JP6272529B1 - Magnesium air battery - Google Patents

Magnesium air battery Download PDF

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JP6272529B1
JP6272529B1 JP2017098877A JP2017098877A JP6272529B1 JP 6272529 B1 JP6272529 B1 JP 6272529B1 JP 2017098877 A JP2017098877 A JP 2017098877A JP 2017098877 A JP2017098877 A JP 2017098877A JP 6272529 B1 JP6272529 B1 JP 6272529B1
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negative electrode
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current collector
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和弘 田所
和弘 田所
正洋 權太
正洋 權太
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DREAM ENGINE CO., LTD.
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Abstract

【課題】負極端子を負極活物質にカシメ加工することで、部品点数と作業工数の簡素化を図り、製造コストを低減させる。【解決手段】マグネシウム又はマグネシウム合金を含むシート状の負極活物質２０と、前記負極活物質にカシメ加工によって接続された負極端子２２と、前記負極活物質２０に当接される、イオン化反応材が含浸されたシート状のセパレータ３０と、前記セパレータ３０のうち前記負極活物質２０と反対側の面に当接される、シート状の正極４０と、前記正極４０のうち前記セパレータ３０と反対側の面に当接される、通気性を有する正極集電体４２と、前記正極集電体４２に接続された正極端子４４と、を備える。【選択図】図１A negative electrode terminal is caulked to a negative electrode active material, thereby simplifying the number of parts and the number of work steps, and reducing manufacturing costs. A sheet-like negative electrode active material 20 containing magnesium or a magnesium alloy, a negative electrode terminal 22 connected to the negative electrode active material by caulking, and an ionization reaction material in contact with the negative electrode active material 20 are provided. An impregnated sheet-like separator 30, a sheet-like positive electrode 40 in contact with a surface of the separator 30 on the side opposite to the negative electrode active material 20, and a side of the positive electrode 40 opposite to the separator 30. A positive electrode current collector 42 having air permeability, which is in contact with the surface, and a positive electrode terminal 44 connected to the positive electrode current collector 42 are provided. [Selection] Figure 1

Description

本発明は、負極の活物質にマグネシウム又はマグネシウム合金を用い、正極の活物質として酸素を用いるマグネシウム空気電池に関する。   The present invention relates to a magnesium-air battery using magnesium or a magnesium alloy as an active material for a negative electrode and oxygen as an active material for a positive electrode.

従来、マグネシウム空気電池において、低中出力で安定的に長期間の電流の取出しが可能なものを提供することを目的として、例えば、特開２０１１−１８１３８２号公報に、マグネシウム合金板の負極の一方の板面及び全ての端面を覆うように密着させた導電性金属層と、その上に形成された絶縁性樹脂層とからなる複合集電層を有し、前記導電性金属層に負極端子を接続したマグネシウム空気電池が開示されている。   Conventionally, in order to provide a magnesium-air battery capable of stably taking out a long-term current with low and medium output, for example, JP 2011-181382A discloses one of negative electrodes of a magnesium alloy plate. A composite current collecting layer composed of a conductive metal layer adhered so as to cover the plate surface and all end surfaces of the substrate and an insulating resin layer formed thereon, and a negative electrode terminal is provided on the conductive metal layer. A connected magnesium air battery is disclosed.

特開２０１１−１８１３８２号公報JP 2011-181382 A

しかし、特許文献１に開示されている技術では、導電性金属層を、負極活物質のマグネシウム合金板の広い面の片面を含む５つの面に導電性接着剤を用いて接着しており、この導電性金属層に負極端子を接続している。このため、負極の構造が複雑となり、製造時のコストが増大するおそれがあった。   However, in the technique disclosed in Patent Document 1, the conductive metal layer is bonded to five surfaces including one side of the wide surface of the magnesium alloy plate of the negative electrode active material using a conductive adhesive. A negative electrode terminal is connected to the conductive metal layer. For this reason, the structure of the negative electrode becomes complicated, which may increase the manufacturing cost.

本発明は、上記の点に鑑みなされたもので、負極端子を負極活物質にカシメ加工することで、部品点数と作業工数の簡素化を図り、製造コストを低減させることができるマグネシウム空気電池を提供することを目的とする。   The present invention has been made in view of the above points, and a magnesium-air battery capable of simplifying the number of parts and the number of work steps and reducing the manufacturing cost by caulking the negative electrode terminal to the negative electrode active material. The purpose is to provide.

（１）本発明のマグネシウム空気電池は、
マグネシウム又はマグネシウム合金を含むシート状の負極活物質と、
前記負極活物質にカシメ加工によって接続された負極端子と、
前記負極活物質に当接される、イオン化反応材が含浸されたシート状のセパレータと、
前記セパレータのうち前記負極活物質と反対側の面に当接される、シート状の正極と、
前記正極のうち前記セパレータと反対側の面に当接される正極集電体と、
前記正極集電体に接続された正極端子と、を備え、
前記負極活物質が、
前記セパレータと当接される反応部と、
前記セパレータの辺縁から突出するとともに前記反応部と同じ幅を有し前記セパレータの辺縁が接する全幅部、及び前記全幅部から延伸されその幅が狭められるとともに前記負極端子が接続される狭小部を備える端子接続部と、
を備えることを特徴とする。 (1) The magnesium-air battery of the present invention is
A sheet-like negative electrode active material containing magnesium or a magnesium alloy;
A negative electrode terminal connected to the negative electrode active material by caulking,
A sheet-like separator impregnated with an ionization reaction material in contact with the negative electrode active material;
A sheet-like positive electrode in contact with a surface of the separator opposite to the negative electrode active material;
A positive electrode current collector in contact with a surface of the positive electrode opposite to the separator;
A positive electrode terminal connected to the positive electrode current collector ,
The negative electrode active material is
A reaction portion in contact with the separator;
A full width part that protrudes from the edge of the separator and has the same width as the reaction part, and a narrow part that extends from the full width part and is narrowed and connected to the negative electrode terminal. A terminal connection comprising:
It is characterized by providing.

本発明のマグネシウム空気電池によれば、負極活物質に負極端子がカシメ加工によって接続されているため、当該部分の電気抵抗を少なくしながら、確実に負極活物質と負極端子とを接続することができる。また、負極端子がカシメ加工によって接続されるため、加工工程が容易なものとなり、部品点数の削減と作業工数の簡素化を実現でき、製造コストの低減を図ることができる。   According to the magnesium-air battery of the present invention, since the negative electrode terminal is connected to the negative electrode active material by caulking, it is possible to reliably connect the negative electrode active material and the negative electrode terminal while reducing the electrical resistance of the part. it can. Further, since the negative electrode terminal is connected by caulking, the machining process is facilitated, the number of parts can be reduced, the number of work steps can be simplified, and the manufacturing cost can be reduced.

また、本発明のマグネシウム空気電池によれば、負極端子が接続される部分ではセパレータが当接されておらず、イオン化反応がなされない。これにより、負極端子を負極活物質に直接接続しても、接続された部分又はその周辺でのイオン化反応のムラが起きず、当該部分における負極活物質の分断を防止することができる。また、負極端子が接続されている端子接続部が、セパレータの辺縁から突出してセパレータと当接していないため、当該部分のマグネシウム空気電池の厚さが変化することがない。 Moreover, according to the magnesium air battery of this invention , the separator is not contact | abutted in the part to which a negative electrode terminal is connected, and ionization reaction is not made. Thereby, even if the negative electrode terminal is directly connected to the negative electrode active material, unevenness of the ionization reaction does not occur in the connected portion or in the vicinity thereof, and the negative electrode active material in the portion can be prevented from being divided. Moreover, since the terminal connection part to which the negative electrode terminal is connected protrudes from the edge of the separator and is not in contact with the separator, the thickness of the magnesium-air battery in that part does not change.

また、本発明のマグネシウム空気電池によれば、負極活物質の端部の端子接続部において、負極端子が接続されている部分の幅が狭められた狭小部となっているため、当該部分の負極活物質の量を減らすことができ、製品のコストダウンを図ることができる。また、セパレータの辺縁が、反応部と同じ幅を有する全幅部で負極活物質と接しているため、狭小部と全幅部との境において、電流密度の上昇による局部的なイオン化反応が起きず、前記境において負極活物質の分断を防止することができる。 Further, according to the magnesium-air battery of the present invention, in the terminal connection part at the end of the negative electrode active material, the width of the part to which the negative electrode terminal is connected is narrowed. The amount of active material can be reduced, and the cost of the product can be reduced. In addition, since the edge of the separator is in contact with the negative electrode active material at the full width part having the same width as the reaction part, local ionization reaction due to the increase in current density does not occur at the boundary between the narrow part and the full width part. In the boundary, the negative electrode active material can be prevented from being divided.

（２）本発明のマグネシウム空気電池は、
前記負極端子に接続されるとともに、前記負極活物質が前記セパレータに当接されるよう前記負極活物質の表面に隙間を設けて這わされた導体からなる負極集電体を備えることを特徴とする。 (2) The magnesium-air battery of the present invention is
A negative electrode current collector comprising a conductor connected to the negative electrode terminal and provided with a gap on the surface of the negative electrode active material so that the negative electrode active material is brought into contact with the separator. .

本発明のマグネシウム空気電池の好ましい例によれば、負極集電体が、負極端子に接続されるとともに、負極活物質が露出してセパレータに当接されるよう負極活物質の表面に隙間を設けて這わされる。このため、負極集電体の面積を負極活物質に対して小さなものとしながら負極の略全域を覆うことが可能となり、集電性能を犠牲にすることなく内部抵抗を低減させることができる。また、負極集電体の隙間から負極活物質が露出しており、負極活物質のイオン化反応を妨げることなく、さらに、マグネシウム空気電池の寿命の終期において、負極活物質が分断されても、残存する負極活物質の略全てから電力を得ることができる。   According to a preferred example of the magnesium-air battery of the present invention, the negative electrode current collector is connected to the negative electrode terminal, and a gap is provided on the surface of the negative electrode active material so that the negative electrode active material is exposed and contacts the separator. I will be deceived. For this reason, it becomes possible to cover the substantially whole area of a negative electrode, making the area of a negative electrode collector small with respect to a negative electrode active material, and can reduce internal resistance, without sacrificing current collection performance. Further, the negative electrode active material is exposed from the gap of the negative electrode current collector, and does not interfere with the ionization reaction of the negative electrode active material, and further remains at the end of the life of the magnesium-air battery even if the negative electrode active material is divided. Electric power can be obtained from substantially all of the negative electrode active material.

（３）本発明のマグネシウム空気電池の好ましい例は、
前記負極集電体が、前記負極活物質に螺旋状に巻着されていることを特徴とする。 (3) A preferred example of the magnesium-air battery of the present invention is:
The negative electrode current collector is spirally wound around the negative electrode active material.

本発明のマグネシウム空気電池の好ましい例によれば、負極集電体が、負極活物質に螺旋状に巻着されている。このため、負極集電体を負極活物質の略全域に設けながら、負極集電体の本数を減らすことができる。例えば、負極集電体が１本の導体であっても負極活物質の略全域から集電することができる。   According to a preferred example of the magnesium-air battery of the present invention, the negative electrode current collector is spirally wound around the negative electrode active material. For this reason, the number of negative electrode current collectors can be reduced while providing the negative electrode current collector over substantially the entire area of the negative electrode active material. For example, even if the negative electrode current collector is a single conductor, current can be collected from substantially the entire area of the negative electrode active material.

（４）本発明のマグネシウム空気電池の好ましい例は、
前記正極と前記正極集電体との当接される面の一部を接着する導電性接着剤を備えることを特徴とする。 (4) A preferred example of the magnesium-air battery of the present invention is:
A conductive adhesive is provided for adhering a part of a surface where the positive electrode and the positive electrode current collector are in contact with each other.

本発明のマグネシウム空気電池によれば、導電性接着剤によって、正極と正極集電体との当接される面の一部が接着されるため、正極と正極集電体との間に電気的な回路が形成されるとともにこれらの密着が良好になされ、正極と正極集電体との間の電気抵抗も低減される。また、導電性接着剤は、正極と正極集電体との当接される面の一部にしか設けられておらず、かつ、正極集電体も通気性を有するため、酸素が正極に十分に供給され、使用時にセパレータに含浸される電解液と酸素との反応を阻害することがない。 According to the magnesium-air battery of the present invention, a conductive adhesive, a part of the surface that contacts the positive electrode and the positive electrode current collector is bonded, electrically between the positive electrode and the positive electrode current collector In addition, a good circuit is formed, and the close contact between the positive electrode and the positive electrode current collector is reduced. In addition, since the conductive adhesive is provided only on a part of the contact surface between the positive electrode and the positive electrode current collector, and the positive electrode current collector is also air permeable, oxygen is sufficient for the positive electrode . The reaction between the electrolyte supplied to the separator and impregnated in the separator during use and oxygen is not hindered.

（５）本発明のマグネシウム空気電池の好ましい例は、
前記負極集電体が、前記負極活物質の面に直交する方向から見て前記導電性接着剤の接着面に対応する位置に設けられていることを特徴とする。 (5) A preferred example of the magnesium-air battery of the present invention is:
The negative electrode current collector is provided at a position corresponding to the adhesive surface of the conductive adhesive when viewed from a direction orthogonal to the surface of the negative electrode active material.

本発明のマグネシウム空気電池の好ましい例によれば、負極集電体が、負極活物質の面に直交する方向から見て導電性接着剤の接着面に対応する位置に設けられている。これは、負極活物質のうち、面に直交する方向から見て導電性接着剤の接着面に対応する場所については、イオン化反応が鈍くなる傾向があり、マグネシウム空気電池の寿命の終期まで当該場所の負極活物質が残存する可能性があるのだが、本発明のマグネシウム空気電池は、この残存した箇所の負極活物質からも電力を得ることができる。   According to a preferred example of the magnesium-air battery of the present invention, the negative electrode current collector is provided at a position corresponding to the adhesive surface of the conductive adhesive when viewed from the direction orthogonal to the surface of the negative electrode active material. This is because, in the negative electrode active material, the location corresponding to the adhesive surface of the conductive adhesive as viewed from the direction orthogonal to the surface tends to be dull and the ionization reaction tends to be slow until the end of the life of the magnesium-air battery. However, the magnesium-air battery of the present invention can also obtain power from the remaining negative electrode active material.

（６）本発明のマグネシウム空気電池の好ましい例は、
前記負極活物質１つに対して前記セパレータ、前記正極、及び前記正極集電体を２つ備え、前記セパレータ、前記正極、及び前記正極集電体が前記負極活物質の両面に設けられていることを特徴とする。 (6) A preferred example of the magnesium-air battery of the present invention is:
The negative active material, one for the separator, the positive electrode, and includes the two positive electrode current collector, the separator, the positive electrode, and the positive electrode current collector is provided on both surfaces of the negative electrode active material It is characterized by that.

本発明のマグネシウム空気電池の好ましい例によれば、負極活物質の両面を用いてそれぞれの面で発電するため、電流が略２倍となり、さらに大電流を取り出すことができる。また、負極集電体の隙間から負極活物質が露出しているため、負極活物質の両面をそのまま使用することができ、電流を２倍としながら、負極活物質が１セルあたり１枚で済む。これらにより、部品点数の削減が可能となり、製造コストの低減を図ることができる。   According to a preferred example of the magnesium-air battery of the present invention, since power is generated on each side using both sides of the negative electrode active material, the current is approximately doubled, and a larger current can be taken out. Further, since the negative electrode active material is exposed from the gap of the negative electrode current collector, both surfaces of the negative electrode active material can be used as they are, and only one negative electrode active material is required per cell while doubling the current. . As a result, the number of parts can be reduced, and the manufacturing cost can be reduced.

（７）本発明のマグネシウム空気電池の好ましい例は、
前記負極活物質の両面に設けられた前記正極の前記導電性接着剤との接着面のそれぞれの位置が、前記負極活物質の面に直交する方向から見て異なる位置にあることを特徴とする。 (7) A preferred example of the magnesium-air battery of the present invention is:
Each position of the adhesion surface of the positive electrode provided on both surfaces of the negative electrode active material with the conductive adhesive is in a different position when viewed from a direction orthogonal to the surface of the negative electrode active material. .

本発明のマグネシウム空気電池の好ましい例によれば、負極活物質の両面に設けられた正極の、導電性接着剤との接着面のそれぞれの位置が、負極活物質の面に直交する方向から見て異なる位置にある。これは、既に述べたように、負極活物質のうち、面に直交する方向から見て導電性接着剤の接着面に対応する場所については、イオン化反応が鈍くなる傾向があるのだが、前記接着面の位置が負極活物質の両面で異なる位置にあるため、イオン化反応が起きにくい部分においても、当該部分の反対側の面からは問題なくイオン化反応がなされ、負極活物質をまんべんなく活用することができる。 According to a preferred example of the magnesium-air battery of the present invention, the positions of the positive electrode provided on both surfaces of the negative electrode active material and the adhesive surface with the conductive adhesive are viewed from the direction orthogonal to the surface of the negative electrode active material. Are in different positions. This is because, as already described, the ionization reaction tends to be slow at the location corresponding to the adhesive surface of the conductive adhesive as viewed from the direction orthogonal to the surface of the negative electrode active material. Since the position of the surface is different on both sides of the negative electrode active material, even in the part where the ionization reaction is difficult to occur, the ionization reaction can be performed from the opposite side of the part without any problem, and the negative electrode active material can be used evenly. it can.

（８）本発明のマグネシウム空気電池の好ましい例は、
前記負極端子がアルミニウム又はアルミニウム合金であることを特徴とする。 (8) A preferred example of the magnesium-air battery of the present invention is:
The negative electrode terminal is made of aluminum or an aluminum alloy.

本発明のマグネシウム空気電池の好ましい例によれば、負極端子がアルミニウム又はアルミニウム合金であるため、負極活物質であるマグネシウム又はマグネシウム合金と酸化還元電位が比較的近い。このため、負極活物質と負極端子との接続部周辺での局部的な反応が起こりにくく、負極活物質が負極端子との接続部周辺で分断されにくくなる。   According to a preferred example of the magnesium-air battery of the present invention, since the negative electrode terminal is aluminum or an aluminum alloy, the redox potential is relatively close to magnesium or the magnesium alloy that is the negative electrode active material. For this reason, a local reaction in the vicinity of the connection portion between the negative electrode active material and the negative electrode terminal hardly occurs, and the negative electrode active material is hardly divided in the vicinity of the connection portion with the negative electrode terminal.

以上、説明したように、本発明のマグネシウム空気電池によれば、負極端子を負極活物質にカシメ加工することで、部品点数と作業工数の簡素化を図り、製造コストを低減させることができる。   As described above, according to the magnesium-air battery of the present invention, the negative electrode terminal is caulked to the negative electrode active material, whereby the number of parts and the number of work steps can be simplified, and the manufacturing cost can be reduced.

本発明の一実施形態に係るマグネシウム空気電池の正面図である。It is a front view of the magnesium air cell concerning one embodiment of the present invention. 図１に示すマグネシウム空気電池の左側面図である。It is a left view of the magnesium air battery shown in FIG. 図２のＡ−Ａ線断面図である。It is the sectional view on the AA line of FIG. 負極活物質及び負極集電体の右側面図において、導電性接着剤の位置を説明する図である。It is a figure explaining the position of a conductive adhesive in the right view of a negative electrode active material and a negative electrode electrical power collector. 負極活物質及び負極集電体の左側面図において、導電性接着剤の位置を説明する図である。It is a figure explaining the position of a conductive adhesive in the left view of a negative electrode active material and a negative electrode electrical power collector. 負極端子を示す図である。It is a figure which shows a negative electrode terminal. 負極活物質のイオン化反応の進行状態を説明する図である。It is a figure explaining the advancing state of the ionization reaction of a negative electrode active material. 負極活物質の他の例を示す図である。It is a figure which shows the other example of a negative electrode active material. 本発明の他の実施形態に係るマグネシウム空気電池の正面図である。It is a front view of the magnesium air battery which concerns on other embodiment of this invention.

以下、本発明のマグネシウム空気電池１０の実施の形態について、添付図面を参照して詳細に説明する。   Hereinafter, embodiments of the magnesium-air battery 10 of the present invention will be described in detail with reference to the accompanying drawings.

図１ないし図６に示すように、本実施形態のマグネシウム空気電池１０は、負極活物質２０と、負極端子２２と、負極集電体２１と、セパレータ３０，３１と、正極４０，４１と、正極集電体４２，４３と、導電性接着剤５０，５１とを備える。また、これらの構成は、図示しない電池ケースに内蔵される。なお、図中においての各構成要素は模式的に表わしており、実際の厚さや大きさとは相違する場合がある（その他の図においても同様。)。 As shown in FIGS. 1 to 6, the magnesium-air battery 10 of the present embodiment includes a negative electrode active material 20, a negative electrode terminal 22, a negative electrode current collector 21, separators 30 and 31, positive electrodes 40 and 41, Positive electrode current collectors 42 and 43 and conductive adhesives 50 and 51 are provided. These configurations are built in a battery case (not shown). In addition, each component in a figure is represented typically and may differ from an actual thickness and magnitude | size (this is the same also in other figures).

負極活物質２０は、シート状のマグネシウム又はマグネシウム合金を含む金属板であり、１セルあたり１枚設けられる。この負極活物質２０は、セパレータ３０，３１と当接され発電のためにイオン化反応がなされる反応部２４と、セパレータ３０，３１が当接されずにセパレータ３０，３１の上側の辺縁３２から突出する端子接続部２５とを備える。また、この端子接続部２５は、反応部２４と同じ幅ｗを備える全幅部２６と、幅が狭められた狭小部２７とを備える。   The negative electrode active material 20 is a metal plate containing a sheet-like magnesium or magnesium alloy, and one negative electrode active material 20 is provided per cell. This negative electrode active material 20 is brought into contact with the separators 30 and 31 and undergoes an ionization reaction for power generation, and from the upper edge 32 of the separators 30 and 31 without contact with the separators 30 and 31. And a protruding terminal connecting portion 25. The terminal connection portion 25 includes a full width portion 26 having the same width w as the reaction portion 24 and a narrow portion 27 having a narrow width.

負極端子２２は、負極活物質２０に電気的に接続されるもので、上記狭小部２７に接続される。この負極端子２２の接続であるが、負極活物質２０と負極端子２２とを重ね合わせた状態で、これらを厚さ方向にカシメ加工することで直接に接続される導電性の端子が好ましく、負極端子２２のうち負極活物質２０と接続される側の一端が、例えばハトメやグロメットと呼ばれるものやリベット状となっているものが採用できる。本実施形態に用いられる負極端子２２は、図６に示すように筒部２３を備え、その筒部２３が負極活物質２０を貫通し、その後、図中の矢印の方向にカシメ加工されることによって接続される。   The negative electrode terminal 22 is electrically connected to the negative electrode active material 20 and is connected to the narrow portion 27. The connection of the negative electrode terminal 22 is preferably a conductive terminal that is directly connected by caulking the negative electrode active material 20 and the negative electrode terminal 22 in the thickness direction with the negative electrode active material 20 and the negative electrode terminal 22 being overlapped. One of the terminals 22 on the side connected to the negative electrode active material 20 may be a so-called eyelet or grommet or a rivet. The negative electrode terminal 22 used in this embodiment includes a cylindrical portion 23 as shown in FIG. 6, and the cylindrical portion 23 penetrates the negative electrode active material 20 and is then crimped in the direction of the arrow in the figure. Connected by.

この負極端子２２の材質としては、銅、真鍮等の銅合金、アルミニウム、又はアルミニウム合金等の導電性材料が採用できるが、この中でもアルミニウム又はアルミニウム合金（以下、「アルミニウム等」と称することがある。）が好ましい。これは、負極端子２２の材質にアルミニウム等を採用すると、負極活物質２０のマグネシウム又はマグネシウム合金と、アルミニウム等との酸化還元電位が近いために、マグネシウム空気電池１０の使用中に負極端子２２の周囲の負極活物質２０が局部的に消耗することがない。これにより、負極活物質２０が分断され難くなり、マグネシウム空気電池１０の寿命の終期まで安定して発電できるからである。   As the material of the negative electrode terminal 22, a copper alloy such as copper or brass, a conductive material such as aluminum, or an aluminum alloy can be employed. Among these, aluminum or an aluminum alloy (hereinafter, referred to as “aluminum or the like”) .) Is preferred. This is because, when aluminum or the like is adopted as the material of the negative electrode terminal 22, since the oxidation-reduction potential between magnesium or a magnesium alloy of the negative electrode active material 20 and aluminum or the like is close, The surrounding negative electrode active material 20 is not locally consumed. Thereby, the negative electrode active material 20 becomes difficult to be divided, and power can be stably generated until the end of the life of the magnesium-air battery 10.

なお、負極活物質２０の端子接続部２５は、上記の様にその上部に狭小部２７を備えることは必須ではなく、例えば、図８に示すように、反応部２４から全幅部のまま延伸される端子接続部１２５を備える負極活物質１２０としてもよい。また、負極端子２２も図６に示す例に限られず、負極端子２２のうちカシメ加工される筒部２３とは反対の他端に、さらに別のリード線を接続する等することができる。また、負極端子と負極活物質との接続にカシメ加工をすることなく、負極端子又は導体を負極活物質の端子接続部２５に当接させて図示しない電池ケースで押圧させる、負極端子をクリップ状にして端子接続部２５を挟む等、様々な態様を採用することができる。   Note that the terminal connection portion 25 of the negative electrode active material 20 is not necessarily provided with the narrow portion 27 in the upper portion as described above. For example, as shown in FIG. Alternatively, the negative electrode active material 120 including the terminal connection portion 125 may be used. Further, the negative electrode terminal 22 is not limited to the example shown in FIG. 6, and another lead wire can be connected to the other end of the negative electrode terminal 22 opposite to the cylindrical portion 23 to be crimped. In addition, the negative electrode terminal or the conductor is brought into contact with the terminal connection portion 25 of the negative electrode active material and pressed by a battery case (not shown) without crimping the connection between the negative electrode terminal and the negative electrode active material. Various modes such as sandwiching the terminal connection portion 25 can be adopted.

なお、端子接続部２５をセパレータ３０，３１の辺縁３２から突出させる理由であるが、端子接続部２５にセパレータ３０，３１が当接されると、負極端子２２周りの厚さの変化により当該部分の負極活物質２０とセパレータと３０，３１との接触が悪くなり、イオン化反応にムラが発生し易くなる。すると、局部的な負極活物質２０の反応が進み、当該部分又はその周辺で負極活物質２０が分断されてしまうおそれがある。一方、本実施形態のマグネシウム空気電池１０では、セパレータ３０，３１は反応部２４のみに当接されているため、そのようなムラが発生し難くなり、負極活物質２０全体で満遍なくイオン化反応がなされる。また、負極端子２２によってセパレータ３０，３１、正極４０，４１、正極集電体４２，４３が押されてマグネシウム空気電池１０全体の厚さが変化することがない。これにより、図示しない電池ケースに収納することが容易となる。 The reason for causing the terminal connection portion 25 to protrude from the edge 32 of the separators 30 and 31 is that when the separators 30 and 31 come into contact with the terminal connection portion 25, the thickness changes around the negative electrode terminal 22. The contact between the negative electrode active material 20 and the separators 30 and 31 of the part is deteriorated, and unevenness is easily generated in the ionization reaction. Then, the reaction of the local negative electrode active material 20 proceeds, and there is a possibility that the negative electrode active material 20 may be divided at the portion or its periphery. On the other hand, in the magnesium-air battery 10 of the present embodiment, since the separators 30 and 31 are in contact with only the reaction part 24, such unevenness hardly occurs, and the negative electrode active material 20 as a whole is uniformly ionized. The Moreover, the separators 30 and 31, the positive electrodes 40 and 41, and the positive electrode current collectors 42 and 43 are not pushed by the negative electrode terminal 22, so that the thickness of the magnesium air battery 10 does not change. This facilitates storage in a battery case (not shown).

また、端子接続部２５のうち全幅部２６にセパレータ３０，３１の上側の辺縁３２が接しており、狭小部２７との境２８までセパレータ３０，３１の辺縁３２が当接していない理由であるが、狭小部２７との境２８までセパレータ３０，３１が当接されると、境２８において電流密度が上昇し局部的なイオン化反応がなされる。これにより、境２８で負極活物質２０が分断されてしまうおそれがあるからである。一方、本実施形態のマグネシウム空気電池１０では、境２８にセパレータ３０，３１が当接されておらず、境２８でのイオン化反応は起きない。このため、境２８において負極活物質２０が分断されることがない。また、端子接続部２５に負極端子２２を接続するための狭小部２７を設けているため、全幅部２６の長さを短くすることができ、負極活物質２０の面積（量）を減らすことができる。   Further, the upper edge 32 of the separators 30 and 31 is in contact with the full width portion 26 of the terminal connection portion 25, and the edge 32 of the separators 30 and 31 is not in contact with the boundary 28 with the narrow portion 27. However, when the separators 30 and 31 are brought into contact with the boundary 28 with the narrow portion 27, the current density is increased at the boundary 28 and a local ionization reaction is performed. This is because the negative electrode active material 20 may be divided at the boundary 28. On the other hand, in the magnesium-air battery 10 of the present embodiment, the separators 30 and 31 are not in contact with the boundary 28, and the ionization reaction at the boundary 28 does not occur. For this reason, the negative electrode active material 20 is not divided at the boundary 28. Moreover, since the narrow part 27 for connecting the negative electrode terminal 22 to the terminal connection part 25 is provided, the length of the full width part 26 can be shortened, and the area (amount) of the negative electrode active material 20 can be reduced. it can.

また、負極端子２２には、導体からなる負極集電体２１の一端が、負極活物質２０とともにカシメ加工によって接続されている。この負極集電体２１は、負極活物質２０のイオン化反応を阻害しないよう、負極活物質２０の表面に隙間ｓを設けて、負極活物質２０に螺旋状に巻着される。この、負極活物質２０が露出するように隙間ｓを設けて負極集電体２１を設けることにより、負極活物質２０の表面が十分にセパレータ３０，３１に当接されるとともに、負極活物質２０の両面を活用することができる。   One end of a negative electrode current collector 21 made of a conductor is connected to the negative electrode terminal 22 together with the negative electrode active material 20 by caulking. The negative electrode current collector 21 is spirally wound around the negative electrode active material 20 with a gap s provided on the surface of the negative electrode active material 20 so as not to inhibit the ionization reaction of the negative electrode active material 20. By providing the negative electrode current collector 21 with the gap s so that the negative electrode active material 20 is exposed, the surface of the negative electrode active material 20 is sufficiently brought into contact with the separators 30 and 31 and the negative electrode active material 20 Can be used on both sides.

また、負極集電体２１は、当接されるセパレータ３０，３１によって負極活物質２０に押し付けられているが、負極集電体２１の占める面積が少ないため、負極活物質２０に対して十分な面圧で接触することができる。このため、負極活物質２０と負極集電体２１とを導電性接着剤で接着することは特に必要ではない。また、負極集電体２１を負極活物質２０の略全域に這わしているため、負極活物質２０における部分的な電流密度の上昇、及び電流密度の上昇による局部的なイオン化反応が抑制され、負極活物質２０全体で満遍なくイオン化反応がなされる。これにより、マグネシウム空気電池１０の寿命の中期以降における負極活物質２０の分断を抑制することができる。   Further, the negative electrode current collector 21 is pressed against the negative electrode active material 20 by the separators 30 and 31 that are in contact with each other. However, since the area occupied by the negative electrode current collector 21 is small, it is sufficient for the negative electrode active material 20. Contact can be made with surface pressure. For this reason, it is not particularly necessary to bond the negative electrode active material 20 and the negative electrode current collector 21 with a conductive adhesive. Further, since the negative electrode current collector 21 is spread over substantially the entire area of the negative electrode active material 20, a partial increase in current density in the negative electrode active material 20 and a local ionization reaction due to the increase in current density are suppressed. The negative electrode active material 20 as a whole is uniformly ionized. Thereby, the division | segmentation of the negative electrode active material 20 after the middle stage of the lifetime of the magnesium air battery 10 can be suppressed.

なお、本実施形態のマグネシウム空気電池１０では、負極集電体２１に銅からなる直径０．０１ｍｍ〜０．３ｍｍ、好ましくは０．０５ｍｍ〜０．１５ｍｍの導線を用いている。この様な細い導線を用いることで、負極活物質２０とセパレータ３０，３１との間に空間ができることを防止し、イオン化反応のムラを防止するとともに効率の良い発電をすることができる。もっとも、負極集電体２１はこれに限られず、発電される電流に応じた太さであればよい。また形状もこれに限られず、例えば帯状の導体を巻着させてもよい。また、負極集電体２１は、負極活物質２０の表面に隙間ｓを空けながら略全域にわたって設けられていればよく、上記の螺旋状に限られず、例えば、負極端子２２から数本の導線等を負極活物質２０の両面に垂らすようにして設けることもできる。また、負極集電体２１の材質としては、銅、真鍮等の銅合金、アルミニウム又はアルミニウム合金、金、銀等の電気抵抗の少ない導体が用いられることが好ましい。なお、負極集電体２１は、既に述べたように負極活物質２０に対して占める面積が小さい。このため、負極集電体２１に、負極活物質２０と酸化還元電位が離れた銅又は真鍮等の銅合金を用いても特に問題はない。   In the magnesium-air battery 10 of this embodiment, the negative electrode current collector 21 is made of a conductive wire having a diameter of 0.01 mm to 0.3 mm, preferably 0.05 mm to 0.15 mm, made of copper. By using such a thin conducting wire, it is possible to prevent a space from being formed between the negative electrode active material 20 and the separators 30 and 31, to prevent uneven ionization reaction, and to generate power efficiently. However, the negative electrode current collector 21 is not limited to this, and may have a thickness corresponding to the current generated. Further, the shape is not limited to this, and a belt-like conductor may be wound, for example. Further, the negative electrode current collector 21 is not limited to the spiral shape as long as the negative electrode current collector 21 is provided over substantially the entire surface while leaving a gap s on the surface of the negative electrode active material 20. May be provided so as to hang down on both surfaces of the negative electrode active material 20. Moreover, as a material of the negative electrode current collector 21, it is preferable to use a conductor having a low electrical resistance, such as a copper alloy such as copper or brass, aluminum or an aluminum alloy, gold, or silver. The negative electrode current collector 21 occupies a small area with respect to the negative electrode active material 20 as described above. For this reason, there is no particular problem even if a copper alloy such as copper or brass having a redox potential separated from the negative electrode active material 20 is used for the negative electrode current collector 21.

セパレータ３０，３１は、本実施形態では１セルあたり２枚設けられており、それぞれのセパレータ３０，３１が上記負極活物質２０の両面の反応部２４に当接される。このセパレータ３０，３１は、吸水性に富んだ不織布等で構成され、イオン化反応材が含浸され流通時には乾燥された状態となっている。そして、使用時には水分が供給されることで湿潤し、負極活物質２０及び正極活物質である酸素とでイオン化反応がなされ発電する。 In this embodiment, two separators 30 and 31 are provided per cell, and the separators 30 and 31 are in contact with the reaction portions 24 on both surfaces of the negative electrode active material 20. The separators 30 and 31 are made of a non-woven fabric with high water absorption, and are impregnated with an ionization reaction material and dried during distribution. In use, moisture is supplied by supplying water, and an ionization reaction is performed between the negative electrode active material 20 and oxygen as the positive electrode active material to generate power.

正極４０，４１は、本実施形態では１セルあたり２枚設けられており、それぞれの正極４０，４１が、上記セパレータ３０，３１のうち負極活物質２０と反対側の面に当接される。この正極４０，４１は、導電性を有しつつ酸素を透過しやすい多孔質体で構成されることが好ましく、例えば炭素を含むシート状のものが採用できる。なお、本実施形態では正極４０，４１として炭素繊維シートを採用している。 In the present embodiment, two positive electrodes 40 and 41 are provided per cell, and each of the positive electrodes 40 and 41 is brought into contact with the surface of the separators 30 and 31 on the side opposite to the negative electrode active material 20. The positive electrodes 40 and 41 are preferably formed of a porous body that has conductivity and easily transmits oxygen. For example, a sheet-like material containing carbon can be employed. In the present embodiment, carbon fiber sheets are employed as the positive electrodes 40 and 41.

正極集電体４２，４３は、本実施形態では１セルあたり２つ設けられており、それぞれの正極集電体４２，４３が、上記正極４０，４１のうちセパレータ３０，３１と反対側の面に当接される。この正極集電体４２，４３は、多くの空気が正極４０，４１に触れ、さらにマグネシウム空気電池１０の使用中に空気が入れ替わり、常に新鮮な空気が正極４０，４１に触れるよう通気性を有するように構成されることが好ましい。詳しくは、正極集電体４２，４３の面に直交する方向に空気を通過させるのみならず、正極集電体４２，４３の面に沿った方向にも空気が流れるようにすることが好ましい。本実施形態では、これらの面に直交する方向と面に沿った方向の両方の通気性を有するものとして、波状に形成された導線を網状に織り込んだメッシュ素材を採用している。なお、正極集電体４２，４３の材質としては、銅、真鍮等の銅合金、アルミニウム又はアルミニウム合金、金、銀等の電気抵抗の少ない導体が用いられることが好ましい。 In the present embodiment, two positive electrode current collectors 42 and 43 are provided per cell, and each of the positive electrode current collectors 42 and 43 is a surface of the positive electrodes 40 and 41 opposite to the separators 30 and 31. Abut. The positive electrode current collectors 42 and 43 have air permeability so that a large amount of air touches the positive electrodes 40 and 41, and the air is replaced while the magnesium-air battery 10 is in use, so that fresh air always touches the positive electrodes 40 and 41. It is preferable to be configured as described above. Specifically, it is preferable that the air flow not only in the direction perpendicular to the surface of the positive electrode current collectors 42 and 43 but also in the direction along the surface of the positive electrode current collectors 42 and 43. In the present embodiment, a mesh material in which wavy conductive wires are woven in a net shape is adopted as having air permeability in both the direction orthogonal to these surfaces and the direction along the surfaces. In addition, as a material of the positive electrode current collectors 42 and 43, it is preferable to use a copper alloy such as copper or brass, a conductor having low electrical resistance such as aluminum or an aluminum alloy, gold or silver.

また、２枚ある正極集電体４２，４３は、ジャンパー線４５等で電気的に接続される。さらに、正極集電体４２，４３のうち１枚の上端部には、正極端子４４が接続される。この正極集電体４２，４３と正極端子４４との接続であるが、はんだ付け、又は負極端子２２同様のカシメ加工による接続等の方法でなされる。   Further, the two positive electrode current collectors 42 and 43 are electrically connected by a jumper wire 45 or the like. Further, a positive electrode terminal 44 is connected to the upper end portion of one of the positive electrode current collectors 42 and 43. The positive current collectors 42 and 43 and the positive terminal 44 are connected by a method such as soldering or connection by caulking similar to the negative terminal 22.

導電性接着剤５０，５１は、正極４０，４１と正極集電体４２，４３との当接される面の一部を接着するものである。この導電性接着剤５０，５１は、負極活物質２０の一方の面側に設けられた正極４０と正極集電体４２の一部、及び他方の面側に設けられた正極４１と正極集電体４３の一部を接着するのである。これらの負極活物質２０の一方の面側の導電性接着剤５０の接着面５２と、他方の面側の接着面５３は、図１、図３、図４、及び図５に示すように、負極活物質２０の面に直交する方向から見て異なる位置にあることが好ましい。 The conductive adhesives 50 and 51 adhere a part of the surface where the positive electrodes 40 and 41 and the positive electrode current collectors 42 and 43 are in contact with each other. The conductive adhesives 50 and 51 are a part of the positive electrode 40 and the positive electrode current collector 42 provided on one surface side of the negative electrode active material 20 and the positive electrode 41 and the positive electrode current collector provided on the other surface side. A part of the body 43 is bonded. The adhesive surface 52 of the conductive adhesive 50 on one surface side of these negative electrode active materials 20 and the adhesive surface 53 on the other surface side are as shown in FIG. 1, FIG. 3, FIG. 4, and FIG. It is preferable that they are at different positions when viewed from the direction orthogonal to the surface of the negative electrode active material 20.

これは、導電性接着剤５０，５１が接着された接着面５２，５３に対応する箇所の負極活物質２０は、イオン化反応が起きにくく、マグネシウム空気電池１０の寿命の終期まで残存する可能性がある。このため、負極活物質２０の一方の面側に接着された導電性接着剤５０の接着面５２と、他方の面側に接着された導電性接着剤５１の接着面５３とが、負極活物質２０の面に直交する方向から見て同じ位置にあると、当該部分の負極活物質２０が最後まで残り、有効な発電容量を確保し難くなるからである。一方、本実施形態のマグネシウム空気電池１０のように、負極活物質２０の一方の面側の接着面５２と、他方の面側に設けられた接着面５３とが、負極活物質２０の面と直交する方向から見て異なる位置に設けられていると、残存した負極活物質２０は、導電性接着剤５０，５１の接着面５２，５３とは反対側の面からのイオン化反応によって発電を続けることができる。   This is because the negative electrode active material 20 corresponding to the bonding surfaces 52 and 53 to which the conductive adhesives 50 and 51 are bonded is unlikely to undergo an ionization reaction and may remain until the end of the lifetime of the magnesium-air battery 10. is there. Therefore, the adhesive surface 52 of the conductive adhesive 50 bonded to one surface side of the negative electrode active material 20 and the adhesive surface 53 of the conductive adhesive 51 bonded to the other surface side are the negative electrode active material. This is because, if they are at the same position as viewed from the direction orthogonal to the plane of 20, the negative electrode active material 20 in the portion remains until the end, and it is difficult to secure an effective power generation capacity. On the other hand, as in the magnesium-air battery 10 of the present embodiment, the adhesive surface 52 on one surface side of the negative electrode active material 20 and the adhesive surface 53 provided on the other surface side are the surface of the negative electrode active material 20. If the negative electrode active material 20 is provided at different positions when viewed from the orthogonal direction, the remaining negative electrode active material 20 continues to generate power by an ionization reaction from the surface opposite to the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51. be able to.

また、負極活物質２０の面に直交する方向から見た導電性接着剤５０，５１の接着面５２，５３の位置は、負極集電体２１がある位置であることが好ましい。本実施形態では、図４及び図５に示すように、負極活物質２０の面に直交する方向から見て接着面５２，５３に対応する位置に、負極活物質２０の表面に巻着された負極集電体２１が存在するように構成される。これは、既に述べたように、負極活物質２０において、導電性接着剤５０，５１の接着面５２，５３に対応する箇所は、マグネシウム空気電池１０の寿命の終期まで残存する可能性がある。この負極活物質２０が残存する可能性がある場所に負極集電体２１を存在させることで、マグネシウム空気電池１０の寿命の終期において、残存した負極活物質２０によって発電される電力を有効に回収することができる。なお、図４及び図５において導電性接着剤５０，５１の接着面５２，５３を表わす円は、実線が負極活物質２０の手前側に導電性接着剤５０，５１の接着面５２，５３が存在し、破線は裏側に接着面５２，５３が存在することを示している。   Moreover, it is preferable that the positions of the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51 viewed from the direction orthogonal to the surface of the negative electrode active material 20 are the positions where the negative electrode current collector 21 is located. In this embodiment, as shown in FIGS. 4 and 5, the negative electrode active material 20 is wound around the surface of the negative electrode active material 20 at positions corresponding to the adhesion surfaces 52 and 53 when viewed from the direction orthogonal to the surface of the negative electrode active material 20. The negative electrode current collector 21 is configured to exist. As described above, in the negative electrode active material 20, the portions corresponding to the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51 may remain until the end of the lifetime of the magnesium-air battery 10. By making the negative electrode current collector 21 exist in a place where the negative electrode active material 20 may remain, the power generated by the remaining negative electrode active material 20 is effectively recovered at the end of the life of the magnesium-air battery 10. can do. 4 and 5, the circles representing the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51 are solid lines, and the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51 are on the front side of the negative electrode active material 20. It exists and the broken line has shown that the adhesive surfaces 52 and 53 exist on the back side.

また、導電性接着剤５０，５１の接着面５２，５３の、正極４０，４１の広い面に占める面積は、１〜３０％が好ましく、２〜１０％がより好ましい。これは、接着面５２，５３の面積が狭すぎると電池の内部抵抗が増大してしまうおそれがあるからであり、広すぎると正極集電体４２，４３からの酸素の供給を阻害してしまうとともに、導電性接着剤の使用量が増えて製造コストが増大してしまうからである。本発明のマグネシウム空気電池では、さらに好ましい例として、接着面５２，５３占める面積を、正極４０，４１の広い面の面積の４〜８％の範囲としている。 Moreover, 1-30% is preferable and, as for the area which the adhesive surfaces 52, 53 of the conductive adhesives 50, 51 occupy in the wide surface of the positive electrodes 40, 41, 2-10% is more preferable. This is because if the area of the bonding surfaces 52 and 53 is too small, the internal resistance of the battery may increase. If it is too wide, the supply of oxygen from the positive electrode current collectors 42 and 43 will be hindered. At the same time, the use amount of the conductive adhesive is increased and the manufacturing cost is increased. In the magnesium-air battery of the present invention, as a more preferable example, the area occupied by the bonding surfaces 52 and 53 is in the range of 4 to 8% of the area of the wide surface of the positive electrodes 40 and 41.

次に、図７を参照しながら、本発明のマグネシウム空気電池１０の使用時の負極活物質２０の状態を説明する。図７（Ａ）はマグネシウム空気電池１０の寿命の中期のときの負極活物質２０を模式的に示した図、図７（Ｂ）はマグネシウム空気電池１０の寿命の終期のときの負極活物質２０を模式的に示した図である。   Next, the state of the negative electrode active material 20 when the magnesium-air battery 10 of the present invention is used will be described with reference to FIG. FIG. 7A schematically shows the negative electrode active material 20 when the magnesium-air battery 10 is in the middle of its life, and FIG. 7B shows the negative electrode active material 20 when the magnesium-air battery 10 is at the end of its life. FIG.

マグネシウム空気電池１０のセパレータ３０，３１に水分を供給し、セパレータ３０，３１を湿潤させると、セパレータ３０，３１に含浸されたイオン化反応剤によって、負極活物質２０及び正極活物質である酸素とでイオン化反応がなされ、発電がなされる。このとき、正極は空気中の酸素とで反応がなされるため、正極４０，４１は消耗しない。一方、負極では負極活物質２０であるマグネシウム又はマグネシウム合金が、水酸化マグネシウムへと変化することで、負極活物質２０は図７（Ａ）に示すように、当初の厚さから減少していく。 When moisture is supplied to the separators 30 and 31 of the magnesium-air battery 10 and the separators 30 and 31 are wetted, the ionization reactant impregnated in the separators 30 and 31 causes the negative electrode active material 20 and oxygen as the positive electrode active material to An ionization reaction is performed to generate electricity. At this time, since the positive electrode reacts with oxygen in the air, the positive electrodes 40 and 41 are not consumed. On the other hand, in the negative electrode, when the magnesium or magnesium alloy that is the negative electrode active material 20 is changed to magnesium hydroxide, the negative electrode active material 20 decreases from the initial thickness as shown in FIG. .

このとき、既に述べたように、負極集電体２１によって負極活物質２０における部分的な電流密度の上昇が抑制されるため、負極活物質２０は略満遍なく反応していくのであるが、導電性接着剤５０，５１の接着面５２，５３において、部分的に負極活物質２０が残存する場合がある。これは、負極活物質２０のうち、導電性接着剤５０，５１の接着面５２，５３に対応する場所以外のところでは、負極活物質２０の両面からイオン化反応がなされ、負極活物質２０が両面から減少する。これに対し、図中の破線ｄ１，ｄ２で示す導電性接着剤５０，５１の接着面５２，５３に対応する場所では、イオン化反応が鈍く、主に接着面５２，５３が存在する側とは反対側の面でイオン化反応がなされる。これによって、負極活物質２０のうち、導電性接着剤５０，５１の接着面５２，５３に対応する場所は、残存しやすい傾向にある。なお、負極集電体２１は、セパレータ３０，３１によって負極活物質２０に押し付けられているため、負極活物質２０の厚みが減少してもともに移動し、負極活物質２０の表面に接触している。   At this time, as described above, since the partial increase in current density in the negative electrode active material 20 is suppressed by the negative electrode current collector 21, the negative electrode active material 20 reacts almost uniformly. In some cases, the negative electrode active material 20 may partially remain on the bonding surfaces 52 and 53 of the adhesives 50 and 51. This is because the negative electrode active material 20 is subjected to an ionization reaction from both sides of the negative electrode active material 20 at locations other than the locations corresponding to the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51, and the negative electrode active material 20 is double-sided. Decrease from. On the other hand, in the place corresponding to the adhesion surfaces 52 and 53 of the conductive adhesives 50 and 51 indicated by the broken lines d1 and d2 in the figure, the ionization reaction is slow, and the side on which the adhesion surfaces 52 and 53 mainly exist An ionization reaction takes place on the opposite side. Thereby, in the negative electrode active material 20, the locations corresponding to the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51 tend to remain. Since the negative electrode current collector 21 is pressed against the negative electrode active material 20 by the separators 30 and 31, the negative electrode current collector 21 moves together even when the thickness of the negative electrode active material 20 decreases and contacts the surface of the negative electrode active material 20. Yes.

次に、図７（Ｂ）に示すように、さらに発電がなされると、負極活物質２０は分断されることがある。このとき、負極活物質２０のうち導電性接着剤５０，５１の接着面５２，５３に対応する場所では、上記の様に負極活物質２０の主に片面からしかイオン化反応がなされないため、マグネシウム空気電池１０の寿命の終期まで残存する可能性がある。また、負極活物質２０のうち、導電性接着剤５０，５１の接着面５２，５３に対応する場所以外のところでも、必ずしも一律に厚さが減少する訳ではなく、分断されながら一部は残存することがある。このとき、負極集電体２１が、負極活物質２０の表面に螺旋状に巻着され、さらに負極活物質２０のうち導電性接着剤５０，５１の接着面５２，５３に対応する場所に設けられているため、残存する負極活物質２０から効率的に電力を回収することができる。   Next, as illustrated in FIG. 7B, when power generation is further performed, the negative electrode active material 20 may be divided. At this time, in the negative electrode active material 20, the ionization reaction is performed mainly from one side of the negative electrode active material 20 at a location corresponding to the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51. The air battery 10 may remain until the end of its life. Further, the thickness of the negative electrode active material 20 is not necessarily reduced uniformly even in places other than the locations corresponding to the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51, and a part remains while being divided. There are things to do. At this time, the negative electrode current collector 21 is spirally wound around the surface of the negative electrode active material 20 and further provided in a location corresponding to the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51 in the negative electrode active material 20. Therefore, electric power can be efficiently recovered from the remaining negative electrode active material 20.

また、負極活物質２０の分断された箇所を通じて、２枚のセパレータ３０，３１が接触し、電解液が多いセパレータ３０，３１から少ないセパレータ３０，３１に供給される。これらにより、マグネシウム空気電池１０の寿命の終期においても、安定した発電が期待できる。なお、既に述べたように、負極活物質２０の表面積に対して負極集電体２１の占める面積は小さく、セパレータ３０，３１と負極活物質２０とは十分な面積で接触しているため、負極集電体２１によってイオン化反応が妨げられることはない。   In addition, the two separators 30 and 31 are in contact with each other through the part where the negative electrode active material 20 is divided, and the separators 30 and 31 with a large amount of electrolyte are supplied to the separators 30 and 31 with a small amount of electrolyte. As a result, stable power generation can be expected even at the end of the life of the magnesium-air battery 10. As already described, the area occupied by the negative electrode current collector 21 is small with respect to the surface area of the negative electrode active material 20, and the separators 30, 31 and the negative electrode active material 20 are in contact with each other with a sufficient area. The current collector 21 does not hinder the ionization reaction.

なお、図９に示すように、他の実施形態のマグネシウム空気電池１００として、１つの負極活物質２０に対して１つずつのセパレータ３０、正極４０、正極集電体４２としてもよいし、このマグネシウム空気電池１００を、複数積層させてもよい。 In addition, as shown in FIG. 9, it is good also as the separator 30, the positive electrode 40, and the positive electrode collector 42 for every one negative electrode active material 20 as the magnesium air battery 100 of other embodiment, A plurality of magnesium air batteries 100 may be stacked.

以上、説明したように、これらの本実施形態のマグネシウム空気電池によれば、負極端子２２を負極集電体２１とともに直接に負極活物質２０にカシメ加工によって接続しているため、当該部分の電気抵抗を低減させることができるとともに、製造コストの低減を図ることができる。また、負極活物質２０に狭小部２７を設けることにより、負極活物質２０の面積を減らすことができ、製造コストの低減を図ることができる。また、セパレータ３０，３１の辺縁３２が当接される部分は、負極活物質２０の全幅部２６であるため、全幅部２６と狭小部２７との境２８において、電流密度の上昇によるイオン化反応の促進が起きず、この境２８において負極活物質２０が分断されることがない。また、負極端子２２及び端子接続部２５がセパレータ３０，３１から突出しているため、当該部分の厚さが変化せず、電池ケース等に収納することが容易となる。   As described above, according to these magnesium-air batteries of this embodiment, since the negative electrode terminal 22 is directly connected to the negative electrode active material 20 together with the negative electrode current collector 21 by caulking, The resistance can be reduced and the manufacturing cost can be reduced. Moreover, by providing the narrow portion 27 in the negative electrode active material 20, the area of the negative electrode active material 20 can be reduced, and the manufacturing cost can be reduced. Moreover, since the part where the edge 32 of the separators 30 and 31 is in contact is the full width part 26 of the negative electrode active material 20, the ionization reaction due to the increase in current density at the boundary 28 between the full width part 26 and the narrow part 27. Is not promoted, and the negative electrode active material 20 is not divided at the boundary 28. Moreover, since the negative electrode terminal 22 and the terminal connection part 25 protrude from the separators 30 and 31, the thickness of the said part does not change and it becomes easy to accommodate in a battery case etc.

また、負極集電体２１が負極活物質２０の表面に隙間ｓを設けて巻着されているため、負極集電体２１を設けながら負極活物質２０の両面を用いて発電することができる。このため、取り出せる電流が２倍となり、実用に耐え得る電流を取り出すことができる。また、負極集電体２１が、負極活物質２０の略全域に巻着されているため、電池の内部抵抗を低減させることができるとともに、負極活物質２０の一部分に電流が集中することなく、負極活物質２０の局部的な反応が避けられ、負極活物質２０全体で略均一な発電をすることができる。   Since the negative electrode current collector 21 is wound around the surface of the negative electrode active material 20 with a gap s, power can be generated using both surfaces of the negative electrode active material 20 while the negative electrode current collector 21 is provided. For this reason, the current that can be extracted is doubled, and a current that can be practically used can be extracted. In addition, since the negative electrode current collector 21 is wound around substantially the entire area of the negative electrode active material 20, the internal resistance of the battery can be reduced, and current does not concentrate on a part of the negative electrode active material 20, A local reaction of the negative electrode active material 20 can be avoided, and substantially uniform power generation can be performed in the entire negative electrode active material 20.

また、負極集電体２１は、負極活物質２０の表面積の一部のみを覆っているため、負極集電体２１自体の材料コストを低減できるとともに、負極集電体２１が比較的高い面圧で負極活物質２０と接触できる。このため、負極活物質２０と負極集電体２１とを導電性接着剤で必ずしも接着する必要がなく、負極集電体２１を設けるコストを低減させることができる。さらに、負極集電体２１の占める面積が、負極活物質２０の面積に対して狭いため、負極集電体２１に酸化還元電位の離れた銅又は銅合金を用いても実質的に問題とならず、製造が容易となる。   Further, since the negative electrode current collector 21 covers only a part of the surface area of the negative electrode active material 20, the material cost of the negative electrode current collector 21 itself can be reduced, and the negative electrode current collector 21 has a relatively high surface pressure. Can contact with the negative electrode active material 20. For this reason, it is not always necessary to bond the negative electrode active material 20 and the negative electrode current collector 21 with a conductive adhesive, and the cost for providing the negative electrode current collector 21 can be reduced. Furthermore, since the area occupied by the negative electrode current collector 21 is narrower than the area of the negative electrode active material 20, even if copper or a copper alloy having a redox potential at a distance is used for the negative electrode current collector 21, there is substantially no problem. Therefore, manufacture becomes easy.

また、負極集電体２１が、負極活物質２０のうち導電性接着剤５０，５１の接着面５２，５３に対応する位置に設けられているため、マグネシウム空気電池１０の寿命の終期において、当該部分の負極活物質２０が分断された状態で残存しても、残存した部分から効率よく電力を回収することができる。さらに、負極活物質２０が分断された場所に置いて、負極活物質２０を挟んで向かい合う２枚のセパレータ３０，３１が接触し、互いに電解液を供給するため、２枚のセパレータ３０，３１の電解液の量が均一となる。   In addition, since the negative electrode current collector 21 is provided at a position corresponding to the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51 in the negative electrode active material 20, at the end of the life of the magnesium-air battery 10, Even if the portion of the negative electrode active material 20 remains in a separated state, power can be efficiently recovered from the remaining portion. Furthermore, since the two separators 30 and 31 facing each other with the negative electrode active material 20 in between are in contact with each other in a place where the negative electrode active material 20 is divided, the electrolyte solution is supplied to each other. The amount of electrolyte is uniform.

また、導電性接着剤５０，５１の接着面５２，５３が、負極活物質２０の一方の面側と他方の面側とで、負極活物質２０の面に直交する方向から見て異なる位置にあるため、負極活物質２０のうち導電性接着剤５０，５１の接着面５２，５３に対応するイオン化反応が起きにくい場所であっても、その反対側の面からイオン化反応がなされ、問題なく発電することができる。   In addition, the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51 are at different positions on one surface side and the other surface side of the negative electrode active material 20 when viewed from the direction orthogonal to the surface of the negative electrode active material 20. Therefore, even in a place where the ionization reaction corresponding to the bonding surfaces 52 and 53 of the conductive adhesives 50 and 51 is difficult to occur in the negative electrode active material 20, the ionization reaction is performed from the opposite surface, and the power generation is performed without any problem. can do.

また、導電性接着剤５０，５１によって、正極４０，４１と正極集電体４２，４３との当接される面の一部を接着するため、正極４０，４１と正極集電体４２，４３との間の内部抵抗を低減させることができ、大電流を取り出すことができる。また、導電性接着剤５０，５１の接着面５２，５３が、正極４０，４１と正極集電体４２，４３との当接される面の一部であること、及び正極集電体４２，４３が通気性を有するため、酸素の供給を阻害することがない。 Further, the conductive adhesive 50, 51, for adhering a portion of the contact the surface to the positive electrode 40, 41 and the positive electrode current collector 42, positive electrode 40, 41 and the positive electrode current collector 42, 43 The internal resistance between them can be reduced, and a large current can be taken out. In addition, the adhesive surfaces 52 and 53 of the conductive adhesives 50 and 51 are a part of the surface where the positive electrodes 40 and 41 and the positive electrode current collectors 42 and 43 are in contact with each other, and the positive electrode current collectors 42 and 43 Since 43 has air permeability, supply of oxygen is not hindered.

これらにより、マグネシウム空気電池の寿命の終期まで、大電流を取出しながら安定した発電をするとともに、低コストなマグネシウム空気電池とすることができる。   As a result, stable power generation is possible while taking out a large current until the end of the life of the magnesium-air battery, and a low-cost magnesium-air battery can be obtained.

なお、上述のマグネシウム空気電池は本発明の例示であり、発明の趣旨を逸脱しない範囲において、その構成を適宜変更することができる。   The above-described magnesium-air battery is an exemplification of the present invention, and the configuration thereof can be changed as appropriate without departing from the spirit of the invention.

１０，１００・・マグネシウム空気電池、
２０，１２０・・負極活物質、２１・・負極集電体、２２・・負極端子、２３・・筒部、２４・・反応部、２５，１２５・・端子接続部、２６・・全幅部、２７・・狭小部、２８・・境、ｗ・・幅、ｓ・・隙間、
３０，３１・・セパレータ、３２・・辺縁、
４０，４１・・正極、４２，４３・・正極集電体、４４・・正極端子、４５・・ジャンパー線、
５０，５１・・導電性接着剤、５２，５３・・接着面、 10,100 ... magnesium air battery,
20, 120 ... Negative electrode active material, 21 ... Negative electrode current collector, 22 ... Negative electrode terminal, 23 ... Tube part, 24 ... Reaction part, 25, 125 ... Terminal connection part, 26 ... Full width part, 27 ·· Narrow part, 28 · · border, w · · width, s · · gap,
30, 31 ... separator, 32 ... edge,
40, 41 ... Positive electrode , 42, 43 ... Positive current collector, 44 ... Positive terminal, 45 ... Jumper wire,
50, 51 ... conductive adhesive, 52, 53 ... adhesive surface,

Claims (8)

マグネシウム又はマグネシウム合金を含むシート状の負極活物質と、
前記負極活物質にカシメ加工によって接続された負極端子と、
前記負極活物質に当接される、イオン化反応材が含浸されたシート状のセパレータと、
前記セパレータのうち前記負極活物質と反対側の面に当接される、シート状の正極と、
前記正極のうち前記セパレータと反対側の面に当接される正極集電体と、
前記正極集電体に接続された正極端子と、を備え、
前記負極活物質が、
前記セパレータと当接される反応部と、
前記セパレータの辺縁から突出するとともに前記反応部と同じ幅を有し前記セパレータの辺縁が接する全幅部、及び前記全幅部から延伸されその幅が狭められるとともに前記負極端子が接続される狭小部を備える端子接続部と、
を備えることを特徴とするマグネシウム空気電池。 A sheet-like negative electrode active material containing magnesium or a magnesium alloy;
A negative electrode terminal connected to the negative electrode active material by caulking,
A sheet-like separator impregnated with an ionization reaction material in contact with the negative electrode active material;
A sheet-like positive electrode in contact with a surface of the separator opposite to the negative electrode active material;
A positive electrode current collector in contact with a surface of the positive electrode opposite to the separator;
A positive electrode terminal connected to the positive electrode current collector ,
The negative electrode active material is
A reaction portion in contact with the separator;
A full width part that protrudes from the edge of the separator and has the same width as the reaction part, and a narrow part that extends from the full width part and is narrowed and connected to the negative electrode terminal. A terminal connection comprising:
A magnesium-air battery comprising: 前記負極端子に接続されるとともに、前記負極活物質が前記セパレータに当接されるよう前記負極活物質の表面に隙間を設けて這わされた導体からなる負極集電体を備えることを特徴とする請求項１に記載のマグネシウム空気電池。 A negative electrode current collector comprising a conductor connected to the negative electrode terminal and provided with a gap on the surface of the negative electrode active material so that the negative electrode active material is brought into contact with the separator. The magnesium air battery according to claim 1 . 前記負極集電体が、前記負極活物質に螺旋状に巻着されていることを特徴とする請求項２に記載のマグネシウム空気電池。 The magnesium-air battery according to claim 2 , wherein the negative electrode current collector is spirally wound around the negative electrode active material. 前記正極と前記正極集電体との当接される面の一部を接着する導電性接着剤を備えることを特徴とする請求項１ないし３のいずれか１項に記載のマグネシウム空気電池。 The magnesium-air battery according to any one of claims 1 to 3, further comprising a conductive adhesive that adheres a part of a surface of the positive electrode and the positive electrode current collector in contact with each other. 前記負極集電体が、前記負極活物質の面に直交する方向から見て前記導電性接着剤の接着面に対応する位置に設けられていることを特徴とする請求項４に記載のマグネシウム空気電池。 5. The magnesium air according to claim 4 , wherein the negative electrode current collector is provided at a position corresponding to an adhesive surface of the conductive adhesive as viewed from a direction orthogonal to the surface of the negative electrode active material. battery. 前記負極活物質１つに対して前記セパレータ、前記正極、及び前記正極集電体を２つ備え、前記セパレータ、前記正極、及び前記正極集電体が前記負極活物質の両面に設けられていることを特徴とする請求項４又は５に記載のマグネシウム空気電池。 The negative active material, one for the separator, the positive electrode, and includes the two positive electrode current collector, the separator, the positive electrode, and the positive electrode current collector is provided on both surfaces of the negative electrode active material The magnesium-air battery according to claim 4 or 5 , characterized in that. 前記負極活物質の両面に設けられた前記正極の前記導電性接着剤との接着面のそれぞれの位置が、前記負極活物質の面に直交する方向から見て異なる位置にあることを特徴とする請求項６に記載のマグネシウム空気電池。 Each position of the adhesion surface of the positive electrode provided on both surfaces of the negative electrode active material with the conductive adhesive is in a different position when viewed from a direction orthogonal to the surface of the negative electrode active material. The magnesium air battery according to claim 6 . 前記負極端子がアルミニウム又はアルミニウム合金であることを特徴とする請求項１ないし７のいずれか１項に記載のマグネシウム空気電池。 The magnesium-air battery according to any one of claims 1 to 7 , wherein the negative electrode terminal is aluminum or an aluminum alloy.
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