JP3523506B2 - Rechargeable air battery - Google Patents

Rechargeable air battery

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Publication number
JP3523506B2
JP3523506B2 JP30196498A JP30196498A JP3523506B2 JP 3523506 B2 JP3523506 B2 JP 3523506B2 JP 30196498 A JP30196498 A JP 30196498A JP 30196498 A JP30196498 A JP 30196498A JP 3523506 B2 JP3523506 B2 JP 3523506B2
Authority
JP
Japan
Prior art keywords
electrode
air
battery
photoelectric conversion
metal electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP30196498A
Other languages
Japanese (ja)
Other versions
JP2000133328A (en
Inventor
敏雄 松島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Telegraph and Telephone Corp
Original Assignee
Nippon Telegraph and Telephone Corp
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Filing date
Publication date
Application filed by Nippon Telegraph and Telephone Corp filed Critical Nippon Telegraph and Telephone Corp
Priority to JP30196498A priority Critical patent/JP3523506B2/en
Publication of JP2000133328A publication Critical patent/JP2000133328A/en
Application granted granted Critical
Publication of JP3523506B2 publication Critical patent/JP3523506B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • 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

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  • Secondary Cells (AREA)
  • Hybrid Cells (AREA)

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、空気中の酸素を酸
化剤に用いて放電する空気電池に関するもので、太陽光
を受けて発電する光電変換部と、補助電極の設置によ
り、放電時に負極になる金属電極の充電を可能とした、
充電式空気電池に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an air battery that uses oxygen in the air as an oxidant for discharging, and by installing a photoelectric conversion unit that receives sunlight to generate electricity and an auxiliary electrode, a negative electrode is provided during discharging. Enabled to charge the metal electrode that becomes
The present invention relates to a rechargeable air battery.

【０００２】[0002]

【従来の技術】空気電池は、空気中の酸素を酸化剤と
し、放電反応の際に電子を放出する物質（還元剤）のみ
を電池内に収納した構造を呈しており、放電にあたって
は酸素の還元と還元剤の酸化反応によって電子の移動を
行なわせ、外部の負荷に電流を取り出すものである。2. Description of the Related Art An air battery has a structure in which oxygen in the air is used as an oxidant and only a substance (reducing agent) that releases an electron during a discharge reaction is housed in the battery. Electrons are transferred by reduction and an oxidation reaction of the reducing agent, and an electric current is taken out to an external load.

【０００３】図１１は、このような空気電池について、
従来品の構造の一例を示したものである。この例は、小
型のいわゆるボタン型と言われるもので、１００はシー
ル紙、１１１は負極、１１２は負極側で放電反応に関わ
る還元剤、１１３はガスケット、１１４はセパレータ
（電解質）、１１５は空気極（正極）、１１６ははっ水
膜、１１７は拡散紙、１１８は空気孔、１１９は正極ケ
ースである。FIG. 11 shows such an air battery,
It is an example of a structure of a conventional product. This example is a small so-called button type, in which 100 is a seal paper, 111 is a negative electrode, 112 is a reducing agent involved in the discharge reaction on the negative electrode side, 113 is a gasket, 114 is a separator (electrolyte), and 115 is air. Electrode (positive electrode), 116 is a water-repellent film, 117 is diffusion paper, 118 is air holes, and 119 is a positive electrode case.

【０００４】この電池は、保存中、シール紙１００で空
気極１１５と酸素の接触が断たれており、使用開始にあ
たってこのシール紙１００を取り除くと、空気中の酸素
が空気孔１１８を通して空気極１１５に到達し放電反応
が開始される。負極の還元剤としては、ボタン型電池の
場合、主に亜鉛が使用され、反応性を高めるために粉末
の亜鉛を糊状にし、さらに親水性の物質を添加する等の
工夫がなされている。In this battery, the contact between the air electrode 115 and oxygen is cut off by the sticker paper 100 during storage. When the sticker paper 100 is removed at the start of use, oxygen in the air passes through the air hole 118 and the air electrode 115. And the discharge reaction is started. In the case of button type batteries, zinc is mainly used as the reducing agent for the negative electrode, and in order to enhance the reactivity, powdered zinc is made into a paste, and a hydrophilic substance is added.

【０００５】このようにこの電池では、電池反応に必要
とされる物質（活物質）のうち、正極側活物質として大
気中の酸素を使用するため、電池内に保存するものは、
電解質と負極側活物質だけとなり、電池のエネルギー密
度の向上が可能である。しかし、一次電池であり、電池
内に収納した負極活物質が放電で消耗しつくせば、その
時点で放電は終了する。As described above, in this battery, among the substances (active materials) required for the battery reaction, oxygen in the atmosphere is used as the active material on the positive electrode side.
Since only the electrolyte and the negative electrode side active material are used, the energy density of the battery can be improved. However, in the case of a primary battery, if the negative electrode active material contained in the battery is exhausted by the discharge, the discharge is terminated at that point.

【０００６】また、放電時の亜鉛の反応はセパレータ
（電解質）の近傍の部分から進行し、放電の進行に伴っ
て反応部は電解質から遠ざかるため、それにつれて電池
の電圧低下が顕著になる。したがって、このような小型
のボタン型電池の製造に適用されている構造のままで
は、大きな容量のものは作製が困難であった。Further, the reaction of zinc at the time of discharging progresses from a portion in the vicinity of the separator (electrolyte), and the reaction part moves away from the electrolyte with the progress of discharging, and accordingly the voltage drop of the battery becomes remarkable. Therefore, it is difficult to manufacture a battery having a large capacity with the structure applied to the manufacture of such a small button type battery.

【０００７】そこで、放電容量の増加を主目的として、
図１２に示すような開放式で、ボックス型構造の空気電
池が作製された。本図において、１２０はケース、１２
１は空気極、１２２は金属電極、１２３は負極端子、１
２４は正極端子である。また、本図は単セルを示してお
り、単セルはケース１２０の一つの面に空気極１２１が
設けられ、ケース１２０の内部に電解液が入れられ、電
解液中に金属電極２２が浸漬して入れられている。この
ような構造とすることで、空気極、金属電極とも大面積
化が図られ、また、金属電極が放電によって消耗しても
新たな電極に交換することで、放電時間の延長が可能な
空気電池となった。Therefore, the main purpose is to increase the discharge capacity.
An open-type, box-type structure air cell as shown in FIG. 12 was produced. In this figure, 120 is a case, 12
1 is an air electrode, 122 is a metal electrode, 123 is a negative electrode terminal, 1
24 is a positive electrode terminal. Further, this figure shows a single cell. In the single cell, an air electrode 121 is provided on one surface of a case 120, an electrolytic solution is placed inside the case 120, and a metal electrode 22 is immersed in the electrolytic solution. Have been put in. With such a structure, both the air electrode and the metal electrode can be made large in area, and even if the metal electrode is consumed due to discharge, it is possible to extend the discharge time by replacing it with a new electrode. It became a battery.

【０００８】このボックス型構造の電池の場合、通常複
数の単セルを直列に接続して使用される。先の空気電池
はボタン型であり、使用開始時にシールをはがすことで
空気極を空気に接触させるが、図１２の方式の電池では
通常、使用時に電解液を注入して放電を開始させる。ま
た、このようなボックス型の電池では、先に述べたよう
にボタン型構造のものより放電容量がアップするが、ボ
タン型電池と同様、電池内に蓄積されている活物質は負
極となる金属電極であり、この金属電極の消耗によって
放電は終了してしまう。In the case of this box-type battery, a plurality of single cells are usually connected in series and used. The above air battery is a button type, and the air electrode is brought into contact with air by peeling off the seal at the start of use, but in the battery of the system of FIG. 12, normally, at the time of use, electrolyte is injected to start discharge. Further, in such a box-type battery, the discharge capacity is higher than that of the button-type structure as described above, but like the button-type battery, the active material accumulated in the battery is a metal serving as a negative electrode. It is an electrode, and the discharge ends due to the consumption of this metal electrode.

【０００９】[0009]

【発明が解決しようとする課題】このように、従来の空
気電池は、エネルギー密度が高いという特徴を有し、電
池の構造によって容量の増加が図れるものの、いずれも
電池内部に蓄積した活物質が消耗すればその時点で放電
は終了する一次電池であり、充電によって再度使用（放
電）することはできないという欠点があった。As described above, the conventional air battery has a feature that the energy density is high, and although the capacity can be increased by the structure of the battery, in any case, the active material accumulated inside the battery is It is a primary battery whose discharge is terminated at that point when it is consumed, and has a drawback that it cannot be used (discharged) again by charging.

【００１０】[0010]

【課題を解決するための手段】上記課題を解決するた
め、本発明による充電式空気電池は、電池部と光電変換
部からなる充電式空気電池であって、前記電池部は金属
電極と電解質と空気極と補助電極とを有し、前記空気極
は片面が空気に他面が前記電解質に接するように配置さ
れ、前記金属電極と前記補助電極は前記電解質中に配置
され、前記金属電極と前記空気極は電力を供給するため
に負荷に接続され、前記光電変換部の正側の出力端は前
記補助電極に接続され、前記光電変換部の負側の出力端
は前記金属電極に接続されていることを特徴とする。In order to solve the above problems, a rechargeable air battery according to the present invention is a rechargeable air battery comprising a battery section and a photoelectric conversion section, wherein the battery section comprises a metal electrode and an electrolyte. and a sky Kikyoku and the auxiliary electrode, the air electrode one side are arranged so that the other surface with air is in contact with the electrolyte, said auxiliary electrode and the metal electrode is disposed in said electrolyte, and said metal electrode the air electrode is connected to a load to supply power, the positive side of the output end of the photoelectric conversion unit is connected to the auxiliary electrode, the negative side of the output end of the photoelectric conversion unit is connected to the metal electrode It is characterized by being.

【００１１】すなわち、充電機能をもった空気電池を実
現するため、光電変換部と電池部から空気電池を構成
し、電池部は、金属電極、電解質、空気極、および補助
電極からなり、空気極は空気中と電解質中に露出し、金
属電極と補助電極は前記電解質中に配置され、かつ、前
記金属電極と前記補助電極間には、金属電極の充電が行
われるような状態に光電変換部の出力が接続され、これ
によって、放電で消耗した金属電極の充電を行うもので
ある。That is, in order to realize an air battery having a charging function, an air battery is composed of a photoelectric conversion unit and a battery unit, and the battery unit is composed of a metal electrode, an electrolyte, an air electrode, and an auxiliary electrode. Is exposed in the air and the electrolyte, the metal electrode and the auxiliary electrode are arranged in the electrolyte, and between the metal electrode and the auxiliary electrode, the photoelectric conversion unit is in a state in which the metal electrode is charged. The output of is connected, and thereby the metal electrode consumed by the discharge is charged.

【００１２】以上の対策によって、放電終了後にも太陽
光による充電で再度の放電を可能としたり、また、放電
中にも太陽光からの充電によって放電持続時間の延長を
可能とする、充電式空気電池の実現を図るものである。[0012] By the above measures, rechargeable air that can be discharged again by charging with sunlight even after the end of discharging and that the duration of discharge can be extended by charging from sunlight even during discharging It is intended to realize a battery.

【００１３】本発明は、金属電極、電解質、空気極、お
よび補助電極から電池部を形成し、これに光電変換部を
適用し、この際、光電変換部の出力を電解質中に配置さ
れた金属電極と補助電極間に接続し、金属電極の充電が
行われるようにしたことを特徴としている。In the present invention, a battery part is formed from a metal electrode, an electrolyte, an air electrode, and an auxiliary electrode, and a photoelectric conversion part is applied to the battery part. At this time, the output of the photoelectric conversion part is a metal arranged in the electrolyte. It is characterized in that it is connected between the electrode and the auxiliary electrode so that the metal electrode is charged.

【００１４】従来の技術では、本発明のように補助電極
を設けた空気電池や、さらにこの補助電極を利用して太
陽光発電によって電池の充電を行うように組み合わされ
た空気電池は考案されておらず、充電式空気電池の構成
そのものが従来のものと異なる。In the prior art, an air battery provided with an auxiliary electrode as in the present invention and an air battery combined so as to charge the battery by solar power generation using the auxiliary electrode have been devised. The structure of the rechargeable air battery is different from the conventional one.

【００１５】[0015]

【実施例】本発明の詳細を、以下図面を用いて説明す
る。The details of the present invention will be described below with reference to the drawings.

【００１６】まず、図１は本発明の要点を説明した図で
あり、本図において、１０はケース、１１は空気極、１
２は金属電極、１３は負極端子、１４は正極端子、１５
は補助電極、１６は電解液、１７は負荷、１８は光電変
換部、１９は補助電極端子、１１０はダイオードであ
る。First, FIG. 1 is a diagram for explaining the main points of the present invention. In this figure, 10 is a case, 11 is an air electrode, and 1
2 is a metal electrode, 13 is a negative electrode terminal, 14 is a positive electrode terminal, 15
Is an auxiliary electrode, 16 is an electrolytic solution, 17 is a load, 18 is a photoelectric conversion unit, 19 is an auxiliary electrode terminal, and 110 is a diode.

【００１７】このような構造になっているので、本発明
の充電式空気電池では、光が照射されていない状態でも
従来の空気電池と同様に、空気極１１と金属電極１２間
での反応により電力を取り出すことが出来る。そして、
所定の時間放電を行った後、負荷１７を取り外し光電変
換部１８に光を照射することで、金属電極１２と補助電
極１５との間で反応を行なわせ、金属電極１２の充電反
応を進めることが出来る。ここで、光電変換部１８が十
分な発電を行うような光量が得られる条件であれば、負
荷への電力供給が行え、また金属電極の充電も可能であ
る。 With such a structure, in the rechargeable air battery of the present invention, the reaction between the air electrode 11 and the metal electrode 12 is caused by the reaction between the air electrode 11 and the metal electrode 12 even when the light is not irradiated. Power can be taken out. And
After discharging for a predetermined period of time, the load 17 is removed and the photoelectric conversion unit 18 is irradiated with light to cause a reaction between the metal electrode 12 and the auxiliary electrode 15, thereby promoting a charging reaction of the metal electrode 12. Can be done. Here, the photoelectric conversion unit 18 is
If the condition is such that sufficient light is generated, negative
Power can be supplied to the load and the metal electrode can be charged.
It

【００１８】なお、本図において、前記補助電極端子１
９の配線内にダイオード１１０を設けた。この理由は、
ダイオード１１０に電流を通じた際の電圧低下が電流の
値に関わらず、ほぼ０．６Ｖ／個である特性を利用し
て、光電変換部１８の出力電圧を金属電極１２の充電に
適した値に調整するためである。すなわち、例えば、結
晶シリコン系太陽電池の出力特性は、図２のように示さ
れ、開放電圧Ｖｏｃは約０．６Ｖで、短絡電流Ｉｓｃは
約３０ｍＡ／ｃｍ2である。この特性は、照射される光
の強度によって影響され、光が強いと電圧値にほとんど
影響を及ぼすこと無しに、取り出しうる電流を増加させ
ることができる。この特性において、最大出力Ｐｍａｘ
は開放電圧Ｖｏｃから若干低い値で得られ、太陽電池の
運用においてはこの最大出力Ｐｍａｘを満足する電圧が
最適動作電圧になる。この最適動作電圧は、光の強度が
変わっても変化せず、ほぼ一定の値である。そこで、こ
こでは、空気電池の充電を行った際の太陽電池側の出力
電圧が、この最適動作電圧になるようダイオードを設け
ている。シリコン系太陽電池において、先の最適動作電
圧が０．４Ｖの場合、太陽電池の直列接続数とダイオー
ドの数、および空気電池の充電電圧との関係は以下のよ
うになる。In this figure, the auxiliary electrode terminal 1
The diode 110 was provided in the wiring of 9. The reason for this is
By utilizing the characteristic that the voltage drop when a current is passed through the diode 110 is approximately 0.6 V / piece regardless of the current value, the output voltage of the photoelectric conversion unit 18 is set to a value suitable for charging the metal electrode 12. This is for adjustment. That is, for example, the output characteristics of the crystalline silicon solar cell are shown in FIG. 2, the open circuit voltage Voc is about 0.6 V, and the short circuit current Isc is about 30 mA / cm 2 . This characteristic is affected by the intensity of the emitted light, and when the light is strong, the current that can be extracted can be increased with little influence on the voltage value. In this characteristic, the maximum output Pmax
Is obtained at a slightly lower value than the open circuit voltage Voc, and in the operation of the solar cell, the voltage that satisfies this maximum output Pmax is the optimum operating voltage. This optimum operating voltage does not change even if the light intensity changes, and is a substantially constant value. Therefore, here, a diode is provided so that the output voltage on the solar cell side when the air battery is charged becomes the optimum operating voltage. In the silicon-based solar cell, when the optimum operating voltage is 0.4 V, the relationship between the number of solar cells connected in series, the number of diodes, and the charging voltage of the air cell is as follows.

【００１９】[0019]

【表１】 [Table 1]

【００２０】すなわち、太陽電池の直列接続数とダイオ
ードの数の選定によって、空気電池の充電電圧の調整が
おおむね可能である。That is, the charging voltage of the air battery can be adjusted generally by selecting the number of solar cells connected in series and the number of diodes.

【００２１】図３は、上記の原理に基づいて構成した、
性能評価のための実験用の充電式空気電池を示したもの
である。なお、図３中の符号は図１に示した符号のもの
と対応している。ここでは、プラスチック製のケース１
０の一面に空気極１１を取り付け、このケースの内部に
金属電極１２と充電時に使用する補助電極１５を設けて
空気電池部を構成した。空気電極の材料には、炭素粉末
とテフロン粉末、アセチレンブラックを用い、これらを
エタノール水溶液で混合攪拌した後、ロールでシート状
に成形し、さらにプレスによって集電用のニッケル網と
一体化させた。このように作製した空気極を、ケースに
設けた取り付け穴にエポキシ樹脂で固定した。FIG. 3 is constructed based on the above principle,
2 shows an experimental rechargeable air battery for performance evaluation. The reference numerals in FIG. 3 correspond to those shown in FIG. Here, plastic case 1
The air electrode 11 was attached to one surface of the cell No. 0, and the metal electrode 12 and the auxiliary electrode 15 used at the time of charging were provided inside the case to form an air battery unit. Carbon powder, Teflon powder, and acetylene black were used as the material for the air electrode.These were mixed and stirred with an aqueous ethanol solution, then formed into a sheet by rolls, and further integrated with a nickel net for current collection by pressing. . The air electrode thus manufactured was fixed with an epoxy resin in a mounting hole provided in the case.

【００２２】金属電極１２には、３ｍｍ厚のアルミニウ
ム板を用いた。また、補助電極１５には、ニッケルで作
製された多孔質体を用いた。補助電極１５の取り付け位
置は、空気極１１と金属電極１２の間とした。これは、
ここに示した構造の電池では、電池の放電によって金属
電極のうち、空気極に面した側の部分が消費されるの
で、充電においてはこの面の反応を促進させるためであ
る。An aluminum plate having a thickness of 3 mm was used as the metal electrode 12. In addition, a porous body made of nickel was used for the auxiliary electrode 15. The attachment position of the auxiliary electrode 15 was between the air electrode 11 and the metal electrode 12. this is,
In the battery having the structure shown here, a portion of the metal electrode on the side facing the air electrode is consumed by discharging the battery, and this is for promoting the reaction on this side during charging.

【００２３】補助電極の形状等に関しては、ここで用い
た多孔質体だけでなく、図４に示すように、網状、また
は格子状であってもよい。なお、空気極の設置方法によ
って、金属電極と補助電極の形や設置方法を変えること
が可能であり、例えば、金属電極の放電反応を阻害しな
い範囲内において、金属電極の外周に沿って補助電極を
設けても良い。Regarding the shape and the like of the auxiliary electrode, not only the porous body used here, but also a net shape or a lattice shape as shown in FIG. The shape and installation method of the metal electrode and the auxiliary electrode can be changed depending on the installation method of the air electrode. May be provided.

【００２４】なお、図３に示すモデルセルの大きさであ
るが、空気極については１００×１００（ｍｍ）、金属
電極と補助電極については、いずれも１００×１２０
（ｍｍ）である。空気極と金属電極の間隔は１ｃｍとし
た。また、電解液には水酸化カリウムの水溶液を用い、
金属電極と補助電極が全て水溶液中に没するようにし
た。モデルセルの外形寸法は、１５０×１５０×３０
（幅×高さ×厚み。単位；ｍｍ）である。なお、太陽電
池部（光電変換部）１８には結晶系シリコン太陽電池１
８１を用いた。サイズは、５０×３０（ｍｍ）で、図５
に示すように、これを７個直列に接続して使用した。そ
して、この出力を金属電極と補助電極の端子１３、１９
に接続した。なお、電圧調整用のダイオードは２個用
い、太陽電池の出力電圧が１．６Ｖになるようにした。The size of the model cell shown in FIG. 3 is 100 × 100 (mm) for the air electrode and 100 × 120 for both the metal electrode and the auxiliary electrode.
(Mm). The distance between the air electrode and the metal electrode was 1 cm. Also, an aqueous solution of potassium hydroxide is used as the electrolytic solution,
The metal electrode and the auxiliary electrode were all immersed in the aqueous solution. The outer dimensions of the model cell are 150 x 150 x 30
(Width x height x thickness. Unit: mm). The solar cell unit (photoelectric conversion unit) 18 has a crystalline silicon solar cell 1
81 was used. The size is 50 × 30 (mm), and it is shown in FIG.
As shown in, seven of them were connected in series and used. Then, this output is used for the terminals 13 and 19 of the metal electrode and the auxiliary electrode.
Connected to. In addition, two diodes for voltage adjustment were used so that the output voltage of the solar cell was 1.6V.

【００２５】この実験用空気電池により放電特性を求め
た。まず、太陽電池を取り付けない状態で、空気電池本
体の連続放電試験をおこなった。試験は、２５℃の温度
条件下で一定電流で放電させることで行った。電池の端
子電圧は、放電中はほぼ一定の安定した値を示し、放電
が終了する時期に急激に０．５Ｖ以下まで低下した。こ
の試験によって、本電池は、各種の電流による放電で以
下のような連続放電が可能であることが分かった。（な
お、ここでは、各電流値における放電は、それぞれ別個
の電池によって行った。）The discharge characteristics were determined using this experimental air battery. First, a continuous discharge test was performed on the air battery body without mounting the solar cell. The test was performed by discharging at a constant current under a temperature condition of 25 ° C. The terminal voltage of the battery showed a substantially constant and stable value during discharge, and drastically dropped to 0.5 V or less at the time when the discharge was completed. From this test, it was found that the present battery is capable of continuous discharge as described below by discharging with various currents. (Here, discharge at each current value was performed by separate batteries.)

【００２６】[0026]

【表２】 [Table 2]

【００２７】次に、太陽電池部の出力を接続し、金属電
極の充電が行われるような状態を作り、放電試験を行っ
た。ここでは、太陽電池への入射光の強度は、１００ｍ
Ｗ／ｃｍ2とした。まず、太陽電池を接続しない状態
で、電流密度１ｍＡ／ｃｍ2の条件で１５時間の連続放
電を行い、ここで負荷１７を開放し太陽電池を取り付け
て金属電極の充電を１時間行った。太陽電池からの出力
電流は、上記の日射強度において、２５ｍＡ／ｃｍ2で
あった。この充電終了後、太陽電池部を取り外し、再び
上記と同一の電流密度で空気電池部の放電試験を行っ
た。この結果、連続して２９時間の放電が可能であるこ
とが確認された。このことから、先の太陽電池により金
属電極の充電が効果的に行われたことが分かる。Next, a discharge test was conducted by connecting the output of the solar cell unit to a state where the metal electrode was charged. Here, the intensity of the incident light on the solar cell is 100 m.
It was set to W / cm 2 . First, without a solar cell connected, continuous discharge was performed for 15 hours under the condition of a current density of 1 mA / cm 2 , the load 17 was opened here, the solar cell was attached, and the metal electrode was charged for 1 hour. The output current from the solar cell was 25 mA / cm 2 at the above solar radiation intensity. After completion of this charging, the solar cell section was removed, and the discharge test of the air cell section was conducted again at the same current density as above. As a result, it was confirmed that continuous discharge for 29 hours was possible. From this, it can be seen that the above solar cell effectively charged the metal electrode.

【００２８】次に、別途準備した未使用の空気電池を用
い、当初から太陽電池を接続した状態において、上記と
同一の電流によって放電を行った。この結果、３０時間
を経過しても電圧は１．０Ｖ以上を保ち、放電が行えな
くなるような値（０．５Ｖ）に低下することは無かっ
た。また、太陽電池の出力を取り外しても、その後、連
続して３０時間の放電が可能であった。これらの特性
は、太陽電池の接続によって、負荷への電力供給が行え
ること、また、金属電極の充電も可能であることを示し
ている。Next, using an unused air battery prepared separately, discharge was performed with the same current as above in the state where the solar cell was connected from the beginning. As a result, the voltage was maintained at 1.0 V or higher even after 30 hours had passed, and never dropped to a value (0.5 V) at which discharge could not be performed. Further, even if the output of the solar cell was removed, it was possible to continuously discharge for 30 hours. These characteristics indicate that the connection of the solar cell can supply electric power to the load, and can also charge the metal electrode.

【００２９】そこで、これらの特性に基づき本発明を適
用した充電式空気電池を作製した。図６、図７、図８は
作製した電池の外観を示したものである。本図におい
て、図６は、電池部Ｃを示しており、６０はケース、６
１は空気極、６２は空気極カバー、６３は正極端子、６
４は負極端子、６４１は充電用負極端子、６５は補助電
極端子である。一方、図７は、太陽電池によって充電す
る状態で空気電池を使用する際に、電池部を取り付ける
ホルダＨの構造を示したものである。図８は図７のＡ方
向から見た平面図である。前記ホルダ内の溝６６には、
一方の内側に、電池に設けられた、充電用負極端子６４
１と補助電極端子６５に接触するような位置に、光電変
換部６８の太陽電池６８１からの出力端子６７が設けら
れている。従って、図６の電池部を図７のホルダに装着
することで充電式空気電池を構成することができる。Therefore, based on these characteristics, a rechargeable air battery to which the present invention is applied was manufactured. 6, 7 and 8 show the appearance of the produced battery. In this figure, FIG. 6 shows a battery section C, 60 is a case, 6
1 is an air electrode, 62 is an air electrode cover, 63 is a positive electrode terminal, 6
Reference numeral 4 is a negative electrode terminal, 641 is a negative electrode terminal for charging, and 65 is an auxiliary electrode terminal. On the other hand, FIG. 7 shows the structure of the holder H to which the battery unit is attached when the air battery is used while being charged by the solar battery. FIG. 8 is a plan view seen from the direction A in FIG. In the groove 66 in the holder,
On one side, the charging negative electrode terminal 64 provided on the battery is provided.
The output terminal 67 from the solar cell 681 of the photoelectric conversion unit 68 is provided at a position where it contacts the 1 and the auxiliary electrode terminal 65. Therefore, the rechargeable air battery can be constructed by mounting the battery unit of FIG. 6 on the holder of FIG. 7.

【００３０】本方式については、空気電池の使用頻度が
高く、電池部が早期に劣化した場合においても、電池の
交換を容易にしているが、これのみならず、このような
構成によって、放電容量の異なる複数の種類の電池部か
ら適宜、必要とするものを選定して使用することが可能
になるという利点も有している。なお、このホルダ部に
は太陽電池が装着されており、その状況は図７、図８に
示した通りである。本図に示された電池において各部の
大きさは、空気極が１２０ｍｍ×８０ｍｍである。ま
た、金属電極は、１３０ｍｍ×９０ｍｍである。各部の
材質は、先の実験用空気電池と同じものである。電解液
は、電池部の中に予め注液された状態で保持される。し
かし、そのような状態においては、電池の自己放電が進
む恐れが有るので、ここでは空気極６１の表面を覆って
カバー６２を設け、使用開始時にこのカバーを除去する
ようにした。In this method, the air battery is frequently used, and the battery can be easily replaced even when the battery part is deteriorated early. There is also an advantage that it is possible to appropriately select and use a necessary one from a plurality of different types of battery parts. A solar cell is attached to this holder portion, and the situation is as shown in FIGS. 7 and 8. In the battery shown in this figure, the size of each part is 120 mm × 80 mm at the air electrode. The metal electrode has a size of 130 mm × 90 mm. The material of each part is the same as that of the above experimental air battery. The electrolytic solution is held in the battery unit in a state of being previously injected. However, in such a state, the self-discharge of the battery may proceed. Therefore, the cover 62 is provided so as to cover the surface of the air electrode 61, and the cover is removed at the start of use.

【００３１】このような構成の電池により、先の実験用
電池と同様に、太陽電池からの充電が無い状態での電池
の単独放電試験、および充電がおこなわれている状態で
の放電試験を行った。さらに、放電と太陽電池による充
電の繰り返し試験を行った。放電試験は、試料電池を暗
室内に置いて行い、太陽電池からの充電の有無は、光の
照射の有無によって調節した。なお、光の強度は、１０
０ｍＷ／ｃｍ2とし、以下の条件で、放電と充電の繰り
返し試験を行った。With the battery having such a structure, as in the case of the above-mentioned experimental battery, a single discharge test of the battery without charging from the solar cell and a discharge test with charging were performed. It was Further, a repeated test of discharging and charging with a solar cell was conducted. The discharge test was performed by placing the sample battery in a dark room, and the presence or absence of charge from the solar cell was adjusted by the presence or absence of light irradiation. The light intensity is 10
A repeated test of discharging and charging was performed under the following conditions at 0 mW / cm 2 .

【００３２】[0032]

【表３】 [Table 3]

【００３３】その結果、上記の条件で放電と充電を５０
回行っても、再度充電することで連続２８時間の放電が
可能であった。従って、太陽光発電によって金属電極が
効果的に充電されていることがわかる。なお、上に述べ
た実験用空気電池のケースを用いて、種々の材質の金属
電極、および補助電極により空気電池を構成し、基本的
な放電特性を求めた。その結果、亜鉛製、マグネシウム
製金属電極、およびカーボン製、白金製補助電極を用い
ても、すでに上で述べた実験用セルと同様の動作を確認
することが出来た。As a result, under the above conditions, discharging and charging are performed 50 times.
Even if the operation was repeated, it was possible to discharge continuously for 28 hours by recharging. Therefore, it can be seen that the metal electrode is effectively charged by solar power generation. In addition, using the case of the experimental air battery described above, an air battery was constructed with metal electrodes of various materials and auxiliary electrodes, and basic discharge characteristics were obtained. As a result, it was possible to confirm the same operation as that of the experimental cell described above even with the use of zinc and magnesium metal electrodes and carbon and platinum auxiliary electrodes.

【００３４】なお、太陽電池の種類が異なると、発電特
性にも違いが現れる。しかし、その場合にも、使用する
太陽電池の特性に基づいて動作電圧の調整を行えば良
い。太陽電池からの出力電圧の調整方法は、結晶シリコ
ン系太陽電池を例に述べた通りであり、基本的には最適
動作電圧となるように太陽電池の直列接続セル数とダイ
オードの数を選定すれば良い。When the type of solar cell is different, the power generation characteristics also differ. However, even in that case, the operating voltage may be adjusted based on the characteristics of the solar cell used. The method of adjusting the output voltage from the solar cell is as described for the crystalline silicon solar cell as an example. Good.

【００３５】図９は、太陽電池と電池部を一体として構
成した、本発明の第２の実施例である。図１０は図９の
Ａ方向矢視図である。各部の部材には、第一の実施例と
同一の材料を使用した。本図において、太陽電池部（光
電変換部）６８は複数のセル６８１を一枚のシート６９
上に配置し、電池部本体ケース６０の背面に貼付されて
いる。電池部との接続は、第一の実施例と同様に、太陽
電池部からの出力を電池部の充電用端子に接続する。接
続には、コネクタを用いる。電池部が劣化した場合、太
陽電池シート６９のみを取り外し、交換した新品の電池
部に再度貼付することによって充電式の空気電池を構成
することが出来る。本実施例の動作も、先に説明した第
一の実施例と同様であり、光の照射状態が変化したり、
さらに、光の照射が無い「暗」状態においても支障無く
放電を行わせることが出来た。なお、本発明の電池は、
太陽光が十分でない時、あるいは、夜間の時間帯に電池
の充電が必要になった場合等には、通常の商用電気を用
いた充電を行っても良い。この場合、充電器の出力電圧
は、電池の充電電圧に適合した値であれば良く、また、
充電電流も電池の放電電流から大きくずれない値が得ら
れれば良い。また。充電用アダプターは、太陽電池を取
り付けたホルダと同様、電池部を取り付ける溝を有し、
溝の内側に充電用端子が設置されていれば良い。FIG. 9 shows a second embodiment of the present invention in which the solar cell and the battery section are integrally formed. FIG. 10 is a view on arrow A in FIG. The same material as in the first embodiment was used for the members of each part. In this figure, the solar cell unit (photoelectric conversion unit) 68 includes a plurality of cells 681 as one sheet 69.
It is arranged on the upper side and attached to the back surface of the battery unit body case 60. As for the connection with the battery unit, the output from the solar battery unit is connected to the charging terminal of the battery unit as in the first embodiment. A connector is used for connection. When the battery part is deteriorated, the rechargeable air battery can be constructed by removing only the solar cell sheet 69 and reattaching it to the replaced new battery part. The operation of this embodiment is the same as that of the first embodiment described above, and the light irradiation state changes,
Furthermore, even in the "dark" state where there is no light irradiation, discharge could be performed without any trouble. The battery of the present invention is
When the sunlight is not sufficient, or when the battery needs to be charged during the nighttime, charging using normal commercial electricity may be performed. In this case, the output voltage of the charger may be a value that matches the charging voltage of the battery, and
It suffices that the charging current also has a value that does not largely deviate from the discharging current of the battery. Also. The charging adapter has a groove for mounting the battery part, similar to the holder that mounts the solar cell,
It suffices if the charging terminal is installed inside the groove.

【００３６】[0036]

【発明の効果】以上説明したように、本発明では、光電
変換部と電池部から空気電池を構成し、電池部には、金
属電極、電解質、空気極のみならず、補助電極を設け、
前記金属電極と前記補助電極間に光電変換部の出力を接
続し、放電で消耗した金属電極の充電が行われるように
し、充電機能をもった空気電池を実現している。従っ
て、エネルギー密度が高いという空気電池の特徴をも
ち、繰り返して使用可能な２次電池が実現され、放電終
了後も太陽光による充電で再度の放電が可能となった
り、また、放電中にも太陽光からの充電によって放電持
続時間の延長が可能という利点を有する。As described above, according to the present invention, an air battery is composed of a photoelectric conversion part and a battery part, and the battery part is provided with an auxiliary electrode as well as a metal electrode, an electrolyte and an air electrode.
The output of the photoelectric conversion unit is connected between the metal electrode and the auxiliary electrode so that the metal electrode consumed by the discharge is charged to realize an air battery having a charging function. Therefore, it has a feature of an air battery that has a high energy density, and a secondary battery that can be used repeatedly is realized. Even after discharging, it can be discharged again by charging with sunlight, and even during discharging. It has the advantage that the discharge duration can be extended by charging from sunlight.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明の要点を説明した断面図。FIG. 1 is a cross-sectional view illustrating the main points of the present invention.

【図２】太陽電池の出力特性（結晶シリコン系の例）を
示す図。FIG. 2 is a diagram showing output characteristics of a solar cell (example of crystalline silicon type).

【図３】 性能評価のために作製した実験用の一実施例
の充電式空気電池を示す斜視図。FIG. 3 is a perspective view showing a rechargeable air battery of an experimental example, which is manufactured for performance evaluation.

【図４】上記充電式電池の補助電極の形状の一例を示す
平面図。FIG. 4 is a plan view showing an example of the shape of an auxiliary electrode of the rechargeable battery.

【図５】上記充電式電池の光電変換部の平面図。FIG. 5 is a plan view of a photoelectric conversion unit of the rechargeable battery.

【図６】 本発明の他の実施例の電池部を示す斜視図。FIG. 6 is a perspective view showing a battery unit according to another embodiment of the present invention.

【図７】本発明の上記実施例のホルダを示す斜視図。FIG. 7 is a perspective view showing the holder of the above embodiment of the present invention.

【図８】上記実施例の光電変換部の平面図。FIG. 8 is a plan view of the photoelectric conversion unit according to the above embodiment.

【図９】本発明の第三の実施例を示す斜視図。FIG. 9 is a perspective view showing a third embodiment of the present invention.

【図１０】上記実施例の光電変換部の平面図。FIG. 10 is a plan view of the photoelectric conversion unit of the above embodiment.

【図１１】従来のボタン型空気電池の構造例（断面図）
を示す図。FIG. 11 is a structural example of a conventional button-type air battery (cross-sectional view).
FIG.

【図１２】従来のボックス型空気電池の構造例（外観
図）を示す図。12 is a diagram showing a configuration Zorei (external view) of a conventional box type air cell.

【符号の説明】[Explanation of symbols]

１０ ケース １１ 空気極 １２ 金属電極 １３ 負極端子 １４ 正極端子 １５ 補助電極 １６ 電解液 １７ 負荷 １８ 光電変換部 １９ 補助電極端子 １１０ ダイオード ６０ ケース ６１ 空気極 ６２ 空気極カバー ６３ 正極端子 ６４ 負極端子 ６４１ 充電用負極端子 ６５ 補助電極端子 ６６ 溝 ６７ 太陽電池からの出力端子 ６８ 光電変換部 ６８１ 太陽電池 ６９ 太陽電池シート １００ シール紙 １１１ 負極 １１２ 負極側で放電反応に関わる還元剤 １１３ ガスケット １１４ セパレータ（電解質） １１５ 空気極（正極） １１６ はっ水膜 １１７ 拡散紙 １１８ 空気孔 １１９ 正極ケース １２０ ケース １２１ 空気極 １２２ 金属電極 １２３ 負極端子 １２４ 正極端子 10 cases 11 air pole 12 metal electrodes 13 Negative electrode terminal 14 Positive terminal 15 Auxiliary electrode 16 Electrolyte 17 load 18 Photoelectric converter 19 Auxiliary electrode terminal 110 diode 60 cases 61 Air electrode 62 Air electrode cover 63 Positive terminal 64 negative terminal 641 Charge negative terminal 65 Auxiliary electrode terminal 66 groove 67 Output terminal from solar cell 68 Photoelectric conversion unit 681 solar cell 69 solar cell sheet 100 sticker paper 111 negative electrode 112 Reducing agent involved in discharge reaction on the negative electrode side 113 gasket 114 separator (electrolyte) 115 Air electrode (positive electrode) 116 Water repellent film 117 Diffusion paper 118 air holes 119 Positive case 120 cases 121 Air electrode 122 Metal electrode 123 Negative electrode terminal 124 Positive terminal

Claims (9)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 電池部と光電変換部からなる充電式空気
電池であって、 前記電池部は金属電極と電解質と空気極と補助電極とを
有し、 前記空気極は片面が空気に他面が前記電解質に接するよ
うに配置され、 前記金属電極と前記補助電極は前記電解質中に配置さ
れ、 前記金属電極と前記空気極は電力を供給するために負荷
に接続され、 前記光電変換部の正側の出力端は前記補助電極に接続さ
れ、 前記光電変換部の負側の出力端は前記金属電極に接続さ
れていることを特徴とする充電式空気電池。1. A rechargeable air cell comprising the battery unit and the photoelectric conversion unit, the battery unit has an electrolyte and air Kikyoku the auxiliary electrode and the metal electrode, the air electrode is the other one side is air A surface is arranged so as to contact the electrolyte, the metal electrode and the auxiliary electrode are arranged in the electrolyte, the metal electrode and the air electrode are connected to a load to supply power, the photoelectric conversion unit of the output terminal of the positive side is connected to the auxiliary electrode, the negative side of the output end of the photoelectric conversion unit is rechargeable air cell, characterized in that it is connected to the metal electrode. 【請求項２】 前記空気極と前記光電変換部が取り付け
られた容器内に、前記電解質と前記金属電極と前記補助
電極とを配置したことを特徴とする請求項１記載の充電
式空気電池。2. The rechargeable air battery according to claim 1, wherein the electrolyte, the metal electrode, and the auxiliary electrode are arranged in a container in which the air electrode and the photoelectric conversion unit are attached. 【請求項３】 光電変換部を外面に取り付けた枠体と該
枠体の内側に設けた溝に取付可能な電池部とからなり、 前記枠体の溝中には、前記光電変換部の正側及び負側の
出力端子が設けられ、 前記電池部には該電池部が前記溝に取り付けられたとき
に前記光電変換部の正側及び負側の出力端子とそれぞれ
接触するように前記補助電極及び前記金属電極に接続さ
れた端子が設けられたことを特徴とする請求項１または
２記載の充電式空気電池。3. A photoelectric conversion unit comprising a frame body attached to an outer surface thereof and a battery unit attachable to a groove provided inside the frame body, wherein a positive electrode of the photoelectric conversion unit is provided in the groove of the frame body. Side and negative side output terminals are provided, and the auxiliary electrode is provided in the battery part so as to contact the positive side and negative side output terminals of the photoelectric conversion part, respectively, when the battery part is mounted in the groove. The rechargeable air battery according to claim 1 or 2, further comprising: a terminal connected to the metal electrode. 【請求項４】 前記光電変換部の正側の出力端子と前記
補助電極との間にダイオードを接続したことを特徴とす
る請求項１乃至３記載のいずれかの充電式空気電池。4. The rechargeable air battery according to claim 1, further comprising a diode connected between the positive side output terminal of the photoelectric conversion section and the auxiliary electrode. 【請求項５】 前記金属電極が、亜鉛またはアルミニウ
ムまたはマグネシウムのうちのいずれか一つの元素、も
しくは該元素を主成分とする合金からなることを特徴と
する請求項１乃至４記載のいずれかの充電式空気電池。5. The metal electrode according to claim 1, wherein the metal electrode is made of any one element of zinc, aluminum or magnesium, or an alloy containing the element as a main component. Rechargeable air battery. 【請求項６】 前記電解質が、水酸イオン伝導体からな
ることを特徴とする請求項１乃至５記載のいずれかの充
電式空気電池。6. The rechargeable air battery according to claim 1, wherein the electrolyte is a hydroxide ion conductor. 【請求項７】 前記空気極が、カーボンと触媒とフッ素
系発水材から構成された多孔質体からなることを特徴と
する請求項１乃至６記載のいずれかの充電式空気電池。7. The rechargeable air battery according to claim 1, wherein the air electrode is made of a porous material composed of carbon, a catalyst, and a fluorine-based water-generating material. 【請求項８】 前記補助電極が、カーボンまたはニッケ
ルまたは白金または亜鉛またはアルミニウムまたはマグ
ネシウムのうちのいずれか一つの元素、もしくは該元素
を主成分とする合金からなることを特徴とする請求項１
乃至７記載のいずれかの充電式空気電池。8. The auxiliary electrode is made of any one element of carbon, nickel, platinum, zinc, aluminum or magnesium, or an alloy containing the element as a main component.
8. A rechargeable air battery according to any one of 7 to 7. 【請求項９】 前記光電変換部が、アモルファスシリコ
ン系太陽電池または結晶系シリコン太陽電池またはＧａ
Ａｓ系太陽電池からなることを特徴とする請求項１乃至
８記載のいずれかの充電式空気電池。9. The photoelectric conversion unit is an amorphous silicon solar cell, a crystalline silicon solar cell, or Ga.
9. The rechargeable air battery according to claim 1, comprising an As solar cell.
JP30196498A 1998-10-23 1998-10-23 Rechargeable air battery Expired - Fee Related JP3523506B2 (en)

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Application Number Priority Date Filing Date Title
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JP5354580B2 (en) * 2009-01-28 2013-11-27 独立行政法人産業技術総合研究所 Lithium-air battery
JP5376586B2 (en) * 2009-06-29 2013-12-25 シャープ株式会社 Metal-air battery module and metal-air battery stack
KR101119514B1 (en) 2009-10-07 2012-02-28 주식회사 이엠따블유에너지 Apparatus for Charging Metal Air Cell and Metal Air Cell Assembly and System for Charging Metal Air Cell Comprising the Same
JP2017084650A (en) * 2015-10-29 2017-05-18 シャープ株式会社 Metal-air battery set
CN108172953A (en) * 2016-12-07 2018-06-15 中国科学院大连化学物理研究所 A kind of zinc-air battery and zinc-air battery group
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