JP2013069493A - Method for manufacturing laminated air cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a laminated metal-air cell, which is capable of suppressing displacement between a laminate and a cathode collector.SOLUTION: The method for manufacturing a laminated metal-air cell using a laminate as an exterior material comprises the steps of: preparing the laminate and a cathode collector; fixing the laminate and the cathode collector; and providing through holes in the laminate and the cathode collector which are fixed.

Description

  The present invention relates to a method for manufacturing a laminated air battery.

  With the spread and progress of devices such as mobile phones in recent years, it has been desired to increase the capacity and weight of batteries as power sources. Under such circumstances, the metal-air battery uses the oxygen in the atmosphere as the positive electrode active material at the air electrode, and the oxygen reduction reaction of the oxygen is performed, while the negative electrode oxidizes the metal constituting the negative electrode. Since the reductive reaction is performed, charging or discharging is possible. Therefore, the energy density is high, and it has been attracting attention as a high-capacity secondary battery that is superior to the currently used lithium ion secondary batteries (Non-patent Document 1). .

  A power generation element including a positive electrode current collector, a positive electrode, a separator, an electrolyte, a negative electrode, and a negative electrode current collector is encapsulated in a laminate sheet using a laminate sheet provided with air holes as an exterior material, and further, a positive electrode tab and a negative electrode tab A laminate-type metal-air battery is disclosed (Patent Document 1).

JP 2004-288571 A

National Institute of Advanced Industrial Science and Technology (AIST), “Development of high-performance lithium-air battery with new structure”, [online], press release on February 24, 2009, [search on August 19, 2011], Internet <http://www.aist.go.jp/aist_j/press_release/pr2009/pr20090224/pr20090224.html>

  During the manufacturing process of a laminated metal-air battery or after completion of the battery, the relative position between the laminate and the positive electrode current collector often deviates from the predetermined position, and the holes formed in the laminate and the positive electrode current collector holes deviate from the design position. It may shift. As a result, it was found that the pore diameter for taking oxygen into the positive electrode layer was reduced and the amount of oxygen gas taken in was insufficient, making it impossible to obtain a battery with desired characteristics.

  Therefore, there is a need for a method for manufacturing a laminate-type metal-air battery that can suppress misalignment between the laminate and the positive electrode current collector.

  The present invention is a method for producing a laminate-type air battery including forming a through hole in a laminate and a positive electrode current collector in a state where the laminate and the positive electrode current collector are fixed.

  The present invention relates to a metal-air battery manufacturing method using a laminate as an exterior material, the step of preparing a laminate and a positive electrode current collector, the step of fixing the laminate and the positive electrode current collector, and the fixed laminate and the positive electrode current collector. A method for producing a laminated metal-air battery, comprising a step of providing a through hole in a body.

  According to the method for manufacturing a laminate type air battery according to the present invention, it is possible to suppress a shift in the relative position between the positive electrode current collector and the laminate in the battery manufacturing process or in the use after the battery is manufactured. .

It is the upper surface schematic diagram of the laminate fixed using the heat sealing | fusion material and a positive electrode electrical power collector. It is the upper surface schematic diagram of what formed the through-hole in the laminate fixed using the heat sealing | fusion material and the positive electrode electrical power collector. It is an upper surface schematic diagram of the laminate which has a notch. It is an upper surface schematic diagram of the positive electrode electrical power collector inserted in the notch | lamination of a laminate. It is an upper surface schematic diagram of what formed the through-hole in the positive electrode electrical power collector inserted in the cut of a laminate.

  The present invention relates to a method for producing a metal-air battery using a laminate as an exterior material. The laminate and the positive electrode current collector are prepared, and the laminate and the positive electrode current collector are fixed. It is a manufacturing method of a laminate type metal air battery including the step of providing a hole.

  Conventionally, when a laminated metal-air battery is manufactured, a laminate for forming air into the positive electrode layer is formed in the laminate, and combined with a positive electrode current collector having a porous structure for incorporating air into the positive electrode layer. Although the laminate and the positive electrode current collector are not fixed, the relative position between the laminate and the positive electrode current collector is a predetermined position after the production process of the laminated metal-air battery or after the battery is completed. Easily deviated from. If the hole formed in the laminate and the hole of the positive electrode current collector deviate from the design position, the hole diameter for taking oxygen into the positive electrode layer decreases, the oxygen gas intake amount becomes insufficient, and the battery characteristics deteriorate. I understood. Accordingly, a method for manufacturing a laminate type air battery including forming a plurality of through holes in the laminate and the positive electrode current collector for taking oxygen gas into the positive electrode layer in a state where the laminate and the positive electrode current collector are fixed has been found. .

  There are several methods for fixing the laminate and the positive electrode current collector.

  In the first embodiment of the method for manufacturing a laminate type air battery according to the present invention, the step of fixing the laminate and the positive electrode current collector includes the step of fixing the laminate and the positive electrode current collector using a heat sealing material. Can be included.

  As shown in FIG. 1, a laminate 1 and a positive electrode current collector 2 are prepared, a positive electrode current collector 2 is disposed on the laminate 1, and at least a part of the boundary between the laminate 1 and the positive electrode current collector 2 is covered. The heat sealing material 3 is arranged in this manner, and the part where the laminate 1 and the heat sealing material 3 are in contact with each other is heat-sealed using, for example, a laminate sealer, and the laminate 1 and the positive electrode current collector 2 are fixed. Can do.

  The heat-sealable material 3 can be disposed at any position as long as the laminate 1 and the positive electrode current collector 2 can be fixed. For example, when a square or rectangular positive electrode current collector as shown in FIG. 1 is used, the heat sealing material 3 is disposed so as to straddle two sides of the positive electrode current collector 2 as shown in FIG. Or can be arranged so as to cover all four sides of the positive electrode current collector 2, or cover two corners, three corners, or four corners of the four corners of the positive electrode current collector 2. Can be arranged.

  As shown in FIG. 2, a plurality of through holes 4 can be formed in the laminate 1 and the positive electrode current collector 2 fixed by heat fusion. The plurality of through holes 4 can be formed using any method that can form a plurality of through holes, such as punches.

  Since the laminate 1 and the positive electrode current collector 2 are fixed by heat fusion, the laminate 1 and the positive electrode current collector 2 are not substantially displaced, and the through-hole 4 formed in the laminate 1 and the positive electrode current collector 2 Even when the battery is used after completion, the predetermined hole diameter can be maintained.

  The heat-sealing material is not particularly limited, and a material that can be heat-sealed can be used. For example, a laminate that can be heat-sealed can be used. Examples of laminates that can be heat-sealed include polypropylene laminates, polyester resin laminates, and polyvinyl chloride laminates. Moreover, as a heat sealing | fusion material, a base material will not be ask | required if the component which can be heat-seal | fused is included.

  As a modification of the first embodiment, an adhesive may be used in place of the heat sealing material. The adhesive is not particularly limited, and an adhesive that can fix the laminate and the positive electrode current collector can be used. For example, a film having an adhesive can be used.

  In the second embodiment of the method for manufacturing a laminate type air battery according to the present invention, the laminate has a notch, and the step of fixing the laminate and the positive electrode current collector includes the positive electrode current collector in the notch provided in the laminate. The step of inserting and fixing can be included.

  A laminate 1 and a positive electrode current collector 2 were prepared, and as shown in FIG. 3, a cut 5 was provided in the laminate 1, and as shown in FIG. 4, four corners of the positive electrode current collector 2 were inserted into the cut 5; The laminate 1 and the positive electrode current collector 2 can be fixed.

  The notch 5 can be formed at any position and length where the laminate 1 and the positive electrode current collector 2 can be fixed. For example, when a square or rectangular positive electrode current collector is used, the notches 5 can be formed at four locations so that four corners of the positive electrode current collector 2 can be inserted, for example, as shown in FIG. The current collector 2 can be formed at two or three places so that two or three corners can be inserted. The cut 5 can be formed in the laminate 1 with a cutter or the like. Alternatively, a laminate 1 having a cut 5 may be prepared in advance.

  As shown in FIG. 5, a plurality of through holes 4 can be formed in the laminate 1 and the positive electrode current collector 2 that are fixed by being inserted into the notches 5. The plurality of through holes 4 can be formed using any method that can form a plurality of through holes, such as punches.

  Since the laminate 1 and the positive electrode current collector 2 are fixed by the notch 5, the laminate 1 and the positive electrode current collector 2 are not substantially displaced, and the through holes 4 formed in the laminate 1 and the positive electrode current collector 2 are used in the battery manufacturing process and the battery. The predetermined hole diameter can be maintained even during use after completion of the above. Further, in the second embodiment, no additional material and energy for fixing are required, and the cost can be reduced.

  In the first embodiment and the second embodiment, the plurality of through holes 4 can be formed at arbitrary positions from the upper surface or the lower surface of the laminate of the laminate 1 and the positive electrode current collector 2. It is preferable that oxygen gas is uniformly taken into the positive electrode layer. Therefore, a plurality of through holes 4 are formed with a uniform pitch from the upper surface or the lower surface of the laminate of the laminate 1 and the positive electrode current collector 2. It is preferable.

  The size of each of the plurality of through holes 4 can be arbitrarily changed according to the desired characteristics and configuration of the battery. For example, holes having a diameter of 1 μm to 20 mm can be formed.

  As a laminate that can be used in the method for producing a metal-air battery according to the present invention, a laminate conventionally used in a battery can be used. For example, a flexible synthetic resin, a thin film made of metal such as aluminum, etc. A multilayer laminate film or the like in which a barrier layer such as aluminum is inserted into a layer made of a synthetic resin can be used.

  As the shape of the laminate, a laminate that can enclose an electrode body including a positive electrode current collector, a positive electrode, an electrolyte, a negative electrode, and a negative electrode current collector can be used. For example, after wrapping an electrode body using a plurality of laminate sheets, the peripheral portions of the laminate sheets can be fused or bonded to be integrated. For example, two laminate sheets arranged on the positive electrode current collector side and the negative electrode current collector side can be used. The electrode body is wrapped with two laminate sheets, and the outer peripheral portion of the laminate sheet can be sealed by heat sealing. it can. Alternatively, an integral laminate sheet can be used to wrap or bend the electrode body, or a bag-like laminate that can contain the electrode body can be used.

  The thickness of the laminate is preferably in the range of 50 to 300 μm from the viewpoints of processability and durability of the laminate and downsizing of the battery.

  As a positive electrode current collector that can be used in the method for producing a metal-air battery according to the present invention, conventionally, a positive electrode current collector that can be used in an air battery and capable of forming a through hole can be used. Metal foils such as aluminum, nickel, SUS, iron, and titanium can be used.

  The thickness of the positive electrode current collector is preferably 1 mm or less, and more preferably 100 μm or less, from the viewpoint of the workability of the positive electrode current collector, the capacity density of the battery, and the like. As the positive electrode current collector, for example, an aluminum foil having a thickness of 20 μm, a nickel foil having a thickness of 30 μm, or the like can be used.

  The metal-air battery manufactured by the manufacturing method according to the present invention can include a positive electrode layer. The positive electrode layer can include a conductive material. Examples of the conductive material include carbon. Examples of the carbon include carbon black such as ketjen black, acetylene black, channel black, furnace black, and mesoporous carbon, activated carbon, carbon carbon fiber, and the like, and carbon having a large specific surface area. Materials are preferably used.

  The positive electrode layer can contain a binder. As the binder, for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), a fluororesin such as fluororubber, a thermoplastic resin such as polypropylene, polyethylene, polyacrylonitrile, or styrene butadiene rubber (SBR) is used. be able to.

  The positive electrode layer may include a redox catalyst. Examples of the redox catalyst include metal oxides such as manganese dioxide, cobalt oxide, and cerium oxide, noble metals such as Pt and Pd, transition metals such as Co, and metal phthalocyanines such as cobalt phthalocyanine. Etc.

  The metal-air battery manufactured by the manufacturing method according to the present invention can include a negative electrode layer. The negative electrode layer is a layer containing a negative electrode active material. Examples of the negative electrode active material include metals, alloy materials, and carbon materials. Examples of the negative electrode active material include alkali metals such as lithium, sodium, and potassium, alkaline earth metals such as magnesium and calcium, and thirteenth aluminum. Examples thereof include transition metals such as group elements, zinc, and iron, or alloy materials and carbon materials containing these metals.

  In addition, an alloy, oxide, nitride, or sulfide containing a lithium element can be used as the negative electrode active material. Examples of the alloy having a lithium element include a lithium aluminum alloy, a lithium tin alloy, a lithium lead alloy, and a lithium silicon alloy. Examples of the metal oxide having a lithium element include lithium titanium oxide. Examples of the metal nitride containing a lithium element include lithium cobalt nitride, lithium iron nitride, and lithium manganese nitride.

  The negative electrode layer may further contain a conductive material and / or a binder. For example, when the negative electrode active material is in the form of a foil, it can be a negative electrode layer containing only the negative electrode active material, and when the negative electrode active material is in a powder form, the negative electrode layer has a negative electrode active material and a binder. be able to. In addition, about a conductive material and a binder, the thing similar to the material which can be used for the above-mentioned positive electrode layer can be used.

  The metal-air battery manufactured by the manufacturing method according to the present invention can include an electrolyte layer between the positive electrode layer and the negative electrode layer. The electrolyte layer conducts metal ions between the positive electrode layer and the negative electrode layer, and is a liquid electrolyte, a solid electrolyte, a gel electrolyte, as long as the material exhibits ion conductivity according to the metal species of the negative electrode layer. Polymer electrolytes, or combinations thereof, can be used.

  Although it does not specifically limit as a liquid electrolyte, Usually used liquid electrolytes, such as an organic electrolyte solution and an ionic liquid, can be used. As the ionic liquid, for example, an ionic liquid in which a solvent having high oxygen radical resistance and a lithium salt are mixed is preferably used. For example, N-methyl-N-propylpiperidinium bistrifluoromethanesulfonylamide and lithium bistrifluoromethanesulfonylamide are used. An ionic liquid mixed with and the like.

The solid electrolyte is not particularly limited, for _{example, Li 2 S-SiS 2,} LiI-Li 2 S-SiS 2, LiI-Li 2 S-P 2 S 5, LiI-Li 2 S-B 2 S 3, Li ₃ PO ₄ —Li ₂ S—Si ₂ S, Li ₃ PO ₄ —Li ₂ S—SiS ₂ , LiPO ₄ —Li ₂ S—SiS, LiI—Li ₂ S—P ₂ O ₅ , LiI—Li ₃ PO Sulfide-based solid electrolyte such as _4- P ₂ S ₅ or Li ₂ S-P ₂ S ₅ , Li ₂ O—B ₂ O ₃ —P ₂ O ₅ , Li ₂ O—SiO ₂ , Li ₂ O—B ₂ O _3, or _{Li 2 O-B 2 O 3} -ZnO oxide-based amorphous solid electrolytes such _{as, Li 1.3 Al 0.3 Ti 0.7 (} PO 4) 3, Li 1 + x + y a x Ti 2-x Si _y P _3−y O ₁₂ (A is Al or Ga, 0 ≦ x ≦ 0.4, 0 <y ≦ 0.6), [(B _1/2 Li _1/2 ) _1−z C _z ] TiO ₃ (B is La, Pr, Nd or Sm, C is Sr or Ba, 0 ≦ z ≦ 0.5) , Li 5 La 3 Ta 2 O 12, Li 7 La 3 Zr 2 O 12, Li 6 BaLa 2 Ta 2 O 12, Or crystalline oxides such as Li _3.6 Si _0.6 P _0.4 O ₄ , crystalline oxynitrides such as Li ₃ PO _{(4-3 / 2w)} N _w (w <1), or LiI, LiI-Al ₂ O _3, Li ₃ N, or Li ₃ N-LiI-LiOH, and the like.

  Although it does not specifically limit as polymer electrolyte, Semi-solid polymer electrolytes, such as polyethylene oxide containing a lithium salt, polypropylene oxide, a polyvinylidene fluoride, or a polyacrylonitrile, are mentioned.

  The metal-air battery manufactured by the manufacturing method according to the present invention may include a separator between the positive electrode layer and the negative electrode layer. Although it does not specifically limit as a separator, For example, microporous films, such as polymer nonwoven fabrics, such as a nonwoven fabric made from a polypropylene and a nonwoven fabric made from a polyphenylene sulfide, olefin resin, such as polyethylene and a polypropylene, or these combinations can be used. When a liquid electrolyte is used as the electrolyte, the separator may be impregnated with an electrolytic solution to form an electrolyte layer.

  In the metal-air battery manufactured by the manufacturing method according to the present invention, the negative electrode current collector can be disposed adjacent to the negative electrode layer. The negative electrode current collector is not particularly limited as long as it is a material conventionally used as a negative electrode current collector, such as a non-porous metal plate or foil. For example, a metal formed from copper, SUS, nickel, or the like A plate or foil can be used.

  The metal-air battery manufactured by the manufacturing method according to the present invention may include an oxygen permeable membrane. The oxygen permeable membrane may be disposed on the positive electrode layer and on the contact portion side with air. As the oxygen permeable membrane, a water-repellent porous membrane that can transmit oxygen in the air and prevent moisture from entering can be used. For example, a porous membrane made of polyester or polyphenylene sulfide can be used. it can. The metal air battery manufactured by the manufacturing method according to the present invention may include a water-repellent film separately.

  Formation of the positive electrode, the electrolyte, and the negative electrode that can be included in the metal-air battery manufactured by the manufacturing method according to the present invention can be performed by any conventional method. For example, in the case of forming a positive electrode containing carbon particles and a binder, an appropriate amount of solvent such as ethanol is added to and mixed with a predetermined amount of carbon particles and a binder, and the resulting mixture is rolled to a predetermined thickness with a roll press, The positive electrode can be obtained by drying and cutting, followed by heating and vacuum drying as desired. Alternatively, a positive electrode can be obtained by adding a suitable amount of a solvent such as ethanol to a predetermined amount of carbon particles and a binder and mixing them to obtain a slurry, and coating and drying the slurry on a substrate. The positive electrode obtained as desired may be press-molded. Examples of the process for coating the positive electrode on the substrate include a doctor blade method and a gravure transfer method. The base material to be used is not particularly limited, and a base material having a film-like flexibility, a hard base material, and the like can be used. For example, a base such as a polyethylene terephthalate (PET) film or Teflon (registered trademark) can be used. Materials can be used.

  The following method is mentioned as one aspect | mode of the assembly method of the metal air battery using the manufacturing method of the metal air battery which concerns on this invention. However, it is not limited to this, and can be performed by any method having substantially the same configuration and effect.

  In accordance with the first embodiment, the second embodiment, or the aspect that has substantially the same configuration as the technical idea described in the claims of the present invention and has the same function and effect, the laminate has a positive electrode. The current collector can be fixed to form a plurality of through holes.

  An electrode body including a positive electrode layer, an electrolyte layer, a negative electrode layer, and a negative electrode current collector in a sandwich shape is disposed on a positive electrode current collector fixed to a laminate having a through hole, and the laminate and the negative electrode disposed on the positive electrode current collector side An electrode body can be put in a laminate disposed on the current collector side, and sealed at the periphery of the laminate by heat fusion or adhesion using an adhesive. When a liquid electrolyte is used as the electrolyte, a separator may be disposed instead of the electrolyte layer, and the laminate may be heat-sealed or bonded in a bag shape so as to wrap the electrode body, and the liquid electrolyte may be injected from the opening of the laminate. it can. When sealing and sealing the laminate, the positive electrode terminal led out from the positive electrode current collector and the negative electrode terminal led out from the negative electrode current collector are arranged so as to extend from the seal seal part to form a metal-air battery. be able to.

  The shape of the metal-air battery obtained by the production method according to the present invention is not particularly limited as long as it can have a plurality of through-holes in the laminate and the positive electrode current collector. Cylindrical shape, square shape, button shape, A desired shape such as a coin shape or a flat shape can be taken.

  The metal-air battery obtained by the production method according to the present invention can be used as a secondary battery, but may be used as a primary battery.

DESCRIPTION OF SYMBOLS 1 Laminate 2 Positive electrode collector 3 Heat sealing material 4 Through-hole 5 Notch

Claims (5)

A method for producing a metal-air battery using a laminate as an exterior material,
Preparing a laminate and a positive electrode current collector;
A step of fixing the laminate and the positive electrode current collector, and a step of providing a through hole in the fixed laminate and the positive electrode current collector,
A method for producing a laminated metal-air battery.   The method for manufacturing a laminate-type metal-air battery according to claim 1, wherein the step of fixing the laminate and the positive electrode current collector includes a step of fixing the laminate and the positive electrode current collector using a heat sealing material. .   The method for producing a laminated metal-air battery according to claim 1, wherein the step of fixing the laminate and the positive electrode current collector includes a step of fixing the laminate and the positive electrode current collector using an adhesive. The laminate has a notch,
The method for producing a laminated metal-air battery according to claim 1, wherein the step of fixing the laminate and the positive electrode current collector includes a step of inserting and fixing the positive electrode current collector into a notch provided in the laminate. .   A laminated metal-air battery manufactured by the method according to any one of claims 1 to 4.

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