JP2003526184A - Method for producing electrode-membrane assembly, method for producing electrode-membrane-electrode assembly, assembly obtained in the manner described above, and fuel cell device provided with these assemblies - Google Patents

Abstract

  (57) [Summary] The present invention is a method of manufacturing an assembly comprising at least one electrode having an active surface and a thermostable polymer film, the method comprising: a) casting a thermostable polymer solution onto a substrate; Forming a stable polymer solution film; b) partially drying the heat stable polymer solution film by evaporating the solvent; c) the surface of the heat stable polymer solution film which is not completely dried but is drying. On top, the electrodes are placed with the active side facing the surface, thereby forming an assembly consisting of the thermostable polymer membrane and the electrodes; d) drying the assembly obtained in step c) above, completely E) removing the membrane and electrode assembly from the substrate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a method for manufacturing an electrode-membrane assembly, a method for manufacturing an electrode-membrane-electrode assembly, and the assembly thus obtained.

More particularly, these assemblies are electrode-membrane-electrode assemblies, where the membrane is a polymer membrane that is an ion exchanger. Such an assembly
More particularly, it is used in fuel cells, especially low temperature fuel cells, which generally operate at ambient temperature and up to 100 ° C. The low temperature fuel cell is, for example, PEMFC (Proton Exchanger Membrane Fuel Cell).
Known as, a proton exchange membrane fuel cell which operates using a gas pair (H ₂ / oxygen in air), or a DMFC (Direct Methanol Fuel).
Cell), such as a fuel cell operating using a methanol / oxygen couple in air.

Accordingly, the present invention also relates to a fuel cell device, and more particularly to a solid electrode type fuel cell device comprising at least one electrode-membrane-electrode assembly as described above.

Therefore, the technical field to which the present invention belongs can be defined as a technical field called a fuel cell. More specifically, it can be defined as a technical field of a solid electrode type fuel cell.

[0005]

[Prior Art and Problems to be Solved by the Invention]

Solid polymer electrolyte type fuel cells are used in particular in electric vehicles. Electric vehicles have been the subject of various current development challenges by being able to provide solutions to pollution caused by vehicles using heat engines.

Solid polymer electrolyte type fuel cells are a problem associated with the use of batteries in electric vehicles by functioning as an electrochemical energy converter coupled to an onboard energy tank such as hydrogen or alcohol. Points, especially problems such as charging time and autonomy, can be overcome.

A schematic configuration of a fuel cell capable of generating electric energy is shown in FIG.

An essential element of such a fuel cell is an ion exchange type membrane. More particularly, it is a proton exchange membrane formed by a solid polymer electrode, more particularly a proton conducting polymer (1). This film is 2H ₂ → 4
In accordance with H ⁺ + 4e ^{−, the} anode chamber (2) where the oxidation of the fuel such as H ₂ (4) occurs and the oxidant such as oxygen O ₂ (5) in the air becomes O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ It is used to separate the cathode chamber (3), which is reduced according to O 2 to produce water (6). Here, the anode and the cathode are connected by an external circuit (10). The water produced here flows into the two compartments by electroosmosis and diffusion (arrows 11, 12).

The volume electrode (13), which is electrically conductive and arranged on both sides of the membrane, generally has an active zone (14) and a diffusion zone (15). The active zone, which is generally located on one electrode surface, consists of porous felt coated with Teflon®, to which carbon black or porous graphite (16) is added. ing. Carbon black or porous graphite is a thin film made of fine particles (for example, granular shape) of a noble metal (16) such as platinum, and an ion-conducting polymer having a structure generally similar to that of a film. And covered by the body. The diffusion zone (15) is a zone of porous material, eg porous felt coated with Teflon®, to which carbon black or the same porous graphite has been added, eg PTFE. It is made hydrophobic by containing such a hydrophobic polymer. By being hydrophobic, liquid water can be excluded. A noble metal, such as platinum, located in the active zone can oxidize hydrogen or methanol at the anode and reduce oxygen at the cathode.

Protons formed by the oxidation of things such as hydrogen at the surface of the particles of noble metal such as platinum at the anode are transported through the membrane to the cathode (arrow 9). At the cathode, the protons recombine with the ions formed by the reduction of, for example, oxygen from air, producing water (6).

The electrons (17) thus formed can be used to supply power to something such as an electric motor (18) connected in an external circuit (10). . In this case, water is only a by-product of the reaction.

The membrane-electrode assembly is a very thin assembly having a thickness of about 1 mm, and is composed of an electrode-membrane-electrode (EME).
) Called assembly. Gas is supplied from the back surface to each electrode by using, for example, a grooved plate.

The power density obtained by this recombination is usually around 0.5 to ² W / cm ² when hydrogen and oxygen are used. Therefore, it is necessary to combine a plurality of such volume electrode-membrane-volume electrode assemblies in order to obtain electric power of, for example, 50 kW required in a standard electric vehicle.

In other words, in order to obtain the desired power, in particular when the fuel cell is used in an electric vehicle, the surface area of the component is approximately 20 × 20 c.
It is important to combine a large number of such structures so as to obtain m ² .

For this purpose, each assembly formed of two electrodes and one membrane and forming a unit cell of a fuel cell therefore has two waterproof plates (7,
It is arranged between 8). The waterproof plate on the anode side supplies hydrogen, and the waterproof plate on the cathode side supplies oxygen. These plates are referred to as bipolar plates.

The ion-conducting membrane is usually an organic membrane containing ionic groups, which allows the conduction of protons (9) formed by the oxidation of hydrogen at the anode in the presence of water.

The thickness of this film is in the range of tens to hundreds of μm and is determined as a compromise between mechanical strength and voltage drop due to electrical resistance. This membrane has also been used to separate gases. The chemical and electrochemical resistance of this membrane generally allows cell operation for over 1,000 hours.

Therefore, the polymer constituting the film must satisfy some conditions regarding its mechanical properties, physicochemical properties and electrical properties.

First of all, the polymer must be capable of forming a dense, defect-free thin film with a thickness of 50-100 μm. Mechanical properties, modulus of shear, and ductility can impart to a polymer suitability for assembly operations, including assembly operations such as being clamped between two metal frames. Must.

The properties of the polymer must be maintained even when going from a dry state to a wet state.

The polymer must have good chemical stability to hydrolysis and must also show good resistance to oxidation and reduction up to 100 ° C. This stability is measured in terms of changes in ionic resistance and in terms of changes in mechanical properties.

Finally, the polymer must have a very good ionic conductivity. Such conductivity is provided by strongly acidic groups, such as phosphate groups, and especially by sulfonic acid groups attached to the polymer chain.
For this reason, polymers are generally defined by equivalent weight. That is, it is defined by the polymer weight in grams per acid equivalent.

By way of example, the best system developed to date can deliver a specific power of 1 W / cm ² . That is, a current density of 4 A / cm ² can be supplied for 0.5 V.

The most effectively used polymers at present are sulfonated fluorinated thermoplastics in which the linear backbone is perfluorinated and the side chains carry sulfonic acid groups. It is a polymer.

Such thermoplastic polymers are commercially available from Du-pont under the trade name NAFION® or for the production of a membrane named “XUS”.
It is marketed by DOW under the brand name ACIPLEX-S (registered trademark).

The electrochemical reaction described by the above-mentioned operation is carried out by protons, electrons, a catalyst arranged on the electrode surface, a reducing agent such as hydrogen or an oxidizing agent such as oxygen in the air. , Known to be done by. In this case, these reactions occur in principle at the edge or at the interface between the membrane and the electrode.

Therefore, it is clear that the performance of the electrode-membrane assembly, and thus of the fuel cell, is closely related to the quality of the electrode-membrane interface. The possibility of simultaneous presence of the various types of species in this zone depends mainly on the interface. The method of manufacturing a fuel cell or the method of manufacturing an electrode-membrane-electrode assembly has a decisive influence on the quality of the electrode-membrane interface.

The manufacture of Electrode-Membrane-Electrode (EME) assemblies has never been described in the literature or is rarely described. In fact, such a manufacturing method is often an individual technology (know-how matter) in each research institute or company that belongs to the field of fuel cell manufacturing.

In the EME manufacturing process most often referred to, an EME assembly is formed by pressing multiple hot electrodes against a proton exchange membrane. In this case, the membranes were individually prepared, usually by casting and then thoroughly dried.

This technique is commonly used in the case of proton exchange membranes. Proton exchange membranes are the most commonly used at the moment, as mentioned above, and are typically NAFION® type polymer membranes.

In order to manufacture an EME assembly, first the electrodes, for example NAFION (
The solution is impregnated and then hot pressed on both sides of the membrane at 120-150 ° C. Due to the thermoplastic properties of NAFION® and to the mechanical properties that it shows excellent adhesion by dipping the electrode with the same polymer that makes up the membrane, and from the viewpoint of the proton-electrode exchange surface. From both of these, excellent quality electrode-membrane interfaces can be obtained.

The electrochemical performance of the fuel cell with such an assembly is therefore satisfactory.

However, this EME assembly manufacturing process has some major drawbacks. First, it is difficult to industrialize the process, and
NAFION® type polymers are very expensive. on the other hand,
For the purpose of developing fuel cells that can be used in electric vehicles, another essential issue recognized by those skilled in the art is the cost of the membrane. The membrane and bipolar plate assembly is the dominant factor affecting fuel cell cost.

As of 1995, the cost of the manufactured membrane or the membrane under development is 1 m ²
The level is about 3,000 to 3,500 French francs, and it is necessary to reduce this cost from 1/10 to even 1/20 in order to use it for industrial development of fuel cells for the automobile industry. Guessed.

From the viewpoint of reducing the cost, poly-1,4- (diphenyl-2,6) -phenyl ether, polyether-sulfone, and polyether-ketone whose main chain is sulfonated are synthesized and used as they are. Were tested for their performance and durability without actually holding themselves against the fluorinated membrane.

Membranes that satisfy the relative conditions of mechanical properties, electrochemical properties, and electrical properties, while maintaining a manufacturing cost much lower than the forbidden cost of the fluorinated film described above. A new sulfonated polyimide polymer was developed to provide This polymer is described in French Patent Application Publication No. 2 748.
No. 485.

On the other hand, the process described above cannot be applied to other types of membranes. That is, it cannot be applied to a film formed of a polymer other than a thermoplastic polymer such as NAFION (registered trademark).

In particular, the processes used in the NAFION® membrane examples include sulfonated polymers with a thermally stable backbone, polyimides, polyether-sulfones, polyetheretherketones, polybenzoxazoles, polybenzimidazoles, It is completely unsuitable for membranes made of polymers such as polyphenylene and their derivatives.

In fact, such membranes have neither thermoplastic properties nor the NAFION® chemical structure. Therefore, it is unattractive for electrodes impregnated with NAFION® solution and the quality of the electrode-membrane interface is mediocre.

In other words, when a thermostable polymer membrane is used, the process involves the addition of some compounds such as a thermostable sulfonated polymer or a proton exchange membrane or NAFION® solution for electrode impregnation. Use is required.

Further, the process becomes an intermittent and complicated process, and is provided with a plurality of stages such as production of a proton exchange membrane, impregnation of electrodes, pressing, and heating.

As a result, the performance and even the advantage of such an assembly using a heat stable polymer membrane and an electrode impregnated with a NAFION® type polymer is extremely limited from an industrial point of view. Will be done.

If all the advantages of the heat-stable sulfonated polymer membranes are maintained, in particular in terms of cost, and especially by improving the quality of the electrode-membrane interface. As long as the drawbacks are overcome, as in the case of NAFION (registered trademark) type polymer membranes, sulfonated polymers having a heat-stable skeleton, such as polyimide, polyether-sulfone, polyetheretherketone, and polyether In the case of polymers such as benzoxazole, polybenzimidazole, polyphenylene and their derivatives, it is envisaged to impregnate the electrode with a solution of the film-forming polymer.

However, due to the mechanical hardness of the polymers of this family, large mechanical strains occur at the interface during solvent evaporation and drying.

In other words, the lack of thermoplasticity in these polymers makes it impossible to establish a satisfactory contact between the membrane and the impregnated electrode. In this case, the electrochemical performance is not so great and the reproducibility between one action and the next is not good. The quality of the interface is not sufficient to bring the proton conductor into intimate contact with the electron conductor or catalyst on the electrode surface. This type of assembly is prone to degradation over time, which quickly degrades over time. Despite the pressing at high temperature, the adhesion between the electrode and the membrane remains small.

Finally, the large number of stages described above, which form part of the manufacture of such assemblies, is an obstacle to large scale manufacture.

US Pat. No. 5,242,764 discloses an assembly process that eliminates the use of proton exchange membranes. In this technique, a large amount of NAFION® solution is used to impregnate the electrodes and then the impregnated electrodes are deposited at high temperature. This technique is also suitable only for NAFION® type thermoplastic polymers, and it is difficult to obtain a uniform gas-impermeable, proton-conducting polymer film.

Therefore, it is simple and reliable for the formation of an assembly comprising electrodes and a membrane formed of a thermostable polymer, such as a unit assembly or an electrode-membrane-electrode assembly. It is reliable, reproducible and safe, has a limited number of stages, is inexpensive to manufacture, is industrializable, and has the inherent advantages of thermostable polymer membranes. There is a need for a manufacturing method that has everything.

Furthermore, in this manufacturing process, an electrode-membrane interface with no defects and excellent quality should be obtained, a very strong bonding force of the electrode-membrane should be obtained, and a catalyst should be obtained. There should be very close contact between the membrane and the membrane and such properties should be stable over time and not subject to degradation over time.

Finally, the resulting electrode-membrane-electrode assembly must have excellent and completely reproducible electrochemical properties.

[0051]

[Means for Solving the Problems]

It is an object of the present invention to provide a manufacturing process for an assembly comprising an electrode and at least one heat stable polymer membrane, more particularly an electrode-membrane-electrode assembly which at least fulfills the above requirements. To provide the process.

It is also an object of the present invention to provide a manufacturing process for an assembly comprising an electrode and a thermostable polymer membrane, more particularly the disadvantages, deficiencies, limitations and deficiencies of prior art methods. It is an object of the present invention to provide a manufacturing process of an electrode-membrane-electrode (EME) assembly including a heat-stable polymer membrane and two electrodes, which does not have and can overcome the problems of the prior art.

According to the invention, the above and other objects, a method of manufacturing an assembly comprising at least one electrode (preferably one electrode) having an active surface and a heat stable polymer membrane. A) forming a heat stable polymer solution film by a) casting the heat stable polymer solution on a substrate; and b) heat by evaporating the solvent in the polymer solution in the heat stable polymer solution film. Partly drying the stable polymer solution film; c) disposing an electrode on the surface of a heat-stable polymer solution film which is not completely dry and is in the process of drying, with the active side facing the surface, To form an assembly consisting of a thermostable polymer membrane and an electrode; d) completely drying the assembly obtained in step c) above; e) the membrane and the electrode. The assembly consisting of removing from said substrate; obtained by the method called.

The process (method) according to the present invention can satisfy the above requirements, and
The above drawbacks can be overcome.

The process according to the invention is particularly suitable for heat-stable polymer membranes, where the inherent advantages of this type of polymer also result for processes using this polymer.

The process according to the invention has only a limited number of steps, which is as simple and easy as it can be performed using the test equipment. The process according to the invention is reliable and reproducible, can be carried out at low temperatures and consumes little energy. The process according to the invention is completed in a relatively short time, uses low amounts of raw materials and uses only limited amounts of polymers, solvents and electrodes.

Unlike the processes according to the prior art, the process according to the invention can be industrialized at low cost.

Basically, in the present invention, the electrode-membrane assembly is formed when the membrane is formed by casting.

In the present invention, in step c) the electrodes are simply placed directly on the surface of the membrane without any other manipulation (eg pressing in the prior art etc.). The membrane is then in the process of drying, i.e. it consists of a heat-stable polymer film which has not yet been dried.

Conventionally, a film of a polymer solution of a heat-stable polymer is formed by casting the polymer solution on a substrate or support, and the polymer solution film is then dried by completely evaporating the solvent, whereby By obtaining a dry extract in the form of a membrane, eg a proton exchange membrane,
Forming a film is known.

In the manufacturing process of electrode-membrane assembly or EME assembly according to the prior art, such as high temperature pressing process, the purpose is to assemble the electrode and the membrane to form a connection between the electrode and the membrane. The assembly operations carried out in all cases are carried out using the finished and completely dried membrane. Therefore, what is used in the prior art process is a totally fully formed and dry film.

In the present invention, contrary to the logic used in the prior art, a film that is in the process of being formed is used at the time of manufacture, that is, it is not yet completely formed and is still wet and completely Use a non-dried membrane for. In the main step c) of the process according to the invention, the electrodes are carefully placed on the surface of the film during the drying process, when the viscosity of the polymer solution film has reached its optimum value.

Thereafter, a well-defined portion of the polymer solution penetrates the electrodes. More specifically, in the active layer located on the active surface facing the surface of the polymer solution film,
Soak. This impregnation simply occurs due to the action of the weight of the electrode into the polymer without the need to apply pressure due to the polymer's still viscous nature.

The process according to the invention, more particularly according to step c), makes the electrode-membrane interface of excellent quality. The fact that interfaces of this quality are obtained using heat-stable polymer membranes, considering that to date only processes using the NAFION® type heat-stable polymers have been obtained in the process according to the invention. ,
That's amazing. It has been demonstrated that the electrode-membrane interface formed using the process according to the invention is perfectly regular and defect free.

The bonding force between the electrode and the membrane is so strong that the electrode and the membrane cannot be separated. This is an assembly formed using a prior art process
Be different. In particular, this strong bonding force is one of the basic effects and advantages brought about by the process according to the invention when compared with the conventional process based on the principle of hot pressing of the electrode and the membrane.

In the process according to the invention, the assembly operation according to step c) is carried out when the membrane is not completely dried and not completely formed, so that the substance that penetrates into the electrode is a thermostable polymer. It can be explained in more detail that it is meant to be composed of a proton-conducting polymer and a small amount of solvent. Thereby, the proton conductor can be uniformly contained in the active layer itself of the electrode. The assembly thus obtained is then dried under moderate temperature conditions, generally between 70 ° C and 150 ° C, preferably between 100 ° C and 120 ° C.
Examples of suitable temperatures are in particular around 70 ° C. This is preferred because the proton conducting polymer is placed in close proximity to the electron conductor and catalyst contained within the electrode.

In other words, the quality of the interface obtained according to the invention results in an intimate contact between the membrane and the electrode, ie the proton conductor is placed in close proximity to the electron conductor and the catalyst on the electrode surface. As a result, the assemblies produced using the process according to the invention have very good and perfectly reproducible electrochemical properties and performance. That is, in particular, it has an evolution of voltage based on current density that is at least similar to the properties of the "all-NAFION®" assembly.

To further improve the mechanical properties of the assembly according to the invention, the reinforcement can be arranged in the heat-stable polymer solution film, for example by laminating, after the completion of step a) above.

Alternatively, for the same purpose, prior to step a) above, a reinforcement can be arranged on the substrate or support.

The present invention more particularly relates to a method of making an electrode-membrane-electrode assembly comprising a thermostable polymer membrane and two electrodes.

In this process, first a first electrode-membrane assembly is formed by the process described above. Then, after completion of step e) above, f) the heat stable polymer solution is cast onto the surface of the membrane of the first assembly to form a heat stable polymer solution film, after which steps b) to e above are performed. )repeat.

In other words, the electrode-membrane assembly obtained after completion of step c) is
It is used as a substrate during the casting operation, the second electrode is placed when the second film is partially dried, and then completely dried.

Therefore, at each step in the process, step a) above
After f), g) partially dry the heat stable polymer solution film by evaporating the solvent in the polymer solution in the heat stable polymer solution film; h) not completely dry and in the process of drying. A second electrode is disposed on the surface of the heat-stable polymer solution film of which the active surface faces the surface, thereby forming an electrode-heat-stable polymer membrane-electrode assembly; i) step h) above. The electrode-membrane-electrode assembly obtained in 1. is thoroughly dried.

The advantages and effects afforded by this process are similar to those described above, in particular the assembly has excellent mechanical properties and excellence compared to the properties of the assembly obtained using prior art processes. It has excellent electrochemical characteristics (evolution of voltage according to current density) and the like.

In one variation of the process according to the invention, referred to as the “impregnation” process as compared to the “coating” process described above, the electrode-membrane-electrode assembly is a) heat-stable polymer solution. Forming a self-supporting reinforced heat-stable polymer solution film by impregnating the reinforcement; b) evaporating the solvent in the polymer solution within the heat-stable polymer solution film to reinforce the self-supporting polymer solution film. And partially drying the heat-stable polymer solution film; c) on each surface of the heat-stable polymer solution film that is not completely dry and is in the process of drying, with each active surface facing the corresponding surface. By placing a plurality of electrodes in a state; d) completely drying the assembly obtained in step c) above.

In a particularly advantageous feature of the process according to the invention, whether it is a coating process or an impregnation process, the process can be carried out continuously. This differs from prior art processes.

The invention also relates to an assembly comprising at least one membrane and at least one electrode, as obtained by the above process, and
It relates to an electrode-membrane-electrode assembly as obtained by the above process. These assemblies have excellent and surprising quality interfaces and consequently also excellent mechanical properties (bond strength, etc.) and electrochemical properties (voltage evolution as a function of current density). By having the following, it has intrinsic properties that differ from and are superior to those of assemblies manufactured using prior art processes.

The present invention further relates to a fuel cell comprising at least one electrode-membrane-electrode assembly obtained by the process according to the invention. Similarly, fuel cells are excellent and of surprising quality based on the nature of the thermostable membrane and on the nature of the EME assembly. The characteristics of such a fuel cell are
It is directly due to the application of the process according to the invention.

[0079]

DETAILED DESCRIPTION OF THE INVENTION

  Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

More particularly, in the process according to the invention, in the “coating” version, first a solution of the heat-stable polymer in a solvent is prepared.

The heat stable polymer can be any known polymer. The process according to the invention applies to all polymers which can be used to form films by casting. The term heat stable is generally understood as being a polymer whose glass transition temperature (for amorphous polymers) or melting temperature (for semicrystalline polymers) is greater than the degradation temperature of the polymer. .

Preferably the polymer is an ion exchange polymer and preferably a proton conducting polymer such as eg a sulfonated polymer. However, polymers with phosphate groups or other functional groups are also suitable. Among the suitable polymers, by way of example, sulfonated polyimides, sulfonated polyether sulfones, sulfonated polystyrenes and sulfonated derivatives thereof, sulfonated polyether ether ketones and Mention may be made of the sulfonated derivatives thereof, sulfonated polybenzoxazoles, sulfonated polybenzimidazoles, sulfonated polyparaphenylenes and sulfonated derivatives thereof.

A particularly preferred polymer is a sulphonated polyimide as described in FR-A-2 748 485. The description of this document, in particular the parts in which this polymer is described, are incorporated herein by reference.

Other sulfonated polyimide type polymers have the following compositional formula (I _x ,
I _y ) is a sequenced sulfonated polyimide formed by a block or sequence represented by I _y ).

[Chemical 1] Here, -x is a real number, preferably a real number of 4 or more, and more preferably 4 to 15
Is a real number. -Y is a real number, preferably a real number of 5 or more, more preferably 5 to 10
Is a real number. The C ₁ group and the C ₂ group may be the same or different and each has at least one aromatic carbocycle having 6 to 10 carbon atoms or a tetravalent group having a substitution product thereof. Groups and / or having 5 to 10 atoms, S, N and O
Represents a tetravalent group having an aromatic heterocyclic compound containing one or more heteroatoms selected from the above or having a substitution product thereof; C ₁ and C ₂ are respectively adjacent imides Together with the group, it forms a ring of 5 or 6 atoms. -Ar ₁ group and Ar ₂ group, which may be the same or different, each has at least one aromatic carbocycle having 6 to 10 carbon atoms or is a divalent group having a substitution product thereof. Groups and / or substituted or substituted aromatic heterocyclic compounds having 5 to 10 atoms and containing one or more heteroatoms selected from S, N and O Represents a divalent group having a structure; at least one of the above aromatic carbocycles and / or Ar ₂ heterocycles is further substituted by at least one sulfonic acid group.

Such sulfonated polyimides can be represented by general formula (I).

[Chemical 2] Here, C ₁ , C ₂ , Ar ₁ , Ar ₂ , x and y have the meanings already given above, z is a number, preferably 1-10, more preferably 2 It is 6. Each of the R ₁ group and the R ₂ group represents an NH ₂ group or a group having the following composition formula.

[Chemical 3] Here, C ₃ is a divalent group having at least one aromatic carbocycle having 6 to 10 carbon atoms or having a substitution product thereof, and / or 5 to 10 atoms. And represents a divalent group having an aromatic heterocyclic compound containing one or more heteroatoms selected from S, N, and O, or having a substituent thereof, C ₃ Forms a ring of 5 or 6 atoms with adjacent imide groups.

[0086]   Most of these polymers are inexpensive and can be easily purchased.

The heat stable polymer must also be soluble in the solvent in solution.
The person skilled in the art can easily select this solvent as being suitable for the polymer used.

Solvents are generally of the aromatic solvent or glycol ether type, such as, for example, dimethylformamide (DMF), dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), or with them, such as xylene. An organic solvent selected from aprotic polar solvents, such as a mixture with a solvent.

The solvent can also be a phenol type solvent. So, for example,
Phenols, phenols substituted with one or more halogens (Cl, I, Br, F), cresols (ortho-, meta- and para-cresols) and halogens (Cl, I, Br). , F) substituted cresols and these compounds.

The concentration, viscosity and temperature of the polymer solution can be adjusted so that a uniform film can be obtained by using the coating system.
For example, the cast system is preferably selected from among hand coater systems.

The concentration, viscosity and temperature of the polymer solution depend on the properties of the polymer solution. However, suitable ranges are, for example, 30-100 g / l for the concentration and 1-10 Pa. s, and 80-130 ° C. for the temperature of the polymer solution used for casting (for sulfonated polyimide type polymers).

The polymer solution is cast on a substrate or support. The substrate or support can be flexible or rigid.

Glass, aluminum, polyester, etc. may be mentioned as examples of suitable materials for the substrate or support. The shape of this base or support is
Generally, the shape is the same as the shape of the membrane to be produced or the final assembly. This substrate is generally flat.

Furthermore, it is preferred that the substrate or support is completely clean with respect to the casting operation.

After casting, an entirely flat film is obtained from the heat-stable polymer solution on the surface of the substrate or support. This is a wet "film". That is, it is solvent rich and contains substantially all of the solvent that was present in the polymer solution used for casting. Wet film thickness varies. However, wet film thicknesses generally range from 500 to
It is calibrated to a thickness of 5,000 μm, for example to a thickness of 3,000 μm.

Thereafter, partial drying of the polymer solution film is carried out by evaporating the solvent in the polymer solution. For this purpose, the substrate or support is generally maintained at a temperature between 40 ° C and 150 ° C, for example at a temperature of 120 ° C. This results in rapid evaporation of the solvent. Such temperatures can be achieved by placing a substrate or support coated with a polymer solution film in an oven,
Obtainable.

The drying operation is partial drying. That is, the polymer solution film still contains the solvent. Generally, it contains some of the solvent. The solvent still present is 5-20% of the amount of solvent initially present.

In other words, the drying process is stopped when the viscosity of the polymer film reaches a large level such that it is sufficient to support the electrode, which is generally between 60 minutes and 120 minutes. It varies like minutes. This viscosity can be easily set by those skilled in the art, and is generally 20 to 30 Pa.s. s.

Therefore, the electrode is placed on the surface of the heat-stable polymer solution film that is not completely dry and is about to dry. In this case, the electrodes are arranged so that the active surface of the electrodes faces the film surface.

The electrodes are readily available as classical electrodes, of the type commonly used in fuel cells as described above. Such electrodes are usually flat, have a thickness of 100 to 500 μm and usually have a surface called the active surface. A catalyst such as platinum carbon is added to the active surface. This active surface must be carefully placed on the surface of the wet heat stable polymer solution film.

The polymer solution slowly penetrates into the active layer, such as a platinum carbon layer. In this way, an assembly of membrane (still wet) and electrodes is formed.

In the following steps, the resulting electrode-membrane assembly was dried at 40 ° C.
It is carried out at a temperature of 150 ° C., for example 120 ° C., for 30 to 60 minutes. This removes any residual solvent that still remains and can form the final assembly. In fact, it is at this step that the "membrane" is effectively formed.

Finally, in a final step, the electrode-membrane assembly is removed from the substrate or support.

[0104]   The thickness of such an assembly is 100-500 μm.

In forming a finished electrode-membrane-electrode assembly using the coating process according to the present invention, first of all, a first assembly is prepared as described above. The electrode-membrane assembly thus obtained is then used as a substrate for a second electrode-membrane assembly forming a further basic unit assembly. That is, another wet film of heat stable polymer solution is cast on the membrane of the first basic unit assembly. Generally, the same solution containing the same polymer used to form the first assembly is used. Then, during the wet film drying process, a second electrode, generally similar to the first electrode, is carefully placed in the same manner as described above. Again, the active side of the electrode is placed on the surface of the wet film.

The drying process is then completed in the same manner as described above for forming the first basic unit assembly.

At the end of the drying process, the finished electrode-membrane-electrode assembly is obtained. Note that in this process, among other things, the gas impermeability of the proton exchange membrane can be improved.

Advantageously, according to the invention, it is possible to form an assembly in which the membrane is reinforced by reinforcements, in particular with improved mechanical properties.

In the coating process, the heat-stable polymer solution can be applied and spread on the substrate or support as described above after the reinforcement has been previously placed on the substrate or support.

Such a reinforcement can be made of, for example, glass, a material such as PEEK or PTFE, a post made of glass, or a porous material made of PEEK or PTFE, for example.

All other steps in the solution preparation and process and process conditions are similar to those described above for the coating process. The only difference is step a
), Only placing the reinforcement on the substrate or support.

That is, a polymer to be used, such as a sulfonated polyimide, is dissolved in a solvent having various properties such as phenol, chlorophenol, cresol, NMP, DMF, and DMAC to obtain a solution. To do. The concentration, viscosity and temperature of the polymer solution can be adjusted so that a uniform film can be obtained by using a coating system such as a hand coater system.

Next, a polymer solution, such as a polymer solution containing a sulfonated polymer, is spread over a flexible or rigid substrate, such as formed from glass. The base body is completely clean, and the reinforcing body is arranged on the base body. The thickness of the wet film is 500 to 5,0
It is calibrated to a thickness of 00 μm, for example to a thickness of 3,000 μm. The substrate is maintained at a temperature of around 120 ° C., for example. Thereby, the solvent can be evaporated quickly.

After a certain period of time (60 minutes to 120 minutes), the viscosity of the polymer film reaches a level that is sufficient to support the electrodes. The electrode active surface, eg containing platinum carbon, is carefully placed onto the surface of the wet film. The polymer solution slowly penetrates into the active layer, such as a platinum carbon layer. By continuing the drying of the electrode-membrane assembly thus obtained for a further predetermined time, it is possible to remove any residual solvent still remaining.

The reinforced electrode-membrane assembly is then removed from the initial substrate and used as a substrate to perform the second step.

A further wet film is cast on the membrane of the first basic unit assembly. During this wet film drying process, the second electrode is
Place it carefully.

At the completion of these two steps, the finished electrode-membrane-electrode assembly is obtained.

Alternatively, for the same purpose of strengthening the membrane, in the coating process the reinforcement can be placed in a wet polymer solution film made by casting in step a). Such a reinforcement is similar to that described above.

All other steps in the solution preparation and process and process conditions are similar to those described above for the coating process. The only difference is the reinforcement
It is only placed inside the wet film itself after step a).
That is, the polymer to be used, such as sulfonated polyimide, can be used, for example, phenol, chlorophenol, cresol, NMP, DMF, D
A solution is prepared by dissolving it in a solvent having various properties such as MAC. By adjusting the concentration, viscosity and temperature of the polymer solution, a uniform film can be obtained by using a coating system such as a hand coater system.

Next, a polymer solution, such as a polymer solution containing a sulfonated polymer, is spread over a flexible or rigid substrate, such as formed from glass. The substrate is completely clean, on which the support is arranged. The thickness of the wet film is 500 to 5,000.
It is calibrated to a thickness of 0 μm, for example to a thickness of 3,000 μm.

The reinforcement is then placed on the substrate by using any suitable technique such as laminating in a wet film. The substrate is maintained at a temperature of around 120 ° C., for example. Thereby, the solvent can be evaporated quickly. After a certain time, the viscosity of the polymer film reaches a large level that is sufficient to support the electrode. The electrode active surface, eg containing platinum carbon, is carefully placed onto the surface of the wet film. The polymer solution penetrates completely into the active layer, for example a platinum carbon layer. By continuing the drying of the electrode-membrane assembly thus obtained for a further predetermined time, it is possible to remove any residual solvent still remaining.

The reinforced electrode-membrane-electrode assembly is then removed from the initial substrate and used to form the finished reinforced electrode-membrane-electrode assembly by the method described above.

The process according to the invention for forming the finished reinforced electrode-membrane-electrode assembly can, in a variant, be carried out by "impregnation".

A polymer solution is prepared in the same manner as described above by using the same polymer and solvent as described above for the coating process.

In this case, the concentration, viscosity and temperature of the polymer solution are adjusted so that the reinforcing body can be impregnated. The reinforcement is of the type described above, for example glass or PE.
It is, for example, a woven fabric, a post, or a porous material made of a material such as EK or PTFE. For this reason, the concentration, viscosity and temperature of the polymer solution may differ from those described above for the coating process.

The concentration, viscosity and temperature of the polymer solution used for impregnation depend on the nature of the polymer solution and in some cases on the nature of the reinforcement. However, suitable ranges are, for example, 80-120 g / l for the concentration and 5-15 for the viscosity.
Pa. s, with respect to the temperature of the polymer solution for impregnating the reinforcement 70-
120 ° C. (for sulfonated polyimide type polymers).

Impregnation is generally done by simply dipping the reinforcement in the polymer solution.

After impregnation, a reinforced, self-supporting, heat-stable polymer solution film is obtained.
This is a wet "film". That is, it is solvent rich and contains substantially all of the solvent that was present in the polymer solution used to impregnate the reinforcement. Wet film thickness varies. However, the thickness of the wet film is typically in the range of 1,000 to 2,000 μm, for example 1,
Calibrated to a thickness of 500 μm.

Partial drying of the reinforced, self-supporting, heat-stable polymer solution film is then carried out by evaporating the solvent in the polymer solution.

For this purpose, reinforced, self-supporting wet films generally have a temperature of 70 ° C.
A temperature of ~ 150 ° C is maintained, for example a temperature of 120 ° C. This results in rapid evaporation of the solvent. Such temperatures can be obtained by placing the reinforced self-supporting wet film in a furnace.

The drying operation is partial drying. That is, the reinforced free-standing polymer solution film still contains solvent. Generally, it contains some of the solvent. The solvent still present is 5-15% of the initially present amount of solvent.

In other words, the drying process is stopped when the viscosity of the reinforced, self-supporting polymer film reaches a level that is sufficient to support the electrodes on both sides, which is Generally, it fluctuates such as 60 minutes to 120 minutes. This viscosity may be different from the viscosity at the same step in the coating process and can be easily set by a person skilled in the art, generally 15-20 Pa.s. s.

Accordingly, the plurality of electrodes are disposed on the surface of a reinforced, self-supporting wet heat stable polymer solution film that is not completely dry and is about to dry. In this case, the active surfaces of the electrodes are arranged so as to face the corresponding surfaces.

[0134]   This operation is performed by a "co-laminate" device.

The electrodes are classical electrodes, of the type commonly used in fuel cells, as mentioned above. Such electrodes usually have a surface called the active surface. A catalyst such as platinum carbon is added to the active surface. The active surface of each electrode must be carefully placed onto each surface of a reinforced, self-supporting wet heat stable polymer solution film.

The polymer solution slowly penetrates into the active layer of the electrode, eg the platinum carbon layer. In this way, the electrode- (still wet) film-
The electrode assembly is formed directly.

In the following steps, the resulting electrode-membrane assembly was dried at 70 ° C.
It is carried out at a temperature of 150 ° C., for example 120 ° C., for 30 to 60 minutes. This removes any residual solvent that still remains and can form the final EME assembly. In fact, it is at this step that the "membrane" is effectively formed.

In this process, the assembly of the finished product can be obtained in two simple steps.

The EME assembly obtained according to the invention can be used in particular in a fuel cell operating using a system such as: At the anode, hydrogen or an alcohol, for example methanol. -Oxygen or air at the cathode.

The invention also comprises a fuel cell with at least one EME assembly manufactured using the process according to the invention.

Such a fuel cell has all the properties associated with a thermostable membrane. For example, due to the excellent mechanical properties of the thermostable film, the thermostable film can withstand the assembly-related strains (clamps, etc.) without any damage.

The properties of sulfonated polyimide-type heat-stable membranes are described, for example, in FR-A-2 748 485 as described above.

The fuel cell can have a structure corresponding to that shown in FIG. 1, for example.

Thus, such a fuel cell comprising an EME assembly manufactured using the process according to the invention is associated with such an EME assembly because it comprises such an EME assembly. And has all the advantages associated with excellent interface quality. In particular, the assembly is robust, reliable, and has excellent mechanical and electrochemical properties ("
NAFION®, which is at least similar to the characteristics of the assembly,
Evolution of voltage based on current density) and gas impermeability. All these properties are completely reproducible and do not deteriorate over time.

These properties are significantly superior to those of fuel cells with assemblies manufactured using the prior art. For example, the fuel cell temperature is generally 50 ° C.
Maintained at -80 ° C, under which conditions a current density of, for example, 0.5 A / cm ² with a voltage value of 0.6 V is produced over a very long period of up to 3,000 hours. This shows excellent properties in terms of thermal stability and mechanical stability, and also shows excellent electrical properties.

The invention will now be described with reference to some experimental examples which are not limiting of the invention and are merely illustrative.

Experimental Example Experimental Example 1 Manufacture of Electrode-Membrane Assembly Using Process According to the Invention This experimental example relates to the manufacture of electrode-membrane assembly using sulfonated polyimide. . The molecular structure of the sulfonated polyimide is as follows.

[Chemical 4]

The values of x and y are generally 0 ≦ x and y ≦ 20. For example, in this experimental example, x = 8 and y = 10.

The sulfonated polyimide was dissolved in meta-cresol to obtain a polymer solution. The concentration, viscosity and temperature of the polymer solution were adjusted to obtain a uniform film by using a hand coater system. In this case: the concentration is 70 g / l, the viscosity is 4 Pa.s. s, the temperature was 120 ° C.

After that, the sulfonated polyimide solution was thoroughly cleaned to 3 m.
It was spread on an m-thick rectangular glass substrate. Wet film thickness is about 3,000
It was calibrated to a thickness of μm. The substrate was maintained at a temperature of about 120 ° C., which caused the solvent to evaporate rapidly.

After a certain time, the viscosity of the polymer film reached a large level that was sufficient to support the electrode. As the electrode, an electrode supplied as SORAPEC (registered trademark) was used.

The electrode active surface containing platinum carbon was carefully placed onto the surface of the wet film. The polymer solution slowly penetrated into the platinum carbon layer on the electrode surface. The electrode-membrane assembly thus obtained was further dried for a predetermined period of time to remove any residual solvent still remaining.

[0153]   The electrode-membrane assembly was then removed from the substrate.

Experimental Example 2 Manufacture of a Finished Electrode-Membrane-Electrode Assembly Using a Coating Process This experimental example shows an electrode-membrane-electrode using sulfonated polyimide in two separate steps. It concerns the manufacture of assemblies.

[Step 1] [Manufacture of Electrode-Membrane Assembly Forming Basic Unit] A first electrode-membrane assembly was manufactured in the same manner as in Experimental Example 1. The electrode-membrane assembly thus obtained was used as a substrate for carrying out the second step.

Step 2 Manufacture of the Second Electrode-Membrane Assembly As the Base Unit Additional wet films were cast on the membrane of the first base unit assembly above. During the drying process of this wet film, the second electrode was carefully placed in the same manner as in Experimental Example 1.

At the completion of these two steps, the finished electrode-membrane-electrode assembly was obtained. This method also improves the gas impermeability of the proton exchange membrane.

Experimental Example 3 Production of Finished Electrode-Reinforced Membrane-Electrode Assembly by Coating The sulfonated polyimide used was the same as above. The concentration, viscosity and temperature of the polymer solution were adjusted so that a uniform film was obtained by using the hand coater system as in the case of Experimental Example 1. The sulfonated polyimide solution was then spread on a perfectly clean glass substrate on which the PEEK material supplied as SEFAR® was mounted. The thickness of the wet film is
It was calibrated to a thickness of about 3,000 μm. The substrate was maintained at a temperature of about 120 ° C., which caused the solvent to evaporate rapidly. After a given time, the viscosity of the polymer film reached a large level that was sufficient to support the electrode.
That is, 15 Pa. I reached s. The electrode active surface containing platinum carbon was then carefully placed onto the surface of the wet film. The polymer solution slowly penetrated into the platinum carbon layer on the electrode surface. Drying of the electrode-membrane assembly thus obtained was continued for a further 60 minutes to remove any residual solvent still remaining.

The electrode-reinforced membrane assembly was then removed from the substrate and used as the substrate for the second step.

An additional wet film was cast on the membrane of the first base unit assembly above. During the drying process of this wet film, the second electrode was carefully placed in the same manner as in Experimental Example 1.

At the completion of these two steps, the finished electrode-membrane-electrode assembly was obtained.

Experimental Example 4 Production of Finished Electrode-Reinforced Membrane-Electrode Assembly by Coating This experimental example is an electrode-membrane reinforced by PEEK material supplied as SEFAR®. -Relating to the manufacture of electrode assemblies.

The sulfonated polyimide used was the same as above and was dissolved in a solvent that was metacresol to give a polymer solution.

The concentration, viscosity and temperature of the polymer solution were adjusted as in Experimental Example 1 so that a uniform film was obtained by using the hand coater system. The sulfonated polyimide solution was then spread on a completely clean glass substrate.
The wet film thickness was calibrated to a thickness of about 3,000 μm.

The reinforcement was then placed in the wet film on the substrate. By the action of the weight of the reinforcing body itself, the reinforcing body sinks inside the film, and finally,
Contacted the substrate. The substrate was maintained at a temperature of about 120 ° C., which caused the solvent to evaporate rapidly. After a certain time, the viscosity of the wet film reached a large level that was sufficient to support the electrodes. The electrode active surface containing platinum carbon was then carefully placed onto the surface of the wet film. The polymer solution slowly penetrated into the platinum carbon layer on the electrode surface. Drying of the electrode-membrane assembly thus obtained was continued for a further 60 minutes to remove any residual solvent still remaining.

Thereafter, the electrode-membrane assembly was removed from the substrate, and the same procedure as in Experimental Example 2 was carried out.
Used to form a reinforced electrode-membrane-electrode assembly.

Experimental Example 5 [Production of Reinforced Electrode-Membrane-Electrode Assembly by Impregnation] This Experimental Example relates to production of a reinforced electrode-membrane-electrode assembly. The sulfonated polyimide used was dissolved in a solvent of metacresol to give a polymer solution. The concentration, viscosity and temperature of the polymer solution were adjusted so that the impregnation could be carried out. In this case: the concentration is 80 g / l, the viscosity is 2 Pa.s. s, the temperature was 120 ° C.

The thickness of the reinforced self-supporting wet film was calibrated to a thickness of about 3,000 μm.

The reinforced self-supporting wet film was maintained at a temperature of about 120 ° C., which caused the solvent to evaporate quickly.

After a certain time, the viscosity of the reinforced self-supporting wet film has reached a level that is sufficient to support the electrode, ie 15 Pa.s. It reached to s. The electrode active surface containing platinum carbon was then carefully placed onto the surface of the reinforced self-supporting wet film. The polymer solution penetrated into the platinum carbon layer on the electrode surface. The electrode-membrane assembly thus obtained was further dried for a predetermined period of time to remove any residual solvent still remaining.

By using a sulfonated polyimide membrane whose structure is shown in Experimental Example 1, the assembly obtained in Experimental Example 1 shows that the electrode-membrane interface is very good as shown in FIG. It was proved that it was of a good quality. In fact, in this picture taken with a scanning electron microscope, the electrode-membrane interface is perfectly regular, defect-free and free of heterogeneity.

Looking at the photographs from bottom to top, several layers can be identified. That is, a layer corresponding to the core of the electrode (a Teflon (registered trademark) felt into which carbon black is introduced, layer (1)) and a platinum carbon layer (bright and bright layer, layer (2)) having a thickness of about 20 μm ) And a proton exchange membrane having a thickness of about 15 μm (layer (3)
) And can be distinguished.

The bond between the electrode and the membrane is so strong that the electrode and membrane can no longer be separated.
This is in contrast to assemblies made using existing processes.

This type of analysis, using a scanning electron microscope, for the purpose of characterizing the electrode-membrane interface indicates that the assembly obtained by the process according to the invention presses the shaped membrane and the electrodes. Allows identification from assemblies obtained by other processes.

Indeed, in all other press-based processes of the shaped (dried) membrane and the electrodes, as shown in FIG. 3, which bears the same reference numbers as in FIG.
Defects occur at the electrode-membrane interface.

In FIG. 3, which shows the electrode-membrane interface of the assembly obtained by pressing according to the state of the art, the vacuoles and other defects can be clearly recognized. These defects cause poor electrochemical performance of the assembly.

In fact, apart from the bonding problem, various heterogeneity is observed in the electrode-membrane interface of the assembly obtained by the conventional method, such as vacuoles and curved parts.

Furthermore, a map of elemental sulfur was obtained by using the casting probe on the assembly obtained according to the invention according to Experimental Example 1. In this map, elemental sulfur makes it possible to recognize the presence of proton conductors.
It is clearly seen that with the process according to the invention it is possible to introduce part of the proton conductor into the platinum-rich zone.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a fuel cell including a plurality of unit cells including an electrode-membrane-electrode assembly and a bipolar plate.

FIG. 2 is an image obtained by using a scanning electron microscope of an electrode-membrane interface obtained using a sulfonated polyimide membrane based on the process according to the invention, with the indicated length. It is 10 μm.

FIG. 3 is an image obtained by using a scanning electron microscope of an electrode-membrane interface obtained using a sulfonated polyimide membrane based on a process according to the prior art, with the indicated length. It is 10 μm.

[Explanation of symbols]

1 layer (electrode core) 2 Platinum carbon layer (active surface) 3 Proton exchange membrane (membrane)

─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Michel Panelli             France ・ F-38330 ・ Monbono ・ Suma             N de la Kourwa-Verte (Street             None) (72) Inventor Regis Mercia             France, F-69540, Illini Avni             Ju Joan-Gazan 17 F-term (reference) 5H026 AA06 BB00 BB01 BB03 BB04                       CX05 EE18

Claims (12)

[Claims] 1. A method of making an assembly comprising at least one electrode having an active surface and a thermostable polymer membrane, comprising: a) casting a thermostable polymer solution onto a substrate, the method comprising: Forming a heat stable polymer solution film; b) partially drying the heat stable polymer solution film by evaporating the solvent in the polymer solution within the heat stable polymer solution film; c) completely drying. An electrode is placed on the surface of the heat-stable polymer solution film which is not being dried and whose active surface faces the surface, thereby forming an assembly comprising the heat-stable polymer film and the electrode. D) completely drying the assembly obtained in step c) above; and e) removing the assembly consisting of the membrane and the electrode from the substrate. To; and wherein the. 2. A method according to claim 1, characterized in that a reinforcing body is arranged on the substrate prior to step a). 3. A method according to claim 1, characterized in that after completion of step a), a reinforcement is placed in the heat-stable polymer solution film. 4. The method of claim 3, wherein the reinforcement is placed by laminating within the heat stable polymer solution film. 5. The method of any of claims 1 to 4, wherein step e) is performed to form an electrode-membrane-electrode (EME) assembly comprising a thermostable polymer membrane and two electrodes. After completion of), f) forming a heat stable polymer solution film by casting the heat stable polymer solution on the surface of the membrane of the assembly; g) in the polymer solution within the heat stable polymer solution film. Partially drying the heat-stable polymer solution film by evaporating the solvent of: h) an active surface on the surface of the heat-stable polymer solution film which is not completely dry and is in the process of drying. The second electrode is arranged so that it faces the surface,
Forming an electrode-thermostable polymer membrane-electrode assembly; i) allowing the electrode-thermostable polymer membrane-electrode assembly obtained in step h) above to dry completely. 6. A method of manufacturing an electrode-membrane-electrode (EME) assembly comprising: a) impregnating a heat-stable polymer solution with a reinforcement to form a self-supporting reinforced heat-stable polymer solution film. B) partially drying the free-standing reinforced heat stable polymer solution film by evaporating the solvent in the polymer solution within the heat stable polymer solution film; c) completely dry. On both surfaces of the heat-stable polymer solution film which is still in the process of drying, a plurality of electrodes are arranged with the respective active surfaces facing the corresponding surfaces; d) obtained in step c) above Completely drying said assembly; 7. The method according to claim 1, wherein   A method characterized by performing as a continuous manufacturing process. 8. The method according to claim 1, wherein the heat stable polymer is an ion exchange polymer such as a proton conducting polymer. 9. The method of claim 8, wherein the polymer is sulfonated polyimide, sulfonated polyether sulfone, sulfonated polystyrene and its sulfonated derivatives, sulfonated. Among the polyether ether ketones and sulfonated derivatives thereof, sulfonated polybenzoxazoles, sulfonated polybenzimidazoles, sulfonated polyparaphenylenes and sulfonated derivatives thereof. A method characterized by selecting. 10. An assembly, comprising at least one electrode and a membrane, by the method according to any of claims 1 to 4 or the method according to any of claims 7 to 9. An assembly characterized in that it is obtained. 11. An electrode-membrane-electrode assembly, obtained by the method according to any one of claims 5 to 9. 12. A fuel cell, comprising at least one electrode-membrane-electrode assembly according to claim 11.