JP2014192076A - Electrode for air cell and air cell module using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode for an air cell which has a relatively simple structure and achieves low connection resistance between members, and to provide an air cell module which enables easy assembling.SOLUTION: An electrode 1 for an air cell includes: a collector plate 2; a negative electrode 3 which is provided on one plate surface of the collector plate 2; a conductive gas diffusion layer 4 which is provided on the other plate surface of the collector plate 2; and a positive electrode 5 provided on a surface of the conductive gas diffusion layer 4 which is opposite to the collector plate 2. The conductive gas diffusion layer 4 includes a conductive carbon material and a high molecular weight polymer. An air cell module 10 includes: an outer container 6 in which multiple insertion grooves 8 are formed; electrodes 1 for the air cell inserted into the insertion grooves 8; and an electrolyte 7 filling regions in the outer container 6 which are divided by the electrodes 1 for the air cell.

Description

  The present invention relates to an air battery electrode and an air battery module using the air battery electrode.

  An air battery is a battery that uses oxygen in the air as a positive electrode active material and a metal as a negative electrode active material. Since air batteries can theoretically have large capacities, in recent years, development for use in, for example, power sources for electric vehicles and portable power sources has been promoted and is expected as one of the future energy-saving technologies. .

  In order to obtain a high voltage by combining batteries for use in electric vehicle power supplies or portable power supplies, it is necessary to electrically connect the positive and negative electrodes of adjacent batteries. At this time, depending on the electrical connection method, a large connection resistance is generated and energy is lost.

  FIG. 10 is a schematic diagram of a conventional air battery cell 100. The negative electrode 101 and the positive electrode 102 are disposed to face each other with the electrolytic solution 103 interposed therebetween. The positive electrode 102 includes a catalyst layer 104, a gas diffusion layer 105, and an extraction electrode 106. The extraction electrode 106 is mostly formed in a mesh shape and is in contact with the catalyst layer 104 or the gas diffusion layer 105. The contact resistance between the extraction electrode 106 and the catalyst layer 104 or the gas diffusion layer 105 causes a loss of the extraction voltage. Connected. The entire air battery is covered with an outer container 107A and an outer container 107B having air holes 108. The outer container 107A and the outer container 107B may be integrated. In FIG. 10, reference numeral 109 denotes a lead-out line for the negative electrode 101.

  FIG. 11 is a schematic diagram of a conventional air battery module 110 in which a plurality of air battery cells 100 shown in FIG. 10 are connected in series. The take-out electrode 106 and the negative electrode 101 of the positive electrode 102 of the adjacent air battery cell 100 are taken out. The wire 109 is electrically connected. However, the air battery module 110 connected in this way has a problem that connection wiring between the air battery cells 100 is troublesome, and complicated wiring may cause disconnection or short circuit. In addition, a wiring space is required for the connection, and there is a problem that the occupied volume of the battery increases due to the wiring.

  Therefore, in order to solve the above-described problem, Patent Document 1 discloses that an electrical connection between a negative electrode of one air battery cell and a positive electrode of an air battery cell adjacent thereto isolates both air battery cells. Bipolar metal-air batteries have been proposed that are provided through wall materials.

JP-A-60-7075

  However, the bipolar electrode described in Patent Document 1 is provided with a bridge including a conductive element having a wire (current collector) press-bonded to a rib in the electrode in order to provide an air flow to the positive electrode. (Refer to claim 3 of patent document 1 and drawings). Therefore, the structure of the bipolar electrode described in Patent Document 1 is complicated, and the current collector has only room for improvement in electrical connection because it only partially joins the positive electrode and the negative electrode through the wall material. .

  The present invention has been made paying attention to the above-described problems, and provides an air battery electrode (bipolar electrode) having a relatively simple structure and low connection resistance between members, and an air battery module that can be easily assembled. The purpose is to do.

  The object of the present invention is to provide a current collector plate, a negative electrode provided on one plate surface of the current collector plate, a conductive gas diffusion layer provided on the other plate surface of the current collector plate, and the conductive material. A positive electrode provided on a surface of the conductive gas diffusion layer opposite to the current collector, and the conductive gas diffusion layer includes a conductive carbon material and a polymer. This is achieved by the battery electrode.

  In the air battery electrode having the above structure, it is preferable that a part of the conductive gas diffusion layer protrudes above the positive electrode.

  In addition, the object of the present invention is to provide an exterior container having a plurality of insertion grooves formed on the inner surface at intervals, a plurality of air battery electrodes having the above-described configuration inserted into the insertion groove, and the interior of the exterior container. It is also achieved by an air battery module comprising: an electrolyte filled in a region partitioned by the plurality of air battery electrodes.

  In the air battery electrode having the above configuration, it is preferable that a part of the conductive gas diffusion layer immersed in the electrolyte is exposed above the electrolyte.

  According to the present invention, it is possible to obtain an air battery electrode that is relatively simple in structure, has a reduced connection resistance between the positive electrode and the negative electrode, and an air battery module that can be easily assembled.

It is a side view of the electrode for air batteries concerning one embodiment of the present invention. It is a top view of the electrode for air batteries of FIG. It is the front view seen from the negative electrode side of the electrode for air batteries of FIG. It is the front view seen from the positive electrode side of the electrode for air batteries of FIG. It is sectional drawing of the air battery module which concerns on one Embodiment of this invention. It is a top view of the air battery module of FIG. It is sectional drawing of the air battery module which concerns on other embodiment. It is sectional drawing of the air battery module which concerns on other embodiment. It is the front view seen from the positive electrode side of the electrode for air batteries of other embodiment. It is sectional drawing of the conventional air battery cell. It is sectional drawing of the conventional air battery module.

  Hereinafter, an air battery electrode according to an embodiment of the present invention and an air battery module using the air battery electrode will be described with reference to the drawings.

  As shown in FIGS. 1 to 4, the air battery electrode 1 of the present embodiment has a rectangular plate-like current collector plate 2 and one plate surface of the current collector plate 2 (right plate surface in FIG. 1). The bonded negative electrode 3, the conductive gas diffusion layer 4 bonded to the other plate surface (the left plate surface in FIG. 1) of the current collector plate 2, and the current collector plate 2 of the conductive gas diffusion layer 4 are And a positive electrode (catalyst layer) 5 bonded to the opposite surface. 3 is a view of the air battery electrode 1 of FIG. 1 viewed from the negative electrode 3 side, and FIG. 4 is a view of the air battery electrode 1 of FIG. 1 viewed from the positive electrode 5 side. In general, a bipolar electrode refers to an electrode having a positive electrode active material on one side of the electrode and a negative electrode active material on the other side. The air battery electrode 1 is a bipolar electrode.

  The negative electrode 3 provided on one plate surface side of the current collector plate 2 has a predetermined thickness and is formed in a rectangular shape whose outer shape viewed from the plate surface side of the current collector plate 2 is smaller than that of the current collector plate 2. ing. That is, at least the length in the vertical direction when the negative electrode 3 is in an upright state is shorter than the current collector plate 2, and the current collector plate 2 protrudes outward from at least the upper edge of the negative electrode 3. In the present embodiment, the negative electrode 3 is formed in a rectangular shape that is slightly smaller than the current collector plate 2, and the current collector plate 2 protrudes outward from the lower edge and the left and right edges of the negative electrode 3. Yes.

  The conductive gas diffusion layer 4 provided on the other plate surface side of the current collector plate 2 has a predetermined thickness. The outer shape of the conductive gas diffusion layer 4 viewed from the plate surface side of the current collector plate 2 is not particularly limited, and may be formed in a rectangular shape having substantially the same size as the current collector plate 2, It may be formed in a rectangular shape smaller than the current collector plate 2. In the present embodiment, the conductive gas diffusion layer 4 is formed in a rectangular shape smaller than the current collector plate 2, and the current collector plate 2 extends outward from the lower edge and the left and right edges of the conductive gas diffusion layer 4. Stick out. Although the position of the upper edge portion of the conductive gas diffusion layer 4 coincides with the position of the upper edge portion of the current collector plate 2, it may protrude outward from the upper edge portion of the current collector plate 2. On the other hand, the positive electrode 5 has a predetermined thickness and is formed in a rectangular shape whose outer shape viewed from the plate surface side of the current collector plate 2 is smaller than that of the conductive gas diffusion layer 4. That is, at least the length in the vertical direction when the positive electrode 5 is in an upright state is shorter than the conductive gas diffusion layer 4, and the conductive gas diffusion layer 4 and the current collector plate 2 are at least from the upper edge of the positive electrode 5 to the outside. It sticks out. In the present embodiment, the positive electrode 5 is formed in a rectangular shape that is slightly smaller than the current collector plate 2, and the current collector plate 2 projects outward from the lower edge and the left and right edges of the positive electrode 5. Yes. In addition, although the external dimensions of the positive electrode 5 and the negative electrode 3 may be different, in the present embodiment, the positive electrode 5 is formed to have the same external shape as the negative electrode 2 and sandwiches the current collector plate 2 therebetween. It is provided at a symmetrical position.

  Since the air battery electrode 1 of the present embodiment has a large bonding area between the current collector plate 2 and the negative electrode 3, it is possible to suppress electrical resistance as compared with the conventional partial connection. Moreover, since the conductive gas diffusion layer 4 contains a conductive carbon material and a polymer as will be described later, the adhesion between the positive electrode 5 and the current collector 2 in contact with the conductive gas diffusion layer 4 is high, and the conductive property is high. Contact resistance (contact resistance between members) generated between the positive electrode 5 and the current collector plate 2 in contact with the gas diffusion layer 4 can be suppressed.

  FIG.5 and FIG.6 has shown the schematic diagram of the air battery module 10 using the electrode 1 for air batteries of this embodiment. The air battery module 10 includes an outer container 6, a plurality of air battery electrodes 1 arranged in the outer container 6, and an electrolyte 7 filled between adjacent air battery electrodes 1. FIG. 6 shows a state in which one of the air battery electrodes 1 is arranged in the insertion groove 8 in the outer container 6.

  The outer container 6 is a box-shaped container having an open top surface in which a bottom surface portion 60 having a rectangular shape in plan view, a front surface portion 61 and a rear surface portion 62 facing each other, and a side surface portion 63 facing each other are integrally provided. is there. A plurality (four in the illustrated example) of insertion grooves 8 for assembling the air battery electrode 1 are formed in the outer peripheral surface of the outer container 6 at predetermined intervals. The insertion groove 8 is a pair of vertical grooves 80 extending in the vertical direction formed so as to face each other on the side surface portions 63 and a pair of vertical grooves 80 formed so as to extend in the width direction on the bottom surface portion 60. It is comprised by the horizontal groove | channel 81 which follows the lower end of this. As shown by the arrow X in FIG. 6, the both side edges and the lower edges of the current collector plate 2 of the air battery electrode 1 are inserted into the pair of vertical grooves 80 and the horizontal grooves 81 from above, so that a plurality of air The battery electrodes 1 are arranged in the exterior container 8, and the interior of the exterior container 8 is partitioned into a plurality of (three in the illustrated example) regions 64 by the air battery electrodes 1. In addition, it is preferable to provide packing in the insertion groove 8 and insert the current collector plate 2 of the air battery electrode 1 through the packing. Thereby, the several area | region 64 partitioned off with each electrode 1 for air cells can be liquid-separated from the adjacent area | region 64. FIG. Then, an air battery is formed by filling the electrolyte 64 into the regions 64 partitioned by the air battery electrodes 1 in the outer container 8. By connecting the lead wire 9 (shown in FIG. 5) to the current collector plate 2 of the air battery electrode 1 at both ends, a voltage can be obtained from the air batteries connected in series. Therefore, in the air battery module 10 of this embodiment, an extra wiring becomes unnecessary.

  In addition, about the air battery electrode 1 of the both ends to which the taking-out line 9 is connected among the several air battery electrodes 1 arrange | positioned in the exterior container 6, it shows in FIG. Thus, the thing of the structure which joined only the negative electrode 3 to the one plate surface side of the electrical power collector 2, and the thing of the structure which only joined the positive electrode 5 to the one surface side of the electroconductive gas diffusion layer 4 are arrange | positioned However, the lead wire 9 may be connected to the current collector 2 and the positive electrode 5, respectively.

  The electrolyte 7 is filled between the adjacent air battery electrodes 1 in the outer container 6, but is preferably filled to the extent that the negative electrode 3 and the positive electrode 5 are entirely immersed in the electrolyte 7. The electrolyte 7 is preferably filled to such an extent that at least the upper edge of the conductive gas diffusion layer 4 is exposed on the electrolyte 7. Thereby, the whole of the negative electrode 3 and the positive electrode 5 can be made to function well, and oxygen can be more efficiently supplied to the positive electrode 5 through the conductive gas diffusion layer 4. If necessary, a blower mechanism may be provided to efficiently supply air to the conductive gas diffusion layer 4.

  Next, the material which comprises the electrode 1 for air batteries and the air battery module 10 of this embodiment is described.

(Current collector)
The current collector plate 2 is not particularly limited as long as it has a certain degree of rigidity and conductivity. For example, a metal plate such as a copper plate or a stainless steel plate can be used. The thickness of the current collector plate 2 is preferably about 0.3 mm to 2 mm, and more preferably about 0.5 mm to 1.0 mm. When a metal plate is used as the current collector plate 2, the surface may be subjected to a surface treatment such as plating or nitriding with nickel or chromium. The nickel-plated copper plate is excellent as the current collector plate 2 because of its low electrical resistance and high corrosion resistance.

(Negative electrode)
For the negative electrode 3, for example, metals such as zinc (Zn), aluminum (Al), iron (Fe), lithium (Li), and magnesium (Mg), alloys, or metal compounds can be used as the negative electrode active material. In order to increase the contact area between the negative electrode 3 and the electrolyte 7, the negative electrode 3 preferably has fine pores. The thickness of the negative electrode 3 is preferably about 1 mm to 10 mm, although it depends on the required battery capacity. As a method of providing the negative electrode 3 on the current collector plate 2, for example, the current collector plate 2 can be provided by directly spraying metal or the like, or by plating the current collector plate 2 with metal or the like. Alternatively, the negative electrode active component metal powder may be dispersed in a binder and applied to the current collector plate 2. Moreover, you may make it provide a void | hole by sintering the coating layer containing the metal powder of this negative electrode active component.

(Conductive gas diffusion layer)
The conductive gas diffusion layer 4 only needs to contain a conductive carbon material such as carbon particles and carbon fibers and a polymer. From the viewpoint of reducing the thickness of the conductive gas diffusion layer 4, the conductive gas diffusion layer 4 is formed by applying a paste composition prepared by dispersing a conductive carbon material and a polymer material with a solvent on a substrate. It can be formed by drying. The conductive gas diffusion layer 4 thus formed may be peeled off from the base material and integrated with other constituent members (such as the current collector plate 2) by hot pressing or the like. When the substrate is a transfer substrate, the substrate with the conductive gas diffusion layer is laminated on the current collector plate 2 and the like, and then the substrate is peeled to form the conductive gas diffusion layer 4 with the current collector plate 2. It can be formed by transferring to Alternatively, the conductive gas diffusion layer 4 may be formed by applying the paste composition directly to the current collector 2 or the positive electrode 5 and drying it. The conductive gas diffusion layer 4 after drying has a structure in which a plurality of pores are formed and gas is easily diffused. The gas diffusivity is preferably about 5 seconds / 100 ml to 500 seconds / 100 ml, more preferably about 10 seconds / 100 ml to 200 seconds / 100 ml. The gas diffusivity can be controlled by adjusting the type of the conductive carbon material, the blending amount of the polymer, and the like. The gas diffusivity is measured according to the method stipulated in the Gurley method (JIS P8117) by placing a measurement sample on a silicon film (a film in which gas does not diffuse and permeate) and the time for 100 ml of air to diffuse. It is the value evaluated by doing. The thickness of the conductive gas diffusion layer 4 is not particularly limited, but is preferably about 50 μm to 1000 μm, and more preferably about 200 μm to 500 μm. By setting it as such thickness, it is easy to introduce gas into the conductive gas diffusion layer 4 from the outside, and the volume energy density can be improved. The size of the conductive gas diffusion layer 4 can be arbitrarily set depending on the cell structure. As described above, in particular, the outer shape on the gas introduction side is made larger than the outer shape of the positive electrode 5 and the outer container 6 has an inner size. It is preferable that the size is such that the entire electrolyte 3 is not immersed in the electrolyte 3 (a size at which the upper edge is exposed from the electrolyte 7). Specifically, the size is preferably about 1 mm to 10 mm protruding above the positive electrode 5, and more preferably about 2 mm to 5 mm. The conductive gas diffusion layer 4 preferably has low electrical resistance and water repellency.

  As the above-described carbon particles, known or commercially available carbon particles can be used as long as they have conductivity. For example, carbon black such as channel black, furnace black, ketjen black, acetylene black, lamp black, graphite, activated carbon, etc. may be used alone or in combination of two or more. Of these, ketjen black and acetylene black are particularly preferred. The arithmetic average particle diameter of the carbon particles is usually about 1 nm to 1000 nm, preferably about 5 nm to 50 nm.

  The above-described carbon fiber may have an aspect ratio (fiber length / fiber diameter) of 50 or more, and more preferably about 60 to 1000. By including such carbon fibers in the conductive gas diffusion layer 4, the porosity of the conductive gas diffusion layer 4 can be improved, or the strength of the conductive gas diffusion layer 4 can be improved. The average fiber diameter is preferably about 100 nm to 300 nm, and the average fiber length is preferably about 10 μm to 100 μm. Examples of the carbon fiber include chemical vapor grown carbon fiber (VGCF) and carbon nanotube.

  As the above-mentioned polymer, vinyl acetate resin, styrene-acrylic copolymer resin, styrene-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, polyester-acrylic copolymer resin, urethane resin, Examples include acrylic resin, phenol resin, polyvinylidene fluoride (PVDF) resin, polytetrafluoroethylene (PTFE) resin, and the like. Moreover, fluorine rubber, silicone rubber, etc., such as a hexafluoropropylene-vinylidene fluoride copolymer and a trifluoroethylene chloride-vinylidene fluoride copolymer, can also be illustrated. These high molecular polymers may be used alone or in combination of two or more. By containing the fluorine-based resin in the conductive gas diffusion layer 4, the conductive gas diffusion layer 4 can have water repellency, and it is difficult for the electrolyte 7 to enter the conductive gas diffusion layer 4. It is possible to suppress the pores in the diffusion layer 4 from being blocked by the electrolyte 7.

  As the above-mentioned solvent, known or commercially available solvents can be widely used. For example, monohydric or polyhydric alcohol having about 1 to 4 carbon atoms such as water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, ethylene glycol, propylene glycol, etc. Can be preferably exemplified. These solvents may be used alone or in combination of two or more.

  In the above-described paste composition for forming the conductive gas diffusion layer 4, a known foaming agent or a pore-forming material is formed in order to efficiently form pores that allow gas to continuously permeate the fired conductive gas diffusion layer 4. An agent may be added.

  Moreover, the above-mentioned paste composition for the conductive gas diffusion layer may contain various additives such as a dispersant in addition to the foaming agent and the pore-forming agent. A known or commercially available dispersant may be used, and examples thereof include polyoxyethylene alkylene alkyl ether, polyethylene glycol alkyl ether, polyoxyethylene fatty acid ester, and acid group-containing structure-modified polyacrylate. .

  Further, the blending ratio of the above-mentioned paste composition for the conductive gas diffusion layer is not particularly limited, but for example, 10 parts by weight to 5000 parts by weight (preferably 30 parts by weight) of the polymer with respect to 100 parts by weight of the carbon particles. Parts by weight to 500 parts by weight), 10 parts by weight to 5000 parts by weight of carbon fiber (preferably 50 parts by weight to 500 parts by weight), and 50 parts by weight to 50000 parts by weight of solvent (preferably 500 parts by weight to 5000 parts by weight). do it.

  The conductive gas diffusion layer 4 can be formed by applying the paste composition for the conductive gas diffusion layer to the current collector plate 2 and then drying the paste composition. The application amount of the paste composition for the conductive gas diffusion layer is not particularly limited. For example, the conductive gas diffusion layer 4 after drying is applied so that the thickness of the conductive gas diffusion layer 4 is about 50 to 1000 μm, preferably about 200 to 500 μm. It is good.

  As a coating method of the paste composition for the conductive gas diffusion layer, for example, knife coater, bar coater, blade coater, spray coater, dip coater, spin coater, roll coater, die coater, curtain coater, screen printing, etc. A general coating method can be used.

  What is necessary is just to perform the drying after application | coating of the paste composition for conductive gas diffusion layers at about 60 degreeC-180 degreeC (preferably 90 degreeC-140 degreeC) in an atmospheric condition, for example. Although drying time is suitably set according to drying temperature etc., what is necessary is just to normally be about 10 minutes-100 minutes. Moreover, the water repellency of the conductive gas diffusion layer 4 to be formed can be improved by baking after drying. The firing temperature is usually 200 ° C. or higher, preferably about 300 ° C. to 380 ° C. The firing time is appropriately set according to the heating temperature and the like, but is usually 30 minutes or longer, preferably about 1 to 2 hours. Note that firing is not necessarily performed.

  The base material is not particularly limited as long as the paste composition for the conductive gas diffusion layer can be applied. For example, polyimide, polyethylene terephthalate, polyparabanic acid aramid, polyamide (nylon), polysulfone, polyethersulfur Examples thereof include polymer films such as phon, polyphenylene sulfide, polyether ether ketone, polyether imide, polyarylate, polyethylene naphthalate, and polypropylene. Also, use ethylene tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluorofluoroalkyl vinyl ether copolymer (PFA), polytetrafluoroethylene (PTFE), etc. Can do. Among these, a polymer film excellent in heat resistance and easily available is preferable. For example, films of polyethylene terephthalate, polyethylene naphthalate, polytetrafluoroethylene (PTFE), polyimide, and the like are preferable. The thickness of the substrate is usually preferably about 6 μm to 100 μm, and more preferably about 10 μm to 60 μm, from the viewpoints of handleability and economy. In addition, it is preferable that the release layer is laminated | stacked on the surface of the base material. Examples of the release layer include those composed of known wax, silicon resin, fluororesin, and the like.

(Positive electrode)
The catalyst of the positive electrode (catalyst layer) 5 is a material capable of reducing oxygen, for example, a carbon material such as platinum or activated carbon, a non-oxide material such as iridium, a manganese oxide such as manganese dioxide, an iridium oxide or titanium, Examples include iridium oxides containing one or more metals selected from the group consisting of tantalum, niobium, tungsten and zirconium, oxide materials such as perovskite complex oxides, and metal-containing pigments such as iron phthalocyanine and cobalt porphyrin. be able to. The positive electrode 5 is prepared by preparing a paste composition for forming a positive electrode including the above-described catalyst and, if necessary, a conductive carbon material and a binder for bonding them to the current collector plate 2, and using the paste composition as a transfer substrate. It can be formed by being applied onto the substrate and dried, and then transferred onto the conductive gas diffusion layer 4. Alternatively, the positive electrode 5 may be formed by directly applying the paste composition onto the conductive gas diffusion layer 4. The drying time and transfer conditions of the paste composition can be appropriately set within the range of known conditions. Alternatively, the above materials may be kneaded and pressed to form a sheet.

  The conductive carbon material is not particularly limited as long as it is a material that can improve the conductivity of the positive electrode 5 (catalyst layer). Specifically, carbon materials such as acetylene black and ketjen black can be exemplified.

  The binder constituting the positive electrode 5 may be any one that does not dissolve in the electrolyte 7 used and does not decompose, such as polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, Preferred examples of the fluororesin include tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, and chlorotrifluoroethylene / ethylene copolymer. it can.

The coating amount of the ink described above is preferably from ^{0.1mg / cm 2 ~20mg / cm 2} , 1mg / cm 2 ~10mg / cm 2 is more preferable.

  In addition, as a method of forming the positive electrode 5, a method of depositing gold ultrafine particles on the conductive gas diffusion layer 4 by electrolyzing a solution containing gold ions can be exemplified. The positive electrode 5 can be formed by electrolytically depositing the gold ultrafine particles on the conductive gas diffusion layer 4 from a solution containing an anion containing gold atoms. For example, the gold ultrafine particles can be uniformly electrolytically deposited using an acidic aqueous solution containing a chloroauric acid anion.

(Electrolytes)
The electrolyte 7 is not particularly limited, and an electrolyte having an appropriate composition can be used depending on the metal material constituting the negative electrode 3 or the like. For example, as the electrolyte 7 of the aluminum air battery, a neutral aqueous electrolyte solution in which sodium chloride, aluminum chloride, manganese chloride or the like is dissolved in water, or an alkaline solution in which sodium hydroxide, potassium hydroxide or the like is dissolved in water. An aqueous electrolyte solution can be used.

  Similarly, as the electrolyte 7 of the magnesium-air battery, the zinc-air battery, and the iron-air battery, similarly to the aqueous electrolyte solution such as a sodium chloride aqueous solution, various known salts or alkaline aqueous electrolyte solutions can be appropriately used. . For example, an aqueous electrolyte solution in which any of ammonium chloride, sodium hydroxide, lithium hydroxide, cesium hydroxide, rubidium hydroxide, and the like is dissolved in water can be used.

  Examples of the electrolyte 7 of the lithium air battery include lithium hexafluorophosphate, lithium perchlorate, lithium borofluoride, lithium hexafluoroarsenate, lithium tetrachloroaluminate, lithium trifluoromethanesulfonate, and hexafluoroantimony. An electrolyte solution in which lithium acid or the like is dissolved in a solvent can be used, but the material is not particularly limited as long as lithium ions are formed in the solution. These materials may be used alone or in combination of two or more.

  As the solvent, water or a known organic solvent of this kind can be used. For example, propylene carbonate, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-dimethoxyethane, 2-methyltetrahydrofuran, sulfolane, diethyl carbonate, dimethylformamide, Examples include acetonitrile, dimethyl carbonate, and ethylene carbonate. These organic solvents may be used alone or in combination of two or more.

  When water is used as the electrolyte solvent of the lithium-air battery, a separator 71 capable of transmitting lithium ions is provided between the negative electrode 3 and the positive electrode 5 in the outer container 6 as shown in FIG. Thus, the region filled with the electrolyte 7 in the outer container 6 may be divided into two regions. Then, the above-described organic solvent electrolyte solution 72 is filled in the region on the negative electrode 3 side, and the aqueous electrolyte solution 73 in which lithium chloride, lithium hydroxide, etc. are dissolved in water is filled in the region on the positive electrode 5 side. The module 10 can be configured. In addition, if a protective layer (for example, lithium ion conductive oxide, lithium ion transmission polymer, etc.) is provided on the surface of the negative electrode 3 (lithium), the separator 71 is not used and the electrolyte 7 is added to the organic solvent electrolyte solution, An electrolyte solution can be used.

  In addition, the electrolyte 7 is not necessarily in a liquid form, and is prepared by adding a coagulant or the like to the above-described electrolyte solution to obtain a solid or gel form, or a metal oxide or solid polymer having ion conductivity. Materials can also be used.

(Exterior container)
The outer container 6 can be formed of, for example, a thermoplastic resin or a metal. If it is the exterior container 6 made from a thermoplastic resin, it can be manufactured by injection molding or pressure molding. The thermoplastic resin can be produced by winding a prepreg impregnated with a thermosetting resin around a mold to form an original mold, and then removing the mold and curing by heating. The metal outer container 6 can be manufactured by cutting and bending a sheet metal and then welding. In the outer container 6, a separator can be provided between the positive electrode 5 and the negative electrode 3 in the electrolyte 7. As the material of the separator, cellulose paper, a nonwoven fabric made of glass fiber, or a nonwoven fabric made of synthetic resin fiber such as aramid, polyester, nylon, vinylon, polyolefin, rayon, or the like can be used.

<Example 1>
A stainless steel plate (SUS304, size 50 mm × 50 mm × 0.5 mm) degreased with acetone as a current collector plate, and a zinc plate (purity 99.9) as a negative electrode using a conductive adhesive (Dotite D362). %, Size 44 mm × 44 mm × 1 mm).

  The paste composition for the conductive gas diffusion layer was prepared as follows. VGCF: 50 parts by weight (carbon fiber manufactured by Showa Denko KK), Denka black: 20 parts by weight (carbon black manufactured by Denki Kagaku Kogyo Co., Ltd.), Solef 6020: 30 parts by weight (manufactured by polyvinylidene fluoride Solvey), N-methyl-2 -Pyrrolidone: 250 parts by weight (Mitsubishi Chemical Corporation) was kneaded with a planetary mixer to prepare a paste composition for a conductive gas diffusion layer. The prepared paste composition for the conductive gas diffusion layer was applied to a polyethylene terephthalate film (Lumirror X44 manufactured by Toray Film Co., Ltd.) using an applicator and dried in an oven at 140 ° C. for 20 minutes. The paste composition was applied so that the thickness of the coating layer after drying was 200 μm.

The paste composition for forming the positive electrode (catalyst layer) was prepared as follows. YP50: 50 parts by weight (activated carbon Kuraray Chemical Co., Ltd.), ketjen black: 20 parts by weight (Carbon Black Lion Co., Ltd.), manganese oxide: 10 parts by weight (manufactured by Kanto Chemical Co., Ltd.), Polyflon D-210C: 33 parts by weight PTFE dispersion manufactured by Daikin Industries, Ltd.), ion-exchanged water: 180 parts by weight were kneaded with a planetary mixer to prepare a paste composition for forming a positive electrode (catalyst layer). The prepared paste composition for forming a positive electrode (catalyst layer) was applied to a polyethylene terephthalate film (Lumirror X44, manufactured by Toray Film Co., Ltd.) using an applicator, and dried in an oven at 100 ° C. for 20 minutes. The paste composition was applied so that the weight of the coating layer after drying was 3 mg / cm ² .

  As shown in FIG. 4, the conductive gas diffusion layer 4 cut out to 44 mm × 47 mm is formed on the surface of the current collector plate 2 that does not have the negative electrode so that the current collector plate 2 and the upper edge coincide with each other. Then, the image was transferred by a hot press at 150 ° C. and 4 MPa. The base film on the conductive gas diffusion layer 4 is peeled off, and the positive electrode 5 (catalyst layer) cut out to 44 mm × 44 mm is transferred onto the conductive gas diffusion layer 4 by a hot press at 150 ° C. and 4 MPa. The base film on the positive electrode 5 (catalyst layer) was peeled off. The laminate was vacuum dried at 200 ° C. for 12 hours to produce an air battery electrode.

<Example 2>
In the same manner as in Example 1, a current collector plate, a negative electrode, a conductive gas diffusion layer, and a positive electrode (catalyst layer) were prepared. As shown in FIG. The conductive gas diffusion layer 4 cut into 44 mm × 48 mm is transferred by a hot press at 150 ° C. and 4 MPa so that the upper edge of the conductive gas diffusion layer 4 protrudes 1 mm from the upper edge of the current collector plate 2. I let you. The base film on the conductive gas diffusion layer 4 is peeled off, and the positive electrode 5 (catalyst layer) cut out to 44 mm × 44 mm is transferred onto the conductive gas diffusion layer 4 by a hot press at 150 ° C. and 4 MPa. The base film on the positive electrode 5 (catalyst layer) was peeled off. The laminate was vacuum dried at 200 ° C. for 12 hours to produce an air battery electrode.

<Example 3>
A stainless steel plate (SUS304, size 50 mm × 50 mm × 0.5 mm) degreased with acetone as a current collector plate, and a zinc plate (purity 99.9) as a negative electrode using a conductive adhesive (Dotite D362). %, Size 44 mm × 44 mm × 1 mm). Further, a mask having an opening of 44 mm × 47 mm was provided on the surface of the current collector plate on the side having no negative electrode so that the upper edge of the opening coincided with the current collector and the upper edge.

  The paste composition for the conductive gas diffusion layer was prepared as follows. VGCF: 50 parts by weight (carbon fiber manufactured by Showa Denko KK), Denka black: 20 parts by weight (carbon black manufactured by Denki Kagaku Kogyo Co., Ltd.), Solef 6020: 30 parts by weight (manufactured by polyvinylidene fluoride Solvey), N-methyl-2 -Pyrrolidone: 250 parts by weight (Mitsubishi Chemical Corporation) was kneaded with a planetary mixer to prepare a paste composition for a conductive gas diffusion layer. The prepared paste composition for the conductive gas diffusion layer was applied to an opening of a mask provided on a current collector plate using an applicator and dried in an oven at 140 ° C. for 20 minutes. The paste composition was applied so that the thickness of the coating layer after drying was 200 μm.

The paste composition for forming the positive electrode (catalyst layer) was prepared as follows. YP50: 50 parts by weight (activated carbon Kuraray Chemical Co., Ltd.), ketjen black: 20 parts by weight (Carbon Black Lion Co., Ltd.), manganese oxide: 10 parts by weight (manufactured by Kanto Chemical Co., Ltd.), Polyflon D-210C: 33 parts by weight PTFE dispersion manufactured by Daikin Industries, Ltd.), ion-exchanged water: 180 parts by weight were kneaded with a planetary mixer to prepare a paste composition for forming a positive electrode (catalyst layer). The prepared paste composition for forming the positive electrode (catalyst layer) is applied to the conductive gas diffusion layer on the current collector plate in a size of 44 mm × 44 mm using an applicator and dried in an oven at 100 ° C. for 20 minutes. I let you. The paste composition was applied so that the weight of the coating layer after drying was 3 mg / cm ² . The laminate was vacuum dried at 200 ° C. for 12 hours to produce an air battery electrode.

  By injection molding, an exterior container made of vinyl chloride provided with four insertion grooves is formed, and the air battery electrodes produced in Examples 1 to 3 are inserted and attached to each insertion groove via packing. did. With each air battery electrode, three independent electrolyte solution tanks partitioned from each other are formed in a region within the outer container. Each electrolyte solution tank was filled with a potassium hydroxide aqueous solution adjusted to a concentration of 10% as an electrolyte solution until the entire negative electrode and positive electrode (catalyst layer) were immersed to form a zinc-air battery. The current collector plate of each air battery electrode and the upper edge of the conductive gas diffusion layer were exposed from the electrolyte solution to the air. When the voltage between the current collector plates of the air battery electrodes at both ends of the zinc air battery module obtained by connecting the three zinc air batteries thus obtained in series was measured, any one of Examples 1 to 3 was measured. It was confirmed that the air battery module using the air battery electrode operated well.

DESCRIPTION OF SYMBOLS 1 Electrode for air batteries 2 Current collector plate 3 Negative electrode 4 Conductive gas diffusion layer 5 Positive electrode 6 Exterior container 7 Electrolyte 8 Insertion groove

The object of the present invention is to provide a current collector plate, a negative electrode provided on one plate surface of the current collector plate, a conductive gas diffusion layer provided on the other plate surface of the current collector plate, and the conductive material. A positive electrode provided on the surface of the conductive gas diffusion layer opposite to the current collector plate, and the conductive gas diffusion layer contains a conductive carbon material and a polymer. This is achieved by the battery electrode. In the method for producing an air battery electrode having the above-described structure, a paste composition containing a conductive carbon material and a polymer is applied on a substrate, and then dried to form a substrate with a conductive gas diffusion layer. A step of stacking and integrating the conductive gas diffusion layer side of the substrate with the conductive gas diffusion layer on the current collector plate or the positive electrode, and peeling the substrate from the conductive gas diffusion layer It is preferable to provide the process to do. Or it is preferable to provide the process of apply | coating the paste composition containing a conductive carbon material and a high molecular polymer to a collector or a positive electrode.

In the air battery electrode having the above structure, it is preferable that a part of the outer peripheral edge portion of the conductive gas diffusion layer protrudes outward from the outer peripheral edge portion of the positive electrode. The outer shape of the conductive gas diffusion layer on the side where the gas is introduced is preferably larger than the outer shape of the positive electrode. Further, the positive electrode has at least a length in the vertical direction when standing upright is shorter than the conductive gas diffusion layer, and the conductive gas diffusion layer protrudes outward from at least the upper edge of the positive electrode. Is preferred.

In the air battery electrode having the above structure, it is preferable that a part of the conductive gas diffusion layer immersed in the electrolyte is exposed from the electrolyte to the air .

Claims (4)

Current collector plate,
A negative electrode provided on one plate surface of the current collector plate;
A conductive gas diffusion layer provided on the other plate surface of the current collector plate;
A positive electrode provided on the surface of the conductive gas diffusion layer opposite to the current collector,
The electrode for an air battery, wherein the conductive gas diffusion layer includes a conductive carbon material and a polymer.   2. The air battery electrode according to claim 1, wherein a part of the conductive gas diffusion layer protrudes above the positive electrode. An outer container in which a plurality of insertion grooves are formed at intervals on the inner peripheral surface;
A plurality of air battery electrodes according to claim 1 or 2 inserted into the insertion groove;
And an electrolyte filled in a region partitioned by the plurality of air battery electrodes in the outer container.   The air battery module according to claim 3, wherein a part of the conductive gas diffusion layer immersed in the electrolyte is exposed above the electrolyte.