation does not have self-supporting properties. This is because a large amount of organic solvent is contained in the casting film 61. In the self-supporting expression step 66, a part of the organic solvent 11a (see FIG. 1) included in the casting film 61 is removed, and each process for expressing self-supporting is performed. The self-supporting expression process 66 includes a cast film drying process 66a and a solvent contact process 66b. The cast film drying step 66a may not be performed, but the effect of the present invention is more remarkable when the cast film drying step 66a is performed.

  In the cast film drying step 66a, the cast film 61 on the support is dried using a cast film drying means. The cast film drying means is disposed in the vicinity of the transport path of the cast film 61. By this drying, the organic solvent contained in the casting film 61 is evaporated. In the cast film drying step 66a, the amount of the organic solvent remaining in the cast film 61 (hereinafter referred to as the residual solvent amount) can be reduced. Further, the efficiency of the solvent contact step 66b can be improved. As the cast film drying means, a heater or a drying device capable of supplying drying air is used.

  Moreover, in the solvent contact process 66b, the casting film 61 conveyed to a support body and the poor solvent of a solid electrolyte are made to contact. By contact with this poor solvent (hereinafter referred to as contact poor solvent), a part of the organic solvent contained in the cast film 61 is replaced with the contact poor solvent. Thereby, two effects of (1) improvement of the self-supporting property of the casting membrane 61 and (2) improvement of the drying efficiency of the casting membrane 61 can be obtained. Further, when a poor solvent having a low boiling point is used as the contact poor solvent, the boiling point of the organic solvent contained in the cast film 61 is reduced by solvent replacement, and thus the organic solvent can be easily removed by the drying means. Thus, the residual solvent amount of the casting film 61 is reduced. That is, by the self-supporting expression step 66, the casting film 61 can easily express the self-supporting property.

In the stripping step 68, the casting film 61 having self-supporting properties is stripped from the support to obtain a precursor film 67. The precursor film 67 that has undergone the self-supporting expression step 66 has self-supporting properties. The precursor film 67 having a predetermined range of elasticity can be conveyed. A preferable range of the elastic modulus of the precursor film 67 in the stripping step 68 is referred to as a transportable region. In the transportable region, the elastic modulus of the precursor film 67 is preferably 6 × 10 ⁵ Pa or more. When the elastic modulus is less than 6 × 10 ⁵ Pa, the precursor film 67 is deformed by its own weight during conveyance, which is not preferable.

  In order to obtain the precursor film 67 having an elastic modulus in the transportable region in the case of a so-called online method in which each step of the solid electrolyte film manufacturing step 60 shown in FIG. 2 is continuously performed, a self-supporting expression step The self-supporting expression step 66 may be performed by setting each parameter in 66 to an optimum value. These parameters include the material (residual solvent amount) constituting the precursor film 67, the temperature and concentration of the casting film 61, and the like. The optimum values of these parameters can be obtained from the experimental results of the self-supporting expression process 66. Further, as a method for measuring the modulus of elasticity of the precursor film 67, in addition to the method described above, it can also be obtained from a variation in tension applied to a roll that transports the precursor film 67.

  In the case of a so-called off-line method in which each step of the solid electrolyte film production process 60 is performed by batch processing, the modulus of elasticity of the precursor film 67 can be measured using a tensile tester in addition to the above-described method. Here, an example of an elastic modulus measurement method using a tensile tester will be briefly described. Using a Toyo Baldwin universal tensile tester (STM T50BP), a tensile test is performed in an atmosphere of 23 ° C. and 70% humidity. Each condition of the tensile test is to measure the stress σ1 of the precursor film 67 when the precursor film 67 is pulled at a tensile speed of 10% / min and the strain ε1 is 0.5%. The elastic modulus of the precursor film 67 can be obtained from the strain ε1 and the stress σ1 thus obtained and the Hooke's law.

  In the solvent replacement step 70, the precursor film 67 and the liquid are brought into contact with each other. As this liquid, a liquid having high compatibility with the organic solvent remaining in the precursor film 67 (hereinafter referred to as “substitution solvent”) is used. By the contact between the substitution solvent and the precursor film 67, the residual organic solvent contained in the precursor film 67 is substituted with the substitution solvent (hereinafter referred to as solvent substitution). By the solvent replacement using the replacement solvent, the residual solvent amount of the precursor film 67 decreases. Thus, solvent replacement is performed until the amount of residual solvent in the precursor film 67 reaches a predetermined value.

  Further, this solvent replacement step 70 may be performed a plurality of times. When the solvent replacement step 70 is performed a plurality of times, it is preferable to select a replacement solvent for each step so that the boiling point becomes lower as the solvent replacement step is performed later. Since the boiling point of the residual solvent contained in the precursor film 67 can be lowered by the plurality of solvent replacement steps, the drying step performed after the solvent replacement step 70 can be facilitated.

  In the draining process 71, an excess liquid adhering to the precursor film 67 is removed using an air shower or the like. By this draining step 71, the time required for drying the precursor film 72 in the precursor film drying step 72 can be shortened.

  In the precursor film drying step 72, the precursor film 67 is dried by a drying means. The drying means is not particularly limited as long as the precursor film 67 can be dried. For example, the drying means includes a drying device and a number of gripping means (for example, clips), and the gripping means. Thus, there is a tenter that promotes drying while the both side ends of the precursor film 67 are fixed and conveyed, which is also adopted in this embodiment. The tenter will be described later.

  In the proton substitution step 76, the precursor film 67 is brought into contact with an acid solution (hereinafter referred to as an acid solution). By contact with this acid solution, the precursor contained in the precursor film 67 is proton-substituted, and the precursor film 67 becomes the hydrogen-substituted film 75. Even when a polymer in which X in Chemical Formula 3 is H is used as a raw material, the proton conductivity of the film can be improved by contacting with an acid solution as in the proton substitution step 76.

  In the water washing step 77, the acid-treated hydrogen replacement film 75 is immersed in a cleaning solution to wash away the acid solution attached to the surface of the hydrogen replacement film 75 or contained in the hydrogen replacement film 75. This washing step 77 can prevent the polymer or the like constituting the hydrogen-substituted film 75 from being contaminated with acid over time. In the present embodiment, after the proton substitution step 76, one washing step is performed. However, in order to completely remove the excess acid adhering to the hydrogen substitution film 75, the number of washings may be multiple. good.

  Further, by performing the proton substitution step 76 and the water washing step 77 as described above, an effect of removing impurities such as inorganic salts contained in the hydrogen substitution film 75 can be obtained. Deterioration can also be prevented.

  In the hydrogen replacement film drying step 78, the hydrogen replacement film 75 is sufficiently dried again by the drying means. Thereby, the solid electrolyte film 79 excellent in proton conductivity can be obtained.

[Solid electrolyte film manufacturing equipment]
FIG. 3 shows a film manufacturing facility 33 used in the first embodiment of the present invention. The film manufacturing facility 33 is a facility designed based on the solid electrolyte film manufacturing process 60 (see FIG. 2). However, this film manufacturing equipment 33 is an example of the present invention and does not limit the present invention. Hereinafter, the film manufacturing facility 33 will be described by taking as an example the case of using a dope 24 containing a polymer that is a precursor of a solid electrolyte.

  The film production facility 33 includes a casting chamber 80 for casting the dope 24 on a support to form a casting film 61, and a drying means while the casting film 61 is transported as the support travels. A transport chamber 81 for drying the film 61, a tenter 83 for promoting the drying of the precursor film 67 after peeling the casting film 61 from the support to obtain the precursor film 67, and A liquid tank 84 that performs proton substitution to produce a hydrogen substitution film 75 from the precursor film 67, a water tank 85 that cleans the hydrogen substitution film 75, and a drying process that promotes drying of the hydrogen substitution film 75 to form a solid electrolyte film 79. A chamber 86, a humidity control chamber 87 for adjusting the humidity of the solid electrolyte film 79, and a winding chamber 88 for winding the humidity-controlled solid electrolyte film 79 in a roll shape are provided.

  The film manufacturing facility 33 is connected to the dope manufacturing facility 10 via the stock tank 32. The stock tank 32 is provided with a stirrer 91 that is rotated by a motor 90. The dope 24 prepared in the dope manufacturing facility 10 is stored in the stock tank 32. Since the stirrer 91 is always rotating, it is possible to keep the dope 24 in a uniform state by suppressing the precipitation and aggregation of solids in the dope 24. In addition, when the dope 24 is stirred in this way, various additives can be appropriately mixed with the dope 24.

The casting chamber 80 is provided with a casting die 92 that flows out of the dope 24 and a casting band 93 that is a traveling support. As a material of the casting die 92, precipitation hardening type stainless steel is preferable, and its thermal expansion coefficient is preferably 2 × 10 ⁻⁵ (° C. ⁻¹ ) or less. And it has almost the same corrosion resistance as SUS316 in the forced corrosion test with electrolyte aqueous solution, and even if it is immersed in a mixed solution of dichloromethane, methanol and water for 3 months, pitting (opening) occurs at the gas-liquid interface. Those having corrosion resistance that do not occur are preferred. The casting die 92 is preferably produced by grinding a material that has passed for one month or more after casting. As a result, the dope 24 flows uniformly in the casting die 92 so that the casting die described later is flown. It is possible to prevent streaks or the like from occurring in the spread film 61. The so-called wetted surface that is in contact with the dope 24 of the casting die 92 preferably has a finishing accuracy of 1 μm or less in terms of surface roughness and a straightness of 1 μm / m or less in any direction. The slit clearance of the casting die 92 can be adjusted in the range of 0.5 mm to 3.5 mm by automatic adjustment. The chamfer radius R of the corner portion of the liquid contact portion at the lip end of the casting die 92 is constant and 50 μm or less over the entire width of the casting die 92. The casting die 92 is preferably a coat hanger type die.

  The width of the casting die 92 is not particularly limited, but is preferably about 1.1 to 2.0 times the width of the solid electrolyte film 79 as the final product. In addition, a temperature controller that controls the temperature of the casting die 92 is preferably attached to the casting die 92 so that the temperature of the dope 24 during film formation is maintained at a predetermined temperature. Furthermore, it is more preferable that the casting die 92 is provided with a plurality of thickness adjusting bolts (heat bolts) provided at predetermined intervals in the width direction and an automatic thickness adjusting mechanism that adjusts the gap between the slits with the heat bolts. . It is preferable to perform film formation by setting a profile for the heat bolt according to the amount of pump 95 supplied by a preset program. In order to precisely control the dope feeding amount, the pump 95 is preferably a high-precision gear pump. In addition, a thickness measuring machine such as an infrared thickness gauge is provided in the film manufacturing facility 33, and feedback control to the automatic thickness adjusting mechanism is performed by an adjustment program based on the thickness profile and a detection result by the thickness measuring machine. Also good. It is preferable to use a casting die 92 that can adjust the slit distance of the tip lip to be ± 50 μm or less so that the difference in thickness at any two positions excluding both ends of the solid electrolyte film 79 as a product is within 1 μm. .

More preferably, a cured film is formed at the lip end of the casting die 92. The method for forming the cured film is not particularly limited, and examples thereof include ceramic coating, hard chrome plating, and a nitriding method. In the case of using ceramics as the cured film, it is preferable to use a ceramic that can be ground, has a low porosity, is not brittle, has good corrosion resistance, and has no affinity or adhesion to the dope 24. Specific examples include tungsten carbide (WC), Al ₂ O ₃ , TiN, Cr ₂ O _{3 and the} like. Among them, WC is particularly preferable. The WC coating can be performed by a thermal spraying method.

  In order to prevent the dope 24 from locally drying and solidifying at the lip tip of the casting die 92, it is preferable to attach a solvent supply device (not shown) for supplying a solvent to the lip tip in the vicinity of the lip tip. The position where the solvent is supplied is preferably a peripheral portion of a three-phase contact line formed by both ends of the casting bead, both ends of the lip tip, and the outside air. The flow rate of the supplied solvent is preferably 0.1 mL / min to 1.0 mL / min for each side. Thereby, it is possible to prevent foreign matters such as solid components precipitated from the dope 24 and those mixed in the casting bead from the outside from being mixed in the casting film 61. In addition, as a pump which supplies a solvent, it is preferable to use a pulsation rate of 5% or less.

  A filtration device 96 is provided between the stock tank 32 and the casting die 92. The filtration device 96 removes fine particles and foreign matters larger than a predetermined particle size contained in the dope 24 and gel-like foreign matters by filtering. In order to remove these foreign substances and the like, the filtration aperture of the filtration device 96 is preferably 10 μm or less.

  A casting band 93 is provided below the casting die 92 so as to span the rotating rollers 97a and 97b. The casting band 93 is continuously conveyed by the driving rotation of at least one of the rotating rollers. The casting band 93 is transported endlessly so as to circulate through the casting chamber 80, the transport chamber 81, and a tank described later.

  The width of the casting band 93 is not particularly limited, but it is preferable to use a casting band having a range of 1.1 to 2.0 times the casting width of the dope 24. Further, it is preferable that the length is 20 m to 200 m, the thickness is 0.5 mm to 2.5 mm, and the surface roughness is polished to be 0.05 μm or less.

  The material of the casting band 93 is not particularly limited, and may be, for example, an inorganic material such as stainless steel or a plastic film made of an organic material. Examples of the plastic film include non-woven plastic films such as polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, nylon 6 film, nylon 6,6 film, polypropylene film, polycarbonate film, and polyimide film. It is preferably a long product having chemical stability and heat resistance that can correspond to the solvent to be used and the film forming temperature. In this embodiment, a PET film that is a plastic film is used as the casting band 93.

  It is preferable to use what has a heat transfer medium attached inside the rotary rollers 97a and 97b, and thereby set the surface temperature of the casting band 93 to a predetermined value. Heat transfer medium flow paths (not shown) are formed in the rotation rollers 97a and 97b, and the heat transfer medium maintained at a predetermined temperature passes through the flow paths, so that the rotation rollers 97a and 97b The temperature is maintained at a predetermined value. The surface temperature of the casting band 93 is appropriately set according to the type of solvent, the type of solid component, the concentration of the dope 24, and the like.

A rotating drum (not shown) may be used as a support instead of the rotating rollers 97a and 97b and the casting band 93. In this case, it is preferable that the rotation can be performed with high accuracy so that the rotation speed unevenness is 0.2% or less. The rotating drum preferably has an average surface roughness of 0.01 μm or less, and preferably has a surface subjected to a hard chrome plating treatment or the like. Thereby, sufficient hardness and durability can be improved. In addition, it is preferable that the surface defects of the rotating drum, the casting band 93, and the rotating rollers 97a and 97b are suppressed to a minimum. Specifically, there is no pinhole of 30 μm or more, and the number of pinholes of 10 μm or more and less than 30 μm is 1 / m ² or less, and the number of pinholes of less than 10 μm is preferably ² / m ² or less.

  It is preferable to provide a decompression chamber (not shown) on the upstream side of the casting bead. The casting bead is a ribbon-like dope 24 formed from the casting die 92 to the casting band 93. Further, the upstream side of the casting bead means that it is upstream of the casting bead in the traveling direction of the casting band 93. With this decompression chamber, the pressure in the area upstream of the casting bead is kept lower than the pressure in the area downstream of the casting bead. Moreover, it is preferable to provide a blower (not shown) in the vicinity of the casting band 93 and to blow air to evaporate the solvent of the casting film 61. In addition, it is preferable to provide a wind-shielding plate in the above-described air blower to suppress the wind that disturbs the shape of the casting film 61 from hitting the casting film 61. In addition, the casting chamber 80 is provided with a temperature controller for keeping the internal temperature at a predetermined value, and a condenser (condenser) (both not shown) for condensing and recovering the evaporated organic solvent. It is done. This capacitor is preferably in the form of being provided with a recovery device for recovering the condensed organic solvent.

  Further, a drying device 98 a is provided on the downstream side of the casting die 92 and in the vicinity of the conveying path of the casting band 93. The drying device 98a applies the drying air to the casting film 61. This drying air is adjusted so as to satisfy the drying conditions of the casting film 61. When the casting membrane 61 absorbs water, the casting membrane 24a is phase-separated and solidified, resulting in a film having a high porosity. Since the cast film 61 immediately after formation is easy to absorb water, it is preferable that the humidity of the drying air is low. Specifically, it is preferably less than 50% RH, and more preferably less than 20% RH.

  Inside the transfer chamber 81, drying devices 98 b to 98 d that send drying air adjusted to a desired temperature to promote drying of the casting film 61 are provided. Moreover, it is preferable that the transfer chamber 81 is divided into a plurality of sections and further adjusted so that the temperature and humidity of each section are different by attaching drying devices 98b to 98d in each section. The number of compartments in the transfer chamber 81 is not particularly limited, but it is preferable to adjust the drying temperature in the transfer chamber 81 to be in the range of 30 ° C. or more and 60 ° C. or less. Thus, since the casting film 61 conveyed to the casting belt 93 can be gradually dried, it is possible to prevent the solvent from abruptly evaporating and causing changes in shape such as wrinkles and wrinkles. The transfer chamber 81 is provided with a condenser (condenser) 99 for recovering the evaporated solvent generated when the casting film 61 is dried. The condenser 99 is preferably provided with a recovery device for recovering the condensed and liquefied organic solvent.

  The drying device 98 b is disposed on the upstream side in the transport direction of the casting band 93 in the transport chamber 81. The drying device 98c is disposed downstream of the drying device 98b, and the drying device 98d is disposed downstream of the drying device 98c. The drying devices 98 b to 98 d apply a predetermined drying air to the casting film 61. The direction of the dry air is substantially the same as the direction of movement of the casting film 61.

  Further, in the inside of the transfer chamber 81, the coating device 100 is disposed in the vicinity of the transfer path of the casting band 93 between the drying device 98c and the drying device 98d. The installation position of the coating device 100 is not limited between the drying device 98c and the drying device 98d, and is any one of the upstream side of the drying device 98b, the drying device 98b and the drying device 98c, or the downstream side of the drying device 98d. It may be the position. The coating apparatus 100 has the same structure as the casting die 92. The coating device 100 is connected to the water tank 101. In this water tank 101, the contact poor solvent 200 is stored.

  The water tank 101 is connected to the temperature adjustment unit 101a. The temperature adjusting unit 101a holds the temperature of the contact poor solvent 200 stored in the water tank 101 in a predetermined temperature range. The temperature of the contact poor solvent 200 is preferably maintained at 10 ° C. or higher and 70 ° C. or lower. When the temperature of the contact poor solvent 200 is 10 ° C. or lower, the effect of gelation is weakened. When the temperature of the contact poor solvent 200 is 70 ° C. or higher, the base is deformed due to rapid gelation. It is because it ends up.

  In view of the efficiency of the solid electrolyte film manufacturing process, the contact poor solvent 200 is preferably a compound having a poor solvent property with respect to the polymer contained in the dope 24. Furthermore, it is more preferable to use a solvent having high compatibility with the organic solvent 11a (see FIG. 1). When a mixture containing a compound that is a good solvent for a polymer and a compound that is a poor solvent is used as the organic solvent for the dope, a compound that is compatible with both the good solvent component and the poor solvent component is used as the contact poor solvent 200. It is preferable to use it. The organic solvent for dope is not limited as long as it dissolves the polymer, but the lower the boiling point, the better. Specific examples of the organic solvent 11a include lower alcohol, acetone, methyl acetate and the like.

  As the contact poor solvent 200, it is preferable to use water, an aqueous solution of an organic solvent, or the like. The water used suitably as a contact poor solvent should just contain no impurity. As this water, it is preferable to use pure water, distilled water, ion-exchanged water or the like. In the first embodiment, pure water is used as the contact poor solvent 200. Further, as the contact poor solvent 200, an aqueous solution of a compound having a good solvent property with respect to the polymer in the dope may be used. For example, when the precursor good solvent is DMSO, the DMSO aqueous solution is used as the contact poor solvent. be able to. By using the DMSO aqueous solution as the poor contact solvent, the solvent extraction rate in the solvent replacement can be controlled. Further, it is more preferable to use a DMSO aqueous solution having a lower boiling point. Specifically, the weight ratio k between water and DMSO is particularly preferably 1% or more and 50% or less. The weight ratio k is represented by 100 × {w1 / (w1 + w2)}. Here, w1 is the weight of water contained in the DMSO aqueous solution, and w2 is the weight of DMSO contained in the DMSO aqueous solution. Moreover, you may use the aqueous solution which consists of 2 or more types of organic solvents as a contact poor solvent. In addition, also when a polymer is a compound shown by the chemical formula 3 mentioned above, the contact poor solvent mentioned above can be used. Among these, it is particularly preferable to use a DMSO aqueous solution that can control the extraction rate of the solvent.

In addition, it is preferable that the amount of the contact poor solvent 200 applied on one surface of the precursor film 67 is 2 ml / m ² or more and 100 ml / m ² or less by using such a coating apparatus 100. When the coating amount of the contact poor solvent 200 is 2 ml / m ² or less, it is not preferable in that the solvent replacement is not sufficiently performed and the precursor film 67 cannot exhibit sufficient self-supporting property. Moreover, when the application amount of the contact poor solvent 200 is 100 ml / m ² or more, it is not preferable because the precursor film 67 cannot be stably conveyed. Instead of the coating apparatus 100 described above, a known coating means such as an E-type Giesa, rod coater or gravure coater may be used. In addition, when manufacturing a solid electrolyte film by what is called an on-line system which apply | coats the contact poor solvent 200 to the casting film 61 conveyed by the casting band 93, it is more preferable to use the coating device 100 and E type | mold Gisa. preferable. In consideration of the coating amount of the contact poor solvent 200 described above, it is more preferable to use the coating apparatus 100 or the E-type Giza as the coating unit.

  A stripping roller 103 is provided in the vicinity of the conveyance path of the casting band 93 outside the conveyance chamber 81. The stripping roller 103 strips the casting film 61 on the casting band 93 having self-supporting properties as a precursor film 67. The casting band 93 from which the casting film 61 has been peeled is guided to the inside of the transfer chamber 81 by a guide roller.

  Further, a tank 105 is disposed downstream of the peeling roller 103. The tank 105 includes a guide roller 105a and a temperature adjustment unit 105b. The temperature adjustment unit 105b maintains the temperature of the substitution solvent 202 stored in the tank 105 at a predetermined value. By contact between the casting film 61 and the substitution solvent 202, solvent substitution is performed between the organic solvent remaining inside the casting film 61 and the substitution solvent 202. In order to perform this solvent replacement smoothly, the temperature of the replacement solvent 202 is preferably maintained at 10 ° C. or higher and 70 ° C. or lower. The guide roller 105 a removes the precursor film 67 peeled off from the casting belt 93 in the replacement solvent 202 and then removes it from the replacement solvent 202.

  As the replacement solvent 202, it is preferable to use a liquid that is highly compatible with the residual solvent contained in the casting film 61 and can control the solvent extraction rate. As the substitution solvent, it is preferable to use pure water, ion-exchanged water, an aqueous solution of a compound that is a good solvent for the polymer among the solvent components of the dope, and the like. When the dope solvent is a mixture of a good solvent and a poor solvent for the polymer, it is particularly preferable that a solution compatible with the good solvent component and the poor solvent component is used as the substitution solvent. Examples of the liquid include a mixture of water and a good solvent component, and a mixture of water and a poor solvent component. However, this substitution solvent may be acetone, for example, regardless of whether it is a substance used as a component of the dope. By this solvent replacement step 70 (see FIG. 2), solvent replacement is performed in the casting film 61, and the residual solvent amount in the casting film 61 is reduced. Further, the dope solvent, the contact poor solvent and the substitution solvent remain in the precursor film 67 generated after the solvent substitution. For this reason, it is more preferable to use a liquid having a low boiling point as the substitution solvent. By using a low-boiling substitution solvent, the boiling point of the residual solvent of the precursor film 67 is lowered, so that the residual solvent can be easily removed in a short time in the precursor film drying step 72 described later. In the first embodiment, pure water is used as the substitution solvent 202.

  In the solvent replacement step, the method of contacting the precursor film 67 and the replacement solvent 202 may be any method such as application or spraying to the precursor film 67 or a method of immersing the precursor film 67 in the replacement solvent. May be used. The contact time between the precursor film 67 and the substitution solvent 202 in the solvent substitution step 70 is preferably 10 minutes or less. This is because if the contact time exceeds 10 minutes, the variation in thickness of the solid electrolyte film 79 after drying increases due to expansion of moisture contained in the precursor film 67. Further, the residual solvent amount of the precursor film 67 in the solvent replacement process 70 is reduced by the self-supporting expression process 66. Therefore, even if the precursor film 67 and the substitution solvent are brought into contact with each other in the solvent substitution step 70, generation of pores in the precursor film 67 can be suppressed and a solid electrolyte film with few defects can be obtained.

  A pair of air showers 106 provided with an air outlet directed in the both-side direction of the precursor film 67 is provided downstream of the tank 105 and upstream of the tenter 83. Further, the tenter 83 is provided with a drying device that sends out the drying air and a number of clips 83a that travel as the chain (not shown) travels. Further, at the downstream side of the tenter 83, an ear clip device 107 for cutting off both end portions (ear portions) of the precursor film 67 is provided. A crusher 107 a for finely cutting the scraps on both side ends (called ears) of the cut precursor film 67 is connected to the ear clip device 107.

  A liquid tank 84 is disposed downstream of the ear clip device 107. The liquid tank 84 stores an acid-containing liquid (hereinafter referred to as an acid solution) 204. The liquid tank 84 includes a temperature adjusting unit 84a and a guide roller 84b. The temperature adjusting unit 84a holds the temperature of the acid solution 204 stored in the liquid tank 84 at a predetermined value. The guide roller 84 b removes the precursor film 67 from the acid solution 204 after immersing the precursor film 67 in the acid solution 204. The precursor film 67 immersed in the acid solution 204 held at a predetermined temperature is proton-substituted to become a hydrogen-substituted film 75.

  Most preferably, the proportion of proton substitution is higher, that is, 100%. However, this proton substitution rate does not have to be 100%, and in this embodiment, 80% or more, more preferably 90% or more of the cationic species to be substituted is sufficient as a solid electrolyte film in consideration of productivity. It is supposed to express its function. The proton substitution rate is a value obtained by (y1 / x1) × 100, where x1 is the total number of cation species to be substituted and y1 is the total number of hydrogen atoms substituting the cation species.

  The acid solution 204 is not limited to an acidic aqueous solution, and any acid solution can be used as long as it can give protons to the precursor proton acceptor. For example, an acid may be used for the acid solution 204 when a compound having a higher proton acceptability than the acid to be used is used as the precursor.

  When an acid having an anion formula weight of 40 or more and 1000 or less is used as the acid solution 204, the anion does not easily enter the film, so that highly efficient proton substitution can be performed on the precursor film 67. Specific examples include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, and organic sulfonic acid. Among them, sulfuric acid having a large formula weight and strong acid is preferably used.

  As the temperature of the acid solution 204 increases, the proton substitution reaction at the time of contact with the precursor film 67 is performed more smoothly. Specifically, the temperature of the acid solution 204 is preferably 30 ° C. or higher and the boiling point of the acid solution 204 or lower. The precursor film 67 and the acid solution 204 may be contacted by any method such as application or spraying of the acid solution to the precursor film 67 or a method of immersing the precursor film 67 in the acid solution. It may be used.

  A water tank 85 is disposed downstream of the liquid tank 84. The water tank 85 stores water 206 as a cleaning liquid. The water tank 85 includes a temperature adjusting unit 85a and a guide roller 85b. The temperature adjustment unit 85a holds the temperature of the cleaning liquid 206 stored in the water tank 85 at a predetermined value. The guide roller 85 b removes the hydrogen substitution film 75 from the cleaning liquid 206 after immersing it in the cleaning liquid 206. In order to obtain a high effect of washing out the acid, the temperature of the cleaning liquid 206 to be used is preferably 30 ° C. or higher and the boiling point of the cleaning liquid 206 or lower.

The cleaning liquid 206 contains almost no dissolved oxygen or the like, and is preferably distilled water, pure water, or ion-exchanged water that is close to theoretical H ₂ O. In the present specification, pure water means water having a specific electric resistance of at least 1 MΩ or more, in particular, metal ions such as sodium, potassium, magnesium and calcium are less than 1 ppm, and anions such as chloro and nitric acid are less than 0.1 ppm. Point to. Pure water can be easily obtained by a simple substance such as a reverse osmosis membrane, an ion exchange resin, distillation, or a combination thereof. It is not always necessary to immerse the hydrogen replacement film 75 in the cleaning liquid 206 as in the water tank 85 described above, and any method that can clean the surface of the hydrogen replacement film 75 by applying or spraying the cleaning liquid 206 may be used. Details of the water washing step 77 and the cleaning liquid 206 will be described later.

  A drying chamber 86 is disposed downstream of the water tank 85. The drying chamber 86 is provided with a number of pass rollers 127, an adsorption recovery device 128 for recovering the evaporated solvent inside the drying chamber 86, and a drying device (not shown) for supplying drying air. Further, the humidity control chamber 87 disposed downstream of the drying chamber 86 is provided with the same pass roller 127, temperature controller, and humidity controller (both not shown) as the drying chamber 86. A neutralization device (not shown) such as a neutralization bar is provided downstream of the humidity control chamber 87, and the charged voltage of the hydrogen substitution film 75 is adjusted to be within a predetermined range (for example, −3 kV to +3 kV). More preferably, a knurling roller pair (not shown) is provided, and knurling is preferably applied to both end portions of the hydrogen-substituted film 75 by embossing. Inside the winding chamber 88, a winding roll 130 for winding the solid electrolyte film 79 and a press roller 131 for controlling the tension during winding are provided.

  Next, an example of a method for manufacturing the solid electrolyte film 79 using the film manufacturing facility 33 will be described.

  The dope 24 stored in the stock tank 32 is sent to the filtration device 96 by the pump 95. In the filtering device 96, the characteristics of the solid electrolyte film 79, particularly impurities that cause a decrease in proton conductivity are removed from the dope 24.

After the filtered dope 24 is fed into the casting die 92, it is cast on the casting band 93 while forming a casting bead from the casting die 92. In this case, the relative positions of the rotary rollers 97a and 97b and at least one of the rotational speeds are adjusted so that the tension generated in the casting band 93 is 10 ³ N / m × 10 ⁶ N / m. Further, the relative speed difference between the casting band 93 and the rotating rollers 97a and 97b is adjusted to be 0.01 m / min or less. At the time of casting, the casting amount of the dope 24 is determined in consideration of the concentration of the dope 24 to be used and the desired thickness of the film product.

  It is preferable that the speed fluctuation of the casting band 93 is 0.5% or less, and the meandering in the width direction that occurs when the casting band 93 goes around is 1.5 mm or less. In order to suppress this meandering, a detector (not shown) that detects the positions of both ends of the casting band 93 and a position adjustment that adjusts the position of the casting band 93 according to the detection data by this detector. It is more preferable to provide a machine (not shown) and feedback control the position of the casting band 93. In addition, it is preferable that the vertical position variation of the casting band 93 immediately below the casting die 92 with the rotation of the rotary rollers 97a and 97b be within 200 μm. The casting chamber 80 is preferably provided with a temperature controller (not shown), so that the temperature is set to -10 ° C to 57 ° C. Solvent evaporated in the casting chamber 80 is recovered by a recovery device (not shown) and then regenerated and reused as a solvent for dope production, which is also preferable for obtaining effects such as reduction in manufacturing cost.

  In order to stabilize the state of the casting bead, it is preferable to control in the decompression chamber so that the upstream area of the bead has a predetermined pressure value. The reduced pressure value by the decompression chamber is preferably −2500 Pa to −10 Pa from the downstream area with respect to the bead. It is preferable to attach a jacket (not shown) to the decompression chamber so that the internal temperature is kept at a predetermined temperature. In order to keep the shape of the casting bead desired, it is preferable to attach a suction device (not shown) to the edge portion of the casting die 92 to suck both sides of the casting bead. The edge suction air volume is preferably in the range of 1 L / min to 100 L / min.

  The casting film 93 on the casting band 93 is driven endlessly by driving the rotary rollers 97a and 97b. In the casting chamber 80 and the transfer chamber 81, drying air is supplied from the drying devices 98 a to 98 d to evaporate the organic solvent contained in the casting film 61. At this time, it is preferable that the temperature of the drying air when hitting the casting film 61 is 30 ° C. or more and less than 100 ° C., more preferably 20 ° C. or more and 70 ° C. or less. In this embodiment, the temperature of the drying air is adjusted so that the average temperature in the vicinity of the casting film 61 is 45 ° C.

  When the casting film 61 on the casting band 93 is dried, the humidity is preferably as low as possible. The humidity can be adjusted by installing a commercially available humidity control device or the like inside the casting chamber 80 or the transfer chamber 81. The form and installation location of the humidity control device are not particularly limited. Further, the condenser 99 condenses and collects the evaporated solvent inside the transfer chamber 81.

  In the coating apparatus 100, the contact poor solvent 200 stored in the water tank 101 and the casting film 61 conveyed by the casting band 93 are brought into contact with each other. Thus, solvent replacement is performed between the organic solvent in the casting film 61 and the contact poor solvent 200 by the coating apparatus 100. When the poor contact solvent 200 having a boiling point lower than that of the good solvent component contained in the cast film 61 is brought into contact with the cast film 61, the cast film 61 can be made into a gel. Then, since the casting film 61 itself has a self-supporting property, the casting film 61 can be easily peeled off from the casting band 93. Further, the solvent component of the dope can be evaporated together with the contact poor solvent 200 in the step of drying the precursor film 67. Furthermore, since the good solvent contained in the cast film 61 is larger than the poor solvent, the proportion of the low boiling point component in the total solvent weight increases. Thereby, sufficient drying can be performed at a temperature at which water is evaporated.

  Thus, self-supporting property is exhibited in the cast film 61 by solvent replacement with the contact poor solvent 200 and drying with the drying devices 98a to 98d. Thus, the elastic modulus of the casting film 61 is such that it can be peeled off.

  The stripping roller 103 strips the casting film 61 from the casting band 93 as the precursor film 67. Further, since the casting band 93 after the casting film 61 has been peeled off travels endlessly with the rotation of the rotary rollers 97a and 97b, it is fed into the casting chamber 80 again. The guide roller 105 a guides the precursor film 67 into pure water that is the substitution solvent 202. By contacting the precursor film 67 and pure water, solvent replacement is performed between the pure water and the organic solvent contained in the casting film 61. The pure water is compatible with the organic solvent remaining in the casting film 61, and solvent replacement is performed between the pure water and the organic solvent contained in the casting film 61.

  When the dope solvent is a mixture of a good solvent component and a poor solvent component and the good solvent casts a dope of 100% by weight or more with respect to the precursor, the contact poor solvent 200 and the substitution solvent The precursor film 67 after being brought into contact with 202 preferably has a good solvent component weight of less than 100% with respect to the weight of the precursor. Thereby, a subsequent drying process can be completed in a short time.

  The total contact time of the cast film 61 and the precursor film 67 with respect to the contact poor solvent 200 and the substitution solvent 202 is preferably 10 minutes or less. More preferably, it is 30 seconds or more and 10 minutes or less, and particularly preferably 1 minute or more and 5 minutes or less. In the present invention, if this time exceeds 10 minutes, the amount of water in the precursor film 67 becomes excessive, the precursor film 67 swells greatly, and the drying time in the subsequent process is lengthened. There are times when it becomes inevitable. On the other hand, when this time is less than 30 seconds, gelation is not sufficiently promoted due to insufficient substitution of the solvent. For this reason, the film cannot be peeled off successfully from the support and cannot be continuously formed, or it becomes difficult to realize a reduction in drying time.

  The precursor film 67 is sent out from the tank 105 by the guide roller 105a. The air shower 106 blows air onto the surface of the precursor film 67 to remove moisture adhering to the surface of the precursor film 67. This precursor film 67 is fed into the tenter 83. In the tenter 83, both end portions of the precursor film 67 are gripped by the clip 83a and are conveyed as the chain travels. During the conveyance of the precursor film 67, drying air adjusted to a desired temperature is applied to the precursor film 67 to promote drying of the precursor film 67. However, the clip 83a may be replaced with a pin, and this pin may be transported after being held by being pierced at both end portions of the precursor film 67. At this time, the temperature inside the tenter 83 is preferably set to 80 ° C. or higher and 150 ° C. or lower by adjusting the temperature of the drying air. In the first embodiment, the internal temperature is adjusted to about 120 ° C. The set temperature can be lowered as the contact poor solvent 200 or the substitution solvent 202 has a lower boiling point. It is preferable that the tenter 83 is divided into four temperature zones whose interiors differ in the transport direction, and the drying conditions are adjusted appropriately for each zone. By drying the tenter 83, the residual solvent amount of the precursor film 67 is set to about 10% by weight on the dry basis. The amount of residual solvent based on this dry amount is a value calculated by {(x2-y2) / y2} × 100, where x2 is the film weight at the time of sampling and y2 is the weight after the sampling film is dried. It is.

  In the tenter 83, the precursor film 67 can be stretched in the width direction. By adjusting the tension in the transport direction applied to the precursor film 67 before being fed into the tenter 83, the precursor film 67 can be stretched in the transport direction. Moreover, when extending | stretching the precursor film 67, it extends | stretches so that it may become a dimension of 100.5%-300% with respect to the dimension before extending | stretching at least 1 direction of the conveyance direction and the width direction of the precursor film 67. It is preferable to do. Thereby, the molecular orientation of the precursor film 67 can be adjusted.

  The precursor film 67 is fed into the ear-cutting device 107, where both side end portions are cut and removed. Thus, the planarity of the precursor film 67 can be improved by excising the both ends of the precursor film 67 damaged by the clip. In addition, the cut | disconnected both side edge part is sent into the crusher 107a with a cutter blower (not shown), and it grind | pulverizes here and becomes a chip | tip. When this chip is reused as a polymer raw material for dope production, it is possible to effectively use the raw material or reduce production costs. In addition, although the process of cut | disconnecting the both-ends part of the precursor film 67 can also be abbreviate | omitted, after peeling off from the support body as the precursor film 67, it is preferable to carry out in any until it winds up a film.

  The precursor film 67 is fed into the liquid tank 84, and the precursor film 67 is immersed in a sulfuric acid aqueous solution as the acid solution 204. Thus, the polymer component of the precursor film 67 is proton-substituted by immersion in the sulfuric acid aqueous solution, and the precursor film 67 becomes the hydrogen-substituted film 75. The acid solution is preferably brought into contact with the precursor film 65 as uniformly as possible.

  Next, the hydrogen substitution film 75 in which proton substitution has been sufficiently performed is fed into the water tank 85 and immersed in the pure water of the water tank 85. Thus, excess sulfuric acid aqueous solution attached to the hydrogen-substituted film 75 can be removed.

  Subsequently, the hydrogen substitution film 75 is fed into the drying chamber 86. In the drying chamber 86, drying air is supplied from the drying device while the hydrogen-substituted film 75 is conveyed while being wound around the pass roller 127 and is dried. The internal temperature of the drying chamber 86 is not particularly limited, but is determined according to the heat resistance of the solid electrolyte (glass transition point Tg, heat distortion temperature, melting point Tm, continuous use temperature, etc.), and is Tg or less. In the present invention, the internal temperature of the drying chamber 86 is preferably 120 ° C. or more and 185 ° C. or less, and the drying is performed until the residual solvent amount of the solid electrolyte film 79 is less than 10% by weight with respect to the dry amount standard. It is preferable to do. The solvent gas generated by evaporation from the solid electrolyte film 79 is adsorbed and collected by the adsorption / recovery device 108, and after removing the solvent component, it is sent again into the drying chamber 86 as dry air.

  It is more preferable that the drying chamber 86 is divided into a plurality of sections in the transport direction in order to change the blowing temperature. In addition, when a preliminary drying chamber (not shown) is provided between the ear opener 107 and the drying chamber 86 to preliminarily dry the hydrogen-substituted film 75, the temperature of the hydrogen-substituted film 75 is prevented from rapidly rising in the drying chamber 86. As a result, a significant change in shape of the hydrogen-substituted film 75 in the drying chamber 86 can be suppressed, and the solid electrolyte film 79 with little change in shape can be obtained.

  When the same quality solvent is used as the contact poor solvent 200 and the substitution solvent 202, the solvent contact step 66, the stripping step 68, and the solvent substitution step 70 may be performed while immersed in the solvent. This will be described later as a second embodiment. By doing in this way, the time which manufactures the solid electrolyte film 79 can further be shortened.

  In the above embodiment, the casting membrane drying step 66a and the contact solvent step 66b are performed in the self-supporting expression step 66, but the casting membrane drying step 66a may not be performed. However, when performing the self-supporting expression process 66 as a whole in a short time, it is preferable to perform the casting film drying process 66a in terms of causing the casting film 61 to exhibit self-supporting characteristics.

  In the contact solvent step 66b, the contact poor solvent 200 is applied to the casting film 61 using the coating apparatus 100. However, the contact poor solvent 200 may be sprayed. Moreover, it is not necessary to use the drying apparatus 98d which dries the casting film 61 after contact with the contact poor solvent 200. The drying of the casting film 61 by the drying device 98d is an effective means as long as the good solvent of the polymer contained in the casting film 61 can be further removed. However, when the contact poor solvent 200 contained in the casting film 61 is volatilized by the drying device 98d, it is better not to dry the casting film 61 after contact with the contact poor solvent 200.

  In the water washing step, when the hydrogen-substituted film is washed, it is not always necessary to immerse the film in the washing liquid, and there is no particular limitation as long as it is a cleaning liquid contact method that can remove acid from the hydrogen-substituted film. . For example, a method of applying a cleaning liquid to the hydrogen-substituted film, a method of spraying the cleaning liquid, and the like can be mentioned. Thus, the method of applying or spraying the cleaning liquid to the hydrogen-substituted film is preferable because the hydrogen-substituted film can be carried while being continuously conveyed.

  Of the above, specific examples of the application method and the spraying method include methods using an application head such as an extrusion coater, fountain coater, frog mouth coater, air humidification and painting, automatic tank cleaning, etc. And a method using a spray nozzle. These coating methods are summarized in “All about Coating” (Edited by Masayoshi Araki, Processing Technology Research Group (1999)), and this description can also be applied to the present invention. In addition, the spray nozzles can be installed so that the water flow collides with the entire width by arranging spray nozzles such as conical and fan shapes from Ikeuchi Co., Ltd. in the width direction of the transparent resin film. .

  The higher the spraying speed of the cleaning liquid, the higher the cleaning effect can be obtained. However, when the washing process is carried out while continuously transporting the hydrogen-substituted film, the transport stability may be impaired. Therefore, the spraying speed of the cleaning liquid is preferably 50 to 1000 cm / second, preferably 100 to 700 cm / second, and more preferably 100 to 500 cm / second.

The amount of the cleaning liquid must be at least an amount exceeding the theoretical dilution rate defined in the following formula (1). In other words, the theoretical dilution rate is assumed on the assumption that all of the cleaning liquid 121 used for cleaning has contributed to the diluted mixing of the acid solution 110. In practice, since complete mixing does not occur, the amount of the cleaning liquid 206 exceeding the theoretical dilution rate is used. Although it depends on the acid concentration of the acid solution 204 used and the type of solvent of the acid solution, it is at least 100 to 1000 times, preferably 500 to 10,000 times, and more preferably 1000 to 100,000 times. The cleaning liquid 206 is used. In the following formula (1), the amount of the cleaning liquid 206 and the acid solution 204 is the amount of each liquid that contacts per unit area of the film.
Theoretical dilution factor = (Amount of cleaning liquid 206 [cc / m ² ]) ÷ (Amount of acid solution 204 [cc / m ² ]] (1)

  When a certain amount of cleaning liquid 206 is used as a cleaning method, it is preferable to perform cleaning several times by dividing the entire amount into several times, rather than bringing the entire amount of cleaning liquid into contact with the hydrogen-substituted film at once. In this case, it is preferable to provide an appropriate space between one cleaning means and the next cleaning means by adjusting the time and distance because the cleaning solution can be diffused to dilute the acid solution. Furthermore, it is preferable to provide a cleaning solution on the film so as to flow along the film surface by providing an inclination in the hydrogen-substituted film to be transported, because a mixed dilution effect by flow can be obtained in addition to diffusion. The most preferable method is to drain the film by providing a draining means between the cleaning means. This method can also increase the dilution efficiency of the acid solution. Specific examples of draining means include a blade, an air knife, or a roll. Although it is advantageous to increase the number of water tanks arranged along the transport path, it is usually 2 to 10 locations, preferably 2 to 5 locations along the transport direction from the viewpoint of installation space and equipment cost. .

  Among the above draining means, it is preferable to use an air knife in order to obtain the most draining effect. In the case of using an air knife, the amount of moisture remaining on the surface can be made close to zero by adjusting the air volume and the air pressure of the air sent to the solid electrolyte film. However, if the air volume is too large, fluttering or shifting may occur, which may affect the film conveyance stability. Therefore, the air flow rate is preferably 10 to 500 m / second, preferably 20 to 300 m / second, and more preferably 30 to 200 m / second. Note that the air volume of the air is not particularly limited, and may be determined based on the amount of moisture originally on the film, the film conveyance speed, and the like.

  In addition, in order to remove moisture uniformly, the air velocity distribution in the width direction of the solid electrolyte film is usually within 10%, and preferably within 5%, and the air supply method to the air knife outlet and the air knife. Adjust. The narrower the gap between the surface of the solid electrolyte film to be conveyed and the air knife outlet, the greater the water draining ability, but there is a higher possibility of contact with and damage to the solid electrolyte film. Usually, an air knife is installed with a gap of 10 μm to 10 cm, preferably 100 μm to 5 cm, more preferably 500 μm to 1 cm. Furthermore, by setting up a backup roll on the opposite side of the solid electrolyte film so that it faces the air knife, the setting of the gap is stabilized and the influence of fluttering, wrinkles, deformation, etc. of the film is reduced. It is preferable because

When performing cleaning, it is preferable to use pure water as the cleaning liquid. The pure water used in the present invention has a specific electric resistance of at least 1 MΩ or more, particularly metal ions such as sodium, potassium, magnesium and calcium are less than 1 ppm, and anions such as chloro and nitric acid are less than 0.1 ppm. Pure water can be easily obtained by a simple substance such as a reverse osmosis membrane, an ion exchange resin, distillation, or a combination thereof. Among these, ultrapure water that has almost no dissolved oxygen and is theoretically close to H ₂ O is preferable. In order to obtain a high effect of removing the acid from the film, the temperature of the cleaning liquid used is preferably 30 ° C. or higher and the boiling point or lower, more preferably 30 ° C. or higher and 120 ° C. or lower. However, the temperature of water is not particularly limited as long as it is in the temperature range from approximately room temperature to the boiling of water. In this embodiment, the acid of the precursor film 65 is removed by immersing in warm water adjusted to 30 ° C.

  When the acid treatment and the washing treatment are performed as described above, an effect of removing impurities such as inorganic salts contained therein at the time of forming the cast film can be obtained. Therefore, the resulting film is suppressed from deterioration due to impurities. In addition, it is preferable that the metal content contained in the film after an acid treatment and washing | cleaning is 1000 ppm or less, More preferably, it is 100 ppm or less. In addition, Na, K, Ca, Fe, Ni, Cr, Zn etc. are mentioned as a target metal, These metal contents are grasped | ascertained by measuring with a commercially available atomic absorption photometer, for example. Can do.

  In the first embodiment, a solid electrolyte film may be manufactured using a polymer that is a solid electrolyte instead of the polymer that is a precursor of the solid electrolyte. In this case, the proton substitution step 76 and the water washing step 77 in the solid electrolyte film production step 60 need not be performed, but are preferably performed from the viewpoint of improving proton conductivity.

  The solid electrolyte film 79 is carried into the humidity control chamber 87. In the humidity control chamber 87, the degree of drying of the solid electrolyte film 79 wound around the roller 127 and transported is controlled to a desired temperature and humidity by the temperature control device and the humidity control device in the same manner as the drying chamber 86, and the degree of drying is controlled. . Although the internal temperature and humidity of the humidity control chamber 87 are not particularly limited, the temperature is preferably 20 ° C. or higher and 30 ° C. or lower, and the humidity is preferably 40 RH% or higher and 70 RH% or lower. Thereby, it can suppress that curling generate | occur | produces on the surface of the solid electrolyte film 79, or winding-up defect generate | occur | produces when winding up. In addition, if a cooling chamber (not shown) is provided between the drying chamber 86 and the humidity control chamber 87 and the solid electrolyte film 79 is cooled to approximately room temperature, the shape change of the solid electrolyte film 79 due to temperature change is suppressed. Is preferable.

  When giving knurling to the solid electrolyte film 79 after humidity control, it is preferable that the height of the unevenness | corrugation of the location which gave knurling is 1 micrometer-200 micrometers.

  The solid electrolyte film 79 is sent to the take-up chamber 88 and taken up on the take-up roll 130 while applying a tension by the press roller 131. Thereby, the roll-shaped solid electrolyte film 79 can be obtained while suppressing generation | occurrence | production of a wrinkle, a twist, etc. In this way, it is preferable to wind the sheet while applying a desired tension to the solid electrolyte film 79 with the press roller 131, because a roll-shaped product having excellent flatness can be obtained. In order to prevent excessive winding in the film roll, it is more preferable to gradually change the tension from the start to the end of winding. Further, the width of the solid electrolyte film 79 to be wound is preferably 100 mm or more, and the present invention is also applied to the production of a thin film having a thickness of 5 μm to 300 μm. .

  The precursor film 67, the hydrogen substitution film 75, and the solid electrolyte film 79 are mainly supported or conveyed by rollers within each process of the film manufacturing facility 33 or between processes. These rollers include a driving roller and a non-driving roller, and the non-driving roller is mainly used for determining a film conveyance path and improving conveyance stability.

  FIG. 4 shows a film manufacturing facility as a second embodiment of the present invention. In FIG. 4, the same reference numerals as those in FIG. The components upstream of the transfer chamber 281, downstream of the drying chamber 86, and inside the casting chamber 80 are the same as those of the film manufacturing facility 33 shown in FIG. The film production facility 233 is casted by a casting chamber 80 in which the dope is sent from the liquid feeding line L1 to form the casting film 61, and drying devices 93b to 93d arranged in the vicinity of the conveying path of the casting film 61. The film 61 is dried, and the solvent contacting step 66b (FIG. 2) is applied to the transfer chamber 281 including the casting chamber 80, and the casting film 61 and the precursor film 267 which is the casting film 61 peeled off from the support. The liquid tank 205 that performs the solvent replacement step 70 (see FIG. 2) on the precursor film 267, the tenter 83, the proton replacement step 76 (see FIG. 2), and the water washing step 77 (see FIG. 2). ) And an drying chamber 86.

  The casting band 93 is transported endlessly around the casting chamber 80 and the liquid tank 215. In order to prevent the surface of the casting film 61 from becoming rough due to the flow of air blown from the drying devices 98b to 98d, which are sequentially arranged in the direction of travel of the casting band 93, a wind shielding plate is appropriately provided. It may be provided.

  A roller 210 for supporting the casting band 93 and a guide roller 215 a for supporting the precursor film 267 for peeling the casting film 61 from the casting band 93 are disposed in the liquid tank 215. The liquid tank 215 has basically the same configuration as the tank 105 (see FIG. 3) in the first embodiment, except that it includes a roller 210 that supports the casting band 93. The roller 210 may be a driving roller or a non-driving roller.

  A liquid tank 215 downstream of the transfer chamber 82 contains a contact liquid 216 that is brought into contact with the casting film 61. The liquid tank 215 is provided with a contact liquid circulation purification device (not shown) that removes the contact liquid 216 from the liquid tank 215, purifies it, purifies it, and sends it to the liquid tank 215 again. The contact liquid 216 has both actions of the contact poor solvent 200 (see FIG. 3) and the substitution solvent 202 (see FIG. 3) in the first embodiment. The contact liquid 216 replaces the solvent in the casting film 61 and gels the casting film 61. In the present specification, gelation means that the fluidity is lost while the solvent or the contact liquid 215 is held in the molecular chain of the precursor, and as a result, the cast film becomes hard. is there. The gelling in this way can also provide the casting film 61 with a self-supporting property.

  The contact liquid 216 has a lower boiling point than the solvent of the dope 24 and is compatible with the solvent. By using a liquid having a boiling point lower than that of the solvent as the contact liquid 216, drying in the tenter 83 and the drying chamber 86 can be performed effectively and efficiently. In addition, since the liquid compatible with the solvent is used as the contact liquid 216, the replacement with the solvent contained in the casting film 61 is performed quickly and effectively, so that the gelation speed is increased and the solvent contact is performed. There are effects that the time of the process and the solvent replacement process can be shortened, the transport path inside the liquid tank 215 can be shortened, and the like.

  When the solvent of the dope is a mixture, the solvent that satisfies at least one of the solvent components having the highest boiling point, the one having the highest affinity with the precursor, and the one having the highest compounding ratio A liquid that is compatible with the components is preferably used as the contact liquid 216. Further, when the solvent of the dope 24 is a mixture of a compound that is a good solvent for a polymer and a compound that is a poor solvent, it is preferable to use a liquid that is compatible with both as the contact liquid 216. When DMSO and methyl alcohol are used as the solvent component of the dope 24, the contact liquid 216 is preferably water. Instead of water, an aqueous solution of the good solvent component of the dope may be used.

  The acid processing chamber 288 is provided with a coating die 211 for applying the acid solution 204 to the precursor film 267 and a plurality of water tanks 85. The precursor film 267 is guided by the roller in the order of the coating die 111 and the water tank 85. In order to avoid complication of the figure, only two water tanks 85 are illustrated, but the number may be three or more.

  The coating die 111 has the same structure as the casting die 92 (see FIG. 3) described above. The coating die 111 flows out the acid solution 204 sent from the tank 218 and applies it to one side of the precursor film 267. The tank 218 includes a temperature adjusting unit for the acid solution 204. By this temperature adjustment unit, the temperature of the acid solution 204 is maintained at a desired temperature. Note that a heater may be provided in the vicinity of the conveyance path between the coating die 111 and the water tank 85 to heat the coating film of the acid solution 204. In Embodiment 2, the acid solution is applied to the precursor film as described above. However, instead of this method, it can be performed by immersion as in the first embodiment, or can be performed by spraying or the like. it can.

  When a solid electrolyte film is manufactured by such a film manufacturing facility 233, the transfer chamber 281 does not actively evaporate a large amount of good solvent. This is because the good solvent usually has a high boiling point as described above, and therefore tends to remain in the casting film 61, and the casting film 61 is likely to be deformed if it is forced to evaporate. In addition, when a poor solvent is used as the solvent component of the dope 24, it is preferable that the poor solvent does not completely evaporate in the transfer chamber 281. This is because by leaving a poor solvent in the casting film up to the liquid tank 215, a network of polymer molecules is more easily formed, and a contact liquid 216 and a casting film 61 described later in the liquid tank 215 are formed. This is because the effect of increasing the rate of substitution with the good solvent component therein can be obtained. In the casting film 61 at the start of contact with the contact liquid 216, the ratio of the weight of the poor solvent component to the weight of the polymer is 2% or more and less than 100%, more preferably 2% or more and 70% or less. It is more preferable to set conditions in the transfer chamber 281, particularly conditions in the drying devices 98 b to 98 d. As described above, in the transfer chamber 281, drying may be performed to such an extent that the casting film 61 does not deform even if it contacts the contact liquid 216. That is, in the second embodiment, the removal of the solvent from the casting film 61 is mainly left to the liquid contact process which is the next process.

  In view of the above, in the second embodiment, the temperature of the drying air from the drying devices 98b to 98d is set lower than the set temperature in the tenter 83 and the drying chamber 86 on the downstream side. Preferably it is less than 100 degreeC, More preferably, it is 20 degreeC or more and 70 degrees C or less, and about 45 degreeC is the most preferable in general. Further, when the cast film 61 absorbs water, it may gel in a phase separated state. In this case, the obtained solid electrolyte film has a high porosity. Therefore, it is preferable to keep the vicinity of the casting film 61 as low as possible. In particular, it is preferable that the casting film 61 immediately after being formed be transported in an environment where the humidity is lower. The humidity of the dry air from the drying devices 98b to 98d is preferably less than 50% RH, more preferably less than 20% RH, and particularly preferably less than 10% RH.

  The relationship between the drying conditions of the cast film and the degree of evaporation of the good solvent component and the poor solvent component of the cast film 61 may be determined separately before production. For example, the conveyance speed, temperature and humidity of the casting film 61, and the flow rate, flow velocity, and flow direction of the drying air supplied by the drying devices 98b to 98d are used as factors of the drying conditions, and these factors and the remaining in the casting membrane. The relationship between the amount of solvent and the solvent composition is determined over time. Based on the obtained relationship, conditions for drying the casting film 61 in the transfer chamber 281 are determined.

  The casting film 61 is guided and immersed in the contact liquid 216 of the liquid tank 215 together with the casting band 93. Then, the casting film 61 is peeled off from the casting band 93 by the roller 205a to form a precursor film 267. The stripping may not be performed in the contact liquid 216 as in the present embodiment, and may be performed when the casting film has self-supporting properties. For example, a plurality of liquid tanks 215 can be arranged in series downstream of the liquid tank 215 or between the liquid tank and the liquid tank. When the casting film 61 has self-supporting properties, it is preferable to peel it off from the casting band 93 as soon as possible. This is because the replacement of the solvent and the contact liquid 216 is performed as early as possible from both surfaces of the precursor film 267, whereby the replacement can be performed efficiently.

  In the second embodiment, the temperature of the contact liquid 216 is preferably 10 ° C. or higher and 80 ° C. or lower, and more preferably 20 ° C. or higher and 50 ° C. or lower. If the temperature is higher than 80 ° C., wrinkles may occur in the cast film 61 or the precursor film 267. If the temperature is lower than 10 ° C., the solvent contained in the cast film 61 and the contact liquid 216 Replacement may not be performed efficiently.

  The time for immersing the casting film 61 in the contact liquid 216 is generally 30 seconds to 10 minutes, more preferably 1 minute to 5 minutes. Thereby, substitution with a solvent and the contact liquid 216 can fully be performed, and the self-supporting property of the casting film 61 can be expressed. However, the immersion time is determined by using at least one of the change in the weight of the solvent in the casting film 61 and the change in the hardness of the casting film 61 as an index, and thus is not necessarily limited to the above range. It is not a thing.

  The method for bringing the casting film 61 and the contact liquid 216 into contact with each other is not limited to the immersion method. As other methods, there are a method of spraying the contact liquid onto the casting film, a method of applying the contact liquid to the casting film, a method of vaporizing the contact liquid and contacting the casting film as vapor. A plurality of these methods and a method by dipping may be combined.

  The step of bringing the casting film 61 and the precursor film 267 into contact with the contact liquid 216 may be performed a plurality of times. For example, the liquid tank 215 may be arranged in series along the transport path, and the casting film 61 and the precursor film 267 after being peeled off may be sequentially fed into the plurality of liquid tanks 215. When this step is performed a plurality of times, the tenter 83 and the drying chamber 86 can be more effectively and efficiently dried by sequentially changing the contact liquids to different ones.

  The precursor film 267 is guided in a predetermined direction by a guide roller. On the other hand, the casting band 93 after the casting film 61 is peeled off is guided again into the casting chamber 80 by driving at least one of the rotating rollers 97a and 97b (see FIG. 3). .

  As in the first embodiment, the acid film 110 is applied to one side of the precursor film 267 that has been cut at both ends by the ear-cutting device 107 using the coating die 111. When heating with a heater (not shown) after application, it is preferable to heat the applied precursor film 267 to 80 ° C. or higher and 100 ° C. or lower. The precursor film 267 is effectively and efficiently subjected to proton substitution, and the precursor film 267 becomes a hydrogen substitution film 275 containing an acid solution.

  Each process of the first embodiment and each process of the second embodiment may be combined. For example, the process up to drying with a tenter is performed in the first embodiment, and after the drying process with the tenter, the method according to the second embodiment is performed, and the process up to the drying process with the tenter is performed according to the second embodiment. The process after the drying process with the tenter may be the method of the first embodiment. Moreover, although both 1st Embodiment and 2nd Embodiment are the aspects which cast continuously and manufacture a elongate solid electrolyte film, this invention is such a continuous type. It is not limited to the manufacturing method. For example, a cast film is formed by dropping a dope on a rectangular support to form a cast film, which is immersed in water together with the support to perform solvent substitution, and then peeled off and dried to produce a sheet-like solid electrolyte film. be able to. In the case of making a sheet like this, it is possible to produce a solid electrolyte film that is good even with a small self-supporting property compared to the case of making it into a long shape, and the drying time is the same as in the case of making it into a long shape. By shortening, the solvent of dope can be effectively and efficiently removed from the film.

  In the first and second embodiments described above, the case where one kind of dope is cast is shown. However, in the present invention, two or more kinds of dopes are co-cast simultaneously to form a laminated type casting film. Alternatively, a laminated type casting film may be formed by sequentially co-casting. In the case where two or more kinds of dopes are co-cast simultaneously, a casting die provided with a feed block may be used, or a multi-manifold casting die may be used. However, as for the film which consists of a multilayer by co-casting, it is preferable that any one of the two layers exposed on the surface is 0.5% to 30% of the total thickness of the film. In addition, when co-casting at the same time, when dope is cast from the die slit to the support, the concentration of each dope is adjusted in advance so that the high-viscosity dope is wrapped and cast by the low-viscosity dope. In the bead formed from the die slit to the support, it is preferable that the dope in contact with the outside world, that is, the exposed dope has a larger proportion of the poor solvent than the inner dope.

  In addition, it replaces with the said method the method of manufacturing a precursor film, a precursor film different from the said embodiment is made to hold | maintain a precursor to the pore of what is called a porous base material in which multiple pores are formed. Can be manufactured. As a method for producing such a precursor film, a method in which a sol-gel reaction liquid containing a precursor is applied onto a porous substrate and the precursor is put into pores, and the porous substrate includes the precursor. There is a method of immersing in a sol-gel reaction solution to fill the precursor in the pores. Preferable examples of the porous substrate include porous polypropylene, porous polytetrafluoroethylene, porous cross-linked heat-resistant polyethylene, and porous polyimide. Alternatively, the precursor film can be formed by processing the precursor into a fiber shape, filling the voids in the fiber with another polymer compound, and forming the film using the fiber. In this case, examples of the other polymer compound for filling the void include the substances mentioned as additives in the present specification. About each of these precursor films, a solid electrolyte film can be manufactured by performing proton substitution by the acid treatment mentioned above.

  The solid electrolyte film of the present invention can be suitably used as a proton conductive membrane for a fuel cell, in particular, a direct methanol fuel cell, and also used as a solid electrolyte film sandwiched between two electrodes of a fuel cell. Can do. Furthermore, as electrolytes, display elements, electrochemical sensors, signal transmission media, capacitors, electrodialysis, electrolytic membranes for electrolysis, gel actuators, salt electrolytic membranes, proton exchange resins in various batteries (redox flow batteries, lithium batteries, etc.) The solid electrolyte film of the present invention can be used.

(Fuel cell)
Hereinafter, an example in which the solid electrolyte film is used for an electrode membrane composite (hereinafter referred to as MEA) and an example in which the electrode membrane composite is used for a fuel cell will be described. However, the modes of the MEA and the fuel cell shown here are examples of the present invention, and the present invention is not limited thereto. The solid electrolyte film used in the MEA and the fuel cell may be any solid electrolyte film in the first and second embodiments described above, but in the following description, only the case where the solid electrolyte film 79 in the first embodiment is used is taken as an example. The modes of the MEA and the fuel cell will be described. FIG. 5 is a schematic cross-sectional view of the MEA. The MEA 161 includes a solid electrolyte film 79 and an anode electrode 162 and a cathode electrode 163 that are opposed to each other with the solid electrolyte film 79 interposed therebetween.

  The anode electrode 132 has a porous conductive sheet 132 a and a catalyst layer 132 b in contact with the solid electrolyte film 79, and the cathode electrode 133 has a porous conductive sheet 133 a and a catalyst layer 133 b in contact with the solid electrolyte film 79. Examples of the porous conductive sheets 132a and 133a include carbon paper. The catalyst layers 132b and 133b are made of a dispersion in which carbon particles carrying a catalyst metal such as platinum particles are dispersed in a proton conductive material. Examples of the carbon particles include ketjen black, acetylene black, and carbon nanotube. Examples of the proton conductive material include Nafion (registered trademark).

As the manufacturing method of the MEA 131, the following four methods are preferable.
(1) Proton conductive material application method: catalyst paste (ink) containing active metal-carrying carbon, proton conductive material, and solvent is directly applied to both surfaces of solid electrolyte film 79, and porous conductive sheets 132a and 133a are applied (heat). A MEA having a five-layer structure is manufactured by pressure bonding to the layers.
(2) Porous conductive sheet coating method: After a liquid containing the material of the catalyst layers 132b and 133b, for example, a catalyst paste, is applied to the surfaces of the porous conductive sheets 132a and 133a to form the catalyst layers 132b and 133b. Then, the solid electrolyte film 79 is pressure-bonded to produce a 5-layer MEA 131.
(3) Decal method: After a catalyst paste is applied on PTFE to form catalyst layers 132b and 133b, only the catalyst layers 132b and 133b are applied to the solid electrolyte film 79 to form a three-layer structure, which is porous. The conductive sheets 132a and 133a are pressure-bonded to produce a MEA 131 having a five-layer structure.
(4) Post-catalyst loading method: A liquid containing platinum ions after coating and forming an ink in which a platinum unsupported carbon material is mixed with a proton conductive material on the solid electrolyte film 79, the porous conductive sheets 132a, 133a or PTFE. Then, the solid electrolyte film 79 is impregnated, and platinum particles are reduced and deposited in the film to form the catalyst layers 132b and 133b. After the formation of the catalyst layers 132b and 133b, the MEA 131 is produced by the above methods (1) to (3).

  However, the method of making the MEA is not limited to the above method, and various known methods can be applied. For example, in addition to the above methods (1) to (4), there are the following methods. A coating solution containing the materials of the catalyst layers 132b and 133b is prepared in advance, and this coating solution is applied to a support and dried. The support on which the catalyst layers 132b and 133b are formed is stacked and pressure-bonded on both surfaces of the solid electrolyte film 79 so that the catalyst layers 132b and 133b are in contact with the solid electrolyte film 79. And after peeling a support body, the solid electrolyte film 79 in which the catalyst layers 132b and 133b were formed in both surfaces is pinched | interposed with the porous conductive sheets 132a and 133a. And MEA can be manufactured by closely contacting the porous conductive sheets 132a and 133a and the catalyst layers 132b and 133b.

  FIG. 6 is a schematic view of a fuel cell. The fuel cell 141 includes an MEA 131, a pair of separators 142 and 143 that sandwich the MEA 131, a current collector 146 made of a stainless net attached to the separators 142 and 143, and a packing 147. An anode pole side opening 151 is provided in the anode pole side separator 142, and a cathode pole side opening 152 is provided in the cathode pole side separator 143. Gas fuel such as hydrogen and alcohols (such as methanol) or liquid fuel such as an alcohol aqueous solution is supplied from the anode electrode side opening 151, and oxidant gas such as oxygen gas and air is supplied from the cathode electrode side opening 152. Is supplied.

  A catalyst in which active metal particles such as platinum are supported on a carbon material is used for the anode electrode 132 and the cathode electrode 133. Commonly used active metal particle sizes are in the range of 2 to 10 nm. However, the smaller the particle size, the greater the surface area per unit weight, which increases the activity and is advantageous. However, if it is too small, it is difficult to disperse without agglomeration, so about 2 nm is said to be the small limit. .

  The active polarization in the hydrogen-oxygen fuel cell is larger in the cathode electrode, that is, the air electrode than in the anode electrode, that is, the hydrogen electrode. This is because the rate of the cathode electrode reaction, that is, the oxygen reduction reaction, is slower than that of the anode electrode. For the purpose of improving the activity of the oxygen electrode, various platinum-based binary metals such as Pt—Cr, Pt—Ni, Pt—Co, Pt—Cu, and Pt—Fe can be used. In a direct methanol fuel cell using a methanol aqueous solution as the anode fuel, in order to suppress catalyst poisoning by CO generated during the oxidation process of methanol, Pt—Ru, Pt—Fe, Pt—Ni, Pt—Co, and Pt—Mo are used. Pt-Ru-Mo, Pt-Ru-W, Pt-Ru-Co, Pt-Ru-Fe, Pt-Ru-Ni, Pt-Ru-Cu, Pt-Ru-Sn, etc. A platinum group ternary metal such as Pt—Ru—Au can be used. As the carbon material for supporting the active metal, acetylene black, Vulcan XC-72, ketjen black, carbon nanohorn (CNH), and carbon nanotube (CNT) are preferably used.

The catalyst layers 132b and 133b are generated by (1) transporting the fuel to the active metal, (2) providing a field for the oxidation (anode electrode) and reduction (cathode electrode) reaction of the fuel, and (3) oxidation / reduction. And (4) transports protons generated by the reaction to the solid electrolyte, that is, the solid electrolyte film 79. For (1), the catalyst layers 132b and 133b are made porous so that liquid and gaseous fuel can permeate deeply. For (2), the active metal catalyst supported on the carbon material is responsible, and (3) is also responsible for the carbon material. In order to fulfill the function (4), a proton conductive material is mixed in the catalyst layers 132b and 133b. The proton conductive material of the catalyst layer is not limited as long as it is a solid having a proton donating group, but a polymer compound having an acid residue, for example, perfluorosulfonic acid represented by Nafion (registered trademark), side chain A sulfonated product of a heat-resistant aromatic polymer such as phosphoric acid group poly (meth) acrylate, sulfonated polyetheretherketone, and sulfonated polybenzimidazole is preferably used. When the solid electrolyte contained in the solid electrolyte film 79 is used for the catalyst layers 132b and 133b, the catalyst layers 132b and 133b and the solid electrolyte film 79 are the same type of material, so that the electrochemical adhesion between the solid electrolyte and the catalyst layer is the same. And is more advantageous in terms of proton conductivity. It is suitable from a viewpoint of battery output and economical efficiency to make the usage-amount of an active metal into the range of 0.03-10 mg / cm < ² >. The amount of the carbon material supporting the active metal is preferably 1 to 10 times the weight of the active metal. The amount of the proton conductive material is preferably 0.1 to 0.7 times the weight of the active metal-carrying carbon.

  The anode electrode 532 and the cathode electrode 533 are also referred to as an electrode base material, a permeable layer, or a backing material, and play a role of collecting current and preventing water accumulation and deterioration of gas permeation. Usually, carbon paper or carbon cloth can be used, and polytetrafluoroethylene (PTFE) treated for water repellency can be used.

MEA is incorporated into a battery, preferably having an area resistance value of 3Omucm ² below by the AC impedance method in a state filled with fuel, more preferably those of 1 .OMEGA.cm ² or less, and most preferably those 0.5Omucm ² below. The area resistance value is obtained from the product of the actually measured resistance value and the area of the sample.

  What can be used as a fuel of a fuel cell will be described. Examples of the anode fuel include hydrogen, alcohols (such as methanol, isopropanol, and ethylene glycol), ethers (such as dimethyl ether, dimethoxymethane, and trimethoxymethane), formic acid, borohydride complex, and ascorbic acid. Examples of the cathode fuel include oxygen (including oxygen in the atmosphere) and hydrogen peroxide.

In the direct methanol fuel cell, a methanol aqueous solution having a methanol concentration of 3 to 64% by weight is used as the anode fuel. According to the anode reaction formula (CH ₃ OH + H ₂ O → CO ₂ + 6H ⁺ + 6e ⁻ ), 1 mol of water is required for 1 mol of methanol, and the methanol concentration at this time corresponds to 64% by weight. The higher the methanol concentration, there is an advantage that the weight and volume of the battery including the fuel tank with the same energy capacity can be reduced. However, as the methanol concentration is higher, the so-called crossover phenomenon, in which methanol permeates the solid electrolyte film and reacts with oxygen on the cathode side to lower the voltage, becomes more prominent, and the output tends to decrease. Therefore, the optimum concentration is determined by the methanol permeability of the solid electrolyte film to be used. The cathode reaction formula of the direct methanol fuel cell is (3/2) O ₂ + 6H ⁺ + 6e ⁻ → H ₂ O, and oxygen (usually oxygen in the air) is used as the fuel.

  As a method of supplying the anode fuel and the cathode fuel to the respective catalyst layers 132b and 133b, (1) a method of forcibly feeding using an auxiliary device such as a pump (active type), and (2) an auxiliary device There are two methods that are not used, for example, a passive type in which the fuel is exposed to the atmosphere by exposing the catalyst layer to the atmosphere due to capillary action or natural fall when the fuel is a liquid, and ( It is also possible to combine 1) and (2). (1) has the advantage that by extracting the water produced on the cathode side, high-concentration methanol can be used as the fuel, and high output can be achieved by air supply, but a fuel supply system is provided. Therefore, there is a drawback that miniaturization is difficult. Although (2) has the advantage that it can be downsized, it has a drawback that the fuel supply is likely to be rate-limiting and it is difficult to produce a high output.

  Since the single cell voltage of the fuel cell is generally 1 V or less, the single cells are used by stacking in series according to the required voltage of the load. As the stacking method, “planar stacking” in which single cells are arranged on a plane and “bipolar stacking” in which single cells are stacked via separators having fuel flow paths formed on both sides thereof are used. The former is suitable for a small fuel cell because the cathode electrode (air electrode) comes out on the surface, so that air can be easily taken in and can be made thin. In addition to this, a method of applying MEMS technology, performing fine processing on a silicon wafer, and stacking has been proposed.

  Fuel cells are considered for various uses such as for automobiles, homes, and portable devices.In particular, direct methanol fuel cells are advantageous in that they can be reduced in size and weight and do not require charging. It is expected to be used as an energy source for various portable devices and portable devices. For example, mobile devices that can be preferably applied include mobile phones, mobile laptop computers, electronic still cameras, PDAs, video cameras, portable game machines, mobile servers, wearable personal computers, mobile displays, and the like. Examples of portable devices that can be preferably applied include portable generators, outdoor lighting devices, flashlights, and electric (assist) bicycles. It can also be preferably used as a power source for industrial or household robots or other toys. Furthermore, it is also useful as a power source for charging secondary batteries mounted on these devices.

  Next, examples of the present invention will be described. In each of the following Examples, Examples 1 to 3 and 5 to 8 are examples of the first embodiment of the present invention, and Example 4 is a comparative experiment with respect to the present invention.

A compound in which X in Chemical Formula 3 is a cationic species other than H was used as a precursor. This precursor is referred to as raw material A. In this raw material A, X in the chemical formula 3 is Na, Y is SO ₂ , Z is the chemical formula (I), n is 0.33, m is 0.67, the number average molecular weight Mn is 61000, and the weight average molecular weight Mw is 159000. The solvent is a mixture of the solvent component 1 and the solvent component 2. The solvent component 1 is a good solvent for the raw material A, and the solvent component 2 is a poor solvent for the raw material A. The raw material A and the solvent were mixed at the ratio shown below, and the raw material A was dissolved in this solvent to produce a dope containing 20% by weight of the precursor based on the total weight. This dope is referred to as dope A in the following description.
-Raw material A; 100 parts by weight-Solvent component 1; 256 parts by weight of dimethyl sulfoxide-Solvent component 2; 171 parts by weight of methanol

[Production of solid electrolyte film]
A dope A was cast from a casting die 92 onto a PET film as a traveling casting band 93 to form a casting film 61. The casting film 61 was dried with a drying air of 45 ° C./10% RH for 30 minutes from the air duct of the drying device 98a, and the casting film 61 was dried until the residual solvent amount reached 180% by weight on the dry basis. Using E-type Giza, pure water 50 ml / m ² was applied to the cast film 61 on the PET film. Then, the casting film 61 was transported while maintaining the surface on which the pure water was applied in a non-contact state for 5 minutes. Thereafter, the casting film 61 was peeled off as a precursor film 67 from the PET film. The self-supporting process from the formation of the casting film 61 until the casting film 61 was peeled off as the precursor film 67 was performed based on the optimum conditions obtained from experiments conducted in advance. At this time, the elastic modulus of the precursor film 67 was 5.5 × 10 ⁶ Pa. The precursor film 67 was immersed in pure water maintained at 30 ° C. for 5 minutes to perform solvent replacement. After the precursor film 67 was removed from the pure water, moisture attached to the surface of the precursor film 67 was removed using an air shower 106. The guide roller 105 a sent the precursor film 67 to the tenter 83. The clip 83a grips both end portions of the precursor film 67. The precursor film 67 passed through the inside of the tenter 83 by the traveling of the clip 83a. In the tenter 83, the precursor film 67 was dried for 10 minutes with 120 ° C. drying air. Thus, a precursor film 67 having a residual solvent amount of 10% by weight based on the dry weight standard was obtained. At the exit of the tenter 83, the clip 83a released the precursor film 67. The edge-cutting device 107 cuts and removes both end portions of the precursor film 67. The guide roller 84b was maintained at a temperature of 80 ° C., and the precursor film 67 was guided into a sulfuric acid aqueous solution having a concentration of 0.5 mol / liter to perform solvent replacement. By this solvent substitution, a hydrogen substitution film 75 was obtained from the precursor film 67. The hydrogen-substituted film 75 was removed from the sulfuric acid aqueous solution and then washed with water. After washing with water, the water adhering to the hydrogen-substituted film 75 was drained using an air shower. The drained hydrogen-substituted film 75 was sent to the drying chamber 86 and dried at 120 to 185 ° C. while being conveyed by a plurality of rollers 127. Then, a solid electrolyte film 79 having a residual solvent amount of less than 5% with respect to the dry weight standard was obtained.

  The characteristics of the obtained solid electrolyte film were evaluated by measuring the following items. In addition, the following measurements are common to all Examples 1 to 8, and the evaluation results in each example are summarized in Table 1. The numbers of the evaluation items in Table 1 correspond to the numbers given to the following evaluation items.

1. Manufacturing continuity is an evaluation of whether or not the solid electrolyte film could be implemented continuously. The description of the results in Table 2 is based on the following criteria.
○: Continuous production was possible.
Δ: Although continuous production was possible, production was sometimes stopped.
X: Cannot be produced.

2. Thickness fluctuation Using an electronic micrometer manufactured by Anritsu Electric Co., Ltd., the thickness of the solid electrolyte film was measured at a speed of 600 mm / min and recorded on a chart paper at a scale of 1/20 and a chart paper speed of 30 mm / min. Using a ruler, the thickness variation of the solid electrolyte film, that is, the thickness variation was measured from the measurement result recorded on the chart paper, and the first decimal place of the obtained measured value was rounded off.

3. Measurement of Residual Ratio of Solvent (DMSO) A substantially rectangular film piece having a length of 7 mm and a width of 35 mm was cut out from each obtained solid electrolyte film. The residual DSMO amount of this film piece was measured using Shimadzu Corporation gas chromatography (GC-18A). The residual DMSO amount is the ratio of the weight of DMSO contained in the film piece, and the numerical values in Table 1 are (y3 / x3) × 100, where x3 is the weight of the sample piece and y3 is the weight of the DMSO. It is a numerical value obtained by the formula.

4). Electrode Adhesiveness MEA was prepared by the same method as (1) and (2) in Evaluation Item 6 described later. And evaluation of adhesion | attachment of each MEA was implemented by observing visually the adhesion state after thermocompression bonding for 210 degreeC and 3 Mpa for 10 minutes.
○: The entire surface was evenly adhered Δ: Partially peeled ×: The area of the peeled portion was 10% or more of the total area

5). Proton conductivity The proton conductivity was measured using a four-terminal AC method according to Journal of the Electronic Society 143, No. 4, 1254-1259 (1996). Specifically, first, a sample cut out from a solid electrolyte film into a length of 2 cm and a width of 1 cm was used as a sample. Next, after placing the previous sample on a PTFE plate with four platinum wires fixed at intervals of 5 mm, a PTFE plate was further placed thereon, and these were fixed with screws to form a test cell. Then, using this test cell and an impedance analyzer combining Solartron 1480 type and 1225B type, proton conductivity was measured by an AC impedance method in 80 ° C. on water.

6). Output density of fuel cell A fuel cell 141 was prepared using a solid electrolyte film, and the output of the fuel cell 141 was measured. The production method of the fuel cell 141 and the measurement method of the power density are as follows.

(1) Preparation of catalyst sheet A as catalyst layers 132b and 133b 2g of platinum-supporting carbon (50% by weight of platinum supported on Vulcan XC72) and 5% alcohol aqueous solution as Nafion solution (registered trademark DuPont) 15 g was mixed and dispersed with an ultrasonic disperser for 30 minutes. The average particle size of the dispersion was about 500 nm. The obtained dispersion was coated on a polytetrafluoroethylene film containing a reinforcing material (manufactured by Saint-Gobain Co., Ltd.), dried, and then punched into a circle with a diameter of 9 mm to prepare a catalyst sheet A.

(2) Production of MEA 131 The catalyst sheet A was laminated on both sides of the solid electrolyte film obtained in Examples 1 to 10 so that the coating film was in contact with the solid electrolyte film, and thermocompression bonded at 210 ° C., 3 MPa for 10 minutes, pressure After the temperature was lowered while applying MEA, the support of the catalyst sheet A was peeled to prepare MEAs in order.

(3) Output density of fuel cell 141 After stacking a gas diffusion electrode (manufactured by E-TEK) cut to the same size as the electrode on the MEA obtained in (2), a standard fuel cell test cell (manufactured by Electrochem) ). The test cell was connected to a fuel cell evaluation system (As-510, manufactured by NF Circuit Design Block Co., Ltd.). Then, a humidified hydrogen gas was supplied to the anode side, and a humidified simulated atmosphere was supplied to the one cathode side until the voltage was stabilized. Thereafter, a load was applied between the anode electrode and the cathode electrode, current-voltage characteristics at that time were recorded, and this was measured as the output density (W / cm ² ).

A compound in which X in Chemical Formula 3 is a cationic species other than H was used as a precursor. This precursor is referred to as raw material B. In addition, the compound of Chemical Formula 3 in this example has X as Na, Y as SO ₂ , Z as Chemical Formula (I), n as 0.33, m as 0.67, number average molecular weight Mn as 68000, amount The average molecular weight Mw is 200,000. The solvent is a mixture of the solvent component 1 and the solvent component 2. The solvent component 1 is a good solvent for the raw material B, and the solvent component 2 is a poor solvent for the raw material B. The raw material B and the solvent were mixed in a predetermined composition, and the solid content of the raw material B was dissolved in the solvent to produce a dope containing 20% by weight of the precursor based on the total weight. This dope is referred to as dope B in the following description.
-Raw material B; 100 parts by weight-Solvent component 1; 200 parts by weight of dimethyl sulfoxide-Solvent component 2; 135 parts by weight of methanol

A solid electrolyte film 79 was produced using the dope B. It is the same as that of Example 1 except having applied 45 degreeC / 10% RH dry air to the casting film for 20 minutes at the casting film drying process. The modulus of elasticity of the precursor film 67 in the stripping step was 6.6 × 10 ⁶ Pa. The evaluation results for the obtained solid electrolyte film 79 are shown in Table 1.

A solid electrolyte film 79 was produced in the same manner as in Example 2 except that 20% by weight DMSO aqueous solution was used as the contact solvent in the contact step, and Dope B was used. The modulus of elasticity of the precursor film 67 in the stripping process was 2.3 × 10 ⁶ Pa. The evaluation results for the obtained solid electrolyte film 79 are shown in Table 1.

  In the casting film drying step using the dope B, drying air of 45 ° C./10% RH was applied to the casting film for 20 minutes, and immediately thereafter, the casting film was peeled off from the PET film as a precursor film. Other conditions are the same as those in Example 2. This precursor film was deformed by its own weight and could not be transported by the film manufacturing facility 33.

Using the dope B, a drying air of 45 ° C./10% RH was applied to the casting membrane for 20 minutes in the casting membrane drying step. Then, it applied with 50 ml / m < ² > of pure water to the casting film 61 on PET film using E type | mold Giza. And the casting film 61 was conveyed for 1 minute in the non-contact state on the surface where the pure water was applied. Other conditions are the same as those in the second embodiment. The modulus of elasticity of the precursor film 67 in the stripping process was 8.9 × 10 ⁴ Pa. When the precursor film 67 was introduced into the water maintained at the water temperature 30, the precursor film 67 was deformed due to shrinkage of the base and could not be transported by the film manufacturing facility 33. As a reference experiment, batch-type casting for forming a sheet-like casting film was performed instead of continuous casting. The other conditions were the same as possible as in the case of continuous casting. In this reference experiment, a sheet-like solid electrolyte film could be obtained.

The precursor film 61 peeled off from the PET film using the dope B was conveyed to a tenter without being immersed in pure water. Other conditions are the same as those in Example 2. The modulus of elasticity of the precursor film 61 in the stripping process was 6.6 × 10 ⁶ Pa. The evaluation results for the obtained solid electrolyte film 79 are shown in Table 1.

Dope B was used, and dimethyl sulfoxide was used in the raw material B instead of methanol. Other conditions are the same as those in Example 2. The modulus of elasticity of the precursor film in the stripping process was 1.8 × 10 ³ Pa. The evaluation results for the obtained solid electrolyte film are shown in Table 1.

In the solvent replacement step using Dope B, the precursor film peeled off from the PET film was immersed in pure water at 30 ° C. for 20 minutes to perform solvent replacement. Other conditions are the same as those in Example 2. The modulus of elasticity of the precursor film in the stripping step was 6.6 × 10 ⁶ Pa. The evaluation results for the obtained solid electrolyte film are shown in Table 1.

  As described above, from Examples 1 to 3 according to the present invention, it was possible to produce solid electrolyte films with little thickness variation. The solid electrolyte films in Examples 1 to 3 had excellent proton conductivity. Moreover, the output density of the fuel cell using the produced solid electrolyte film is 0.49 or more, which is an excellent value as a fuel cell. On the other hand, in Examples 4 and 5, since the solvent contact step was not sufficiently performed, it was found that the precursor film obtained in the stripping step did not have sufficient self-supporting property. However, when the casting of Example 5 was carried out batchwise, a small sheet-like solid electrolyte film could be obtained, so it can be said that the conditions are sufficient for producing a sheet. In Examples 6 and 7, a solid electrolyte film could be produced. However, the solid electrolyte films produced in Examples 6 and 7 were inferior in terms of thickness fluctuation, proton conductivity and power density as compared with Examples 1 to 3. This is due to the poor adhesion between the solid electrolyte film and the electrode in the production of MEA. The decrease in the adhesiveness of the solid electrolyte film is presumed that a solid electrolyte film having a non-smooth surface was produced as a result of peeling off the cast film having no sufficient elastic modulus in the peeling step. For this reason, in order to produce a solid electrolyte film excellent in quality and performance, the dope 24 as a raw material requires a polymer good solvent and a polymer poor solvent in addition to the polymer, and contact. It was found that a process and a solvent replacement process were necessary. In addition, from the results of Example 8, it was found that when the solvent substitution step was performed for a long time, the variation in the thickness of the film after drying increased due to the expansion of water contained in the film. Furthermore, according to the manufacturing method of the solid electrolyte film of this invention, it turned out that the time which film formation requires is less than 2 hours.

  In the following Examples, Examples 9 to 13, 15, and 16 are examples of the second embodiment of the present invention, and Example 14 is a comparative experiment with respect to the present invention.

[Production of solid electrolyte film]
The same dope A as in Example 1 was cast from a casting die 92 to a running PET film to form a casting film 61, and 45 ° C / 10% RH dry air was blown out from the air ducts of the drying devices 98a to 98d. . The time for which the dry air hits an arbitrary position of the casting film 61 was continuously 30 minutes. This time is a time set so that the casting film 61 when starting contact with the contact liquid 206 contains 240 parts by weight of DMSO and 20 parts by weight of methanol with respect to 100 parts by weight of the raw material A. The casting film 61 was immersed in water at 30 ° C. together with the PET film as the casting band 93, and the casting film 61 was peeled off from the PET film in this water to obtain a precursor film 267. The time required from the start of immersion to stripping was 5 minutes. The precursor film 267 was conveyed in water as it was, removed from the water, and drained with an air shower 106. This precursor film 267 was sent to the tenter 83, and both ends of the clip 105 were gripped and conveyed inside the tenter 83. In the tenter 83, the precursor film 267 was dried for 10 minutes with a drying air of 120 ° C. Thus, the residual solvent amount of the precursor film 267 was set to less than 10% by weight on a dry basis. The precursor film 267 was detached from the clip 105 at the exit of the tenter 83, and both end portions held by the clip 83a were cut and removed by the ear clip device 107. The acid solution 204 was applied to one side of the precursor film 267 by the coating die 211, and this film was washed with water. The hydrogen-substituted film 275 that was incompletely dried was sent to the drying chamber 86 and dried at 120 to 185 ° C. while being conveyed by a plurality of rollers 127. Then, a solid electrolyte film 77 having a residual solvent amount of less than 3% by weight based on the dry weight standard was obtained. This solvent residual amount includes the weight of water used in the washing. Evaluation about the obtained solid electrolyte membrane was implemented about the below-mentioned item.

  Dope B was made by replacing the raw material A in Example 9 with the same raw material B as in Example 2. Moreover, the time for which dry air hits an arbitrary position of the casting film 61 from the air duct of the drying devices 98a to 98d was set to 20 minutes continuously. This time is a time set so that the casting film 61 at the start of the liquid contact process includes 185 parts by weight of DMSO and 10 parts by weight of methanol with respect to 100 parts by weight of the raw material B. The other conditions are the same as in Example 9.

  The conditions were the same as in Example 10 except that the dry air was continuously applied to any position of the casting film 61 from the air ducts of the drying devices 98a to 98d for 5 minutes. The above times in the drying devices 98a to 98d were set so that the casting film 61 when starting contact with the contact liquid 206 contained 195 parts by weight of DMSO and 100 parts by weight of methanol with respect to 100 parts by weight of the raw material B. It's time.

  The conditions are the same as in Example 10 except that the temperature of the dry air from the air ducts of the drying devices 98a to 98d is 110 ° C.

  The conditions are the same as those in Example 10 except that the humidity of the dry air from the air ducts of the drying devices 98a to 98d is 75% RH.

  The conditions were the same as in Example 10 except that the peeling step was performed before contacting the contact liquid 206. The precursor film did not have sufficient self-supporting property and was deformed by its own weight. As a result, a homogeneous solid electrolyte film could not be produced continuously.

  The conditions were the same as those in Example 10 except that the drying air was continuously applied from the air ducts of the drying devices 98a to 98d to any position of the casting membrane for 60 minutes. The above time in the air ducts of the drying devices 98a to 98d is a time set so that the casting film at the start of the liquid contact process does not contain methanol and contains 150 parts by weight of DMSO with respect to 100 parts by weight of the raw material B. is there.

Instead of the dope B, a dope C having the following composition was used. The other conditions are the same as in Example 10.
-Raw material B; 100 parts by weight-Solvent component 1; DMSO 335 parts by weight

  About each solid electrolyte film obtained in Examples 9-16, the characteristic was evaluated by measuring the following items, respectively. In addition, the following evaluation methods and evaluation criteria are common to all of Examples 9 to 16, and the evaluation results are summarized in Table 2. The numbers of the evaluation items in Table 2 correspond to the numbers given to the following evaluation items. The description is omitted when the evaluation method is the same as in Examples 1-9.

1. Manufacturing continuity Average thickness and variation of thickness Using an electronic micrometer manufactured by Anritsu Electric Co., Ltd., the thickness of the film 62 was continuously measured at a speed of 600 mm / min. Data obtained by the measurement was recorded on the chart paper at a scale of 1/20 and a chart speed of 30 mm / min. And after measuring with respect to a data curve with a ruler, the average value of thickness and the dispersion | variation in the thickness with respect to this average value were calculated | required based on the measured value. In Table 2, (a) represents the average thickness (unit: μm), and (b) represents the thickness variation (unit: μm) relative to (a).
3. 3. Measurement of residual ratio of solvent (DMSO) 4. Adhesion of electrodes 5. Proton conductivity Fuel cell power density

  Each production experiment of Examples 17-23 of a solid electrolyte film was conducted. Examples 17 to 22 were performed using the manufacturing facility 33 in the first embodiment. In addition, Example 23 is a comparative experiment with respect to the present invention, and a part of the manufacturing equipment 33 was not used. And about the solid electrolyte film obtained in Examples 17-23, it evaluated by the same evaluation item as Examples 9-16. The evaluation items in Table 3 are the same as in Table 2.

  A casting film 61 was formed by casting the same dope A as in Example 1 onto the casting band 93. The casting film 61 was dried by applying drying air of 45 ° C./10% RH for 30 minutes with the drying devices 98a to 98d. The casting band 93 is a PET film. Next, after spraying 30 ° C. pure water from the coating apparatus 100 for 2 minutes onto the surface of the casting film 61, the casting film 61 was peeled off from the casting band 93 to obtain a precursor film 67. The amount of DMSO in the casting film 61 immediately before peeling off from the casting band 93 was 65% by weight.

  The precursor film 67 was fed into the tank 105 containing 30 ° C. pure water as the substitution solvent 202, and was immersed therein for 3 minutes. The precursor film 67 sent out from the tank 105 was drained by the air shower 99 and then sent into the tenter 83. In the tenter 83, while the both ends of the precursor film 67 are held and transported by the clips 83a, 120 ° C. drying air is emitted from a drying device (not shown) provided in the tenter 83 to Drying proceeded. The drying time in the tenter 83 was 10 minutes so that the residual solvent amount of the precursor film 67 was less than 10% by weight.

  After the precursor film 67 released from the clip 83a was sent out from the tenter 83, both side ends thereof were cut. Subsequently, after feeding the precursor film 67 to the liquid tank 84 in which the 0.5 mol / L sulfuric acid aqueous solution kept at 30 ° C. is put, the water tank 85 in which pure water at 30 ° C. is put in I sent it. Then, the hydrogen-substituted film 75 was fed into the drying chamber 74 whose temperature was adjusted to 120 ° C. to 185 ° C. and dried while being supported by a large number of rollers 127 for 30 minutes to obtain a solid electrolyte film 79.

  The dope B was used, the temperature and humidity of the drying air from the drying devices 98a to 98d to the casting film 61 were 45 ° C./10% RH, and the corresponding time was 20 minutes. Other conditions are the same as those in Example 17.

  Pure water at 30 ° C. was sprayed onto the casting film 61 for 1 minute from the coating apparatus 100. The casting film 61 was peeled off from the casting band 93 to obtain a precursor film 67. Other conditions are the same as in Example 18. However, in the tank 105, the precursor film 67 is greatly shrunk and changed in shape, so that it cannot be transferred to the subsequent process, and as a result, the film 70 cannot be manufactured. The cast film 61 after contacting pure water with the coating apparatus 100 had a DMSO amount of 130% by weight. As a reference experiment, batch-type casting was performed to produce a sheet-like solid electrolyte film. In this reference experiment, the precursor film contracted a little, but a sheet-like film having a sufficient appearance was obtained.

  All were the same as Example 18 except that the film 79 was produced without feeding the precursor film 67 into the tank 105.

  A solid electrolyte film 79 was produced in the same manner as in Example 18 except that the methanol of the dope B was replaced with dimethyl sulfoxide.

  A solid electrolyte film 79 was manufactured in the same manner as in Example 18 except that the time for immersing the precursor film 67 in the tank 105 was 20 minutes. As a result, a solid electrolyte film 79 in which the amount of DMSO was 0.1% by weight was obtained.

  The casting film 61 was peeled off from the casting band 93 without contacting the pure water by the coating apparatus 100 to form a precursor film. All other conditions are the same as in Example 18. However, immediately after the precursor film was formed, the film was deformed by its own weight and could not be transported, so that a solid electrolyte film could not be continuously formed. As a reference experiment, batch-type casting was carried out to make a sheet-like solid electrolyte film, but it was deformed and a sheet having a good appearance could not be obtained.

  From the results of Examples 17 to 23, when focusing attention on the drying time, for example, according to the prior art, 5 to 14 hours or more are spent on the drying time, whereas in Examples 17 and 18 according to the present invention, It can be seen that the drying time is about 65 to 75 minutes throughout the process, and the drying time can be greatly shortened. This is based on the fact that when the compound, which is a poor solvent of the solid electrolyte, is brought into contact with the cast film, the cast film can be gelled, and the amount of the poor solvent contained in the cast film can be increased. From Example 19 and this reference experiment, it can be seen that the production conditions for the long solid electrolyte film and the sheet-like solid electrolyte film can be separated depending on the degree of self-supporting property to be given to the cast film. Further, from Examples 17 to 23, according to the present invention, a solid electrolyte film showing high proton conductivity without being affected by the environment such as temperature and humidity can be produced in large quantities with excellent productivity. Recognize. And it turns out that the fuel cell using this solid electrolyte film exhibits a high output density.

  The process up to the drying process in the tenter was performed according to the second embodiment shown in FIG. 4, and the process after the tenter drying process was performed by the method of the first embodiment.

  Similarly to Example 9, the dope A was cast to form a cast film 61, and the cast film 61 was dried with dry air for 30 minutes. The casting film 61 placed on the casting band 93 is sent to the liquid tank 205 and immersed in warm water at 30 ° C. Then, the casting film 61 is removed from the casting band 93 by the peeling roller 210. The precursor film 267 was peeled off. During this time, the total immersion time of the casting film 61 and the precursor film 267 in the liquid tank 205 was set to 5 minutes.

  The water adhering to the surface of the gel-like precursor film 267 was removed by air shower. Thereafter, in the same manner as in Example 9, the precursor film 267 was dried with the tenter 83, and the side end portion was cut with the ear clip device 107.

  The precursor film 267 whose both ends were cut was sent to the liquid tank 84 shown in FIG. 3, and proton substitution was performed with a 0.5 mol / L sulfuric acid aqueous solution maintained at 70 ° C. Thereby, Na contained in the precursor film 267 was replaced with a hydrogen atom to obtain a hydrogen-substituted film.

  Another water tank was provided downstream of the water tank 85, and the hydrogen substitution film was washed several times. The temperature of all the water tanks was 70 ° C. Thereafter, the water on the surface of the hydrogen-substituted film was removed by an air shower and dried in the drying chamber 86. The internal temperature of the drying chamber 86 was 60 to 120 ° C. The obtained solid electrolyte film was conditioned in the humidity control chamber 87 and then rolled in the winding chamber 88.

  With respect to the manufactured solid electrolyte film, the following items 1 to 3 were evaluated. The evaluation results are shown in Table 4. The numbers of the evaluation items in Table 4 correspond to the numbers in the following evaluation methods, respectively. The following evaluation is common to all the following Examples 25 to 30. Description of the evaluation items of the same evaluation method as in Example 1 is omitted.

1. Manufacturing continuity Proton substitution rate After sampling from the solid electrolyte film and measuring the weight of the sample piece, the sample piece was alkali-treated. The alkali treatment was performed by immersion in a 0.1 mol / liter NaOH aqueous solution for 2 hours. During the immersion, the NaOH aqueous solution was stirred. Next, a sample piece of the solid electrolyte film was taken out, and the ion exchange capacity (ICE) of the solid electrolyte film was determined by performing back titration on the used aqueous NaOH solution with an aqueous hydrochloric acid solution. Then, by comparing the ion exchange capacity with the theoretical value, the amount of the precursor Na substituted with H was calculated, and this was used as the proton substitution rate. In addition, said theoretical value is the introduction amount of sulfonic acid groups derived from structural analysis by NMR measurement or the like.
3. 3. Proton conductivity Fuel cell power density

  The dope A of Example 24 was cast instead of the same dope B as in Example 2. The casting film 61 on the casting band 93 was dried for 20 minutes with a 45 ° C./10% RH wind.

  A solid electrolyte film was produced in the same manner as in Example 25 except that the temperature of the aqueous sulfuric acid solution in the liquid tank 84 was maintained at 80 ° C.

  All were the same as in Example 25 except that the temperature of the sulfuric acid aqueous solution in the bath 84 was kept at 20 ° C.

  All were the same as Example 25 except that the acid solution in the liquid tank 84 was changed to a 1 mol / L hydrochloric acid aqueous solution.

  From Examples 24-26, it can be seen that the solid electrolyte film according to the present invention is very excellent in any of proton conductivity, proton substitution rate and power density. Further, from the results of Examples 27 and 30, it can be seen that the temperature and formula amount of the acid solution used during the acid treatment affect the proton conductivity and the proton substitution rate.

  In addition, according to the present invention, a high proton conductivity film can be continuously produced in large quantities while performing on-line acid treatment. Moreover, when the solid electrolyte film obtained by this manufacturing method is used as a solid electrolyte layer of a fuel cell, an excellent output density can be realized.

It is the schematic of an example of the dope manufacturing equipment used by this embodiment. It is a manufacturing-process figure of the film which concerns on this invention. It is the schematic of the film manufacturing equipment of 1st Embodiment. It is the schematic of the film manufacturing equipment of 2nd Embodiment. It is sectional drawing of an electrode membrane composite. It is sectional drawing of a fuel cell.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Dope manufacturing equipment 11a Solvent 12a Precursor 24 Dope 33 Film manufacturing equipment 60 Solid electrolyte film manufacturing process 61 Casting film 66 Self-supporting expression process 66a Casting film drying process 66b Solvent contact process 67 Precursor film 68 Stripping process 70 Solvent replacement step 75 Hydrogen replacement film 79 Solid electrolyte film 100 Coating device 103 Stripping roller 105 Tank 131 Electrode membrane composite (MEA)
132 Anode electrode 133 Cathode electrode 141 Fuel cell 146 Current collector 200 Contact solvent 202 Substitution solvent

Claims (20)

A first step of casting a dope in which a solid electrolyte is dissolved in an organic solvent from a casting die onto a support to form a casting film;
A second step of bringing the cast film into contact with a poor contact solvent that is a poor solvent for the solid electrolyte, and causing the cast film to exhibit self-supporting properties;
A third step of peeling the cast film having self-supporting property from the support as a wet film;
A fourth step of drying the wet film to form a solid electrolyte film;
A method for producing a solid electrolyte film, comprising:   2. The method for producing a solid electrolyte film according to claim 1, wherein the organic solvent is a mixture containing a first compound that is a good solvent for the solid electrolyte and a second compound that is a poor solvent.   The method for producing a solid electrolyte film according to claim 1 or 2, wherein the poor contact solvent is any one of water and an aqueous solution of a compound that is a good solvent for the solid electrolyte.   The contact time between the cast film and the contact poor solvent is at least one of the hardness of the cast film that changes due to the contact and the weight of the first compound in the cast film that changes due to the contact. The method for producing a solid electrolyte film according to any one of claims 1 to 3, wherein the solid electrolyte film is determined according to one of them. 5. The method for producing a solid electrolyte film according to claim 1, wherein an elastic modulus of the wet film in the third step is 6 × 10 ⁵ Pa or more.   The method for producing a solid electrolyte film according to claim 1, further comprising a fifth step of bringing the wet film into contact with a liquid compatible with the organic solvent.   The method for producing a solid electrolyte film according to claim 6, wherein the liquid is any one of water and an aqueous solution of the organic solvent.   The method for producing a solid electrolyte film according to claim 6 or 7, wherein a contact time between the wet film and the liquid is 10 minutes or less.   The method for producing a solid electrolyte film according to any one of claims 1 to 8, further comprising a sixth step of drying the cast film before the second step.   The solid electrolyte film according to any one of claims 1 to 9, wherein the first compound is dimethyl sulfoxide, and the second compound is alcohol (however, the carbon number is 1 or more and 5 or less). Method.   An acid contact step in which the wet film is brought into contact with an acid solution that is a proton donor while being transported, and a washing step in which the wet film is washed with a washing solution after the acid contact step are provided before the fourth step. The method for producing a solid electrolyte film according to any one of claims 1 to 10.   12. The method for producing a solid electrolyte film according to claim 11, wherein the acid is a compound having a formula weight of 40 to 1000 when ionized when ionized.   The method for producing a solid electrolyte film according to any one of claims 1 to 12, wherein the solid electrolyte is a hydrocarbon polymer.   The method for producing a solid electrolyte film according to claim 13, wherein the hydrocarbon polymer is an aromatic polymer. 15. The method for producing a solid electrolyte film according to claim 14, wherein the aromatic polymer is a copolymer composed of structural units represented by general formulas (I) to (III) of Chemical Formula 1.

(However, X is a cation species excluding a hydrogen atom, Y is SO ₂ , Z is a structure shown in Chemical Formula (I) or (II), and n and m are 0.1 ≦ n / (m + n) ≦ 0.5 is satisfied.)

A cast film forming apparatus for casting a dope in which a solid electrolyte is dissolved in an organic solvent on a support that runs, and forming a cast film on the support;
A solvent contact device for bringing the casting membrane into contact with a poor contact solvent that is a poor solvent for the solid electrolyte, and expressing the casting membrane with a self-supporting property;
A stripping device for stripping the cast film as a wet film;
A liquid contact device for contacting the wet film and a liquid compatible with the organic solvent;
A drying device for drying the wet film to form a solid electrolyte film;
A facility for producing a solid electrolyte film, comprising:   An acid contact device in which an acid solution as a proton donor is accommodated and guide means for guiding the wet film in the acid solution is provided between the liquid contact device and the drying device. 17. The manufacturing facility for a solid electrolyte film according to claim 16,   A solid electrolyte film for a fuel cell, which is produced by the method for producing a solid electrolyte film according to any one of claims 1 to 15. A solid electrolyte film according to claim 18;
An anode electrode that is provided in close contact with one surface of the solid electrolyte film and generates protons from a hydrogen-containing substance supplied from the outside;
A cathode electrode that is provided in close contact with the other surface of the solid electrolyte film and synthesizes water from the proton that has passed through the solid electrolyte film and a gas supplied from the outside;
An electrode membrane composite comprising: The electrode membrane composite according to claim 19,
A current collector that is provided in contact with the electrode of the electrode membrane composite, and transfers electrons between the anode electrode and the cathode electrode and the outside;
A fuel cell comprising:

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