JP3196151B2 - Light air secondary battery - Google Patents

Light air secondary battery

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Publication number
JP3196151B2
JP3196151B2 JP00543593A JP543593A JP3196151B2 JP 3196151 B2 JP3196151 B2 JP 3196151B2 JP 00543593 A JP00543593 A JP 00543593A JP 543593 A JP543593 A JP 543593A JP 3196151 B2 JP3196151 B2 JP 3196151B2
Authority
JP
Japan
Prior art keywords
light
negative electrode
battery
air
positive 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
JP00543593A
Other languages
Japanese (ja)
Other versions
JPH06215806A (en
Inventor
敬治 阿久戸
直樹 加藤
努 尾形
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Telegraph and Telephone Corp filed Critical Nippon Telegraph and Telephone Corp
Priority to JP00543593A priority Critical patent/JP3196151B2/en
Publication of JPH06215806A publication Critical patent/JPH06215806A/en
Application granted granted Critical
Publication of JP3196151B2 publication Critical patent/JP3196151B2/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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

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  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は、充電と放電の双方が可
能な２次電池に係わり、空気中の酸素をエネルギー源と
して放電し、光エネルギーにより充電する光空気２次電
池に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a secondary battery capable of both charging and discharging, and more particularly to a light-air secondary battery which discharges using oxygen in air as an energy source and charges it with light energy. .

【０００２】[0002]

【従来の技術】太陽可視光等の光エネルギーで２次電池
を充電する試みは、以前からなされており、この種の電
池としては、アモルファスシリコン太陽電池とニッケル
−カドミウム蓄電池や鉛蓄電池等の２次電池を組合せた
太陽光蓄電池が知られている。2. Description of the Related Art Attempts to charge a secondary battery with light energy such as solar visible light have been made before. Such batteries include amorphous silicon solar batteries and nickel-cadmium storage batteries and lead storage batteries. 2. Description of the Related Art A solar storage battery in which a secondary battery is combined is known.

【０００３】この光２次電池を図６ないし図７を参照し
て説明する。図６は従来の光２次電池の斜視図であり、
図７は図６の光２次電池の等価回路図である。図６、図
７に示す光２次電池は、太陽電池１と、この太陽電池１
で得られた電力を貯蔵する蓄電池２と、太陽電池１に生
じた電圧を調整する電圧調整回路３と、太陽電池１から
蓄電池２に流れる電流が逆流するのを防止する逆流防止
ダイオード４とから構成されている。光２次電池は、太
陽電池１で発電し、この太陽電池１で得られた電力を蓄
電池２に貯蔵させる二段階型（間接型）方式に構成され
ている。The photo secondary battery will be described with reference to FIGS. 6 and 7. FIG. 6 is a perspective view of a conventional light secondary battery,
FIG. 7 is an equivalent circuit diagram of the light secondary battery of FIG. The optical secondary battery shown in FIGS. 6 and 7 includes a solar cell 1 and this solar cell 1
From a storage battery 2 for storing the power obtained in step 1, a voltage adjustment circuit 3 for adjusting the voltage generated in the solar cell 1, and a backflow prevention diode 4 for preventing a current flowing from the solar cell 1 to the storage battery 2 from flowing back. It is configured. The optical secondary battery is configured in a two-stage type (indirect type) in which the solar cell 1 generates power and the power obtained by the solar cell 1 is stored in the storage battery 2.

【０００４】[0004]

【発明が解決しようとする課題】しかしながら、このよ
うな従来の光２次電池にあっては、電圧調整回路３や逆
流防止ダイオード４等の構成部品が必須であるため、光
２次電池の構造が複雑で大きなものとなるという欠点を
有している。However, in such a conventional photorechargeable battery, the components such as the voltage regulating circuit 3 and the backflow prevention diode 4 are indispensable. Has the disadvantage of being complex and large.

【０００５】また、従来の光２次電池を適正に機能させ
るには、太陽電池１で発電した電力を蓄電池２へ充電す
るのに適した電圧に調整する必要があり、この調整のた
めに消費されるエネルギー損失が大であるという問題が
あった。また、上記光２次電池は、光→電気→電気化学
の３段階のエネルギー変換ステップを経るため、このエ
ネルギー変換ステップのための構成部品数の増加や、あ
るいはこのエネルギー変換ステップに起因するエネルギ
ーロスの増大といった問題も有している。さらに、太陽
電池１を製造するには、ｐｎ接合設備等の比較的高度の
製造設備が必要となるなど、太陽電池１の製造上の困難
性も有している。In addition, in order for the conventional light secondary battery to function properly, it is necessary to adjust the power generated by the solar cell 1 to a voltage suitable for charging the storage battery 2, and the power consumed for this adjustment is required. There is a problem that the energy loss is large. In addition, since the above-mentioned photorechargeable battery undergoes three energy conversion steps of light → electricity → electrochemistry, the number of components for this energy conversion step is increased, or energy loss due to this energy conversion step is caused. There is also a problem such as an increase in Furthermore, there are also difficulties in manufacturing the solar cell 1 such that relatively advanced manufacturing equipment such as pn junction equipment is required to manufacture the solar cell 1.

【０００６】一方、図８は、従来の光蓄電池を示す図で
ある。この光蓄電池は、透明ガラス基板７と、ｐ型半導
体８と、ｉ型半導体９と、集電体１０、１１と、陰極１
２と、陽極１３と、固体電解質１４と、パッシベーショ
ン層１５と、透明電極１６とを具備してなる電池であ
る。この光蓄電池も、上述の説明と同様、構造が複雑で
あり、半導体電極製造の問題やエネルギー密度が小さい
といった欠点がある。FIG. 8 is a view showing a conventional light storage battery. This photovoltaic battery includes a transparent glass substrate 7, a p-type semiconductor 8, an i-type semiconductor 9, current collectors 10 and 11, and a cathode 1
2, an anode 13, a solid electrolyte 14, a passivation layer 15, and a transparent electrode 16. This photovoltaic storage battery also has a complicated structure, as described above, and has drawbacks such as a problem in manufacturing a semiconductor electrode and a low energy density.

【０００７】図９は、従来の光化学２次電池の構成図を
示したものである。図中符号１７は電池容器、１７ａは
電池容器を密閉するための蓋、１８はセパレータ、１９
はｎ型半導体よりなる光電極、２０ａは充電用の電極、
２０ｂは放電用の電極である。図１０は、光化学２次電
池の簡単な構成とエネルギー準位図を示したものであ
る。FIG. 9 shows a configuration diagram of a conventional photochemical secondary battery. In the figure, reference numeral 17 is a battery container, 17a is a lid for sealing the battery container, 18 is a separator, 19
Is a photoelectrode made of an n-type semiconductor, 20a is a charging electrode,
20b is an electrode for discharge. FIG. 10 shows a simple configuration and an energy level diagram of a photochemical secondary battery.

【０００８】これらの光化学２次電池は、半導体−電解
質界面の電気化学特性を利用したものであり、即ち、半
導体電極を電解質と接触させた時に生じるエネルギーバ
ンドの曲りを利用して光エネルギーを電気化学的に蓄積
するものである。図９に示す光化学２次電池の光変換部
は、半導体電極１９を電解質Ｓに浸漬させるだけで構成
されており、この点、太陽電池等の必要な図６や図７に
示した従来の光空気２次電池に比べ優れている。[0008] These photochemical secondary batteries make use of the electrochemical characteristics of the semiconductor-electrolyte interface, that is, convert the light energy into electricity using the bending of the energy band generated when the semiconductor electrode is brought into contact with the electrolyte. It accumulates chemically. The light conversion section of the photochemical secondary battery shown in FIG. 9 is configured by merely immersing the semiconductor electrode 19 in the electrolyte S. In this regard, the light conversion section shown in FIGS. It is superior to air secondary batteries.

【０００９】しかし、光エネルギーから電気化学エネル
ギーへの変換には比較的高価な半導体材料よりなる光電
極が必要となり、この電極の存在なしには、光充電が行
えず、２次電池として機能しないのは言うまでもないこ
とである。従って、これらの従来電池は、それぞれ、４
電極および３電極で構成されており、正極と負極の他に
１〜２電極必要な多電極型電池とならざるを得ないとい
った問題が有った。また、図１０に示すように、放電か
ら充電に移る（あるいは、その逆）には、スイッチ等を
使用して電極の接続を切り替えなければならないといっ
た欠点が有った。さらに、これらの電池の反応は電解質
の酸化還元反応に基づくものであり、容量増大の為には
多量の電解質が必要となり、基本的には大きなエネルギ
ー密度が望めないという欠点が有った。However, conversion of light energy to electrochemical energy requires a photoelectrode made of a relatively expensive semiconductor material. Without this electrode, light charging cannot be performed and the cell does not function as a secondary battery. It goes without saying. Therefore, these conventional batteries have 4
It is composed of electrodes and three electrodes, and there has been a problem that it has to be a multi-electrode battery which requires one or two electrodes in addition to the positive electrode and the negative electrode. Further, as shown in FIG. 10, there is a disadvantage that the connection of the electrodes must be switched using a switch or the like in order to shift from discharging to charging (or vice versa). Further, the reaction of these batteries is based on the oxidation-reduction reaction of the electrolyte, and a large amount of electrolyte is required for increasing the capacity, and there is a disadvantage that a large energy density cannot be basically expected.

【００１０】本発明は、上記事情に鑑みてなされたもの
で、空気中の酸素をエネルギー源として放電し、光エネ
ルギーにより充電し、充電器を必要としない省エネルギ
ー性に優れ、高エネルギー密度の光空気２次電池を得る
ことにあり、特に、半導体や光化学励起物質よりなる光
電極を必ずしも必要とせず、２電極系よりなる簡単な構
成とした光空気２次電池を実現することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and uses oxygen in the air as an energy source to discharge and charge with light energy. It is an object of the present invention to provide an air secondary battery, and in particular, to realize a light air secondary battery having a simple configuration including a two-electrode system without necessarily requiring a photoelectrode made of a semiconductor or a photochemically excited substance.

【００１１】[0011]

【課題を解決するための手段】請求項１記載の光空気２
次電池は、正極と、負極と、これら正極と負極とに接触
する電解質と、上記正極と上記負極と上記電解質とが収
容される電池ケースとを有し、該電池ケースには、上記
負極をなす負極部材に光を入射する受光部が設けられ、
上記正極は、酸素触媒を有する構成にされ、上記負極を
なす金属製の負極部材の酸化反応と酸素の還元反応とに
より放電され、該放電により負極部材に生成した放電生
成物に光エネルギーを作用させることにより、該生成物
を還元させて充電される光空気２次電池において、上記
電池ケースは、角箱状、多角柱状又は円柱状に形成さ
れ、上記正極は、負極をなす負極部材の端部付近に位置
する該電池ケースの側面に配設されることを特徴とする
ものである。A light air 2 according to claim 1.
The secondary battery has a positive electrode, a negative electrode, an electrolyte in contact with the positive electrode and the negative electrode, and a battery case in which the positive electrode, the negative electrode, and the electrolyte are accommodated. A light-receiving portion for making light incident on the negative electrode member is provided,
The positive electrode is configured to have an oxygen catalyst, it is discharged by the oxidation reaction and oxygen reduction reaction of the metal of the negative electrode member having a top SL negative electrode, the light energy to discharge products generated on the anode member by electric discharge In the light-air secondary battery charged by reducing the product by acting ,
The battery case is formed in the shape of a square box, polygonal column, or column.
The positive electrode is located near the end of the negative electrode member forming the negative electrode.
The battery case is disposed on a side surface of the battery case .

【００１２】請求項２記載の光空気２次電池は、請求項
１記載の光空気２次電池であって、上記負極をなす金属
製の負極部材の少なくとも一部が、該金属の酸化物、又
は複数の金属よりなる複合成分系金属や合金よりなるこ
とを特徴とするものである。The light-air secondary battery according to claim 2 is the light-air secondary battery according to claim 1, wherein at least a part of the metal negative electrode member forming the negative electrode includes an oxide of the metal; Alternatively, it is characterized by being composed of a composite component metal or alloy composed of a plurality of metals.

【００１３】請求項３記載の光空気２次電池は、請求項
１または２記載の光空気２次電池であって、上記受光部
は、少なくとも上記電池ケースの互いに対向する二面に
配設されていることを特徴とするものである。[0013] Light air battery of claim 3, wherein is an optical air battery of claim 1 or 2 wherein said light receiving portion is disposed on two surfaces opposite to each other of at least the battery case It is characterized by having.

【００１４】[0014]

【００１５】請求項４記載の光空気２次電池は、請求項
１〜３いずれか記載の光空気２次電池であって、上記電
池ケースには、正極に外部の空気を接触させる空気孔が
正極近傍に少なくとも一つ以上配設されていることを特
徴とするものである。A light-air secondary battery according to a fourth aspect is the light-air secondary battery according to any one of the first to third aspects, wherein the battery case has an air hole for bringing external air into contact with the positive electrode. At least one or more are provided near the positive electrode.

【００１６】請求項５記載の光空気２次電池は、請求項
１〜３いずれか記載の光空気２次電池であって、上記電
池ケースの少なくとも正極近傍部分が、酸素透過性部材
よりなることを特徴とするものである。A light-air secondary battery according to a fifth aspect is the light-air secondary battery according to any one of the first to third aspects, wherein at least a portion near the positive electrode of the battery case is made of an oxygen-permeable member. It is characterized by the following.

【００１７】請求項６記載の光空気２次電池は、請求項
４又は５記載の光空気２次電池であって、上記正極が、
酸素触媒と、電池ケースの空気孔または酸素透過性部材
よりなる部分を通して電池ケース内の電解質の電池外部
への流出と透過とを防止する撥水剤とで構成されている
ことを特徴とするものである。According to a sixth aspect of the present invention, there is provided a light-air secondary battery.
The photo-air secondary battery according to 4 or 5 , wherein the positive electrode is:
A battery comprising: an oxygen catalyst; and a water-repellent agent that prevents the electrolyte in the battery case from flowing out and permeating out of the battery through a portion formed of an air hole or an oxygen-permeable member of the battery case. It is.

【００１８】請求項７記載の光空気２次電池は、請求項
４又は５記載の光空気２次電池であって、正極と電池ケ
ースとの間に、該電池ケースの空気孔または酸素透過性
部材よりなる部分を通して電解質の電池ケース内から電
池外部への流出と透過を防止する撥水膜または撥水板が
設けられたことを特徴とするものである。The optical air battery of claim 7, wherein the claim
6. The light-air secondary battery according to 4 or 5 , wherein between the positive electrode and the battery case, the electrolyte flows out of the battery case to the outside of the battery through an air hole or a portion made of an oxygen-permeable member of the battery case. A water-repellent film or a water-repellent plate for preventing transmission is provided.

【００１９】請求項８記載の光空気２次電池は、請求項
４又は５記載の光空気２次電池であって、正極と電池ケ
ースとの間に、酸素を正極表面に一様に拡散せしめる拡
散紙が設けられたことを特徴とするものである。The photo-air secondary battery according to claim 8 is a photo-air secondary battery.
6. The light-air secondary battery according to 4 or 5 , wherein a diffusion paper for uniformly diffusing oxygen to the surface of the positive electrode is provided between the positive electrode and the battery case.

【００２０】請求項９記載の光空気２次電池は、請求項
７記載の光空気２次電池であって、撥水膜または撥水板
と電池ケースとの間に、酸素を正極表面に一様に拡散せ
しめる拡散紙が設けられたことを特徴とするものであ
る。The light-air secondary battery according to the ninth aspect is the invention
7. The light-air secondary battery according to 7 , wherein diffusion paper is provided between the water-repellent film or the water-repellent plate and the battery case to uniformly diffuse oxygen to the positive electrode surface. is there.

【００２１】請求項１０記載の光空気２次電池は、請求
項１〜９いずれか記載の光空気２次電池であって、負極
をなす負極部材に、該負極部材と空気中の酸素、窒素、
二酸化炭素、あるいは電解質との接触により生成した金
属酸化物、窒化物、炭化物、水酸化物等の化合物、ある
いはこれらの複合化合物が含有されていることを特徴と
するものである。A light-air secondary battery according to a tenth aspect is the light-air secondary battery according to any one of the first to ninth aspects, wherein a negative electrode member serving as a negative electrode is connected to the negative electrode member and oxygen and nitrogen in the air. ,
It is characterized by containing compounds such as metal oxides, nitrides, carbides and hydroxides generated by contact with carbon dioxide or an electrolyte, or composite compounds thereof.

【００２２】[0022]

【作用】本発明の光空気２次電池にあっては、以下の作
用を有する。請求項１記載の光空気２次電池では、負極
をなす金属製の負極部材やその酸化物の酸化反応により
放電され、該放電により該負極部材に生成した放電生成
物に光エネルギーを作用させ、該生成物を還元させて充
電される構成としたので、放電時には、空気中の酸素に
より負極をなす金属製の負極部材やその酸化物が酸化さ
れることにより放電され、充電時には、負極をなす負極
部材に受光部から光を入射し、該酸化により負極部材に
生成した生成物に光エネルギーを作用させることにより
上記生成物が還元される。従って、かかる光空気２次電
池は、電気と光の何れのエネルギー形態でも充電可能で
あり、放電中でも充電反応が進行可能である。また、上
記電池ケースが角箱状、多角柱状又は円柱状に形成さ
れ、上記正極が、負極をなす負極部材の端部付近に位置
する電池ケースの側面にて配設されているから、電池ケ
ースの中央部に負極部材が配設される。 The light-air secondary battery of the present invention has the following functions. In the light-air secondary battery according to claim 1, a metal negative electrode member serving as a negative electrode and an oxide thereof are discharged by an oxidation reaction, and light energy acts on a discharge product generated in the negative electrode member by the discharge, Since the product is configured to be reduced and charged, at the time of discharging, the metal negative electrode member or the oxide thereof forming the negative electrode is oxidized by oxygen in the air and discharged, and at the time of charging, the negative electrode is formed. Light is incident on the negative electrode member from the light receiving portion, and light energy is applied to a product generated on the negative electrode member by the oxidation, whereby the product is reduced. Therefore, such a light-air secondary battery can be charged in any of energy forms of electricity and light, and a charging reaction can proceed even during discharging. Also on
The battery case is formed in the shape of a square box, polygonal column, or column.
The positive electrode is located near the end of the negative electrode member forming the negative electrode.
The battery case is located on the side of the battery case.
A negative electrode member is provided at the center of the base.

【００２３】請求項２記載の光空気２次電池では、請求
項１記載の作用を有するとともに、上記負極をなす金属
製の負極部材の少なくとも一部が、該金属の酸化物、又
は複数の金属よりなる複合成分系金属や合金よりなるか
ら、負極部材の金属の酸化物等が半導体特性を示し、こ
の半導体特性を示す負極部材が光充電反応を促進する。According to a second aspect of the present invention, there is provided the photo-air secondary battery having the function of the first aspect, wherein at least a part of the metal negative electrode member forming the negative electrode comprises an oxide of the metal or a plurality of the metal negative electrodes. Since it is composed of a composite component metal or alloy, the metal oxide or the like of the negative electrode member exhibits semiconductor characteristics, and the negative electrode member exhibiting the semiconductor characteristics promotes the photocharge reaction.

【００２４】請求項３記載の光空気２次電池では、請求
項１または２記載の作用を有するとともに、上記受光部
は、少なくとも上記電池ケースの互いに対向する二面に
配設されているから、電池ケースの対向する受光部から
負極部材の表裏面に光が入射される。[0024] In light air battery of claim 3, wherein, as well as has the effect of claim 1 or 2 wherein said light receiving portion, from being disposed on two surfaces opposite to each other of at least the battery case, Light is incident on the front and back surfaces of the negative electrode member from opposing light receiving portions of the battery case.

【００２５】[0025]

【００２６】請求項４記載の光空気２次電池では、請求
項１〜３いずれか記載の作用を有するとともに、上記電
池ケースには、正極に外部の空気を接触させる空気孔が
正極近傍に少なくとも一つ以上配設されているから、空
気孔を外部の空気が通り、この空気が正極に接触する。[0026] In light air battery of claim 4, wherein, as well as has the effect of any one of claims 1 to 3, in the battery case, the air holes to the positive electrode into contact with external air at least in the vicinity of the cathode Since at least one is provided, outside air passes through the air holes, and this air contacts the positive electrode.

【００２７】請求項５記載の光空気２次電池では、請求
項１〜３いずれか記載の作用を有するとともに、上記電
池ケースの少なくとも正極近傍部分が、酸素透過性部材
よりなるから、この酸素透過性部材を酸素が通過し、こ
の酸素が正極に接触する。According to a fifth aspect of the present invention, the light-air secondary battery has the function of any one of the first to third aspects, and at least a portion near the positive electrode of the battery case is made of an oxygen-permeable member. Oxygen passes through the conductive member, and this oxygen contacts the positive electrode.

【００２８】請求項６記載の光空気２次電池では、請求
項４又は５記載の作用を有するともに、上記正極が、酸
素触媒と、電池ケースの空気孔または酸素透過性部材よ
りなる部分を通して電池ケース内の電解質の電池外部へ
の流出と透過とを防止する撥水剤とで構成されているか
ら、酸素触媒で酸素が還元され、電池ケースの空気孔ま
たは酸素透過性部材よりなる部分を通して電池ケース内
の電解質の電池外部への流出と透過とが撥水剤で防止さ
れる。According to a sixth aspect of the present invention, there is provided a light-air secondary battery having the functions of the fourth and fifth aspects, wherein the positive electrode passes through an oxygen catalyst and a portion formed of an air hole or an oxygen-permeable member of a battery case. Since the electrolyte in the case is composed of a water repellent which prevents the electrolyte from flowing out and permeating out of the battery, oxygen is reduced by the oxygen catalyst, and the battery is passed through the air holes of the battery case or the portion made of the oxygen-permeable member. The outflow and permeation of the electrolyte in the case to the outside of the battery are prevented by the water repellent.

【００２９】請求項７記載の光空気２次電池では、請求
項４又は５記載の作用を有するとともに、正極と電池ケ
ースとの間に設けた撥水膜または撥水板が、電池ケース
の空気孔または酸素透過性部材よりなる部分を通して電
解質の電池ケース内から電池外部への流出と透過とを防
止する。According to a seventh aspect of the present invention, the light-air secondary battery has the functions of the fourth and fifth aspects, and further comprises a water-repellent film or a water-repellent plate provided between the positive electrode and the battery case. The electrolyte is prevented from flowing out of the battery case to the outside of the battery through the holes or the portion made of the oxygen-permeable member.

【００３０】請求項８記載の光空気２次電池では、請求
項４又は５記載の作用を有するとともに、正極と電池ケ
ースとの間に設けた拡散紙が、電池ケースの空気孔また
は酸素透過性部材から酸素を正極表面に一様に拡散す
る。The light-air secondary battery according to the eighth aspect has the function according to the fourth or fifth aspect , and the diffusion paper provided between the positive electrode and the battery case has an air hole or an oxygen permeability in the battery case. Oxygen is uniformly diffused from the member to the positive electrode surface.

【００３１】請求項９記載の光空気２次電池では、請求
項７記載の作用を有するとともに、撥水膜または撥水板
が電解質の流出と透過とを防止し、電池ケースの空気孔
または酸素透過性部材から酸素を拡散紙が正極表面に一
様に拡散せしめる。According to a ninth aspect of the present invention, the light-air secondary battery has the function of the seventh aspect , and the water-repellent film or the water-repellent plate prevents the outflow and permeation of the electrolyte, and the air holes or the oxygen holes in the battery case. The diffusion paper uniformly diffuses oxygen from the permeable member to the positive electrode surface.

【００３２】請求項１０記載の光空気２次電池では、請
求項１〜９いずれか記載の作用を有するとともに、負極
をなす負極部材に、該負極部材と空気中の酸素、窒素、
二酸化炭素、あるいは電解質との接触により生成した金
属酸化物、窒化物、炭化物、水酸化物等の化合物、ある
いはこれらの複合化合物が含有されているから、金属酸
化物等の負極部材が半導体特性を示し、この半導体特性
を示す負極部材が光充電反応を促進する。According to a tenth aspect of the present invention, the photo-air secondary battery has the function of any one of the first to ninth aspects, and further includes a negative electrode member serving as a negative electrode and oxygen, nitrogen,
Since it contains compounds such as carbon dioxide, metal oxides, nitrides, carbides and hydroxides generated by contact with the electrolyte, or composite compounds thereof, the negative electrode members such as metal oxides have semiconductor characteristics. The negative electrode member having the above semiconductor characteristics promotes the photocharge reaction.

【００３３】[0033]

【実施例】図１および図２は、本発明に係る光空気２次
電池の第１の実施例を示す図で、図中符号２１は多孔性
酸素触媒よりなる正極、２２は負極、２２ａは負極をな
す金属製の負極部材、２３は正極２１と負極２２とに接
触する電解質、２４はセパレータ、２５は正極２１に電
気的に接続された正極端子、２６は負極部材２２ａに電
気的に接続された負極端子、２７は電池ケース、２８は
撥水膜である。1 and 2 show a first embodiment of a light-air secondary battery according to the present invention. In the drawings, reference numeral 21 denotes a positive electrode made of a porous oxygen catalyst, 22 denotes a negative electrode, and 22a denotes a negative electrode. A negative electrode member made of metal forming a negative electrode, 23 is an electrolyte that comes into contact with the positive electrode 21 and the negative electrode 22, 24 is a separator, 25 is a positive electrode terminal electrically connected to the positive electrode 21, and 26 is electrically connected to the negative electrode member 22a. The reference numeral 27 denotes a battery case, and 28 denotes a water-repellent film.

【００３４】電池ケース２７は、角箱状に形成されてお
り、上下両面を兼ねる光透過材等からなる一対の受光部
２７ａと、一方の側面に設けられた側部２７ｂとを有
し、この側部２７ｂには多数の空気孔２９が形成されて
いる。電池ケース２７には、側部２７ｂ側に配設された
正極２１と、その端面が正極２１に対向するように受光
部２７ａに沿って配設された負極２２と、これら正極２
１と負極２２との間、および受光部２７ａと負極２２と
の間に充満された液状電解質２３と、上記正極２１と負
極２２との間に設けられ、電解質２３が通過可能なガラ
ス繊維等からなるセパレータ２４とが収納されている。
撥水膜２８は、正極２１と側部２７ｂとの間に配設さ
れ、通気性を有するとともに、電解質２３が外部へ流出
するのを防止する構成にされている。The battery case 27 is formed in the shape of a rectangular box, and has a pair of light receiving portions 27a made of a light transmitting material or the like which also serves as upper and lower surfaces, and side portions 27b provided on one side surface. Many air holes 29 are formed in the side part 27b. The battery case 27 includes a positive electrode 21 disposed on the side portion 27 b side, a negative electrode 22 disposed along the light receiving portion 27 a such that an end face thereof faces the positive electrode 21,
1 and the negative electrode 22, and between the light receiving portion 27a and the negative electrode 22, a liquid electrolyte 23 filled between the positive electrode 21 and the negative electrode 22, and a glass electrolyte or the like through which the electrolyte 23 can pass. And a separator 24 formed therein.
The water-repellent film 28 is disposed between the positive electrode 21 and the side portion 27b, has a gas permeability, and is configured to prevent the electrolyte 23 from flowing out.

【００３５】本実施例では、負極２２をなす負極部材２
２ａと正極２１をなす酸素触媒とを積層方向に対向させ
るものでなく、電池ケース２７の側壁部（一部）２７ｂ
に正極２１の酸素触媒を配置し、この酸素触媒に負極部
材２２ａの端部を対向配置した。これにより、電池ケー
ス２７の表裏面に受光部２７ａを配設し、この受光部２
７ａに沿って負極部材２２ａを延在させることにより、
この負極部材２２ａ上に形成される全放電生成物に対す
る受光可能な放電生成物の占める割合を増大できるとと
もに、電池ケース２７の表裏面からの受光も可能にな
り、光充電の時間を短縮することができるという利点が
ある。In this embodiment, the negative electrode member 2 forming the negative electrode 22
2a and the oxygen catalyst forming the positive electrode 21 are not opposed to each other in the stacking direction.
The oxygen catalyst of the positive electrode 21 was disposed at the end, and the end of the negative electrode member 22a was disposed to face the oxygen catalyst. Thus, the light receiving section 27a is disposed on the front and back surfaces of the battery case 27, and the light receiving section 2a is provided.
By extending the negative electrode member 22a along 7a,
It is possible to increase the ratio of the discharge products that can be received to all the discharge products formed on the negative electrode member 22a, and also to receive light from the front and back surfaces of the battery case 27, thereby shortening the time for light charging. There is an advantage that can be.

【００３６】本実施例の光空気２次電池では、空気中の
酸素の還元に基づく放電反応を円滑に進行させるため、
酸素と電解質２３および正極２１（酸素触媒）とで構成
される気−液−固三相界面の場を効果的に形成すること
が必要である。従って、該三相界面場の増大を目的とし
て、正極２１が多孔性の酸素触媒で構成されている。た
だし、低率（低電流）放電で使用する電池を構成する場
合には、必ずしも多孔性である必要はなく、板状の正極
２１を用いてもよい。In the photo-air secondary battery of this embodiment, the discharge reaction based on the reduction of oxygen in the air proceeds smoothly.
It is necessary to effectively form a gas-liquid-solid three-phase interface field composed of oxygen, the electrolyte 23, and the positive electrode 21 (oxygen catalyst). Therefore, the positive electrode 21 is formed of a porous oxygen catalyst for the purpose of increasing the three-phase interface field. However, when configuring a battery used for low-rate (low-current) discharge, the battery need not necessarily be porous, and a plate-shaped positive electrode 21 may be used.

【００３７】上記正極２１は、カーボン（多孔炭素）や
多孔ニッケル、および、これらにＰｔやＰｄを担持した
多孔性酸素触媒（Ｐｔ−Ｃ，Ｐｄ−Ｃ，Ｐｔ−Ｎｉ，Ｐ
ｄ−Ｎｉ）、さらに、Ｐｔ，Ｐｄ，Ｉｒ，Ｒｈ，Ｏｓ，
Ｒｕ，Ｐｔ−Ｃｏ，Ｐｔ−Ａｕ，Ｐｔ−Ｓｎ，Ｐｄ−Ａ
ｕ，Ｒｕ−Ｔａ，Ｐｔ−Ｐｄ−Ａｕ，Ｐｔ−酸化物，Ａ
ｕ，Ａｇ，Ａｇ−Ｃ，Ｎｉ−Ｐ，Ａｇ−Ｎｉ−Ｐ，ラネ
ーニッケル，Ｎｉ−Ｍｎ，Ｎｉ−酸化コバルト、Ｃｕ−
Ａｇ，Ｃｕ−Ａｕ，ラネー銀等の貴金属および合金，ホ
ウ化ニッケル，ホウ化コバルト，炭化タングステン，水
酸化チタン，リン化タングステン，リン化ニオブ，遷移
金属の炭化物，スピネル化合物，酸化銀，酸化タングス
テン，遷移金属のペロブスカイト型イオン結晶等の無機
化合物、および、バクテリア、非イオン活性剤、フタロ
シアニン，金属フタロシアニン，活性炭，キノン類等の
有機化合物のいずれかで構成されるのが好ましい。The positive electrode 21 is made of carbon (porous carbon), porous nickel, and a porous oxygen catalyst (Pt-C, Pd-C, Pt-Ni, Pt) carrying Pt or Pd on them.
d-Ni), and further, Pt, Pd, Ir, Rh, Os,
Ru, Pt-Co, Pt-Au, Pt-Sn, Pd-A
u, Ru-Ta, Pt-Pd-Au, Pt-oxide, A
u, Ag, Ag-C, Ni-P, Ag-Ni-P, Raney nickel, Ni-Mn, Ni-cobalt oxide, Cu-
Noble metals and alloys such as Ag, Cu-Au and Raney silver, nickel boride, cobalt boride, tungsten carbide, titanium hydroxide, tungsten phosphide, niobium phosphide, carbides of transition metals, spinel compounds, silver oxide, tungsten oxide And inorganic compounds such as perovskite-type ionic crystals of transition metals, and organic compounds such as bacteria, nonionic activators, phthalocyanines, metal phthalocyanines, activated carbon, and quinones.

【００３８】また、負極２２をなす負極部材２２ａの材
料としては、Ｔｉ，Ｚｎ，Ｆｅ，Ｐｂ，Ａｌ，Ｃｏ，Ｈ
ｆ，Ｖ，Ｎｂ，Ｎｉ，Ｐｄ，Ｐｔ，Ｃｕ，Ａｇ，Ｃｄ，
Ｉｎ，Ｇｅ，Ｓｎ，Ｂｉ，Ｔｈ，Ｔａ，Ｃｒ，Ｍｏ，
Ｗ，Ｐｒ，Ｂｉ，Ｕ等のその酸化物が半導体特性を示す
金属、又は該金属の少なくとも一部が該金属の酸化物、
および、これらの複合成分系金属、合金等で構成され
る。なお、負極２２をなす負極部材２２ａは、空気中の
酸素、窒素、二酸化炭素、あるいは、電解質との接触に
より微量の金属酸化物、窒化物、炭化物、水酸化物、あ
るいはこれらの複合化合物をその表面に自然生成する
が、半導体特性を示す生成物は光充電反応を促進するの
で、これらのような化合物が負極２２中に含まれること
は好ましい。The material of the negative electrode member 22a constituting the negative electrode 22 is Ti, Zn, Fe, Pb, Al, Co, H
f, V, Nb, Ni, Pd, Pt, Cu, Ag, Cd,
In, Ge, Sn, Bi, Th, Ta, Cr, Mo,
A metal such as W, Pr, Bi, U or the like whose oxide shows semiconductor properties, or at least a part of the metal is an oxide of the metal;
And it is composed of these composite component metals, alloys and the like. The negative electrode member 22a constituting the negative electrode 22 is formed by contacting oxygen, nitrogen, carbon dioxide, or a trace amount of metal oxide, nitride, carbide, hydroxide, or a composite compound thereof in the air. It is preferable that such a compound be contained in the negative electrode 22 because a product which is naturally formed on the surface but exhibits semiconductor characteristics promotes a photocharge reaction.

【００３９】また、本実施例の電解質２３として、水酸
化カリウム、水酸化ナトリウム、塩化アンモニウム等の
塩基や、その他弱酸等の液状電解質が用いられる。ま
た、充電性能は低下するが、硫酸、塩酸等の強酸や塩を
使うこともできる。なお、本実施例においては、上述し
たように液状の電解質２３を用いているが、電解質２３
は、液状に限定されることなく、この電解質２３を介す
る正極２１と負極２２間の電子移動が妨げられないもの
であれば、固体状やペースト状等どのような形態の電解
質でも用いることができる。As the electrolyte 23 of this embodiment, a base such as potassium hydroxide, sodium hydroxide, or ammonium chloride, or a liquid electrolyte such as a weak acid is used. Further, although the charging performance is deteriorated, a strong acid or a salt such as sulfuric acid or hydrochloric acid can be used. In this embodiment, the liquid electrolyte 23 is used as described above.
Is not limited to a liquid, and any electrolyte such as a solid or a paste can be used as long as electron transfer between the positive electrode 21 and the negative electrode 22 through the electrolyte 23 is not hindered. .

【００４０】セパレータ２４は、ガラス繊維やポリアミ
ド系繊維不織布、ポリオレフィン系繊維不織布、セルロ
ース、合成樹脂等の電解質に対する耐久性を有するもの
であれば特に限定されない。The separator 24 is not particularly limited as long as it has durability against electrolytes such as glass fiber, polyamide fiber nonwoven fabric, polyolefin fiber nonwoven fabric, cellulose, and synthetic resin.

【００４１】電池ケース２７は、ＡＢＳ樹脂やフッ素樹
脂等の電解質２３に侵されない材質であれば特に限定さ
れない。ただし、電池ケース２７の負極側に位置する受
光部２７ａ部分は、少なくとも可視光の一部や紫外光の
一部を透過する（無色あるいは有色の）部材、例えば、
ガラス、石英ガラス、アクリル、スチロール等からなる
透明板や透明フィルム等で構成される。もちろん電池ケ
ース２７全体をこれら透明板や透明フィルム等の部材で
構成してもよい。The battery case 27 is not particularly limited as long as the battery case 27 is made of a material such as ABS resin or fluororesin which is not affected by the electrolyte 23. However, the light receiving portion 27a located on the negative electrode side of the battery case 27 is a (colorless or colored) member that transmits at least a part of visible light and a part of ultraviolet light, for example,
It is composed of a transparent plate or a transparent film made of glass, quartz glass, acrylic, styrene, or the like. Of course, the entire battery case 27 may be made of a member such as a transparent plate or a transparent film.

【００４２】このように受光部２７ａ部分を光が透過さ
れる構成としたのは、光充電反応を進行させるために、
負極２２をなす負極部材２２ａの表面に照射光を到達さ
せる際、この照射光が電池ケース２７によって吸収ある
いは反射されて、負極２２をなす負極部材２２ａの表面
に到達する光エネルギーが極端に低下するのを防止する
ためである。The reason why the light receiving portion 27a is configured to transmit light is that the light charging reaction proceeds,
When the irradiation light reaches the surface of the negative electrode member 22a forming the negative electrode 22, the irradiation light is absorbed or reflected by the battery case 27, and the light energy reaching the surface of the negative electrode member 22a forming the negative electrode 22 is extremely reduced. This is to prevent the situation.

【００４３】一方、空気中の酸素の還元に基づく放電反
応を円滑に進行させるためには、空気中の酸素が酸素触
媒よりなる正極２１表面へ拡散移動しなければならな
い。この様な酸素の拡散移動を実現することを目的とし
て、本実施例の光空気２次電池は、電池ケース２７の側
部２７ｂに、小径の空気孔２９を少なくとも１つ以上設
ける構成とした。この空気孔２９は、空気中からの酸素
取り込み口として働くものであるので、空気を取り込む
ことができれば、大径の空気孔としても開口部としても
よい。On the other hand, in order for the discharge reaction based on the reduction of oxygen in the air to proceed smoothly, oxygen in the air must diffuse and move to the surface of the positive electrode 21 composed of the oxygen catalyst. For the purpose of realizing such diffusion transfer of oxygen, the light-air secondary battery of this embodiment has a configuration in which at least one small-diameter air hole 29 is provided in the side portion 27b of the battery case 27. The air hole 29 functions as a port for taking in oxygen from the air. Therefore, as long as air can be taken in, the air hole 29 may be a large-diameter air hole or an opening.

【００４４】撥水膜２８は、正極２１と、電池ケース２
７の側部２７ｂとの間に設けられている。この撥水膜２
８は、正極２１の孔を通過した電解質２３が空気孔２９
を通して光空気２次電池の外部へ透過し、流出するのを
（その撥水性により）防止するとともに、酸素と電解質
２３及び正極２１とで構成される三相界面場の増大にも
寄与している。撥水膜（撥水板）２８としては、例えば
多孔性四フッ化エチレン等のフッ素系樹脂やシリコン系
樹脂等で構成するのが好ましい。The water-repellent film 28 is composed of the positive electrode 21 and the battery case 2
7 is provided between the side portion 27b and the side portion 27b. This water-repellent film 2
8 shows that the electrolyte 23 passing through the hole of the positive electrode 21
Through the light-air secondary battery through the air and prevent it from flowing out (due to its water repellency), and also contributes to an increase in the three-phase interface field composed of oxygen, the electrolyte 23 and the positive electrode 21. . The water-repellent film (water-repellent plate) 28 is preferably made of, for example, a fluorine-based resin such as porous tetrafluoroethylene or a silicon-based resin.

【００４５】なお、上記撥水膜２８の代りに撥水板を用
いて本実施例の光空気２次電池を構成してもよい。ま
た、これら撥水膜２８や撥水板を設ける代りに、酸素触
媒中に撥水剤を混入させて酸素触媒と撥水剤とから正極
２１を構成し、これら酸素触媒と撥水剤とからなる正極
２１に撥水膜２８（撥水板）と同様の機能を付与しても
よい。この場合には、上記三相界面場の増大効果は更に
大きくなる。The light-air secondary battery of this embodiment may be constructed by using a water-repellent plate instead of the water-repellent film 28. Instead of providing the water repellent film 28 and the water repellent plate, a water repellent is mixed in an oxygen catalyst to form the positive electrode 21 from the oxygen catalyst and the water repellent. A function similar to that of the water-repellent film 28 (water-repellent plate) may be provided to the positive electrode 21. In this case, the effect of increasing the three-phase interface field is further increased.

【００４６】なお、空気孔２９が小さく形成される場
合、空気孔２９から取り込んだ酸素を正極２１面全体へ
一様に拡散させるために、電池ケース２７の側部２７ｂ
と撥水膜２８または撥水剤を含む正極２１との間にセル
ロース等からなる拡散紙３０を設けてもよい。When the air hole 29 is formed small, the side portion 27b of the battery case 27 is formed in order to uniformly diffuse oxygen taken in from the air hole 29 over the entire surface of the positive electrode 21.
A diffusion paper 30 made of cellulose or the like may be provided between the water repellent film 28 and the positive electrode 21 containing a water repellent.

【００４７】図３は本発明の第２の実施例を説明する図
であり、この第２の実施例は、電池ケース２７の側部２
７ｂ′部分を酸素透過性部材で構成したものである。第
２の実施例の他の構成は第１の実施例と同様である。上
記電池ケース２７の側部２７ｂ′部分を酸素透過性部材
で構成したのは、電池外部の酸素を酸素触媒よりなる正
極２１表面へ拡散移動させるためで、第１の実施例にお
いて電池ケース２７に空気孔２９を形成した趣旨と同様
である。FIG. 3 is a view for explaining a second embodiment of the present invention.
The portion 7b 'is made of an oxygen-permeable member. Other configurations of the second embodiment are the same as those of the first embodiment. The side portion 27b 'of the battery case 27 is formed of an oxygen-permeable member in order to diffuse and move oxygen outside the battery to the surface of the positive electrode 21 made of an oxygen catalyst. This is similar to the purpose of forming the air holes 29.

【００４８】酸素透過性部材は、エチルセルロース，セ
ルロース，アセテート、およびブチレート等の材料によ
り構成されるのが好ましいが、酸素透過性を有する部材
であればこれらに限定されるものではない。The oxygen permeable member is preferably made of a material such as ethyl cellulose, cellulose, acetate, and butyrate, but is not limited to these as long as it has oxygen permeability.

【００４９】次に、本発明の光空気２次電池の第３の実
施例を図４ないし図５を用いて説明する。図４、図５に
示すように、電池ケース２７は、外形円柱状に形成され
ており、筒状に配設された側部（側面）２７ｂ″と、こ
の側部２７ｂ″の一方の端部に取り付けられ、表面を兼
ねる受光部２７ａを有する構成にされている。この受光
部２７ａに対して負極部材２２ａが対向配置され、この
負極部材２２ａは、電池ケース２７の裏面を兼ねるとと
もに、この電池ケース２７の側部２７ｂ″の他方の端部
に取り付けられている。かかる負極部材２２ａの外側に
負極端子２６が取り付けられている。Next, a third embodiment of the photo-air secondary battery of the present invention will be described with reference to FIGS. As shown in FIGS. 4 and 5, the battery case 27 is formed in an outer cylindrical shape, and has a cylindrical side portion (side surface) 27 b ″ and one end portion of the side portion 27 b ″. And has a light receiving portion 27a which also serves as a surface. The negative electrode member 22a is disposed to face the light receiving portion 27a. The negative electrode member 22a also serves as the back surface of the battery case 27 and is attached to the other end of the side portion 27b ″ of the battery case 27. A negative electrode terminal 26 is attached to the outside of the negative electrode member 22a.

【００５０】電池ケース２７の側部２７ｂ″は、該電池
ケース２７の内側に開口する断面視凹状に形成され、こ
の凹状のくぼみ部分に撥水膜２８を介在させて正極２１
が収納される構成にされている。この正極２１は負極部
材２２ａの周縁部（端部）の沿うリング状に形成され、
この正極２１に接続される正極端子２５が電池ケース２
７の側部２７ｂ″から露出されている。なお、電池ケー
ス２７の側部２７ｂ″の凹状のくぼみ部分と撥水膜２８
との間に拡散紙（図示略）が設けられている。The side portion 27b ″ of the battery case 27 is formed in a concave shape in a sectional view that opens inside the battery case 27, and the water repellent film 28 is interposed between the concave portion and the positive electrode 21b.
Is stored. The positive electrode 21 is formed in a ring shape along the peripheral edge (end) of the negative electrode member 22a.
The positive electrode terminal 25 connected to the positive electrode 21 is connected to the battery case 2
7 is exposed from the side portion 27b ". The concave portion of the side portion 27b" of the battery case 27 and the water repellent film 28 are exposed.
And a diffusion paper (not shown).

【００５１】これら電池ケース２７の受光部２７ａと、
電池ケース２７の側部２７ｂ″に収納された正極２１
と、負極２２をなす負極部材２２ａとで空間が形成され
ている。この空間内には、電解質２３が充満され、受光
部２７ａに一端を取り付け、他端を側部２７ｂ″に取り
付けたセパレータ２４が正極２１の内周面に沿って配設
されている。The light receiving portion 27a of the battery case 27,
Positive electrode 21 housed in side portion 27b ″ of battery case 27
And a negative electrode member 22a forming the negative electrode 22 forms a space. This space is filled with an electrolyte 23, and a separator 24 having one end attached to the light receiving portion 27 a and the other end attached to the side portion 27 b ″ is provided along the inner peripheral surface of the positive electrode 21.

【００５２】このように電池ケース２７の側部２７ｂ″
に正極２１を配設することにより、この正極２１をなす
酸素触媒が電池ケース２７の側部２７ｂ″全体にわたっ
て配されるから、電池ケース２７の側部２７ｂ″の周囲
の外気から電池ケース２７内に効率的に酸素を取り込む
ことができ、高率（大電流）放電特性が向上するという
利点がある。As described above, the side portion 27b ″ of the battery case 27
By disposing the positive electrode 21 in the battery case 27, the oxygen catalyst forming the positive electrode 21 is disposed over the entire side portion 27 b ″ of the battery case 27, so that the outside air around the side portion 27 b ″ of the battery case 27 Oxygen can be taken in efficiently, and high rate (large current) discharge characteristics are improved.

【００５３】なお、前記負極端子２６を電池ケース２７
の裏面に配設したが、本願はこれに限定するものでな
く、負極端子２６を正極２１と絶縁して電池ケース２７
の側部２７ｂ″に配してもよい。負極端子２６を電池ケ
ース２７の側部２７ｂ″に配し、負極部材２２ａを電解
質２３内に配し、電池ケース２７の裏面に別の受光部２
７ａを設けてもよい。かかる構成にすることにより、電
池ケース２７の表裏面に受光部２７ａを配設することが
できる。The negative terminal 26 is connected to the battery case 27.
However, the present invention is not limited to this, and the battery terminal 27 is provided by insulating the negative electrode terminal 26 from the positive electrode 21.
The negative electrode terminal 26 is disposed on the side portion 27b ″ of the battery case 27, the negative electrode member 22a is disposed in the electrolyte 23, and another light receiving portion 2 is provided on the back surface of the battery case 27.
7a may be provided. With this configuration, the light receiving unit 27a can be provided on the front and back surfaces of the battery case 27.

【００５４】なお、第１〜第３の実施例の光空気２次電
池では、電池ケース２７内に酸素を取り入れるために、
電池ケース２７に空気孔２９を設けた構成としたり、電
池ケース２７の一部を酸素透過性部材により構成した
が、上記構成とせず、電池ケース２７内に存在する酸素
と、充電により生成する酸素のみを利用して放電反応を
進行させることも可能である。従って、電池ケース２７
の側部２７ｂに空気孔２９を設けたり、この側部２７ｂ
部分を酸素透過性の部材で構成することは必須ではな
い。但し、この場合には、外部からの酸素取り込みが不
可能となるため、電池の放電容量、即ちエネルギー密度
が上記実施例に比べて低下する。In the light-air secondary batteries of the first to third embodiments, in order to take oxygen into the battery case 27,
Although the battery case 27 has a configuration in which the air holes 29 are provided, or a part of the battery case 27 is configured by an oxygen-permeable member, the above configuration is not adopted, and oxygen existing in the battery case 27 and oxygen generated by charging It is also possible to make the discharge reaction proceed using only the above. Therefore, the battery case 27
The air hole 29 is provided in the side portion 27b,
It is not essential that the portion is made of an oxygen-permeable member. However, in this case, since oxygen cannot be taken in from the outside, the discharge capacity of the battery, that is, the energy density, is lower than that in the above embodiment.

【００５５】以下、上述した実施例における光空気２次
電池の充放電時の動作を簡単に説明する。放電時には、
負極２２上で、負極２２をなす金属製の負極部材２２ａ
と電解質２３中の水酸イオンや水分子とが反応して、最
終的に金属酸化物が生成するとともに、負極端子２６を
通じて電子を外部負荷に供給する。The operation at the time of charging and discharging of the photo-air secondary battery in the above embodiment will be briefly described below. When discharging,
On the negative electrode 22, a metal negative electrode member 22 a forming the negative electrode 22
Reacts with hydroxyl ions and water molecules in the electrolyte 23 to finally generate a metal oxide and supply electrons to an external load through the negative electrode terminal 26.

【００５６】一方、正極２１上では、空気中から取り込
んだ酸素と電解質２３と酸素触媒（正極）２１により形
成される三相界面において、酸素と電解質２３中の水及
び負極から外部負荷を通して供給（放出）されてきた電
子とが反応して、水酸イオンを生成する。この放電反応
においては、電池系全体では正極２１と負極２２での反
応が相殺される結果、電解質２３の減少は全く起きな
い。また、正極活物質である酸素は、電池ケース２７の
側部２７ｂを介して空気中から取り込むため、その消費
は問題とならない。結局、本放電反応によって変化する
のは負極２２をなす負極部材２２ａであり、放電反応に
より金属酸化物が生成する。従って、本実施例の光空気
２次電池を充電するということは、該金属酸化物を元の
金属や該金属の低次酸化物に還元するということにほか
ならない。On the other hand, on the positive electrode 21, oxygen and water in the electrolyte 23 and the negative electrode are supplied through an external load at a three-phase interface formed by oxygen taken from the air, the electrolyte 23, and the oxygen catalyst (positive electrode) 21. The emitted electrons react with each other to generate hydroxyl ions. In this discharge reaction, the reaction in the positive electrode 21 and the negative electrode 22 is offset in the entire battery system, and thus the electrolyte 23 does not decrease at all. Further, oxygen as the positive electrode active material is taken in from the air via the side portion 27b of the battery case 27, so that its consumption does not matter. After all, what changes by the main discharge reaction is the negative electrode member 22a forming the negative electrode 22, and a metal oxide is generated by the discharge reaction. Therefore, charging the light-air secondary battery of this embodiment is nothing but reducing the metal oxide to the original metal or a lower oxide of the metal.

【００５７】ところで、一般に光充電を実現するために
は、正極２１と負極２２の他に光反応を行うための光電
極が必要である。しかし、本実施例の光空気２次電池
は、その構成に光電極が存在しないにもかかわらず光充
電を行うことができる。これは、以下の理由によるもの
である。By the way, in general, in order to realize light charging, a photoelectrode for performing a photoreaction is required in addition to the positive electrode 21 and the negative electrode 22. However, the photo-air secondary battery of the present embodiment can perform photo-charging even though there is no photoelectrode in its configuration. This is for the following reason.

【００５８】簡単にいえば、本実施例においては上記放
電反応により負極２２をなす負極部材２２ａの表面に形
成された金属酸化物が光電極として機能する結果、光電
極が存在しなくても光充電反応が進行するということで
ある。すなわち、放電生成物である金属酸化物は半導体
特性を示し、電解質２３と放電生成物との接触界面にお
いて該放電生成物のエネルギーバンドは、電解質２３側
へ向って上方曲りとなる。今、この放電生成物表面へ太
陽や蛍光燈等の光エネルギーが照射されると、伝導帯に
電子を励起し、価電子帯にホールを生む。このホール
は、上記エネルギーバンドの曲りに添って電解質２３側
へ運ばれ、負極２２をなす負極部材２２ａの表面で水酸
イオンと反応して酸素と水を生成する。Briefly, in the present embodiment, the metal oxide formed on the surface of the negative electrode member 22a forming the negative electrode 22 by the discharge reaction functions as a photoelectrode. This means that the charging reaction proceeds. That is, the metal oxide serving as the discharge product has semiconductor characteristics, and the energy band of the discharge product at the contact interface between the electrolyte 23 and the discharge product bends upward toward the electrolyte 23 side. Now, when the surface of the discharge product is irradiated with light energy such as the sun or a fluorescent lamp, it excites electrons in the conduction band and creates holes in the valence band. The holes are carried toward the electrolyte 23 along the bending of the energy band, and react with hydroxyl ions on the surface of the negative electrode member 22 a forming the negative electrode 22 to generate oxygen and water.

【００５９】一方、伝導帯に励起された電子は、バンド
の曲りに添って負極２２中のまだ酸化されていない金属
側へと向かって移動し、やがて、金属−金属酸化物−電
解質の界面に達する。そこで上記電子が電解質２３中の
水と反応して水酸イオンを生成するとともに、未反応の
金属部分はこれ以上還元できないため、金属酸化物であ
る放電生成物を金属部材に還元する。以上の経過を経
て、光充電反応が進行する。On the other hand, the electrons excited in the conduction band move toward the unoxidized metal side in the anode 22 along the bending of the band, and eventually reach the metal-metal oxide-electrolyte interface. Reach. Then, the electrons react with water in the electrolyte 23 to generate hydroxyl ions, and the unreacted metal portion cannot be reduced any more, so that the discharge product which is a metal oxide is reduced to the metal member. Through the above process, the photocharge reaction proceeds.

【００６０】以上説明したように、前記実施例に示した
構成をとることによって、従来の光空気２次電池にはな
い、空気中の酸素をエネルギー源とした放電と光エネル
ギーによる充電が可能で、充電器を必要としない省エネ
ルギー性に優れ、高エネルギー密度の光空気２次電池を
提供することができる。特に、半導体や光化学励起物質
よりなる光電極の存在しない、２電極系よりなる簡単な
構成で、該電池を実現することができる。また、電気と
光の何れのエネルギー形態でも充電可能で、放電中でも
光充電反応が進行する電池を提供することができる。As described above, by employing the configuration shown in the above embodiment, it is possible to perform discharge using oxygen in air as an energy source and charge using light energy, which are not available in the conventional light-air secondary battery. In addition, it is possible to provide a light air secondary battery which is excellent in energy saving and does not require a charger and has a high energy density. In particular, the battery can be realized with a simple configuration composed of a two-electrode system without a photoelectrode composed of a semiconductor or a photochemically excited substance. Further, it is possible to provide a battery which can be charged in any form of energy of electricity and light, and in which a photocharge reaction proceeds even during discharging.

【００６１】[0061]

【発明の効果】以上説明したように、本発明の光空気２
次電池にあっては、以下の効果を奏することができる。
請求項１記載の光空気２次電池によれば、負極をなす金
属製の負極部材の酸化反応と酸素の還元反応とにより放
電され、該放電により該負極部材に生成した放電生成物
に光エネルギーを作用させ、該生成物を金属に変化させ
て充電される構成としたので、放電時には、負極をなす
負極部材の表面に形成される放電生成物の光反応性を利
用して、光エネルギーによる充電が実現する。従って、
従来の光２次電池でその構成に必須であった半導体や化
学励起物質によりなる光電極を省略でき、これにより本
発明の光空気２次電池の構造は簡易なものとなり、さら
に製造も容易となる。As described above, the light air 2 of the present invention is used.
The following effects can be obtained with the secondary battery.
According to the photo-air secondary battery of the first aspect, a discharge is generated by the oxidation reaction and the oxygen reduction reaction of the metal negative electrode member that forms the negative electrode, and the discharge product generated in the negative electrode member by the discharge emits light energy. And the product is converted to metal and charged, so that at the time of discharging, the photoreactivity of the discharge product formed on the surface of the negative electrode member forming the negative electrode is used to generate light. Charging is realized. Therefore,
The photoelectrode made of a semiconductor or a chemically excited substance, which is essential for the configuration of the conventional photorechargeable battery, can be omitted, thereby simplifying the structure of the photo-air rechargeable battery of the present invention, and further facilitating the manufacture. Become.

【００６２】上記正極は、酸素触媒を有する構成にさ
れ、該正極は、負極をなす負極部材の端部に位置する電
池ケースの側面に配設される構成にしたから、負極をな
す負極部材と正極をなす酸素触媒とを積層させたときに
比べ、負極をなす負極部材上に形成される全放電生成物
に対して、受光可能な放電生成物の占める割合を増大で
きるとともに、負極をなす負極部材の表裏面が受光可能
になる。このため、負極をなす負極部材の受光面積を増
大できるから、光充電の時間を短縮することができる。
また、上記電池ケースが、角箱状、多角柱状又は円柱状
に形成され、上記正極が、負極をなす負極部材の端部付
近に位置する電池ケースの側面に配設されるので、電池
ケースの周囲に存在する外気から酸素を効率的に取り込
むことができ、高率（大電流）放電特性を向上させた電
池を提供することができる。[0062] The positive electrode is configured to have an oxygen catalyst, positive electrode, since was configured to be disposed on a side surface of the battery case located at the end of the negative electrode member having a negative electrode, a negative electrode member having a negative electrode Compared to the case where the oxygen catalyst serving as the positive electrode is stacked, the ratio of the light-receiving discharge products to the total discharge products formed on the negative electrode member serving as the negative electrode can be increased, and the negative electrode serving as the negative electrode The front and back surfaces of the member can receive light. For this reason, the light receiving area of the negative electrode member forming the negative electrode can be increased, so that the time for photocharging can be reduced.
In addition, the battery case has a rectangular box shape, a polygonal column shape, or a column shape.
The positive electrode is formed at an end of a negative electrode member forming a negative electrode .
Since the battery is disposed on the side surface of the battery case located close to the battery case, oxygen can be efficiently taken in from the outside air existing around the battery case, and a battery with improved high-rate (large current) discharge characteristics can be provided. be able to.

【００６３】また、正極に酸素触媒を用いているので、
空気中の酸素をエネルギー源（活物質）とした放電が可
能である。従って、実質的に正極活物質は空気中から簡
単に充分な量が補給でき、高エネルギー密度で、経済性
や省エネルギー性に優れたの光空気２次電池を実現でき
る。Since an oxygen catalyst is used for the positive electrode,
Discharge using oxygen in the air as an energy source (active material) is possible. Therefore, a sufficient amount of the positive electrode active material can be easily replenished from the air, and a light-air secondary battery having a high energy density and excellent in economy and energy saving can be realized.

【００６４】請求項２記載の光空気２次電池によれば、
請求項１記載の効果を奏することができるとともに、上
記負極をなす金属製の負極部材の少なくとも一部が、該
金属の酸化物、又は複数の金属よりなる複合成分系金属
や合金よりなる構成にしたから、負極部材が半導体特性
を示し、この負極部材が光充電反応を促進する。このた
め、負極部材の金属の酸化物等が光電極をなし、別途に
光電極を設ける場合に比べ、光空気２次電池を簡易な構
造にすることができる。According to the light-air secondary battery of the second aspect,
The effect according to claim 1 can be obtained, and at least a part of the metal negative electrode member forming the negative electrode has an oxide of the metal, or a composite component metal or an alloy including a plurality of metals. Therefore, the negative electrode member exhibits semiconductor characteristics, and the negative electrode member promotes the photocharge reaction. For this reason, the light-air secondary battery can have a simple structure as compared with a case where a metal oxide or the like of the negative electrode member forms a photoelectrode and a photoelectrode is separately provided.

【００６５】請求項３記載の光空気２次電池によれば、
請求項１または２記載の効果を奏することができるとと
もに、上記受光部は、少なくとも上記電池ケースの互い
に対向する二面に配設されている構成にしたから、電池
ケースの対向する受光部から負極部材の表裏面に光が入
射される。このため、受光可能な放電生成物の占める割
合を増大できるから、光充電の時間を短縮することがで
きる。According to the light-air secondary battery of the third aspect,
It is possible to achieve the effect according to claim 1 or 2 wherein said light receiving portion, since was configurations that are disposed in two sides facing each other of at least the battery case, the negative electrode from the light receiving part opposed to the battery case Light is incident on the front and back surfaces of the member. For this reason, the ratio of the discharge products that can receive light can be increased, so that the time for light charging can be shortened.

【００６６】[0066]

【００６７】請求項４記載の光空気２次電池によれば、
請求項１〜３いずれか記載の効果を奏することができる
とともに、上記電池ケースには、正極に外部の空気を接
触させる空気孔が正極近傍に少なくとも一つ以上配設さ
れている構成にしたから、空気孔から外部の空気を正極
に充分に補給でき、光空気２次電池のエネルギー密度を
高めることができる。According to the photo-air secondary battery of the fourth aspect ,
The effect of any one of claims 1 to 3 can be achieved, and the battery case has a configuration in which at least one or more air holes for bringing external air into contact with the positive electrode are provided near the positive electrode. In addition, external air can be sufficiently supplied to the positive electrode from the air holes, and the energy density of the light-air secondary battery can be increased.

【００６８】請求項５記載の光空気２次電池によれば、
請求項１〜３いずれか記載の効果を奏することができる
とともに、上記電池ケースの少なくとも正極近傍部分
が、酸素透過性部材よりなる構成にしたから、外部の酸
素が酸素透過性部材を通過して正極表面に拡散移動す
る。このため、正極に充分な酸素を補給でき、光空気２
次電池のエネルギー密度を高めることができる。According to the light-air secondary battery of the fifth aspect ,
The effect of any one of claims 1 to 3 can be achieved, and at least a portion near the positive electrode of the battery case is formed of an oxygen-permeable member, so that external oxygen passes through the oxygen-permeable member. It diffuses and moves to the positive electrode surface. Therefore, sufficient oxygen can be supplied to the positive electrode, and light air 2
The energy density of the secondary battery can be increased.

【００６９】請求項６記載の光空気２次電池によれば、
請求項４又は５記載の効果を奏することができるととも
に、上記正極が、酸素触媒と、電池ケースの空気孔また
は酸素透過性部材よりなる部分を通して電池ケース内の
電解質の電池外部への流出と透過とを防止する撥水剤と
で構成したから、電池ケースの空気孔または酸素透過性
部材よりなる部分を通して電池ケース内の電解質の電池
外部への流出と透過とを撥水剤で防止した状態で、空気
孔または酸素透過性部材を通る酸素が酸素触媒で還元さ
れる。このため、酸素と電解質と正極とで界面を形成す
ることができ、酸素の還元に基づく放電反応を円滑に進
行させることができる。According to the light-air secondary battery of the sixth aspect ,
An effect according to claim 4 or 5 , wherein the positive electrode flows out and permeates the electrolyte in the battery case to the outside of the battery through a portion formed of an oxygen catalyst and an air hole or an oxygen-permeable member of the battery case. And a water repellent to prevent the electrolyte in the battery case from flowing out and permeating out of the battery through the air hole or the portion made of the oxygen permeable member. The oxygen passing through the air holes or the oxygen permeable member is reduced by the oxygen catalyst. Therefore, an interface can be formed between oxygen, the electrolyte, and the positive electrode, and the discharge reaction based on the reduction of oxygen can smoothly proceed.

【００７０】請求項７記載の光空気２次電池によれば、
請求項４又は５記載の効果を奏することができるととも
に、正極と電池ケースとの間に、該電池ケースの空気孔
または酸素透過性部材よりなる部分を通して電解質の電
池ケース内から電池外部への流出と透過を防止する撥水
膜または撥水板が設けられた構成にしたから、酸素と電
解質と正極とで界面を形成することができる。このた
め、酸素の還元に基づく放電反応を円滑に進行させるこ
とができる。According to the light-air secondary battery according to the seventh aspect ,
The electrolyte according to claim 4 or 5 , wherein the electrolyte flows from the inside of the battery case to the outside of the battery between the positive electrode and the battery case through an air hole or an oxygen-permeable member of the battery case. Since a water-repellent film or a water-repellent plate for preventing permeation is provided, an interface can be formed between oxygen, the electrolyte, and the positive electrode. Therefore, the discharge reaction based on the reduction of oxygen can smoothly proceed.

【００７１】請求項８記載の光空気２次電池によれば、
請求項４又は５記載の効果を奏することができるととも
に、正極と電池ケースとの間に、酸素を正極表面に一様
に拡散せしめる拡散紙が設けられた構成にしたから、酸
素を正極表面に移動でき、酸素の還元反応を円滑に進行
させることができる。According to the light-air secondary battery of the eighth aspect ,
The structure according to claim 4 or 5 , wherein the diffusion paper is provided between the positive electrode and the battery case to uniformly diffuse oxygen to the surface of the positive electrode. It can move, and the reduction reaction of oxygen can proceed smoothly.

【００７２】請求項９記載の光空気２次電池によれば、
請求項７記載の効果を奏することができるとともに、撥
水膜または撥水板と電池ケースとの間に、酸素を正極表
面に一様に拡散せしめる拡散紙が設けられた構成にした
から、酸素を正極表面に移動でき、酸素と電解質と正極
とで形成される界面の増大に寄与させ、酸素の還元反応
を円滑に進行させることができる。According to the light-air secondary battery of the ninth aspect ,
The structure according to claim 7 , wherein the diffusion paper is provided between the water-repellent film or the water-repellent plate and the battery case, and a diffusion paper for uniformly diffusing oxygen to the surface of the positive electrode is provided. Can be transferred to the surface of the positive electrode, which contributes to an increase in the interface formed between oxygen, the electrolyte, and the positive electrode, and allows the reduction reaction of oxygen to proceed smoothly.

【００７３】請求項１０記載の光空気２次電池によれ
ば、請求項１〜９いずれか記載の効果を奏することがで
きるとともに、負極をなす負極部材に、該負極部材と空
気中の酸素、窒素、二酸化炭素、あるいは電解質との接
触により生成した金属酸化物、窒化物、炭化物、水酸化
物等の化合物、あるいはこれらの複合化合物が含有され
ている構成にしたから、負極部材の複合化合物等が半導
体特性を示し、かかる負極部材が光電極をなす。このた
め、別途に光電極を設ける場合に比べ、光空気２次電池
を簡易な構造にすることができる。According to the photo-air secondary battery of the tenth aspect, the effects of any one of the first to ninth aspects can be obtained, and the negative electrode member forming the negative electrode is provided with the negative electrode member and oxygen in the air. Compounds such as metal oxides, nitrides, carbides, and hydroxides generated by contact with nitrogen, carbon dioxide, or an electrolyte, or composite compounds of these compounds are included. Shows semiconductor characteristics, and such a negative electrode member forms a photoelectrode. Therefore, the light-air secondary battery can have a simple structure as compared with a case where a photoelectrode is separately provided.

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

【図１】本発明の光空気２次電池に係る第一の実施例の
外観を示した斜視図である。FIG. 1 is a perspective view showing an appearance of a first embodiment of a light-air secondary battery according to the present invention.

【図２】図１に示す第一の実施例の光空気２次電池のＸ
−Ｘ’線に添う断面図である。FIG. 2 shows the X of the light-air secondary battery of the first embodiment shown in FIG.
It is sectional drawing which follows the -X 'line.

【図３】本発明の光空気２次電池に係る第二の実施例を
示す断面図である。FIG. 3 is a sectional view showing a second embodiment of the photo-air secondary battery according to the present invention.

【図４】本発明の光空気２次電池に係る第三の実施例の
外観を示した斜視図である。FIG. 4 is a perspective view showing the appearance of a third embodiment of the light-air secondary battery according to the present invention.

【図５】図４に示す第三の実施例の光空気２次電池のＸ
−Ｘ’線に添う断面図である。FIG. 5 is a cross-sectional view of a light-air secondary battery according to a third embodiment shown in FIG.
It is sectional drawing which follows the -X 'line.

【図６】従来の光空気２次電池の外観図を示したもので
ある。FIG. 6 shows an external view of a conventional light air secondary battery.

【図７】図６の等価回路を示したものである。FIG. 7 shows an equivalent circuit of FIG. 6;

【図８】従来型光蓄電池の構成図を示したものである。FIG. 8 shows a configuration diagram of a conventional photo-storage battery.

【図９】第１例の従来型光化学２次電池の構成図を示し
たものである。FIG. 9 shows a configuration diagram of a conventional photochemical secondary battery of the first example.

【図１０】第２例の従来型光化学２次電池の簡単な構成
とエネルギー準位図を示したものである。FIG. 10 shows a simple configuration and an energy level diagram of a conventional photochemical secondary battery of a second example.

【符号の説明】[Explanation of symbols]

２１…正極 ２２…負極 ２２ａ…負極部材 ２３…電解質 ２４…セパレータ ２７…電池ケース ２７ａ…受光部 ２８…撥水膜（撥水板） ２９…空気孔 ３０…拡散紙 DESCRIPTION OF SYMBOLS 21 ... Positive electrode 22 ... Negative electrode 22a ... Negative electrode member 23 ... Electrolyte 24 ... Separator 27 ... Battery case 27a ... Light-receiving part 28 ... Water-repellent film (water-repellent plate) 29 ... Air hole 30 ... Diffusion paper

───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−198319（ＪＰ，Ａ) 特開 平６−215807（ＪＰ，Ａ) 特開 平５−266932（ＪＰ，Ａ) 特開 平４−171681（ＪＰ，Ａ) 特開 昭52−74831（ＪＰ，Ａ) 特開 昭56−93270（ＪＰ，Ａ) 特開 昭58−127389（ＪＰ，Ａ) 特開 昭63−19775（ＪＰ，Ａ) 電子情報通信学会技術研究報告、Ｖｏ ｌ．91 Ｎｏ．439 ｐ．15−20（平４ −１−24) 電気化学協会第59回大会講演要旨集、 ｐ．222（平４−３−19) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 14/00 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-198319 (JP, A) JP-A-6-215807 (JP, A) JP-A-5-266932 (JP, A) JP-A-4-1983 171681 (JP, A) JP-A-52-74831 (JP, A) JP-A-56-93270 (JP, A) JP-A-58-127389 (JP, A) JP-A-63-19775 (JP, A) IEICE Technical Report, Vol. 91 No. 439 p. 15-20 (Heisei 4-1-24) Proceedings of the 59th Annual Meeting of the Electrochemical Society, p. 222 (Heisei 4-3-19) (58) Field surveyed (Int. Cl. 7 , DB name) H01M 14/00

Claims (10)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 正極と、負極と、これら正極と負極とに
接触する電解質と、上記正極と上記負極と上記電解質と
が収容される電池ケースとを有し、該電池ケースには、
上記負極をなす負極部材に光を入射する受光部が設けら
れ、上記正極は、酸素触媒を有する構成にされ、上記負
極をなす金属製の負極部材の酸化反応と酸素の還元反応
とにより放電され、該放電により負極部材に生成した放
電生成物に光エネルギーを作用させることにより、該生
成物を還元させて充電される光空気２次電池において、
上記電池ケースは、角箱状、多角柱状又は円柱状に形成
され、上記正極は、負極をなす負極部材の端部付近に位
置する該電池ケースの側面に配設されることを特徴とす
る光空気２次電池。A positive electrode, a negative electrode, an electrolyte in contact with the positive electrode and the negative electrode, and a battery case in which the positive electrode, the negative electrode, and the electrolyte are accommodated.
The light receiving unit which light enters the anode member having a negative electrode are provided discharge, the positive electrode is configured to have an oxygen catalyst, by the oxidation reaction and oxygen reduction reaction of the metal of the negative electrode member having a top SL negative electrode The light-air secondary battery is charged by applying light energy to a discharge product generated on the negative electrode member by the discharge to reduce the product and charge the product .
The battery case is formed in the shape of a square box, polygonal column, or column
The positive electrode is located near the end of the negative electrode member forming the negative electrode.
A light-air secondary battery disposed on a side surface of the battery case to be placed . 【請求項２】 上記負極をなす金属製の負極部材の少な
くとも一部が、該金属の酸化物、又は複数の金属よりな
る複合成分系金属や合金よりなることを特徴とする請求
項１記載の光空気２次電池。2. The method according to claim 1, wherein at least a part of the metal negative electrode member forming the negative electrode is made of an oxide of the metal, or a composite component metal or alloy composed of a plurality of metals. Light air secondary battery. 【請求項３】 上記受光部は、少なくとも上記電池ケー
スの互いに対向する二面に配設されていることを特徴と
する請求項１又は２記載の光空気２次電池。Wherein said light receiving portion, at least the battery light air battery of claim 1 or 2, wherein the disposed on the two surfaces facing each other of the case. 【請求項４】 上記電池ケースには、正極に外部の空気
を接触させる空気孔が正極近傍に少なくとも一つ以上配
設されていることを特徴とする請求項１〜３いずれか記
載の光空気２次電池。The method according to claim 4, wherein said battery case, light air according to claim 1-3, wherein one of the air holes of contacting the positive electrode to the outside air, characterized in that it is arranged at least one adjacent cathode Secondary battery. 【請求項５】 上記電池ケースの少なくとも正極近傍部
分が、酸素透過性部材よりなることを特徴とする請求項
１〜３いずれか記載の光空気２次電池。Wherein said at least positive electrode vicinity of the battery case, according to claim 1 to 3 light air secondary battery according to any one characterized by comprising from oxygen permeability member. 【請求項６】 上記正極が、酸素触媒と、電池ケースの
空気孔または酸素透過性部材よりなる部分を通して電池
ケース内の電解質の電池外部への流出と透過とを防止す
る撥水剤とで構成されていることを特徴とする請求項４
又は５記載の光空気２次電池。6. The positive electrode comprises an oxygen catalyst and a water-repellent agent for preventing the electrolyte in the battery case from flowing out and permeating out of the battery through an air hole or a portion formed of an oxygen-permeable member of the battery case. 5. The method according to claim 4, wherein
Or 5 Light air secondary battery according. 【請求項７】 正極と電池ケースとの間に、該電池ケー
スの空気孔または酸素透過性部材よりなる部分を通して
電解質の電池ケース内から電池外部への流出と透過を防
止する撥水膜または撥水板が設けられたことを特徴とす
る請求項４又は５記載の光空気２次電池。7. A water-repellent film or a water-repellent film for preventing electrolyte from flowing out of the battery case to the outside of the battery between the positive electrode and the battery case through an air hole or a portion made of an oxygen-permeable member of the battery case. light air battery of claim 4 or 5, wherein the water plate is provided. 【請求項８】 正極と電池ケースとの間に、酸素を正極
表面に一様に拡散せしめる拡散紙が設けられたことを特
徴とする請求項４または５記載の光空気２次電池。Between 8. cathode and the battery case, the oxygen light air battery of claim 4 or 5, wherein uniformly be diffused allowed to spread sheet is provided on the positive electrode surface. 【請求項９】 撥水膜または撥水板と電池ケースとの間
に、酸素を正極表面に一様に拡散せしめる拡散紙が設け
られたことを特徴とする請求項７記載の光空気２次電
池。9. A light-air secondary according to claim 7 , wherein a diffusion paper is provided between the water-repellent film or the water-repellent plate and the battery case to uniformly diffuse oxygen to the surface of the positive electrode. battery. 【請求項１０】 負極をなす負極部材に、該負極部材と
空気中の酸素、窒素、二酸化炭素、あるいは電解質との
接触により生成した金属酸化物、窒化物、炭化物、水酸
化物等の化合物、あるいはこれらの複合化合物が含有さ
れていることを特徴とする請求項１〜９いずれか記載の
光空気２次電池。10. A compound such as a metal oxide, a nitride, a carbide, or a hydroxide formed by contacting the negative electrode member with oxygen, nitrogen, carbon dioxide, or an electrolyte in the air, Alternatively, the light-air secondary battery according to any one of claims 1 to 9, further comprising a composite compound thereof.
JP00543593A 1993-01-14 1993-01-14 Light air secondary battery Expired - Fee Related JP3196151B2 (en)

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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP00543593A JP3196151B2 (en) 1993-01-14 1993-01-14 Light air secondary battery

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Publication Number Publication Date
JPH06215806A JPH06215806A (en) 1994-08-05
JP3196151B2 true JP3196151B2 (en) 2001-08-06

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Country Link
JP (1) JP3196151B2 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5111799B2 (en) * 2006-07-07 2013-01-09 株式会社フジクラ Solar cell and solar cell module

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
電子情報通信学会技術研究報告、Ｖｏｌ．９１ Ｎｏ．４３９ ｐ．１５−２０（平４−１−２４）
電気化学協会第５９回大会講演要旨集、ｐ．２２２（平４−３−１９）

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