JP6155864B2 - Positive electrode structure of lithium air battery and positive electrode manufacturing method - Google Patents

Positive electrode structure of lithium air battery and positive electrode manufacturing method Download PDF

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JP6155864B2
JP6155864B2 JP2013121211A JP2013121211A JP6155864B2 JP 6155864 B2 JP6155864 B2 JP 6155864B2 JP 2013121211 A JP2013121211 A JP 2013121211A JP 2013121211 A JP2013121211 A JP 2013121211A JP 6155864 B2 JP6155864 B2 JP 6155864B2
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positive electrode
current collector
air
electrode current
lithium
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JP2014238985A (en
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泉　博章
博章 泉
カリール ラーマン
カリール ラーマン
良 小松
良 小松
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Suzuki Motor Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
    • H01M50/548—Terminals characterised by the disposition of the terminals on the cells on opposite sides of the cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/533—Electrode connections inside a battery casing characterised by the shape of the leads or tabs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/562—Terminals characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/564—Terminals characterised by their manufacturing process
    • H01M50/566—Terminals characterised by their manufacturing process by welding, soldering or brazing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Description

本発明は、正極端子と、カーボンファイバを含有するシート状の空気極集電体とを有するリチウム空気電池の正極構造及び正極製造方法に関する。   The present invention relates to a positive electrode structure and a positive electrode manufacturing method of a lithium air battery having a positive electrode terminal and a sheet-like air electrode current collector containing a carbon fiber.

負極活物質にリチウム金属を、空気極（正極）活物質に空気中の酸素をそれぞれ用いるリチウム空気電池は、理論的にエネルギー密度が高く、例えば電気自動車の本格的な普及に必要とされるリチウムイオン電池を数倍上回るエネルギー密度が得られる電池として期待されている。   Lithium-air batteries that use lithium metal as the negative electrode active material and oxygen in the air as the air electrode (positive electrode) active material have a theoretically high energy density. For example, lithium required for full-scale popularization of electric vehicles It is expected as a battery that can obtain an energy density several times higher than that of an ion battery.

このリチウム空気電池は、水溶液系電解液を用いたリチウム空気電池と、非水系電解液を用いたリチウム空気電池とに大別される。研究開発の主流は、電池の構造が単純な非水系電解液のリチウム空気電池であるが、水溶液系電解液のリチウム空気電池が次の理由から検討されている。つまり、水溶液系電解液を用いたリチウム空気電池は、非水系電解液のリチウム空気電池に対して、より高い理論エネルギー密度をもつこと、電解液が安価で不燃性であること等の長所があるからである。特に、エネルギー密度が高い長所をより効果的に生かす電池セル構造として、ラミネート型セル構造のリチウム空気電池が提案されている。   This lithium-air battery is roughly classified into a lithium-air battery using an aqueous electrolyte and a lithium-air battery using a non-aqueous electrolyte. The mainstream of research and development is a non-aqueous electrolyte lithium-air battery with a simple battery structure, but an aqueous electrolyte-type lithium-air battery is being studied for the following reasons. In other words, lithium-air batteries using aqueous electrolytes have advantages such as higher theoretical energy density and non-flammable electrolytes than non-aqueous electrolyte lithium-air batteries. Because. In particular, a lithium-cell battery having a laminated cell structure has been proposed as a battery cell structure that takes advantage of the high energy density more effectively.

水溶液系電解液を用いたラミネート型セル構造のリチウム空気電池は、例えば非特許文献１及び特許文献１に開示されている。図８は、非特許文献１に記載のリチウム空気電池１００であり、正極１０１、複合負極１０２及び電解液１０３を有して構成される。   Non-patent Document 1 and Patent Document 1 disclose, for example, a lithium-air battery having a laminated cell structure using an aqueous electrolyte. FIG. 8 shows a lithium-air battery 100 described in Non-Patent Document 1, which includes a positive electrode 101, a composite negative electrode 102, and an electrolytic solution 103.

複合負極１０２は、例えばリチウム金属製の負極１０４と、例えば銅製の負極端子１０５と、負極保護層１０６と、例えばガラスセラミックス製のＬＴＡＰ板１０７とを有して構成される。また、正極１０１は、カーボンファイバを含有するシート状の例えばカーボンクロス製の空気極集電体１０８上に、白金、アルミニウムまたはニッケル製の金属メッシュ１０９が載置され、この金属メッシュ１０９に例えばアルミニウム製の正極端子１１０が接続されて構成される。   The composite negative electrode 102 includes a negative electrode 104 made of, for example, lithium metal, a negative electrode terminal 105 made of, for example, copper, a negative electrode protective layer 106, and an LTAP plate 107 made of, for example, glass ceramics. The positive electrode 101 has a metal mesh 109 made of platinum, aluminum, or nickel placed on a sheet-like air electrode current collector 108 made of carbon cloth, for example, made of carbon cloth. A positive electrode terminal 110 made of metal is connected.

上述の正極１０１と複合負極１０２間に電解液１０３が介在され、これらの正極１０１、複合負極１０２及び電解液１０３が、例えばアルミラミネートフィルムであるガスバリアフィルム１１１及び１１２により両側から袋状に包み込まれてリチウム空気電池１００が構成される。ガスバリアフィルム１１１には、空気導入口となる開口１１３が形成されている。   The electrolyte solution 103 is interposed between the positive electrode 101 and the composite negative electrode 102, and the positive electrode 101, the composite negative electrode 102, and the electrolyte solution 103 are wrapped in a bag shape from both sides by gas barrier films 111 and 112, which are aluminum laminate films, for example. Thus, the lithium air battery 100 is configured. The gas barrier film 111 has an opening 113 serving as an air inlet.

また、特許文献１に記載のリチウム空気電池は、箱状容器内に負極、緩衝層、耐水層（ガラスセラミックス）、電解液、空気極（正極）、酸素透過体が順次配置されたものである。尚、この特許文献１には、正極の構造について何ら開示されていない。   The lithium-air battery described in Patent Document 1 has a negative electrode, a buffer layer, a water-resistant layer (glass ceramics), an electrolyte, an air electrode (positive electrode), and an oxygen permeable body sequentially arranged in a box-shaped container. . Note that Patent Document 1 does not disclose the structure of the positive electrode.

特開２０１０−１９２３１３号公報JP 2010-192313 A 株式会社ジーエス・ユアサ・コーポレーションのレポート「水溶液系リチウム／空気電池の現状と課題」（２０１０年６月）GS Yuasa Corporation Report “Current Status and Challenges of Aqueous Lithium / Air Battery” (June 2010)

非特許文献１に記載のリチウム空気電池１００の正極１０１は、正極端子１１０が接続された金属メッシュ１０９が空気極集電体１０８に載置されて構成されるので、空気極集電体１０８と金属メッシュ１０９との密着性が不十分になって、リチウム空気電池１００の電気伝導性が低下してしまう。   Since the positive electrode 101 of the lithium-air battery 100 described in Non-Patent Document 1 is configured by placing the metal mesh 109 connected to the positive electrode terminal 110 on the air electrode current collector 108, Adhesiveness with the metal mesh 109 becomes insufficient, and the electrical conductivity of the lithium-air battery 100 is lowered.

また、図９に示すように、空気極集電体１０８の周端部１０８Ａとガスバリアフィルム１１１の開口１１３周縁との間に隙間１１４が形成されてしまうので、電解液１０３が上記隙間１１４から漏洩する恐れがある。   Further, as shown in FIG. 9, since a gap 114 is formed between the peripheral end portion 108 </ b> A of the air electrode current collector 108 and the periphery of the opening 113 of the gas barrier film 111, the electrolytic solution 103 leaks from the gap 114. There is a fear.

更に、水溶液系の電解液１０３は、電池反応により生成される水酸化リチウム等によって強アルカリ性になる。金属メッシュ１０９がアルミニウムやニッケルなどにより構成されると、強アルカリ性の電解液１０３によって腐食し、腐食生成物が空気極集電体１０８に付着することで、この空気極集電体１０８の電気抵抗が増大してしまう。このため、金属メッシュ１０９は、耐食性が高いが高価な白金が用いられることになり、この結果、リチウム空気電池１００のコストが上昇してしまう。   Further, the aqueous electrolyte 103 becomes strongly alkaline due to lithium hydroxide or the like produced by the battery reaction. When the metal mesh 109 is made of aluminum, nickel, or the like, it is corroded by the strong alkaline electrolyte 103, and the corrosion product adheres to the air electrode current collector 108, so that the electric resistance of the air electrode current collector 108 is increased. Will increase. For this reason, the metal mesh 109 has high corrosion resistance, but expensive platinum is used. As a result, the cost of the lithium-air battery 100 increases.

また、図８に示すように、空気極集電体１０８を構成する例えばカーボンクロスなどが繊維状であることから、この空気極集電体１０８は剛性が低く、このため、複合負極１０２などの他部材との位置合せが容易でない。従って、空気極集電体１０８の位置決め精度が低くなり、リチウム空気電池１００の組付性が低下してしまう。   Further, as shown in FIG. 8, for example, the carbon cloth or the like constituting the air electrode current collector 108 is in the form of a fiber, so that the air electrode current collector 108 has low rigidity. Alignment with other members is not easy. Therefore, the positioning accuracy of the air electrode current collector 108 is lowered, and the assembling property of the lithium air battery 100 is lowered.

本発明の目的は、上述の事情を考慮してなされたものであり、空気極集電体と正極端子との密着性を高めて電池の電気伝導性を向上できると共に、空気極集電体の周端部からの電解液の漏洩を防止できるリチウム空気電池の正極構造及び正極製造方法を提供することにある。   The object of the present invention has been made in consideration of the above-mentioned circumstances, and can improve the electrical conductivity of the battery by improving the adhesion between the air electrode current collector and the positive electrode terminal. An object of the present invention is to provide a positive electrode structure for a lithium-air battery and a positive electrode manufacturing method capable of preventing leakage of an electrolyte from a peripheral end portion.

本発明に係るリチウム空気電池の正極構造は、リチウム空気電池が正極と複合負極と電解液とを有して構成され、前記正極が正極端子と、カーボンファイバを含有するシート状の空気極集電体と、を有するリチウム空気電池の正極構造であって、前記空気極集電体に前記正極端子が接触した状態で前記空気極集電体と前記正極端子とが熱可塑性樹脂により熱溶着されると共に、前記空気極集電体の周端部に前記熱可塑性樹脂が含浸されて構成されたことを特徴とするものである。 The positive electrode structure of the lithium air battery according to the present invention is configured such that the lithium air battery includes a positive electrode, a composite negative electrode, and an electrolyte solution, and the positive electrode is a positive electrode terminal and a sheet-like air electrode current collector containing carbon fiber. A positive electrode structure of a lithium air battery, wherein the air electrode current collector and the positive electrode terminal are thermally welded by a thermoplastic resin in a state where the positive electrode terminal is in contact with the air electrode current collector. In addition, the peripheral end portion of the air electrode current collector is impregnated with the thermoplastic resin.

また、本発明に係るリチウム空気電池の正極製造方法は、リチウム空気電池が正極と複合負極と電解液とを有して構成され、前記正極が正極端子と、カーボンファイバを含有するシート状の空気極集電体と、を有するリチウム空気電池の正極製造方法であって、前記空気極集電体に前記正極端子を接触させる接触工程と、前記空気極集電体の周端部と前記正極端子とを、熱可塑性樹脂からなり且つ開口を備えた枠形状の複数の樹脂フィルムによって挟み込む挟み込み工程と、前記空気極集電体と前記正極端子とを前記樹脂フィルムにより熱溶着すると共に、前記空気極集電体の前記周端部に前記熱可塑性樹脂を含浸させる熱溶着・含浸工程と、を有することを特徴とするものである。 The positive electrode manufacturing method for a lithium-air battery according to the present invention includes a lithium-air battery having a positive electrode, a composite negative electrode, and an electrolyte, wherein the positive electrode is a positive electrode terminal and a sheet-like air containing a carbon fiber. and electrode current collector, a positive electrode manufacturing method of the lithium-air battery having a contact step of contacting the positive terminal to the air electrode current collector, wherein a peripheral end portion of the air electrode current collector a positive terminal Are sandwiched between a plurality of frame-shaped resin films made of a thermoplastic resin and provided with openings, and the air electrode current collector and the positive electrode terminal are thermally welded by the resin film, and the air electrode And a thermal welding / impregnation step of impregnating the thermoplastic resin into the peripheral end portion of the current collector.

本発明によれば、空気極集電体と正極端子とが熱溶着により一体に構成され、または一体成形されたので、空気極集電体と正極端子との密着性が高まり、電池の電気伝導性を向上させることができる。また、空気極集電体の周端部に熱可塑性樹脂が含浸されたので、この空気極集電体の周端部が液密構造になって、この周端部からの電解液の漏洩を防止できる。   According to the present invention, since the air electrode current collector and the positive electrode terminal are integrally formed or integrally formed by heat welding, the adhesion between the air electrode current collector and the positive electrode terminal is increased, and the electric conductivity of the battery is increased. Can be improved. In addition, since the peripheral end portion of the air electrode current collector is impregnated with the thermoplastic resin, the peripheral end portion of the air electrode current collector has a liquid-tight structure, and the electrolyte solution leaks from the peripheral end portion. Can be prevented.

本発明に係るリチウム空気電池の正極構造における第１実施形態が適用されたリチウム空気電池の構成を示す分解斜視図。1 is an exploded perspective view showing a configuration of a lithium air battery to which a first embodiment of a positive electrode structure of a lithium air battery according to the present invention is applied. 図１の正極を示す斜視図。The perspective view which shows the positive electrode of FIG. 図１のリチウム空気電池を示す断面図。Sectional drawing which shows the lithium air battery of FIG. 本発明に係るリチウム空気電池の正極構造における第２実施形態が適用された正極を示し図２に対応する斜視図。The perspective view corresponding to FIG. 2 which shows the positive electrode to which 2nd Embodiment in the positive electrode structure of the lithium air battery which concerns on this invention was applied. 図４の正極を示し、（Ａ）が正面図、（Ｂ）が裏面図。The positive electrode of FIG. 4 is shown, (A) is a front view, (B) is a back view. 本発明に係るリチウム空気電池の正極構造における第３実施形態が適用されたリチウム空気電池を示す断面図。Sectional drawing which shows the lithium air battery with which 3rd Embodiment in the positive electrode structure of the lithium air battery which concerns on this invention was applied. 本発明に係るリチウム空気電池の正極構造における第３実施形態の変形形態が適用されたリチウム空気電池を示す断面図。Sectional drawing which shows the lithium air battery with which the modification of 3rd Embodiment in the positive electrode structure of the lithium air battery which concerns on this invention was applied. 従来のリチウム空気電池を示す分解斜視図。The disassembled perspective view which shows the conventional lithium air battery. 図８のリチウム空気電池を示す部分断面図。The fragmentary sectional view which shows the lithium air battery of FIG.

以下、本発明を実施するための実施形態を図面に基づき説明する。
［Ａ］第１実施形態（図１〜図３）
図１は、本発明に係るリチウム空気電池の正極構造における第１実施形態が適用されたリチウム空気電池の構成を示す分解斜視図である。この図１に示すリチウム空気電池１０は、ラミネート型セル構造であり、正極１１と複合負極１２と電解液１３とを有して構成される。電解液１３は、本実施形態では水溶液系の例えば塩化リチウム水溶液などであり、反応生成物を貯蔵する機能も果たす。 DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings.
[A] First embodiment (FIGS. 1 to 3)
FIG. 1 is an exploded perspective view showing a configuration of a lithium air battery to which the first embodiment of the positive electrode structure of a lithium air battery according to the present invention is applied. A lithium-air battery 10 shown in FIG. 1 has a laminate type cell structure, and includes a positive electrode 11, a composite negative electrode 12, and an electrolytic solution 13. In the present embodiment, the electrolytic solution 13 is an aqueous solution system such as an aqueous lithium chloride solution, and also serves to store a reaction product.

複合負極１２は、負極１４と負極端子１５と有機電解液１６とＬＴＡＰ板１７とが樹脂フィルムとしての例えばアルミラミネートフィルム１８及び１９により袋状に包み込まれて構成され、アルミラミネートフィルム１８とＬＴＡＰ板１７との間にＴＢＦ接着シート２０が介在される。   The composite negative electrode 12 is configured by a negative electrode 14, a negative electrode terminal 15, an organic electrolyte solution 16, and an LTAP plate 17 wrapped in a bag shape with, for example, aluminum laminate films 18 and 19 as resin films, and the aluminum laminate film 18 and the LTAP plate TBF adhesive sheet 20 is interposed between

負極１４は、アルカリ金属元素のリチウムまたはナトリウムなどの単体若しくは化合物からなる。なかでもリチウムは、エネルギー密度の高い電池を得るのに適している。本実施形態の負極１４は、リチウムの単体から構成されている。また、この負極１４に接合される負極端子１５は、電気伝導性の高い金属、例えば銅にて構成される。   The negative electrode 14 is made of a simple substance or a compound such as lithium or sodium as an alkali metal element. Among these, lithium is suitable for obtaining a battery having a high energy density. The negative electrode 14 of this embodiment is composed of a simple substance of lithium. The negative electrode terminal 15 joined to the negative electrode 14 is made of a metal having high electrical conductivity, for example, copper.

ＬＴＡＰ板１７は、空気極集電体２２（後述）と負極１４とのセパレータであり、リチウムイオンの導電性が高いガラスセラミックスが用いられる。このＬＴＡＰ板１７は、負極１４への水分などの浸入防止の機能も果たす。また、ＴＢＦ接着シート２０は、ＬＴＡＰ板１７をアルミラミネートフィルム１８に接着させる。   The LTAP plate 17 is a separator between the air electrode current collector 22 (described later) and the negative electrode 14, and glass ceramics having high lithium ion conductivity is used. The LTAP plate 17 also functions to prevent moisture and the like from entering the negative electrode 14. Further, the TBF adhesive sheet 20 adheres the LTAP plate 17 to the aluminum laminate film 18.

アルミラミネートフィルム１８及び１９は、熱可塑性樹脂からなる耐熱性の基材層（例えばＰＥＴ（ポリエチレンテレフタレート））と、接着層（例えばＰＰ（ポリプロピレン）、ＰＥ（ポリエチレン）、ＥＶＡ（エチレンビニルアセテート））との間に、アルミニウム箔が介在されて構成される。アルミラミネートフィルム１８は、上面側が基材層であり、下面側が接着層である。また、アルミラミネートフィルム１９は、上面側が接着層であり、下面側が基材層である。これらのアルミラミネートフィルム１８と１９は、接着層同士が接着することで、負極１４、有機電解液１６及びＬＴＡＰ板１７を袋状に包み込んで複合負極１２を構成する。   Aluminum laminate films 18 and 19 are made of a heat-resistant base layer made of a thermoplastic resin (for example, PET (polyethylene terephthalate)) and an adhesive layer (for example, PP (polypropylene), PE (polyethylene), EVA (ethylene vinyl acetate)). An aluminum foil is interposed between the two. The aluminum laminate film 18 has a base layer on the upper surface side and an adhesive layer on the lower surface side. The aluminum laminate film 19 has an adhesive layer on the upper surface side and a base material layer on the lower surface side. These aluminum laminate films 18 and 19 form a composite negative electrode 12 by wrapping the negative electrode 14, the organic electrolyte solution 16 and the LTAP plate 17 in a bag shape by bonding the adhesive layers together.

正極１１は、図１〜図３に示すように、正極端子２１と、カーボンファイバを含有するシート状の空気極集電体２２とを有してなる。そして、正極１１は、空気極集電体２２の表面または裏面に正極端子２１の先端部２１Ａが接触した状態で、空気極集電体２２と正極端子２１とが熱可塑性樹脂により熱溶着されると共に、空気極集電体２２の全周端部２２Ａに熱可塑性樹脂が含浸されて構成される。   As shown in FIGS. 1 to 3, the positive electrode 11 includes a positive electrode terminal 21 and a sheet-like air electrode current collector 22 containing a carbon fiber. In the positive electrode 11, the air electrode current collector 22 and the positive electrode terminal 21 are thermally welded with a thermoplastic resin in a state where the front end portion 21 </ b> A of the positive electrode terminal 21 is in contact with the front surface or the back surface of the air electrode current collector 22. At the same time, the entire peripheral end 22A of the air electrode current collector 22 is impregnated with a thermoplastic resin.

図２及び図３中の符号２３は、空気極集電体２２の周端部２２Ａに熱可塑性樹脂が含浸された含浸部位である。また、符号２５は、正極端子２１の先端部２１Ａが空気極集電体２２に熱溶着して固着された溶着部位である。   Reference numeral 23 in FIGS. 2 and 3 is an impregnation portion in which the peripheral end portion 22A of the air electrode current collector 22 is impregnated with a thermoplastic resin. Reference numeral 25 denotes a welding portion where the tip end portion 21 </ b> A of the positive electrode terminal 21 is thermally welded to the air electrode current collector 22.

正極端子２１は、アルミニウムまたはニッケルの単体若しくは化合物から構成される。また、空気極集電体２２は、電気伝導性及びガス拡散性を備えたカーボンクロス、カーボンペーパー、カーボン不織布、多孔質ニッケルまたは多孔質アルミニウムなどから構成され、必要に応じて、反応を促進させるための触媒（例えば白金など）や結着剤を含有する。   The positive electrode terminal 21 is made of a simple substance or a compound of aluminum or nickel. The air electrode current collector 22 is made of carbon cloth, carbon paper, carbon nonwoven fabric, porous nickel, porous aluminum, or the like having electrical conductivity and gas diffusibility, and promotes the reaction as necessary. Contains a catalyst (for example, platinum) and a binder.

ここで、カーボンクロスは、一般にカーボンファイバを規則正しく編み込んだシート状のものである。また、カーボン不織布は、カーボンファイバをランダムに絡み合せたシート状のものである。カーボンファイバは、電子が繊維を通じて伝導するため電気伝導性が高く、金属と比較してエネルギー密度が高くなるので、正極１１の空気極集電体２２に適している。本実施形態の空気極集電体２２は、カーボンクロスに白金などの触媒が担持されたものである。   Here, the carbon cloth is generally in the form of a sheet in which carbon fibers are knitted regularly. The carbon non-woven fabric is a sheet-like material in which carbon fibers are randomly entangled. The carbon fiber is suitable for the air electrode current collector 22 of the positive electrode 11 because the electron is conducted through the fiber and has high electric conductivity and the energy density is higher than that of the metal. The air electrode current collector 22 of the present embodiment is one in which a catalyst such as platinum is supported on a carbon cloth.

正極端子２１の先端部２１Ａを空気極集電体２２に熱溶着させ、且つ空気極集電体２２の全周端部２２Ａに含浸される熱可塑性樹脂は、熱可塑性樹脂からなり且つ中央部に開口２４を備えて窓枠形状に形成された樹脂フィルムとしてのラミネートフィルム２６及び２７を構成する上記熱可塑性樹脂である。このラミネートフィルム２６の開口２４により、正極１１の空気導入口２８が形成される。   The thermoplastic resin in which the front end portion 21A of the positive electrode terminal 21 is thermally welded to the air electrode current collector 22 and impregnated in the entire peripheral end portion 22A of the air electrode current collector 22 is made of a thermoplastic resin and has a central portion. It is the said thermoplastic resin which comprises the laminated films 26 and 27 as a resin film provided with the opening 24 and formed in the window frame shape. An air introduction port 28 of the positive electrode 11 is formed by the opening 24 of the laminate film 26.

ここで、アルミラミネートフィルム２６及び２７は、熱可塑性樹脂としての例えばＰＥＴ（ポリエチレンテレフタレート）等からなる耐熱性の基材層と、熱可塑性樹脂としての例えばＰＰ（ポリプロピレン）、ＰＥ（ポリエチレン）、ＥＶＡ（エチレンビニルアセテート）等からなる接着層とを有して構成される。ラミネートフィルム２６は、上面側が基材層であり、下面側が接着層である。また、ラミネートフィルム２７は、上面側が接着層であり、下面側が基材層である。   Here, the aluminum laminate films 26 and 27 include a heat-resistant base material layer made of, for example, PET (polyethylene terephthalate) as a thermoplastic resin, and PP (polypropylene), PE (polyethylene), EVA as thermoplastic resins. And an adhesive layer made of (ethylene vinyl acetate) or the like. The laminate film 26 has a base layer on the upper surface side and an adhesive layer on the lower surface side. The laminate film 27 has an adhesive layer on the upper surface side and a base material layer on the lower surface side.

正極１１は、ラミネートフィルム２６及び２７を用いて次のように製造される。まず、正極端子２１の先端部２１Ａを空気極集電体２２の例えば表面に接触させる接触工程を行う。次に、空気極集電体２２の周端部２２Ａと正極端子２１の先端部２１Ａとを、ラミネートフィルム２６及び２７によって上下方向から挟み込む挟み込み工程を行う。その後、例えば熱プレスなどを用いて、空気極集電体２２と正極端子２１の先端部２１Ａとをラミネートフィルム２６及び２７により熱溶着して一体に構成すると共に、空気極集電体２２の全周端部２２Ａにラミネートフィルム２６及び２７の熱可塑性樹脂を含浸させて含浸部位２３を形成する熱溶着・含浸工程を行う。   The positive electrode 11 is manufactured using the laminate films 26 and 27 as follows. First, a contact process is performed in which the tip 21 </ b> A of the positive electrode terminal 21 is brought into contact with, for example, the surface of the air electrode current collector 22. Next, a sandwiching step is performed in which the peripheral end portion 22A of the air electrode current collector 22 and the tip end portion 21A of the positive electrode terminal 21 are sandwiched from above and below by the laminate films 26 and 27. Thereafter, the air electrode current collector 22 and the tip end portion 21A of the positive electrode terminal 21 are heat-welded with the laminate films 26 and 27, for example, using a heat press or the like. A thermal welding / impregnation step is performed in which the peripheral end portion 22A is impregnated with the thermoplastic resin of the laminate films 26 and 27 to form the impregnation portion 23.

熱溶着・含浸工程における熱プレスの条件は、ラミネートフィルム２６及び２７の接着層がＰＰの場合には、加熱温度が１６０〜１８０℃で、加圧力が２０ｋｇｆ／ｃｍ２（３０秒間）であり、また、ラミネートフィルム２６及び２７の接着層がＥＶＡの場合には、加熱温度が１４０〜１６０℃で、加圧力が２０ｋｇｆ／ｃｍ２（３０秒間）である。 When the adhesive layer of the laminate films 26 and 27 is PP, the heating conditions in the heat welding / impregnation step are a heating temperature of 160 to 180 ° C. and a pressing force of 20 kgf / cm 2 (30 seconds), When the adhesive layers of the laminate films 26 and 27 are EVA, the heating temperature is 140 to 160 ° C., and the applied pressure is 20 kgf / cm 2 (30 seconds).

図１に示すように、上述のように構成された正極１１と、前述のように構成された複合負極１２との間に電解液１３が介在され、正極１１のラミネートフィルム２６と複合負極１２のアルミラミネートフィルム１９との接着層同士が接着されることで、正極１１、複合負極１２及び電解液１３がユニット化されたラミネート型セル構造のリチウム空気電池１０が製造される。   As shown in FIG. 1, an electrolyte solution 13 is interposed between the positive electrode 11 configured as described above and the composite negative electrode 12 configured as described above, and the laminate film 26 of the positive electrode 11 and the composite negative electrode 12 are By bonding the adhesive layers to the aluminum laminate film 19, the lithium-air battery 10 having a laminated cell structure in which the positive electrode 11, the composite negative electrode 12, and the electrolytic solution 13 are unitized is manufactured.

従って、本第１実施形態におけるリチウム空気電池１０の特に正極１１によれば、次の効果（１）〜（５）を奏する。
（１）図２に示すように、空気極集電体２２と正極端子２１の先端部２１Ａとが熱溶着により一体に構成されたので、空気極集電体２２と正極端子２１との密着性が高まり、リチウム空気電池１０の電気伝導性を向上させることができる。従って、空気極集電体２２上に金属メッシュ１０９（図８）を載置する必要がなくなるので、リチウム空気電池１０を軽量化できると共に薄肉化できる。 Therefore, according to especially the positive electrode 11 of the lithium air battery 10 in the first embodiment, the following effects (1) to (5) are obtained.
(1) As shown in FIG. 2, the air electrode current collector 22 and the tip end portion 21 </ b> A of the positive electrode terminal 21 are integrally formed by heat welding, and thus the adhesion between the air electrode current collector 22 and the positive electrode terminal 21. The electrical conductivity of the lithium air battery 10 can be improved. Therefore, since it is not necessary to place the metal mesh 109 (FIG. 8) on the air electrode current collector 22, the lithium air battery 10 can be reduced in weight and thinned.

（２）図３に示すように、空気極集電体２２の全周端部２２Ａに、ラミネートフィルム２６及び２７を構成する熱可塑性樹脂が含浸されて、空気極集電体２２の全周端部２２Ａに含浸部位２３が設けられたので、空気極集電体２２の周端部２２Ａが液密構造になって、この周端部２２Ａ及びその付近からの電解液１３の漏洩を防止できる。このため、正極１１をラミネート型のリチウム空気電池セルの上部構造にできると共に、この正極１１を用いた複数のリチウム空気電池１０を積層化できる。   (2) As shown in FIG. 3, the entire circumferential end 22 </ b> A of the air electrode current collector 22 is impregnated with the thermoplastic resin that constitutes the laminate films 26 and 27, so that the entire circumferential edge of the air electrode current collector 22 is obtained. Since the impregnation portion 23 is provided in the portion 22A, the peripheral end portion 22A of the air electrode current collector 22 has a liquid-tight structure, and leakage of the electrolytic solution 13 from the peripheral end portion 22A and its vicinity can be prevented. For this reason, while being able to make the positive electrode 11 into the upper structure of a laminate-type lithium air battery cell, the several lithium air battery 10 using this positive electrode 11 can be laminated | stacked.

（３）図３に示すように、熱可塑性樹脂による正極端子２１と空気極集電体２２との熱溶着により、正極端子２１の先端部２１Ａが熱可塑性樹脂で被覆されるので、正極端子２１と電解液１３との接触を防止できる。このため、電池反応により水酸化リチウムが生成されて強アルカリ性となる電解液１３により正極端子２１が腐食することを抑制できる。この結果、正極端子２１を構成するアルミニウム、ニッケルが腐食することで生成される腐食生成物が空気極集電体２２に付着して、この空気極集電体２２の電気抵抗が増大することを防止できる。従って、リチウム空気電池１０内で反応に必要な有効面積が減少して電池容量が低下したり、出力及び寿命が低下するなどのリチウム空気電池１０の特性劣化を抑制できる。   (3) As shown in FIG. 3, the tip portion 21A of the positive electrode terminal 21 is covered with the thermoplastic resin by the thermal welding of the positive electrode terminal 21 and the air electrode current collector 22 with the thermoplastic resin. Can be prevented from contacting the electrolyte solution 13. For this reason, it can suppress that the positive electrode terminal 21 corrodes with the electrolyte solution 13 which lithium hydroxide is produced | generated by battery reaction and becomes strong alkalinity. As a result, corrosion products generated by corrosion of aluminum and nickel constituting the positive electrode terminal 21 adhere to the air electrode current collector 22, and the electrical resistance of the air electrode current collector 22 increases. Can be prevented. Therefore, the characteristic area of the lithium air battery 10 such as the effective area required for the reaction in the lithium air battery 10 can be reduced, the battery capacity can be reduced, and the output and life can be reduced.

（４）上述の如く電解液１３による正極端子２１の腐食が抑制されるので、正極端子２１の材質として高価な白金を用いる必要がなく、アルミニウムまたはニッケルなどで足りるので、正極端子２１のコストを低減できる。   (4) Since the corrosion of the positive electrode terminal 21 by the electrolytic solution 13 is suppressed as described above, it is not necessary to use expensive platinum as the material of the positive electrode terminal 21, and aluminum or nickel is sufficient, so the cost of the positive electrode terminal 21 is reduced. Can be reduced.

（５）図２に示すように、空気極集電体２２の全周端部２２Ａには、ラミネートフィルム２６及び２７を構成する熱可塑性樹脂が含浸されて含浸部位２３が形成され、これにより、空気極集電体２２の周端部２２Ａが補強されてその剛性が向上する。従って、この空気極集電体２２を備える正極１１は、複合負極１２などの他部材に容易に位置合せできるので、正極１１の位置決め精度及び組付性が良好になる。この結果、リチウム空気電池１０の製造作業性を向上できると共に、リチウム空気電池１０の歩留まりの低下を抑制でき、このリチウム空気電池１０を複数用いて製造されるリチウム空気電池１０の積層化を容易に実現できる。   (5) As shown in FIG. 2, the entire circumferential end 22A of the air electrode current collector 22 is impregnated with the thermoplastic resin constituting the laminate films 26 and 27 to form the impregnation portion 23. The circumferential end portion 22A of the air electrode current collector 22 is reinforced to improve its rigidity. Therefore, since the positive electrode 11 including the air electrode current collector 22 can be easily aligned with other members such as the composite negative electrode 12, the positioning accuracy and assembling property of the positive electrode 11 are improved. As a result, the manufacturing workability of the lithium air battery 10 can be improved, and the decrease in the yield of the lithium air battery 10 can be suppressed, and the stacking of the lithium air battery 10 manufactured using a plurality of the lithium air batteries 10 can be facilitated. realizable.

［Ｂ］第２実施形態（図４、図５）
図４は、本発明に係るリチウム空気電池の正極構造における第２実施形態が適用された正極を示し図２に対応する斜視図である。この第２実施形態において、第１実施形態と同様な部分については、同一の符号を付すことにより説明を簡略化し、または省略する。 [B] Second Embodiment (FIGS. 4 and 5)
FIG. 4 is a perspective view corresponding to FIG. 2, showing a positive electrode to which the second embodiment of the positive electrode structure of a lithium-air battery according to the present invention is applied. In the second embodiment, the same parts as those in the first embodiment are denoted by the same reference numerals, and the description is simplified or omitted.

本第２実施形態のリチウム空気電池１０における正極３０が第１実施形態の正極１１と異なる点は、正極端子３１が空気極集電体２２と同一材料でこの空気極集電体２２と一体に成形され、正極端子３１の少なくとも片面（本実施形態では図５（Ｂ）に示すように正極端子３１の裏面）に熱可塑性樹脂が溶着された点である。図５（Ｂ）の符号３２は、正極端子３１の裏面における熱可塑性樹脂の溶着部位である。   The positive electrode 30 in the lithium air battery 10 of the second embodiment is different from the positive electrode 11 of the first embodiment in that the positive electrode terminal 31 is made of the same material as the air electrode current collector 22 and is integrated with the air electrode current collector 22. The point is that the thermoplastic resin is welded to at least one surface of the positive electrode terminal 31 (in this embodiment, the back surface of the positive electrode terminal 31 as shown in FIG. 5B). Reference numeral 32 in FIG. 5B denotes a welded portion of the thermoplastic resin on the back surface of the positive electrode terminal 31.

更に、正極端子３１では、図５（Ａ）に示すように、溶着部位３２が設けられていない他の片面（本実施形態では正極端子３１の表面）の空気極集電体２２側が、電解液１３による短絡防止のために熱可塑性樹脂で被覆されている。図５（Ａ）中の符号３３は、正極端子３１の表面における熱可塑性樹脂による被覆部位である。   Furthermore, in the positive electrode terminal 31, as shown in FIG. 5A, the air electrode current collector 22 side on the other side (in this embodiment, the surface of the positive electrode terminal 31) where the welding site 32 is not provided is the electrolyte solution. In order to prevent short circuit due to 13, it is coated with a thermoplastic resin. Reference numeral 33 in FIG. 5A denotes a portion covered with the thermoplastic resin on the surface of the positive electrode terminal 31.

また、正極３０における空気極集電体２２は、その全周端部２２Ａが、第１実施形態と同様に熱可塑性樹脂により含浸されて構成される。図５（Ａ）及び（Ｂ）の符号３４は、空気極集電体２２の全周端部２２Ａにおける熱可塑性樹脂の含浸部位を示す。尚、図５（Ａ）及び（Ｂ）中の破線３５は、熱可塑性樹脂が熱溶着及び含浸される前の、一体成形された正極端子３１及び空気極集電体２２の形状を示す。   Further, the air electrode current collector 22 in the positive electrode 30 is configured such that the entire peripheral end 22A is impregnated with a thermoplastic resin as in the first embodiment. Reference numerals 34 in FIGS. 5A and 5B indicate thermoplastic resin impregnation sites in the entire peripheral end 22 </ b> A of the air electrode current collector 22. 5A and 5B indicate the shapes of the integrally formed positive electrode terminal 31 and air electrode current collector 22 before the thermoplastic resin is thermally welded and impregnated.

空気極集電体２２の周端部２２Ａに含浸部位３４を形成する熱可塑性樹脂は、図４に示すように、樹脂フィルムとしてのラミネートフィルム３６、３７の窓枠形状部３８である。また、正極端子３１の表面に被覆部位３３を形成する熱可塑性樹脂は、ラミネートフィルム３６の第１舌片部３９である。更に、正極端子３１の裏面に溶着部位３２を形成する熱可塑性樹脂は、ラミネートフィルム３７の第２舌片部４０である。   As shown in FIG. 4, the thermoplastic resin that forms the impregnation portion 34 in the peripheral end portion 22 </ b> A of the air electrode current collector 22 is a window frame shape portion 38 of laminate films 36 and 37 as resin films. The thermoplastic resin that forms the covering portion 33 on the surface of the positive electrode terminal 31 is the first tongue piece portion 39 of the laminate film 36. Further, the thermoplastic resin that forms the welding portion 32 on the back surface of the positive electrode terminal 31 is the second tongue piece portion 40 of the laminate film 37.

ラミネートフィルム３６の窓枠形状部３８は第１実施形態のラミネートフィルム２６と、また、ラミネートフィルム３７の窓枠形状部３８は第１実施形態のラミネートフィルム２７と、それぞれ同一形状である。また、窓枠形状部３８及び第１舌片部３９を備えたラミネートフィルム３６は第１実施形態のラミネートフィルム２６と、また、窓枠形状部３８及び第２舌片部４０を備えたラミネートフィルム３７は第１実施形態のラミネートフィルム２７と、それぞれ同一材質にて構成される。   The window frame shape portion 38 of the laminate film 36 has the same shape as the laminate film 26 of the first embodiment, and the window frame shape portion 38 of the laminate film 37 has the same shape as the laminate film 27 of the first embodiment. The laminate film 36 having the window frame shape portion 38 and the first tongue piece portion 39 is the laminate film 26 of the first embodiment, and the laminate film having the window frame shape portion 38 and the second tongue piece portion 40. 37 is composed of the same material as the laminate film 27 of the first embodiment.

本第２実施形態のリチウム空気電池１０における正極３０は、次のようにして製造される。まず、カーボンファイバを含有するシート状の例えばカーボンクロスからなる空気極集電体２２と、この空気極集電体２２に一体成形された正極端子３１とを用意、つまり一体成形された空気極集電体２２及び正極端子３１を用意する準備工程を行う。次に、空気極集電体２２の周端部２２Ａを、ラミネートフィルム３６の窓枠形状部３８とラミネートフィルム３７の窓枠形状部３８とによって上下方向から挟み込む挟み込み工程を行う。この挟み込み工程では、ラミネートフィルム３６の第１舌片部３９が正極端子３１の表面の空気極集電体２２側部分に接触し、またラミネートフィルム３７の第２舌片部４０が正極端子３１の裏面全体に接触する。   The positive electrode 30 in the lithium air battery 10 of the second embodiment is manufactured as follows. First, an air electrode current collector 22 made of, for example, carbon cloth containing a carbon fiber and a positive electrode terminal 31 integrally formed with the air electrode current collector 22 are prepared, that is, an air electrode current collector formed integrally. A preparation process for preparing the electric body 22 and the positive electrode terminal 31 is performed. Next, a sandwiching step is performed in which the peripheral end portion 22A of the air electrode current collector 22 is sandwiched between the window frame shape portion 38 of the laminate film 36 and the window frame shape portion 38 of the laminate film 37 from above and below. In this sandwiching step, the first tongue piece portion 39 of the laminate film 36 is in contact with the air electrode current collector 22 side portion of the surface of the positive electrode terminal 31, and the second tongue piece portion 40 of the laminate film 37 is the positive electrode terminal 31. Touch the entire back surface.

その後、例えば熱プレス等を用いて、空気集電体２２の全周端部２２Ａにラミネートフィルム３６及び３７の両窓枠形状部３８における熱可塑性樹脂を含浸させて含浸部位３４を形成する含浸工程を行う。この含浸工程では、空気極集電体２２の周端部２２Ａへの熱可塑性樹脂の含浸と同時に、正極端子３１の表面の空気極集電体２２側部分にラミネートフィルム３６の第１舌片部３９における熱可塑性樹脂を溶着して被覆部位３３を形成し、更に、正極端子３１の裏面全体にラミネートフィルム３７の第２舌片部４０における熱可塑性樹脂を溶着して溶着部位３２を形成する。この含浸工程における熱プレスの条件は、第１実施形態の熱溶着・含浸工程と略同一である。   Thereafter, the impregnation step of forming the impregnation portion 34 by impregnating the thermoplastic resin in the window frame shape portions 38 of the laminate films 36 and 37 into the entire peripheral end portion 22A of the air current collector 22 using, for example, a heat press or the like. I do. In this impregnation step, the first tongue piece portion of the laminate film 36 is formed on the air electrode current collector 22 side portion of the surface of the positive electrode terminal 31 simultaneously with the impregnation of the thermoplastic resin into the peripheral end portion 22A of the air electrode current collector 22. The thermoplastic resin in 39 is welded to form the covering portion 33, and the thermoplastic resin in the second tongue piece portion 40 of the laminate film 37 is welded to the entire back surface of the positive electrode terminal 31 to form the welding portion 32. The hot press conditions in this impregnation step are substantially the same as those in the thermal welding / impregnation step of the first embodiment.

従って、本第２実施形態におけるリチウム空気電池１０の正極３０によれば、第１実施形態の効果（１）〜（５）と同様な効果を奏するほか、次の効果（６）〜（８）を奏する。   Therefore, according to the positive electrode 30 of the lithium-air battery 10 in the second embodiment, the same effects as the effects (1) to (5) of the first embodiment are obtained, and the following effects (6) to (8). Play.

（６）正極３０は、正極端子３１が、カーボンファイバを含有するシート状の例えばカーボンクロス製の空気極集電体２２と一体成形されたので、正極端子３１と空気極集電体２２との密着性を考慮する必要がなく、リチウム空気電池１０の導電性をより一層向上させることができる。   (6) Since the positive electrode terminal 31 is integrally formed with the sheet-like air electrode current collector 22 made of, for example, carbon cloth containing the carbon fiber, the positive electrode 30 is formed between the positive electrode terminal 31 and the air electrode current collector 22. There is no need to consider the adhesion, and the conductivity of the lithium-air battery 10 can be further improved.

（７）更に、カーボンファイバを含有する正極端子３１は、電池反応により生成される水酸化リチウム等によって強アルカリ性となる電解液１３に対し高い耐食性を有するので、正極端子３１の腐食をより一層防止できる。   (7) Furthermore, since the positive electrode terminal 31 containing carbon fiber has high corrosion resistance with respect to the electrolyte solution 13 which becomes strong alkalinity by lithium hydroxide etc. produced | generated by a battery reaction, corrosion of the positive electrode terminal 31 is prevented further. it can.

（８）カーボンファイバを含有する正極端子３１は、その裏面に熱可塑性樹脂が溶着されて溶着部位３２が形成されたので、この溶着部位３２によって正極端子３１の強度を十分に確保できる。   (8) The positive electrode terminal 31 containing carbon fiber has a welded portion 32 formed by welding a thermoplastic resin on the back surface thereof, and thus the strength of the positive electrode terminal 31 can be sufficiently secured by the welded portion 32.

［Ｃ］第３実施形態（図６、図７）
図６は、本発明に係るリチウム空気電池の正極構造における第３実施形態が適用されたリチウム空気電池を示す断面図である。この第３実施形態において、第１実施形態と同様な部分については、同一の符号を付すことにより説明を簡略化し、または省略する。 [C] Third embodiment (FIGS. 6 and 7)
FIG. 6 is a cross-sectional view showing a lithium air battery to which the third embodiment of the positive electrode structure of the lithium air battery according to the present invention is applied. In the third embodiment, the same parts as those in the first embodiment are denoted by the same reference numerals, and description thereof is simplified or omitted.

本第３実施形態におけるリチウム空気電池１０の正極５０が第１実施形態と異なる点は、ラミネートフィルム２６の開口２４から形成される空気導入口２８によって外部に露出する空気極集電体２２の外側に、防水性及び通気性を備えた多孔質樹脂５１が配置された点である。   The positive electrode 50 of the lithium-air battery 10 in the third embodiment is different from that of the first embodiment in that the outside of the air electrode current collector 22 exposed to the outside by the air inlet 28 formed from the opening 24 of the laminate film 26. In addition, a porous resin 51 having waterproofness and air permeability is disposed.

上記多孔質樹脂５１は、多孔質ＰＥ（ポリエチレン）樹脂または多孔質フッ素系樹脂等である。また、多孔質樹脂５１は、図６に示すように、その周端部５１Ａがラミネートフィルム２６の外表面に固着される場合と、図７に示すように、空気極集電体２２とラミネートフィルム２６との間に介在される場合とのいずれか一方または両方である。   The porous resin 51 is a porous PE (polyethylene) resin or a porous fluororesin. Further, as shown in FIG. 6, the porous resin 51 has a case where the peripheral end 51 </ b> A is fixed to the outer surface of the laminate film 26, and as shown in FIG. 7, the air electrode current collector 22 and the laminate film. 26 or any one or both of them.

図６の場合、多孔質樹脂５１が多孔質ＰＥ樹脂であれば、空気極集電体２２の周端部２２Ａに正極端子２１を熱溶着し且つ熱可塑性樹脂を含浸させる熱溶着・含浸工程の後に、多孔質樹脂５１の周端部５１Ａをラミネートフィルム２６の外表面に熱溶着して多孔質樹脂配置工程を行うことが好ましい。また、図６の場合、多孔質樹脂５１が多孔質フッ素系樹脂であれば、前記熱溶着・含浸工程の後に、ラミネートフィルム２６の外表面に例えばポリオレフィン系のプライマを塗布し、その後に、例えばシアノアクリレート系接着剤を用いて多孔質樹脂５１の周端部５１Ａをラミネートフィルム２６の外表面に接着して多孔質樹脂配置工程を行うことが好ましい。   In the case of FIG. 6, if the porous resin 51 is a porous PE resin, a thermal welding / impregnation step of thermally welding the positive electrode terminal 21 to the peripheral end portion 22 </ b> A of the air electrode current collector 22 and impregnating the thermoplastic resin is performed. Later, it is preferable to perform the porous resin arrangement step by thermally welding the peripheral end portion 51 </ b> A of the porous resin 51 to the outer surface of the laminate film 26. In the case of FIG. 6, if the porous resin 51 is a porous fluororesin, for example, a polyolefin-based primer is applied to the outer surface of the laminate film 26 after the thermal welding / impregnation step, and then, for example, It is preferable to perform the porous resin arrangement step by adhering the peripheral end portion 51A of the porous resin 51 to the outer surface of the laminate film 26 using a cyanoacrylate adhesive.

図７の場合、多孔質樹脂５１が多孔質ＰＥ樹脂であれば、熱プレスなどによる前記熱溶着・含浸工程と同時に、上記熱プレスなどによって多孔質樹脂５１の周端部５１Ａをラミネートフィルム２６、空気極集電体２２間に固着して多孔質樹脂配置工程を行うことが好ましい。また、図７の場合、多孔質樹脂５１が多孔質フッ素系樹脂であれば、その周端部５１Ａに多数の細孔を開け、熱プレスなどによる前記熱溶着・含浸工程と同時に、上記熱プレスなどによって多孔質樹脂５１の周端部５１Ａをラミネートフィルム２６、空気極集電体２２間に固着して多孔質樹脂配置工程を行うことが好ましい。   In the case of FIG. 7, if the porous resin 51 is a porous PE resin, the peripheral end portion 51 </ b> A of the porous resin 51 is bonded to the laminate film 26 by the above-described hot pressing or the like simultaneously with the thermal welding / impregnation step by hot pressing. It is preferable that the porous resin placement step is performed while being fixed between the air electrode current collectors 22. In the case of FIG. 7, if the porous resin 51 is a porous fluororesin, a large number of pores are opened in the peripheral end portion 51A, and at the same time as the thermal welding / impregnation step by hot pressing or the like, It is preferable to perform the porous resin arrangement step by fixing the peripheral end portion 51 </ b> A of the porous resin 51 between the laminate film 26 and the air electrode current collector 22 by, for example.

従って、本第３実施形態におけるリチウム空気電池１０の正極５０によれば、第１実施形態の効果（１）〜（５）と同様な効果を奏するほか、次の効果（９）を奏する。   Therefore, according to the positive electrode 50 of the lithium-air battery 10 in the third embodiment, the same effects (1) to (5) as in the first embodiment are exhibited, and the following effect (9) is achieved.

（９）空気導入口２８によって外部に露出する空気極集電体２２の外側に、防水性及び通気性を備えた多孔質樹脂５１が配置されたので、保水性の高い電池構造を実現でき、従って電解液１３の揮発による減少を確実に防止できる。   (9) Since the porous resin 51 having waterproofness and air permeability is disposed outside the air electrode current collector 22 exposed to the outside by the air inlet 28, a battery structure with high water retention can be realized, Therefore, a decrease due to volatilization of the electrolytic solution 13 can be reliably prevented.

以上、本発明の実施形態を説明したが、これらの各実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これらの実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。   As mentioned above, although embodiment of this invention was described, these each embodiment was shown as an example and is not intending limiting the range of invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention.

例えば、本実施形態では電解液１３が水溶液系の場合を述べたが、電解液１３が非水溶液であっても、リチウム空気電池１０の正極１１、３０、５０の構造を適用することができる。また、第２実施形態のリチウム空気電池１０の正極３０における空気極集電体２２の外側に、第３実施形態の多孔質樹脂５１を、含浸工程と同時または含浸工程の後に配置してもよい。   For example, although the case where the electrolytic solution 13 is an aqueous solution system has been described in the present embodiment, the structure of the positive electrodes 11, 30, and 50 of the lithium air battery 10 can be applied even when the electrolytic solution 13 is a non-aqueous solution. Further, the porous resin 51 of the third embodiment may be disposed outside the air electrode current collector 22 in the positive electrode 30 of the lithium air battery 10 of the second embodiment at the same time as the impregnation step or after the impregnation step. .

１０ リチウム空気電池
１１ 正極
２１ 正極端子
２２ 空気極集電体
２２Ａ 周端部
２３ 含浸部位
２４ 開口
２５ 溶着部位
２６、２７ ラミネートフィルム（樹脂フィルム）
２８ 空気導入口
３０ 正極
３１ 正極端子
３２ 溶着部位
３４ 含浸部位
３６、３７ ラミネートフィルム（樹脂フィルム）
５０ 正極
５１ 多孔質樹脂 DESCRIPTION OF SYMBOLS 10 Lithium air battery 11 Positive electrode 21 Positive electrode terminal 22 Air electrode current collector 22A Peripheral end 23 Impregnation part 24 Opening 25 Welding part 26, 27 Laminate film (resin film)
28 Air inlet 30 Positive electrode 31 Positive electrode terminal 32 Welding part 34 Impregnating part 36, 37 Laminate film (resin film)
50 Positive electrode 51 Porous resin

Claims (8)

リチウム空気電池が正極と複合負極と電解液とを有して構成され、前記正極が正極端子と、カーボンファイバを含有するシート状の空気極集電体と、を有するリチウム空気電池の正極構造であって、
前記空気極集電体に前記正極端子が接触した状態で前記空気極集電体と前記正極端子とが熱可塑性樹脂により熱溶着されると共に、前記空気極集電体の周端部に前記熱可塑性樹脂が含浸されて構成されたことを特徴とするリチウム空気電池の正極構造。 A lithium air battery includes a positive electrode, a composite negative electrode, and an electrolyte, and the positive electrode has a positive electrode terminal and a sheet-like air electrode current collector containing carbon fiber. There,
The air electrode current collector and the positive electrode terminal are thermally welded by a thermoplastic resin in a state where the positive electrode terminal is in contact with the air electrode current collector, and the heat is applied to a peripheral end portion of the air electrode current collector. A positive electrode structure of a lithium-air battery, characterized by being impregnated with a plastic resin. リチウム空気電池が正極と複合負極と電解液とを有して構成され、前記正極が正極端子と、カーボンファイバを含有するシート状の空気極集電体と、を有するリチウム空気電池の正極構造であって、
前記正極端子が前記空気極集電体と一体に成形され、
前記空気極集電体の周端部に熱可塑性樹脂が含浸されて構成されたことを特徴とするリチウム空気電池の正極構造。 A lithium air battery includes a positive electrode, a composite negative electrode, and an electrolyte, and the positive electrode has a positive electrode terminal and a sheet-like air electrode current collector containing carbon fiber. There,
The positive electrode terminal is molded integrally with the air electrode current collector,
A positive electrode structure of a lithium air battery, wherein a peripheral end portion of the air electrode current collector is impregnated with a thermoplastic resin. 前記正極端子が、アルミニウムまたはニッケルの単体若しくは合金から構成されたことを特徴とする請求項１に記載のリチウム空気電池の正極構造。 2. The positive electrode structure of a lithium air battery according to claim 1, wherein the positive electrode terminal is made of a simple substance or an alloy of aluminum or nickel. 前記正極端子は、少なくとも片面に熱可塑性樹脂が溶着されて構成されたことを特徴とする請求項２に記載のリチウム空気電池の正極構造。 3. The positive electrode structure of a lithium air battery according to claim 2, wherein the positive electrode terminal is configured by welding a thermoplastic resin on at least one surface. 4. 前記空気極集電体の周端部は、熱可塑性樹脂からなり且つ開口を備えた枠形状の樹脂フィルムにおける前記熱可塑性樹脂により含浸され、前記樹脂フィルムの前記開口によって外部に露出する前記空気極集電体の外側に、防水性及び通気性を備えた多孔質樹脂が配置されたことを特徴とする請求項１乃至４のいずれか１項に記載のリチウム空気電池の正極構造。 The air electrode current collector is impregnated with the thermoplastic resin in a frame-shaped resin film made of a thermoplastic resin and having an opening, and is exposed to the outside through the opening of the resin film. The positive electrode structure of a lithium air battery according to any one of claims 1 to 4, wherein a porous resin having waterproofness and air permeability is disposed outside the current collector. リチウム空気電池が正極と複合負極と電解液とを有して構成され、前記正極が正極端子と、カーボンファイバを含有するシート状の空気極集電体と、を有するリチウム空気電池の正極製造方法であって、
前記空気極集電体に前記正極端子を接触させる接触工程と、
前記空気極集電体の周端部と前記正極端子とを、熱可塑性樹脂からなり且つ開口を備えた枠形状の複数の樹脂フィルムによって挟み込む挟み込み工程と、
前記空気極集電体と前記正極端子とを前記樹脂フィルムにより熱溶着すると共に、前記空気極集電体の前記周端部に前記熱可塑性樹脂を含浸させる熱溶着・含浸工程と、を有することを特徴とするリチウム空気電池の正極製造方法。 Lithium air battery has a positive electrode, a composite negative electrode, and an electrolyte solution, and the positive electrode has a positive electrode terminal and a sheet-like air electrode current collector containing carbon fiber. Because
A contacting step of contacting the positive terminal to the air electrode current collector,
A sandwiching step of sandwiching the peripheral end portion of the air electrode current collector and the positive electrode terminal with a plurality of frame-shaped resin films made of a thermoplastic resin and having openings;
A thermal welding / impregnation step of thermally welding the air electrode current collector and the positive electrode terminal with the resin film, and impregnating the thermoplastic resin into the peripheral end portion of the air electrode current collector. A method for producing a positive electrode for a lithium-air battery. リチウム空気電池が正極と複合負極と電解液とを有して構成され、前記正極が正極端子と、カーボンファイバを含有するシート状の空気極集電体と、を有するリチウム空気電池の正極製造方法であって、
前記空気極集電体と、この空気極集電体に一体成形された前記正極端子とを用意する準備工程と、
前記空気極集電体の周端部を、熱可塑性樹脂からなり且つ開口を備えた枠形状の複数の樹脂フィルムによって挟み込む挟み込み工程と、
前記空気極集電体の前記周端部に前記熱可塑性樹脂を含浸させる含浸工程と、を有することを特徴とするリチウム空気電池の正極製造方法。 Lithium air battery has a positive electrode, a composite negative electrode, and an electrolyte solution, and the positive electrode has a positive electrode terminal and a sheet-like air electrode current collector containing carbon fiber. Because
And said air electrode current collector, a preparation step of preparing the integrally molded the positive terminal to the air electrode current collector,
A sandwiching step of sandwiching the peripheral end portion of the air electrode current collector with a plurality of frame-shaped resin films made of a thermoplastic resin and having openings,
And a impregnation step of impregnating the thermoplastic resin into the peripheral end portion of the air electrode current collector. 前記樹脂フィルムの開口から露出する空気極集電体の外側に、防水性及び通気性を備えた多孔質樹脂を、熱溶着・含浸工程若しくは含浸工程と同時または後に配置する多孔質樹脂配置工程を有することを特徴とする請求項６または７に記載のリチウム空気電池の正極製造方法。 A porous resin disposing step in which a porous resin having waterproofness and air permeability is disposed at the same time as or after the heat welding / impregnation step or the impregnation step on the outside of the air electrode current collector exposed from the opening of the resin film. The positive electrode manufacturing method of a lithium air battery according to claim 6 or 7, wherein
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