JP2005297531A - Manufacturing method of laminated body comprising particles and electrolyte body, laminated body comprising particles and electrolyte body, electrochemical element, fuel cell and mobile equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To simply produce a laminated body carrying functional particles and to produce it in large quantities in a short time. <P>SOLUTION: The laminated body 1 comprising particles 3 and an ionic conductive film 7 can be produced by charging a photo-semiconductor 10 being an electrostatic carrier carrying a static electricity in a given polarity, contacting the photo-semiconductor 10 already charged with a dispersion liquid 15 formed by dispersing the particles 3 charged with the inverse polarity to the polarity of which the photo-semiconductor 10 is charged in a dispersing medium and transferring the particles 3 adhering to the photo-semiconductor 10 to the ionic conductive film 7 being an electrolyte body. In this way, the laminated body 1 carrying the particles 3 can be simply produced further more in large quantities in a short time. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a laminate of particles and an electrolyte body, a laminate of particles and an electrolyte body, an electrochemical element, a fuel cell, and a portable device.

  Many electrochemical devices, particularly devices capable of generating or storing electrical energy, are composed of a layer capable of generating and storing electrons (charges) and a layer that propagates ions. Specifically, there are a primary battery, a secondary battery, a fuel cell, a solar cell, a capacitor, an electrolysis element, various sensors, and the like. In these configurations, an anode layer and a cathode layer capable of conducting electrons are disposed on both sides of an ion conductive layer (which may be a liquid or a solid). For these laminates, for example, laminates used for primary batteries and secondary batteries, a method of applying and drying a paste mainly composed of an active material on the ion conductive layer, or applying and drying the paste to a current collector Thereafter, it is fabricated by a method of integrating with an ion conductive film. In the case of a fuel cell or an electrolysis device, a method of applying a paste mainly containing carbon and containing a catalytic metal to the ion conductive layer, or after applying the paste on carbon paper or carbon cloth as a current collector It is manufactured by a method of integrating with an ion conductive film. In either case, this is a method of forming a “layer capable of generating or accumulating electrons” by coating.

  Currently, a blade coating method, a die coating method, a wire bar coating method, a screen printing method and a flexographic printing method are applied to this coating method (coating step). The blade coating method, die coating method, and wire bar coating method are methods that can apply a large area with high productivity because they are continuously applied to a long substrate.

  Moreover, methods other than coating include methods such as filtration, electrophoresis, and micelle electrolysis. The filtration method is a method applied to the lamination of a solid substance on a porous substrate, and is also applied to the production of an electrode of an electrochemical device (see Non-Patent Document 1). Electrophoresis is a technique for moving particles in the direction of an electric field having a polarity opposite to that of the charged particles by applying a direct current electric field to the charged particles in a liquid. This technique is also applied to the production of electrodes for electrochemical devices (Non-patent Document 2). This is a technique in which a membrane and particles are combined by disposing a porous membrane or an ion conductive membrane between positive and negative electrodes (between DC electric fields). In micellar electrolysis, micelles made with a surfactant (micellet agent) having a site capable of redox, such as ferrocene, are collapsed by oxidizing or reducing on the electrode surface, and the substance inside the micelle is brought to the electrode surface. It is the method of making it deposit (refer patent document 1).

Japanese Patent Publication No. 3-59998 2003 Electrochemical Spring Conference, 3N08, P313 2003 Electrochemical Spring Conference, 3N09, P314

  However, in the blade coating method, the die coating method, and the wire bar coating method, various pastes cannot be applied at an arbitrary position in an arbitrary size (for example, in a shape such as a square or a rectangle). Also, the application position accuracy is not high. In the method using a printing plate such as the screen printing method or flexographic printing method, it is possible to apply to any position and any size, but in order to change the printing position and shape, the plate must be remade. It has a problem that it must not be.

  Moreover, in the filtration method (refer nonpatent literature 1), since the lamination | stacking shape is prescribed | regulated by the shape of a filtration surface, the response | compatibility with respect to a shape change or shape control is bad. Furthermore, the finer the particles, the longer the time required for lamination (filtration) and the lower the productivity.

  In addition, in the electrophoresis method (see Non-Patent Document 2), since the laminated shape is determined by the cross-sectional shape of the liquid formed by the membrane and the liquid, the correspondence to the shape change and the shape control is low as in the filtration method.

  Furthermore, since the micelle electrolysis method uses an electrochemical reaction on the electrode surface, it has a drawback that it can be applied only to the electrode surface, that is, a substrate having electronic conductivity.

  An object of the present invention is to easily produce a laminate holding functional particles, and to produce it in a large amount in a short time. In addition, it is easy to produce a laminate of any shape.

  According to a first aspect of the present invention, there is provided a method for producing a laminate of particles and an electrolyte body, comprising: charging a static electricity carrier carrying static electricity with a predetermined polarity; and charging particles having a reverse polarity with respect to the predetermined polarity. Contacting the charged electrostatic carrier with a dispersion formed by dispersing in a dispersion medium, and transferring the particles attached to the electrostatic carrier to an electrolyte formed by an electrolyte. Prepare.

  According to a second aspect of the present invention, in the method for manufacturing a laminate of particles and an electrolyte body according to the first aspect, the method includes a step of removing only a predetermined region of the charged electrostatic carrier.

  According to a third aspect of the present invention, in the method for producing a laminate of particles and an electrolyte body according to the second aspect, the electrostatic carrier is an optical semiconductor, and the step of removing only a predetermined area of the charged electrostatic carrier Irradiates a predetermined region of the charged electrostatic carrier with light, thereby neutralizing only the predetermined region of the charged electrostatic carrier.

  According to a fourth aspect of the present invention, in the method for producing a laminate of particles and an electrolyte body according to the first, second, or third aspect, the dispersion includes a polymer compound having binding properties.

  According to a fifth aspect of the present invention, in the method for producing a laminate of particles and an electrolyte body according to the fourth aspect, the polymer compound is an ion conductive polymer.

  According to a sixth aspect of the present invention, in the method for producing a laminate of particles and an electrolyte body according to the fourth aspect, the polymer compound is a fluoropolymer.

  According to a seventh aspect of the present invention, in the method for producing a laminate of particles and an electrolyte body according to any one of the first to sixth aspects, the dispersion has a conductive agent.

  According to an eighth aspect of the present invention, in the method for producing a laminate of particles and an electrolyte body according to the seventh aspect, the conductive agent is carbon.

  According to a ninth aspect of the present invention, in the method for producing a laminate of the particle and electrolyte body according to any one of the first to eighth aspects, the particle is a metal catalyst.

  According to a tenth aspect of the present invention, in the method for manufacturing a laminate of particles and an electrolyte body according to the ninth aspect, the metal catalyst is composed of Pt or Pt and Ru or Pt and Ir.

  According to an eleventh aspect of the present invention, in the method for producing a laminate of particles and an electrolyte body according to the ninth aspect, the metal catalyst is composed of Pt and Ru and / or Ir and / or W and / or Sn. It consists of more than one type of catalyst component.

  The invention according to claim 12 is the method for producing a laminate of particles and an electrolyte body according to any one of claims 1 to 8, wherein the particles are a substance that ionizes by the entry and exit of electrons, or a substance that reacts with ions, Or it has the substance which can form a compound with ion.

  The laminate of the particle and the electrolyte body according to the thirteenth aspect of the invention is manufactured by the method for manufacturing a laminate of the particle and the electrolyte body according to any one of the first to twelfth aspects.

  An electrochemical element according to a fourteenth aspect of the present invention includes the laminate of the particle according to the thirteenth aspect and an electrolyte body.

  A fuel cell according to a fifteenth aspect of the present invention includes the laminate of the particle and the electrolyte body according to the thirteenth aspect of the invention, and generates electric power using the fuel supplied to the laminate.

  In a sixteenth aspect of the present invention, in the fuel cell according to the fifteenth aspect, the fuel is a fuel containing alcohol.

  According to a seventeenth aspect of the present invention, in the fuel cell according to the sixteenth aspect, the alcohol is ethanol.

  A portable device according to an eighteenth aspect of the invention includes the fuel cell according to any one of the fifteenth to seventeenth aspects.

  According to invention of Claim 1, the laminated body holding functional particle | grains can be manufactured simply, and also can be manufactured in large quantities in a short time.

  According to invention of Claim 2, since it becomes possible to transfer particle | grains to an electrolyte body by arbitrary shapes, the laminated body of arbitrary shapes can be manufactured.

  According to the invention described in claim 3, it is possible to easily manufacture a laminated body having an arbitrary shape.

  According to the invention described in claim 4, the binding property of the particles can be improved.

  According to the fifth aspect of the present invention, it is possible to reduce the interfacial resistance and to simplify the dispersion while maintaining the binding property of the particles.

  According to the invention described in claim 6, it is possible to improve the electrochemical stability of the polymer compound while maintaining the binding property of the particles.

  According to invention of Claim 7, reduction of interface resistance is realizable.

  According to the eighth aspect of the invention, it is possible to reduce the interface resistance and improve the electrical stability.

  According to invention of Claim 9, an electrochemical catalytic reaction is realizable.

  According to the invention described in claim 10, it is possible to realize an oxidation reaction of hydrogen or methanol, an electrolysis reaction of water, or the like.

  According to invention of Claim 11, the oxidation reaction of methanol and ethanol, and the electrolysis reaction of water are realizable.

  According to the invention of claim 12, electrochemical energy storage can be realized.

  According to the invention of the thirteenth aspect, the same effect as that of any one of the first to twelfth aspects of the invention can be achieved.

  According to the invention of claim 14 or 15, the same effect as that of the invention of claim 13 is obtained.

  According to the sixteenth aspect of the present invention, it is possible to improve the driving time of the fuel cell by using the fuel having a high energy density.

  According to the invention of the seventeenth aspect, it is possible to provide a fuel cell using a fuel having high environmental conservation and safety.

  According to the eighteenth aspect of the invention, the same effect as that of the fifteenth aspect of the invention can be achieved.

  The best mode for carrying out the present invention will be described with reference to FIGS.

  Initially, the manufacturing method which produces the laminated body 1 of this Embodiment is demonstrated with reference to FIG. FIG. 1 is an explanatory diagram for explaining the flow of the manufacturing method of the laminate 1 of the present embodiment.

  A substrate 2 which is an electrostatic carrier that carries static electricity is prepared, and the substrate 2 is charged (charged with static electricity). Next, the charged substrate 2 is brought into contact (soaked) with the dispersion liquid 4 containing the particles 3 charged with the opposite polarity (reverse sign) to the polarity of the substrate 2, and the particles 3 are adhered to the substrate 2. Next, the substrate 2 to which the particles 3 are attached is taken out and immersed in a liquid 5 not containing the particles 3. Then, the substrate 6 is immersed in the liquid 5 so as to face the substrate 2, and an ion conductive film (or porous film) 7 that is an electrolyte is immersed between them. The substrate 2 and the substrate 6 to which the particles 3 are attached are connected via a power source 8. A DC electric field is applied so that the substrate 6 has a polarity opposite to that of the particles 3 (minus in FIG. 1), and the particles 3 attached to the substrate 2 are electrophoresed on the ion conductive film 7 and attached. Let By such a method, the laminate 1 of the ion conductive film 7 and the particles 3 is produced. Finally, the stacked body 1 is neutralized. In addition, by bringing the substrate 2, the ion conductive film 7, and the substrate 6 close to each other, the particles 3 can be directly transferred to the ion conductive film 7 without using the liquid 5.

  Here, the electrostatic carrier (substrate 2) can be basically used as long as it can carry static electricity, specifically, if the surface is insulative or semiconductive. As a method for charging the electrostatic carrier, charging by physically rubbing two or more kinds of materials (friction charging), charging using a charge generated by applying a high electric field to air (corona discharge) ), Various methods such as charging (charge injection) with an electron gun or the like can be used.

  Furthermore, the electrostatic carrier (substrate 2) is preferably an electrostatic carrier having an optical semiconductor layer. The photo semiconductor layer (photo semiconductor) here is one that can generate positive charges / negative charges by light irradiation. When such a material is used for the electrostatic carrier of the present embodiment, it is possible to eliminate the charge by irradiating the electrostatic carrier with the entire surface charged by various methods as described above. It becomes. In other words, it is possible to leave static electricity on the surface in an arbitrary shape by controlling the portion irradiated with light.

  A manufacturing method using such light irradiation will be described with reference to FIG. FIG. 2 is an explanatory diagram for explaining the flow of the manufacturing method of the laminate 1 by light irradiation according to the present embodiment. Here, the electrostatic carrier having the optical semiconductor layer is referred to as an optical semiconductor 10.

  A charging process (positive (+) charging) is performed on the optical semiconductor 10 by the charger 11 (see FIG. 2A). Thereafter, the charged optical semiconductor 10 is irradiated with light through a mask 13 having an opening 12 of an arbitrary shape, and the charge is lost only in the irradiated portion (see FIG. 2B). That is, only a predetermined region of the charged photoconductor 10 is neutralized. As a result, the positive charging portion 14 is formed on the optical semiconductor 10. Next, the dispersion liquid 15 (negatively charged dispersion) in which the particles 3 are dispersed is adhered onto the charging roller 16 (negatively charged roller), and simultaneously, a DC electric field is applied, and the particles 3 are electrophoresed on the positively charged portion 14. (See FIG. 2C). Next, the particles 3 are transferred to the ion conductive film 7 by the positively charged charging roller 17 (see FIG. 2D). Thereby, the laminated body 1 of the ion conductive film 7 and the particle | grains 3 is produced. Finally, the optical semiconductor 10 is cleaned and reused (see FIG. 2E).

  As described above, according to the manufacturing method as shown in FIG. 1 or FIG. 2, the particles 3 can be transferred to the ion conductive film 7 or the optical semiconductor 10 in an arbitrary shape. The laminated body 1 having an arbitrary shape can be easily manufactured. Further, the optical semiconductor 10 can be reused. Moreover, according to the manufacturing method by light irradiation as shown in FIG. 2, the laminated body 1 can be manufactured in large quantities in a short time. In general, the exposure (light irradiation) has an advantage that a shape having a higher resolution than that of a normal coating method can be formed.

  Here, as a light irradiation method for forming an arbitrary shape, collective irradiation with a photomask (mask 13) of light such as a halogen lamp, drawing irradiation in which a semiconductor laser beam is scanned with a mirror, or the like, linear with an LED array A method such as irradiation is used. In particular, drawing with a laser beam or drawing with an LED array is preferable because it has a high resolution, can have a complicated shape, and does not require a plate (Max 13) and has high compatibility with shape changes.

  The configuration of the optical semiconductor 10 is preferably a shape in which at least an optical semiconductor layer is provided on the conductive substrate. By adopting such a form, it becomes possible to quickly separate charges generated by light irradiation into positive and negative charges, and the resolution is improved. In particular, it is preferable from the viewpoint of charge separation that the conductive substrate has a polarity (or ground) opposite to the surface charging.

  Further, the particles 3 insoluble in the dispersion medium are not particularly limited as long as they are stable in the dispersion medium to be used, but should be appropriately selected depending on the function given to the laminate 1. Further, the particles 3 used in the present embodiment are charged in a dispersion medium. Using this charging, the particles 3 are adhered to the optical semiconductor (electrostatic carrier) 10 and further transferred to the ion conductive film (or porous film) 7. This basically uses the electrophoresis phenomenon. Electrophoresis is caused by movement caused by electrostatic attraction acting on the electric charge existing on the surface of the particle 3. The positively charged particle 3 is in a negative electric field, and the negatively charged particle 3 is in a positive electric field. It will migrate to. When the dispersion medium itself is a dissociating liquid (for example, water (hydrogen ion and hydroxide ion)), the charge of the particle 3 is adsorbed specifically on the surface by ions having high affinity with the particle 3 surface. The particles 3 are charged with the charges of the ions. Further, ions having a charge opposite to that of the adsorbed ions surround the particles 3 to form counter ions. When the liquid is not a dissociable liquid (usually a large amount of organic solvent), generally, a charge control substance (such as one having an electrolyte structure) is added to cause specific adsorption as described above, whereby the particles 3 Will be charged. The charge can be controlled by adding a charge control substance to a dissociating liquid such as water.

  When a dissociating liquid is used as the dispersion 15 used in the present embodiment, the basic configuration can be configured only by the liquid and the particles 3. However, in this case, the charge determining component and the charge amount are uniquely determined by the combination of the material of the particles 3 and the dispersion medium (that is, cannot be controlled). For this reason, in order to freely control the charge amount and the sign, it is preferable to add a charge control substance. The charge control substance used here is not particularly limited, such as an inorganic salt or an organic salt, but is preferably selected according to the properties of the surface of the particles 3 and the sign to be charged. What has is preferable. In addition, in a system in which only particles and a dissociative liquid are added or a charge control substance is added, the dispersion 15 cannot be stabilized (aggregates) unless the particles are made small. A surfactant can also be added for the purpose of enhancing. In this case, when the surfactant is ionic, the surfactant itself plays a role of giving a charge to the particles 3. Surfactants used here are nonionic (polyethylene glycol type, polyhydric alcohol type), cationic (amine salt type, ammonium salt type), anionic (carboxylate type, sulfonate type, Either a sulfate ester salt type or a phosphate ester salt type) or an amphoteric (amino acid type, betaine type) can be used. In particular, in order to add a small amount of charge to the particles 3, it is preferable to use a cationic or anionic activator. When a non-dissociable liquid is used, a charge control substance (including a surfactant) is essential. For the same reason, the charge control substance having no surfactant effect can control the charge, but it is preferable to use a surfactant because the dispersion 15 is not stable.

  The dispersion 15 is prepared by refining and mixing the particles 3 insoluble in the dispersion medium and, if necessary, a binder polymer compound / conductive agent / charge control agent and the like by various dispersion methods. Is done. As a dispersion method, a homogenizer for refining and mixing the particles 3 with a rotating blade, a three-roll mill for refining and mixing the particles 3 with a gap of three rotating rolls, and mixing and stirring the beads. A dispersion method such as a sand mill for refining and mixing the particles 3 by ultrasonic wave and an ultrasonic dispersion method for refining and mixing the particles 3 by ultrasonic vibration are used.

  The polymer compound having binding properties used in the present embodiment is stable in a dispersion medium and has a property of binding itself and other substances (films and particles 3). Specifically, polyfluoroethylene, polyethylene, nitrile rubber, polybutadiene, butyl rubber, polystyrene, styrene / butadiene rubber, nitrocellulose, cyanoethyl cellulose, polyacrylonitrile, polyvinyl fluoride, polyvinylidene fluoride, polychloroprene, polyvinyl pyridine Etc. These may be used alone, or may be used with enhanced chemical stability by mixing or copolymerization.

  The ion conductive film 7 used in the present embodiment has a self-holding property. The material is an organic material, an inorganic material, a single material, a composite material, etc., and must be chemically stable at least with respect to the dispersion medium and have ion conductivity in the film thickness direction. Preferably, it is a high molecular compound, and what has an ion dissociation group in a molecule | numerator can be used. An ion dissociation group is a group that can ionize itself (hydroxyl group, carboxyl group, sulfonic acid group, etc.) or a group that can dissociate a dissociative substance (electrolyte salt, etc.) (alkylene oxide group, alkyleneimine group, etc.). Point to. More specifically, polyacrylic acid, polystyrene sulfonic acid, polyethylene oxide, polypropylene oxide, and derivatives or cross-linked products thereof can be used. In the case where the self-holding film cannot be formed by itself, for example, it can be used while being held in a porous film.

  The porous membrane 7 used in the present embodiment can be used as long as it is stable to the dispersion medium, but must be capable of containing (holding) an ion conductive substance. When the porous membrane 7 is used, the ion conductive material can be used in various forms such as liquid, gel, and solid. The ion conductive material may be retained on the porous film 7 after the insoluble particles 3 are stacked in the dispersion medium used in the present embodiment, or the ion conductive material may be previously placed on the porous film 7. May be carried out by laminating insoluble particles 3 in the dispersion medium. More specifically, glass fiber, polyester, Teflon (registered trademark), polyflon, polyethylene, polypropylene, a porous body made of polymer fiber such as polyimide, glass fiber, a mixture of these polymer fibers, as described above A high polymer foam or the like can be used.

  When applying the laminated body 1 of this Embodiment as an electrochemical element, it is preferable to use an ion conductive polymer as a binder. This is because a single material can serve the two functions of binding and ionic conductivity. Specifically, a one-dimensional polymer compound having an ion dissociation group in the molecule can be used. An ion dissociation group is a group that can ionize itself (hydroxyl group, carboxyl group, sulfonic acid group, etc.) or a group that can dissociate a dissociative substance (electrolyte salt, etc.) (alkylene oxide group, alkyleneimine group, etc.). Point to. More specifically, polyacrylic acid, polystyrene sulfonic acid, polyethylene oxide, polypropylene oxide, and derivatives thereof can be used. In addition, a polymer compound having a dissociable group typified by these can also function as the charge control substance. Further, from the viewpoint of electrochemical (oxidation reduction) and chemical (thermal) stability of the material, it is preferable to use a fluorine-based polymer as the binder. Specifically, polyfluoroethylene, polyvinylidene fluoride, or the like can be used.

  As the most preferable form of the polymer material contained in the dispersion medium used in the present embodiment, 1. Function as a charge control material 2. Function as an ion conductor 3. Functions as a binder Those having both (electrical) chemical stability are preferable in terms of small size, light weight, low cost, and improvement of the electrochemical performance of the laminate 1. Specifically, a polymer material having a fluorocarbon structure in the main chain or side chain and containing an ion dissociation group in the molecular chain is preferable. More specifically, a structure having a perfluoroethylene structure and containing an ion dissociation group is preferable. The ion dissociation group is appropriately set depending on the ion species to be conducted, but if it is a proton, it has a carboxyl group, a sulfonic acid group, and if it is a lithium ion, it has an ethylene oxide structure or a propylene oxide structure. preferable.

  The conductive agent referred to in this embodiment has a function of assisting the propagation of electrons generated in the vicinity of the particles, which is stable in the dispersant. In the case of using a conductive agent, any electron conductive material that is stable in the dispersion medium and stable in the operating environment of the laminate 1 may be used. In particular, it is carbon-based material rather than metal-based material because of its stability against both redox, light weight, good dispersibility in dispersion medium, and the ability to adsorb ion-conducting polymers as charge control materials. Is preferred. As such a material, natural graphite or artificial graphite can be used.

  As the particles 3 insoluble in the dispersion medium used in the present embodiment, an electrochemical catalytic reaction is performed in the laminate 1 of the present embodiment by using at least a substance having a catalytic action. Is possible. The substance having a catalytic action here is a substance that promotes a chemical reaction without changing itself. As for the form of the particles 3, the catalytic activity, durability, and utilization are that the substance having catalytic action is supported on a non-catalytic support (referring to a support that is a medium supporting the catalyst). It is preferable from the viewpoint of efficiency. Further, in the manufacturing method of the present embodiment, the particles 3 need to be charged, but this charging can be adjusted by the charge control material as described above. Coating or adsorbing a charge control substance on a substance having a catalytic ability is not preferable because it lowers the catalytic activity. The production method of the present embodiment can be carried out without degrading the catalytic ability by selectively covering or adsorbing the charge control material on the carrier by selecting the carrier.

  Although there is no restriction | limiting in particular as a substance which has a catalytic action, Since one form of this Embodiment is lamination | stacking of the catalyst substance on an ion conductive film, it is preferable that an ion participates in a catalytic reaction. Specifically, a noble metal simple substance such as platinum or an alloy or a composite of a second element or a third element containing a noble metal and a noble metal can be used as a catalytic agent. The carrier is appropriately selected depending on the substance having the catalytic action to be used and the conditions under which the laminate functions, and light represented by aluminum oxide, silicon oxide, carbon, silicon carbide or titanium oxide. Semiconductor 10 etc. can be used. More specifically, a catalyst mainly composed of platinum is preferable for the oxidation of hydrogen and organic substances and the electrolysis of water. In particular, a catalyst comprising Pt and Ru or Pt and Ir is preferable for the oxidation of alcohol, especially methanol or ethanol.

In addition, as the particles 3 that are insoluble in the dispersion medium, it is particularly preferable to use a substance that ionizes by the entry and exit of electrons, a substance that reacts with ions, or a substance that can form compounds with ions. Thus, electrochemical energy can be accumulated using the laminate 1 manufactured by the manufacturing method of the present embodiment. Specifically, it is a material that functions as a so-called battery active material, such as metals such as Li, Mg, Pb, PbO ₂ , Cd, Fe, and Zn, and metal oxides such as HgO, PbO ₂ , NiOOH, AgO, and MnO _2. An oxide, sulfide, hydrogen storage alloy, interphase compound, conductive polymer, or the like can be used. In particular, the following substances are preferable because energy can be stored at a high density. Specifically, transition metal oxides such as TiS ₂ , MoS ₂ , Co ₂ S ₆ , V ₂ O ₅ , MnO ₂ , CoO ₂ , transition metal chalcogen compounds, and composites of these with Li (Li composite oxides) : LiMnO ₂ , LiMn ₂ O ₄ , LiCoO ₂ , LiNiO _2, etc.), polyaniline, polypyrrole, poloazulene, polyphenylene, polyacetylene, polyphthalocyanine, poly-3-methylthiophene, polypyridine, polydiphenylbenzidine and the like conductive polymers, A carbon material that can be combined with lithium can be used. From the viewpoint of increasing the energy density, a composite oxide having a layered structure represented by LiMnO ₂ such as lithium cobalt oxide or lithium nickel oxide, or a composite oxide having a spinel structure represented by LiMn ₂ O ₄ is used. It is preferable to use it. Among these, spinel LiMn ₂ O ₄ is particularly preferable because it is a resource-rich and inexpensive manganese oxide. Furthermore, it is preferable to use LiMn (2-n) XnO _{4 in} which a part of the Mn atom of LiMn ₂ O ₄ is substituted with another atom X as the positive electrode active material. In particular, it is preferable to use a mixture of spinel LiMn ₂ O ₄ and LiMn (2-n) XnO ₄ .

  As described above, the present embodiment basically uses primary materials, secondary cells, fuel cells, solar cells, capacitors, electrolysis elements by using insoluble particles 3 in the dispersion medium and using various materials. Moreover, the laminated body 1 applicable to various electrochemical elements, such as various sensors, can be provided.

  Here, the usage example of the laminated body 1 is demonstrated with reference to FIG. 3 for the fuel cell 20 as a specific example. FIG. 3 is a schematic diagram schematically showing the internal structure of the fuel cell 20. The fuel cell 20 using the proton conducting solid polymer electrolyte will be described as an example.

  The fuel cell 20 is provided with an ion conductor 21 (here, for example, a proton conductor) as an ion conductive membrane 7 at the center as a basic component, and an anode catalyst layer 22 and a cathode catalyst layer on both sides thereof. 23 is arranged. The anode catalyst layer 22 and the cathode catalyst layer 23 are connected via an external circuit (load) 24. The anode catalyst layer 22 and the cathode catalyst layer 23 are each provided with a separator 26 having a fuel flow path 25 for supplying fuel thereto.

With such a configuration, fuel (hydrogen (H ₂ ), alcohol, or the like) serving as a proton source is supplied to the anode side, and hydrogen ions (H ⁺ ) are generated from the fuel by the catalytic action in the catalyst layer 22 of the anode. At this time, the generated electrons (e ⁻ ) flow to the external circuit 24. The generated hydrogen ions propagate through the ion conductor 21 and reach the cathode catalyst layer 23. By supplying an oxidizing agent (air, oxygen (O ₂ ), etc.) to the cathode side, hydrogen ions, oxygen, and electrons flowing through the external circuit 24 react to generate water (H ₂ O). . This is the concept of power generation, which can be expressed as the following reaction equation.

Anode reaction: H ₂ → 2H ⁺ + 2e ⁻ (in the case of hydrogen fuel)
Cathode reaction: 2H ⁺ + 1 / 2O ₂ + 2e ⁻ → H ₂ O
Total reaction: H ₂ + 1 / 2O ₂ → H ₂ O
As described above, the laminate 1 of the present embodiment is applied to a portion in which the anode catalyst layer 22 and the cathode catalyst layer 23 are arranged on both sides of the ion conductor 21. In the fuel cell 20, it is necessary to stack the catalyst layers 22 and 23 on both sides of the ion conductor 21. This can be produced by repeating the manufacturing method of the present embodiment twice on the front and back of the ion conductor 21. In this case, different particles 3 can be laminated on the anode side and the cathode side. Further, when the same particle 3 exists on the anode side and the cathode side, light irradiation is performed on one part of the ion conductor 21 by irradiating two parts on the optical semiconductor 10 by a method such as a photomask or laser drawing. Since the catalyst layers 22 and 23 can be laminated at two locations, the fuel cell 20 can also be folded by folding the catalyst layers 22 and 23 with the ion conductor 21 inside (the catalyst layers 22 and 23 being outside). It can be used as a functional member.

  Further, in the method for manufacturing the laminated body 1 of the present embodiment, particularly the method using the optical semiconductor 10, as described above, a plurality of regions are formed in one step within the same plane of the ion conductive film (or porous film) 7. Thus, the catalyst layers 22 and 23 can be formed (elements of a plurality of fuel cells 20 can be formed), and this is a highly productive method. Further, by using each of the portions where the catalyst layers 22 and 23 are formed in a plurality of regions of the front and back surfaces of the ion conductive membrane 7 by such a method as elements of the fuel cell 20 (in parallel and / or in series connection), A high voltage / high output thin fuel cell 20 can be produced. Therefore, the manufacturing method of the laminated body 1 of this Embodiment is suitable for the manufacturing method of the laminated body 1 for thin fuel cells 20.

The fuel cell 20 using the laminate 1 of the present embodiment is appropriate depending on the type of catalyst, but basically any fuel can be used. However, it is preferable to use a fuel excellent in volume and weight energy density. Since the fuel is usually stored in a finite space (such as a container), it has only a fixed volume. Therefore, it is preferable to use a fuel excellent in volume and weight energy density. In particular, a fuel excellent in volume energy density is preferable. Gaseous fuel is not preferred because it is inferior in volumetric energy density, and liquid fuel and solid fuel are preferred. This is because, for example, the number of electrons that can be extracted by oxidation reaction of one molecule is 2 if hydrogen, 6 if methanol, and 12 if ethanol, so the amount of Coulomb that can be extracted from 1 mol of each molecule is theoretical. The values are 96500 × 2C, 96500 × 6C, and 96500 × 12C. Considering density and molecular weight of each, 1 cm ³ per coulomb amount converted to the about 9C / cm ³ with hydrogen, approximately methanol 14400C / cm ^3, the energy density of 15200C / cm ³ with ethanol. Hydrogen as a normal pressure gas has a significantly low energy density per unit volume. Methanol and ethanol each require one molecule and three molecules of water for the oxidation reaction (see the following formula), but it is clear that liquid fuel is superior even when this is taken into account.

CH ₃ OH + H ₂ O → 6H ⁺ + 6e ⁻ + CO ₂
C ₂ H ₅ OH + 3H ₂ O → 12H ⁺ + 12e ⁻ + 2CO ₂
Although it is possible to use high-pressure hydrogen or liquid hydrogen, it is necessary to make the container robust, and considering the energy density of the container, liquid or solid fuel at room temperature and normal pressure is excellent. Yes. Specifically, hydrogen stored in the hydrogen storage alloy, solid fuel such as gasoline, liquid hydrocarbon, liquid alcohol, or liquid fuel can be used, but the main fuel cell can be downsized, volume energy From the viewpoint of excellent density, it is preferable to use an alcohol fuel. By using alcohol fuel, a portable fuel cell 20 with improved driving time can be formed. Among these, it is preferable to use an alcohol having 4 or less carbon atoms, and it is particularly preferable to use ethanol from the viewpoint of high safety and biosynthesis (environmental aspect). The fuel cell 20 having such a form is excellent in volume energy density and weight energy density, and is particularly preferable when used in a portable device to be carried.

  Further, instead of direct oxidation of liquid fuel, a so-called reformation is performed in which liquid fuel such as liquefied natural gas (LNG) or methane gas, or liquid fuel such as methanol is reformed to obtain hydrogen to be used as fuel for the fuel cell 20. Quality fuel type fuel cells are also being studied. In this case, there is a problem (catalyst poisoning) that impairs the function of the fuel cell 20 due to carbon monoxide (CO) present in a trace amount in the hydrogen gas fuel obtained by reforming the raw fuel and other trace amounts of impurities. . The problem of catalytic CO poisoning has been studied, and a platinum-ruthenium (Pt—Ru) alloy catalyst is proposed as a catalyst for reducing this problem. However, in many cases, CO poisoning cannot explain the factors that inhibit the catalytic chemical reaction in the anodic oxidation of methanol and ethanol in solution. This is because the oxidation reaction of methanol or ethanol is oxidized through a number of elementary reactions that cannot be compared with hydrogen or CO. According to the present embodiment, a catalyst composed of Pt and Ru or Ir is preferable for the oxidation of methanol, and the oxidation of ethanol is based on Pt and Ru and / or Ir and / or W and / or Sn. It is preferable to use three or more kinds of catalyst components. The reason why these catalysts are preferable is that these media contribute to the promotion of the progress of the complex reactant processes of methanol and ethanol.

  Furthermore, as described above, the laminate 1 according to the method of the present embodiment is suitable for manufacturing a thin fuel cell 20, and can be preferably used particularly for a portable device having a thin shape. Similarly, the manufacturing method of the present embodiment is also suitable for manufacturing thin batteries for so-called batteries (primary batteries and secondary batteries). Similarly, such a battery can be preferably used for a thin portable device.

<Example 1>
First, an amorphous selenium layer 31 is formed on a 10 cm × 10 cm Al substrate 30 by vacuum deposition. The Al substrate 30 is grounded, and the amorphous selenium layer 31 is positively charged to a charging potential of about 1 kV by a charger (scorotron) 32 (see FIG. 4A). Thereafter, the charged potential of the irradiated portion of the amorphous selenium layer 31 is attenuated by irradiating with halogen lamp light through a glassy photomask 34 having four openings 33 of 20 mm × 20 mm (see FIG. 4B). ). As a result, the positively charged portion 35 is formed on the amorphous selenium layer 31. Separately from this, carbon having platinum supported on isopar (manufactured by Electrochem Co., Ltd.) is added in an amount of 8 wt% and perfluorosulfonic acid is 4 wt% to prepare a dispersion liquid 36 subjected to a dispersion treatment. The dispersion 36 contains particles 3 mainly composed of carbon carrying platinum.

  Next, the dispersion liquid 36 is applied onto the amorphous selenium layer 31 irradiated with light as described above by the conductive rubber roller 37 having negative polarity, and the particles 3 are electrophoresed on the positively charged portion 35 (FIG. 4 (c)). Thereafter, the ion conductive film 7 (manufactured by DuPont: Nafion (registered trademark)) is brought into contact with the amorphous selenium layer 31 with the conductive rubber roll 38 having a positive polarity, and the ion conductive film 7 is substantially simultaneously with the amorphous selenium layer 31. By peeling from above, the particles 3 mainly composed of carbon carrying platinum are transferred to the ion conductive film 7 (see FIG. 4D).

  By performing such a process, the laminated body 1 of the ion conductive film 7 and the particles 3 was produced. (See FIG. 4 (e)). It was confirmed that the transferred shape after drying substantially coincided with the shape of the photomask 34. After the amorphous selenium layer 31 was washed again and the same process was performed, the same laminate 1 could be produced. This indicates that the particles (functional particles) 3 can be combined with the ion conductive film 7 at an arbitrary position in an arbitrary size (for example, a shape such as a square or a rectangle). Indicates that it can be reused.

<Example 2>
Here, the amorphous selenium layer 31 / Al substrate 30 is irradiated with light directly on the amorphous selenium layer 31 using an LED array with a resolution of 600 dots / inch while scanning the amorphous selenium layer 31 / Al substrate 30 at a constant speed (the photomask 34 is not used). Except for this, the same steps as in Example 1 are performed (the light irradiation shape is adjusted to be the same as in Example 1). By performing such a process, the laminated body 1 of the ion conductive film 7 and the particles 3 was produced. The transferred shape was approximately 20 × 20 mm. This indicates that the particles (functional particles) 3 can be combined with the ion conductive film 7 at an arbitrary position in an arbitrary size (for example, a shape such as a square or a rectangle), and without a mask. It shows that the laminate 1 can be formed.

<Example 3>
Here, light is irradiated directly onto the amorphous selenium layer 31 with a line width of 84 μm using an LED array having a resolution of 600 dots / inch while scanning the amorphous selenium layer 31 / Al substrate 30 at a constant speed. Except this, the same processes as in Example 1 are performed. By performing such a process, the laminated body 1 of the ion conductive film 7 and the particles 3 was produced. The transferred shape was approximately 100 μm. This is because the particles (functional particles) 3 can be combined with the ion conductive film 7 at an arbitrary position in an arbitrary size (for example, a shape such as a square or a rectangle), and the laminate 1 can be formed without a mask. In addition, it shows that the laminate 1 having a high resolution (fine pattern) can be produced.

<Example 4>
Using the manufacturing process of Example 2, a laminate 1 in which 5 cm ² of platinum-supporting carbon layers were formed on both surfaces of the ion exchange membrane was produced. After this laminate 1 is subjected to acid treatment, the acid-treated laminate is loaded into a fuel cell performance evaluation cell (US Electrochem Corp .: FC05-01SP), humidified hydrogen on the anode side, and humidified on the cathode side. Supplied oxygen. Thereby, an electromotive force of 0.91 V was generated, and it was confirmed that the laminate 1 functions as an electrochemical element.

<Example 5>
Using the manufacturing process of Example 2, a platinum-carrying carbon layer of 5 cm ² was formed on one side of the ion exchange membrane. Next, separately from this, carbon having platinum ruthenium supported on isopar (manufactured by Electrochem Inc., USA) was added to 10 wt% and perfluorosulfonic acid was added to 5 wt% to prepare a dispersion liquid 36 subjected to dispersion treatment. did.

  Next, using this dispersion liquid 36, platinum ruthenium-carrying carbon was transferred to the back surface of the portion where the platinum-carrying carbon of the ion exchange membrane was laminated in the same manner as in Example 2 and dried. The obtained laminate 1 is subjected to an acid treatment, and then loaded into a fuel cell performance evaluation cell (manufactured by Electrochem, Inc .: FC05-01SP), and 3% methanol aqueous solution is supplied to the anode side and humidified oxygen is supplied to the cathode side. did. Thereby, an electromotive force of 0.87 V was generated, and it was confirmed that the laminate 1 functions as an electrochemical element.

<Example 6>
First, an amorphous selenium layer 31 was formed on a 10 cm × 10 cm Al substrate 30 by vacuum deposition. The Al substrate 30 is grounded, and the amorphous selenium layer 31 is positively charged to a charging potential of about 1 kV by a charger (scorotron) 32 (see FIG. 4A). Thereafter, the charged potential of the irradiated portion of the amorphous selenium layer 31 is attenuated by irradiating with halogen lamp light through a glassy photomask 34 having an opening 33 of 5 cm (see FIG. 4B). As a result, the positively charged portion 35 is formed on the amorphous selenium layer 31. Separately, electrolytic manganese dioxide in which carbon is coated on isopar is added in an amount of 10 wt% and perfluorosulfonic acid is added in an amount of 5 wt% to prepare a dispersion liquid 36 subjected to a dispersion treatment.

  Next, the dispersion liquid 36 is applied onto the amorphous selenium layer 31 irradiated with light as described above by the conductive rubber roller 37 having a negative polarity, and the particles 3 are electrophoresed on the positively charged portion 35 (FIG. 4). (See (c)). Thereafter, the porous porous film 7 is peeled off from the amorphous selenium layer 31 almost simultaneously with the polypropylene porous film 7 being brought into contact with the amorphous selenium layer 31 with a conductive rubber roll 38 having a positive polarity. The coated particles 3 mainly composed of electrolytic manganese dioxide are transferred to the porous film 7 (see FIG. 4D).

  By performing such a process, the laminated body 1 of the ion conductive film 7 and the particle | grains 3 was produced (refer FIG.4 (e)). The transferred shape after drying almost coincided with the shape of the photomask 34. This indicates that the particles (functional particles) 3 can be combined with the ion conductive film 7 at an arbitrary position in an arbitrary size (for example, a shape such as a square or a rectangle).

<Example 7>
The laminate 1 of Example 6 was dipped in an aqueous solution containing 9% zinc chloride and 26% ammonium chloride, the porous membrane 7 was sufficiently impregnated with the aqueous solution, the laminate 1 was taken out, and a corrosion-resistant stainless steel plate, porous on the manganese dioxide side. A zinc plate was brought into contact with the membrane side. When the electromotive force between stainless steel and zinc was measured in this state, the electromotive force was about 1.6 V, and it was confirmed that the laminate 1 functions as an electrochemical element.

It is explanatory drawing for demonstrating the flow of the manufacturing method of the laminated body of one Embodiment of this invention. It is explanatory drawing for demonstrating the flow of the manufacturing method of the laminated body by the light irradiation of one Embodiment of this invention. It is a schematic diagram which shows schematically the internal structure of the fuel cell of one Embodiment of this invention. It is explanatory drawing for demonstrating the flow of the manufacturing method of the laminated body by the light irradiation of the Example of this invention.

Explanation of symbols

1 Laminated body 2 Electrostatic carrier (substrate)
3 Particles 4 Dispersion liquid 7 Electrolyte (ion conductive membrane, porous membrane)
10 Electrostatic carrier (optical semiconductor)
15 Dispersion 20 Fuel Cell 21 Electrolyte (Ion Conductor (Ion Conductive Membrane))
36 Dispersion

Claims (18)

Charging the electrostatic carrier carrying static electricity with a predetermined polarity;
Contacting the charged electrostatic carrier with a dispersion formed by dispersing particles charged in a polarity opposite to the predetermined polarity in a dispersion medium;
Transferring the particles adhering to the electrostatic carrier to an electrolyte body formed of an electrolyte;
A method for producing a laminate of particles and an electrolyte body.   The manufacturing method of the laminated body of the particle | grains and electrolyte body of Claim 1 provided with the process of static-removing only the predetermined area | region of the said electrostatic support body already charged. The electrostatic carrier is an optical semiconductor,
The step of neutralizing only the predetermined region of the charged electrostatic carrier carries out the neutralization of only the predetermined region of the charged electrostatic carrier by irradiating the predetermined region of the charged electrostatic carrier with light. Item 3. A method for producing a laminate of particles and an electrolyte body according to Item 2.   4. The method for producing a laminate of particles and an electrolyte body according to claim 1, wherein the dispersion contains a polymer compound having binding properties.   The method for producing a laminate of particles and an electrolyte body according to claim 4, wherein the polymer compound is an ion conductive polymer.   The method for producing a laminate of particles and an electrolyte body according to claim 4, wherein the polymer compound is a fluorine-based polymer.   The method for producing a laminate of particles and an electrolyte body according to any one of claims 1 to 6, wherein the dispersion liquid contains a conductive agent.   The method for producing a laminate of particles and an electrolyte body according to claim 7, wherein the conductive agent is carbon.   The method for producing a laminate of particles and an electrolyte body according to any one of claims 1 to 8, wherein the particles are a metal catalyst.   The method for producing a laminate of particles and an electrolyte body according to claim 9, wherein the metal catalyst is composed of Pt or Pt and Ru or Pt and Ir.   10. The method for producing a laminate of particles and an electrolyte body according to claim 9, wherein the metal catalyst is composed of three or more kinds of catalyst components comprising Pt and Ru and / or Ir and / or W and / or Sn. .   The laminate of particles and an electrolyte body according to any one of claims 1 to 8, wherein the particles have a substance that ionizes by entering and exiting electrons, a substance that reacts with ions, or a substance that can form a compound with ions. Manufacturing method.   A laminate of particles and an electrolyte body produced by the method for producing a laminate of particles and an electrolyte body according to any one of claims 1 to 12.   An electrochemical device comprising the laminate of the particles and the electrolyte body according to claim 13.   A fuel cell comprising the laminate of the particles and the electrolyte body according to claim 13, and generating electric power with the fuel supplied to the laminate.   The fuel cell according to claim 15, wherein the fuel is a fuel containing alcohol.   The fuel cell according to claim 16, wherein the alcohol is ethanol. A portable device comprising the fuel cell according to any one of claims 15 to 17.

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