JP2673337B2 - Air-metal hydride secondary battery - Google Patents
Air-metal hydride secondary batteryInfo
- Publication number
- JP2673337B2 JP2673337B2 JP6073487A JP7348794A JP2673337B2 JP 2673337 B2 JP2673337 B2 JP 2673337B2 JP 6073487 A JP6073487 A JP 6073487A JP 7348794 A JP7348794 A JP 7348794A JP 2673337 B2 JP2673337 B2 JP 2673337B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- air
- hydrogen
- gas
- metal hydride
- 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 - Lifetime
Links
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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、正極として空気極を、
負極として水素吸蔵合金極（以下、ＭＨ極とも称する）
を有し、さらに充電用の第三電極を有する空気−金属水
素化物二次電池（以下、空気−ＭＨ電池とも称する）に
関するものである。The present invention relates to an air electrode as a positive electrode,
Hydrogen storage alloy electrode (hereinafter also referred to as MH electrode) as the negative electrode
And an air-metal hydride secondary battery (hereinafter, also referred to as an air-MH battery) having a third electrode for charging.
【０００２】[0002]
【従来の技術】近年、高エネルギー密度なアルカリ二次
電池としてＮｉ−ＭＨ電池が実用化されているが、この
電池の正極をガス拡散電極としての空気極と置き換えた
空気−ＭＨ電池も検討され（Ｊ．Ｓａｒｒａｄｉｎ，
Ｇ．Ｂｒｏｎｅｉｌ，Ａ．Ｐｅｒｃｈｅｒｏｎ−Ｇｕｅ
ｇａｎ ａｎｄ Ｊ．Ｃ．Ａｃｈａｒｄ，“Ｐｏｗｅｒ
Ｓｏｕｒｃｅｓ”，７巻，ｐ．３４５（１９７
９）．）、また、アルカリ電解液の代わりにイオン交換
膜を用いて二酸化炭素の影響を除くアイディアも提案さ
れてきた（Ｃ．Ｆｏｌｏｎａｒｉ，Ｇ．Ｉｅｍｍｉ，
Ｆ．Ｍａｎｆｅｒｄｉ ａｎｄ Ａ．Ｒｏｌｌｅ，“Ｊ
ｏｕｒｎａｌ ｏｆ ｔｈｅ Ｌｅｓｓ−Ｃｏｍｍｏｎ
Ｍｅｔａｌｓ”，．７４巻，ｐ．３７１（１９８
０）．）。2. Description of the Related Art In recent years, Ni-MH batteries have been put into practical use as alkaline secondary batteries with high energy density. Air-MH batteries in which the positive electrode of this battery is replaced with an air electrode as a gas diffusion electrode have also been studied. (J. Sarradin,
G. FIG. Broneil, A .; Percheron-Gue
gan and J.K. C. Achard, “Power
Sources ”, Volume 7, p.345 (197)
9). ), And the idea of eliminating the effect of carbon dioxide by using an ion exchange membrane instead of the alkaline electrolyte has been proposed (C. Folonari, G. Iemmi,
F. Manferdi and A.M. Rolle, "J
individual of the Less-Common
Metals ", Vol. 74, p. 371 (198).
0). ).
【０００３】また、正極に空気極、負極にＭＨ極を配し
て、水素ガスで充電する新しいエネルギー変換システム
も提案されている（Ｋ．Ｖｉｄｅｍ，“Ｈｙｄｒｉｄｅ
ｓｆｏｒ Ｅｎｅｒｇｙ Ｓｔｏｒａｇｅ”，ｐ．４６
３（１９７８），Ｐｅｒｇａｍｏｎ Ｐｒｅｓｓ，Ｏｘ
ｆｏｒｄ）。上記の空気−ＭＨ電池はＭＨ極のみを充電
すれば良い。よって、充電時にはＮｉスクリーンなどの
第三電極を用いて充電することも出来るし、ＭＨ極に直
接水素ガスを吸収させて再生することも可能である。Also, a new energy conversion system has been proposed in which an air electrode is arranged at the positive electrode and an MH electrode is arranged at the negative electrode, and the battery is charged with hydrogen gas (K. Video, "Hyride").
sfor Energy Storage ", p.46
3 (1978), Pergamon Press, Ox
ford). The above air-MH battery only needs to charge the MH electrode. Therefore, at the time of charging, it is possible to charge by using a third electrode such as a Ni screen, or it is possible to make the MH electrode directly absorb hydrogen gas for regeneration.
【０００４】[0004]
【発明が解決しようとする課題】上記の空気−ＭＨ電池
では、ＭＨ極は電解液に濡れているために、水素ガスを
電極表面上にフローしても反応速度が遅くガス再生に時
間がかかるという問題点があった。また、空気極は充電
時の加圧水素やＭＨ極の膨潤によって破損することがあ
った。In the above air-MH battery, since the MH electrode is wet with the electrolytic solution, the reaction speed is slow even when hydrogen gas flows on the electrode surface, and it takes time to regenerate the gas. There was a problem. Further, the air electrode may be damaged by pressurized hydrogen during charging or swelling of the MH electrode.
【０００５】[0005]
【課題を解決するための手段】本発明は、上記のような
課題を解決するものであり、水素ガスを透過するＭＨ極
を用い、ＭＨ極に接した水素ガスを導入する部屋（電解
液室を兼ねた水素室）を備え、ガス再生時に該電解液室
を兼ねた水素室に水素ガスを加圧導入し、電解液室を兼
ねた水素室から電解液を排出し、ＭＨ極中に水素ガスを
透過させることにより、電気化学的充電と同等な再生速
度でガス再生できるとの新規な知見に基づくものであ
る。Means for Solving the Problems The present invention is intended to solve the above problems and uses a MH electrode that transmits hydrogen gas, and a room for introducing hydrogen gas in contact with the MH electrode ( electrolysis
Comprising a hydrogen chamber) which also serves as a liquid chamber, the electrolyte chamber at gas regeneration
Hydrogen gas is introduced under pressure into the hydrogen chamber that also functions as an electrolyte chamber.
This is based on the novel finding that gas can be regenerated at a regeneration rate equivalent to that of electrochemical charging by discharging the electrolytic solution from the entrained hydrogen chamber and permeating hydrogen gas into the MH electrode.
【０００６】すなわち、本発明の空気−ＭＨ電池は、正
極として空気極を用い且つ負極としてＭＨ極を用いる空
気−ＭＨ電池において、ＭＨ極が水素ガスを透過できる
多孔度を有し、ＭＨ極と接した電解液室を兼ねた水素室
を有し且つガス再生時にＭＨ極中を透過した水素ガスを
排出するための水素ガス排出口を備えたことを特徴とす
る空気−ＭＨ電池であって、該電解液室を兼ねた水素室
に、放電時又は電気化学的充電時には電解液を存在さ
せ、また、ガス再生時には外部から水素ガスを加圧導入
し、電解液室を兼ねた水素室から電解液を排出し、ＭＨ
極中に水素ガスを透過させて充電することができること
を特徴とする。Namely, the air -MH battery of the present invention is the air -MH battery using MH pole as and negative electrode using an air electrode as a positive electrode, MH poles can penetrate the hydrogen gas
Has a porosity, the hydrogen gas has passed through the MH Kyokuchu hydrogen chamber which also serves as a electrolyte chamber in contact with the MH electrode when an organic and and gas regeneration
An air -MH cell characterized by having a hydrogen gas discharge port for discharging, to the hydrogen chamber which also serves as the electrolyte chamber, the discharge time or the electrochemical charging the presence of electrolyte, also During gas regeneration, hydrogen gas is introduced under pressure from the outside, and the electrolyte is discharged from the hydrogen chamber that also serves as the electrolyte chamber.
It is characterized in that hydrogen gas can be passed through the electrode for charging.
【０００７】本発明の空気−ＭＨ電池は、また、ガス再
生時に、ＭＨ極を透過した水素ガスがＭＨ極表面上に留
まること無く、外部へ排出される様に、ＭＨ極の水素透
過側に接した多孔性のシートを有することを特徴とす
る。The air-MH battery of the present invention also has a hydrogen permeation side of the MH electrode so that the hydrogen gas permeated through the MH electrode does not remain on the surface of the MH electrode but is discharged outside during gas regeneration. It is characterized by having a porous sheet in contact therewith.
【０００８】本発明の空気−ＭＨ電池は、さらに、ガス
再生時に、ＭＨ極を透過した水素ガスが空気極を破損し
ない様に、水素ガスの透過しにくいセパレーターをＭＨ
極と空気極の間に有することを特徴とする。また、この
セパレーターが水素ガスの圧力で破損しないように多孔
体上にて支持する。[0008] The air-MH battery of the present invention further comprises a separator which is hard to permeate hydrogen gas so that hydrogen gas permeating the MH electrode does not damage the air electrode during gas regeneration.
It is characterized by having between the pole and the air pole. Further, the separator is supported on the porous body so as not to be damaged by the pressure of hydrogen gas.
【０００９】本発明の空気−ＭＨ電池は、さらにまた、
ガス再生時にＭＨ極を透過した水素ガスや、ＭＨ極の膨
潤によって空気極が破損しない様に、空気極の空気側に
多孔質な支持体（多孔性支持体）を有することを特徴と
する。The air-MH battery of the present invention further comprises:
It is characterized by having a porous support (a porous support) on the air side of the air electrode so that the hydrogen gas that has permeated the MH electrode during gas regeneration and the air electrode due to swelling of the MH electrode will not be damaged.
【００１０】空気−ＭＨ電池の構成 図１に準じて、本発明の空気−ＭＨ電池の構成を詳細に
説明する。図１は、本発明の空気−ＭＨ電池の実施例の
断面図である。 Structure of Air-MH Battery The structure of the air-MH battery of the present invention will be described in detail with reference to FIG. FIG. 1 is a cross-sectional view of an embodiment of the air-MH battery of the present invention.
【００１１】〔空気極〕１は空気極であり、正極として
作用する。空気極１としては、ガス拡散電極として作用
するものであれば特に限定はなく、公知の空気極を使用
できる。具体的には、Ｎｉ焼結体に所望の触媒を担持し
たものをＰＴＦＥ（ポリテトラフルオロエチレン）等の
高分子により撥水化処理したもの、カーボン粉末に所望
の触媒を担持したものをテフロン系の樹脂で結着したも
の、その他のガス拡散電極を空気極として用いることが
できる。触媒としては、Ｎｉ焼結体、カーボン粉末等の
電極基体を、空気極として作用させるものであり、具体
的には、銀、白金などの貴金属を用いることが可能であ
る。[Air electrode] 1 is an air electrode and functions as a positive electrode. The air electrode 1 is not particularly limited as long as it functions as a gas diffusion electrode, and a known air electrode can be used. Specifically, a Ni sintered material carrying a desired catalyst is treated to be water repellent with a polymer such as PTFE (polytetrafluoroethylene), or a carbon powder carrying a desired catalyst is Teflon-based. Any of the gas diffusion electrodes bonded with the resin described in 1. above can be used as the air electrode. As the catalyst, an electrode substrate such as a Ni sintered body or carbon powder is made to act as an air electrode, and specifically, a noble metal such as silver or platinum can be used.
【００１２】〔多孔性支持体〕１５は空気極（多孔性）
支持体である。空気極支持体１５は、空気極１の空気側
に備えられ、ガス再生時にＭＨ極を透過した水素ガスや
ＭＨ極の膨潤によって空気極が破損しない様に作用す
る。空気極支持体１５は特に限られたものではなく、樹
脂、金属の多孔質体や棒状、板状の硬質体を用いること
が出来る。具体的には、テフロン樹脂製の薄板を格子上
に張り付けたものを空気極支持体１５として使用でき
る。空気極支持体の空気極上に占める面積は空気極面積
の５〜３０％であり、特に１０〜１５％であることが望
ましい。これは、５％より低いと機械的強度が低く支持
体として機能せず、３０％を超えると酸素の拡散を疎外
して空気極としての性能が低下するからである。[Porous support] 15 is an air electrode (porous)
It is a support. The air electrode support 15 is provided on the air side of the air electrode 1 and acts so that the hydrogen electrode that has passed through the MH electrode during gas regeneration or the swelling of the MH electrode does not damage the air electrode. The air electrode support 15 is not particularly limited, and a resin or metal porous body or a rod-shaped or plate-shaped hard body can be used. Specifically, a thin plate made of Teflon resin attached to a lattice can be used as the air electrode support 15. The area occupied by the air electrode support on the air electrode is 5 to 30% of the air electrode area, and particularly preferably 10 to 15%. This is because if it is less than 5%, the mechanical strength is low and does not function as a support, and if it exceeds 30%, the diffusion of oxygen is alienated and the performance as an air electrode deteriorates.
【００１３】〔ＭＨ極〕２はＭＨ極であり、負極として
作用する。ＭＨ極２としては、水素吸蔵合金として作用
するものであれば特に限定はなく、公知の水素吸蔵合金
の成形体を使用できる。ＭＨ極の作製方法は特に限られ
たものではなく、ガス再生のための撥水性と多孔性を備
える様にすれば良い。具体的には、粉末状の水素吸蔵合
金を結着剤で結着してシート状にしたものを集電体上に
ホットプレスしたものをＭＨ極２として使用できる。[MH electrode] 2 is an MH electrode and functions as a negative electrode. The MH electrode 2 is not particularly limited as long as it acts as a hydrogen storage alloy, and a known molded body of hydrogen storage alloy can be used. The method for producing the MH electrode is not particularly limited, and it may be provided with water repellency and porosity for gas regeneration. Specifically, the MH electrode 2 can be obtained by hot pressing a sheet-shaped product obtained by binding a powdery hydrogen storage alloy with a binding agent onto a current collector.
【００１４】用いる水素吸蔵合金としては、ＬａＮｉ5
又はＭｍＭｉ5 をベースとした水素吸蔵合金、例えば、
ＭｍＮｉ3.5 Ｃｏ0.7 Ａｌ0.8 （但し、Ｍｍはミッシュ
メタルを示す）等、ＴｉＮｉ系又はＴｉ（Ｚｒ）Ｎｉ2
ラーベス系の水素吸蔵合金を用いることが出来る。その
粒径は１５０μｍ以下であり、望ましくは７５μｍ以下
である。水素吸蔵合金粉末の粒径が１５０μｍを超える
と表面積が小さくなり再生速度が遅くなり、また、初期
活性化が遅くなる。いずれにしても、水素吸蔵合金は吸
放出サイクルを繰り返すことによって微粉化する。The hydrogen storage alloy used is LaNi 5
Or a hydrogen storage alloy based on MmMi 5 , for example,
MmNi 3.5 Co 0.7 Al 0.8 (where Mm represents misch metal), TiNi-based or Ti (Zr) Ni 2
A Laves-based hydrogen storage alloy can be used. The particle size is 150 μm or less, preferably 75 μm or less. If the particle size of the hydrogen storage alloy powder exceeds 150 μm, the surface area becomes small, the regeneration speed becomes slow, and the initial activation becomes slow. In any case, the hydrogen storage alloy is pulverized by repeating the absorption / desorption cycle.
【００１５】結着剤としては、例えば、ＰＴＦＥ、ＦＥ
Ｐ（テトラフルオロエチレン−ヘキサフルオロプロピレ
ン共重合体）、シリコーンゴム等を用いることができ
る。集電体としては、エキスパンドＮｉ、発泡Ｎｉ、Ｎ
ｉメッシュ等を使用できる。結着剤の混合量は水素吸蔵
合金粉末に対して０．１〜１０重量％であり、好ましく
は１〜５重量％である。これは、０．１％より少ないと
結着性が不十分で放電中に合金が脱落するようになり、
１０％を超えると電気抵抗が大きくなるために放電電圧
が低下するためである。また、集電体の種類によって電
極の機械的強度が変化するので、集電体として発泡Ｎｉ
を使用するならば１％以下で十分であるが、その他のも
の、例えばＮｉメッシュを用いた場合には２〜５％は必
要である。Examples of the binder include PTFE and FE
P (tetrafluoroethylene-hexafluoropropylene copolymer), silicone rubber or the like can be used. As the current collector, expanded Ni, foamed Ni, N
An i-mesh or the like can be used. The amount of the binder mixed is 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the hydrogen storage alloy powder. This is because if it is less than 0.1%, the binding property is insufficient and the alloy comes off during discharge,
This is because if it exceeds 10%, the electric resistance increases and the discharge voltage decreases. In addition, since the mechanical strength of the electrode changes depending on the type of the current collector, foamed Ni is used as the current collector.
If 1% or less is used, 1% or less is sufficient, but if other materials such as Ni mesh are used, 2 to 5% is necessary.
【００１６】ＭＨ電極２は水素ガスを透過できるもので
あり、具体的には、例えば、水素ガスを透過できる多孔
度を有する。ＭＨ電極２の多孔度は１０〜４０％であ
り、好ましくは２０〜３０％である。これは、１０％よ
り低いとガスが透過しにくくなるため再生速度が遅くな
り、４０％を超えると電極のエネルギー密度が低下する
ためである。The MH electrode 2 is permeable to hydrogen gas, and specifically has, for example, a porosity capable of permeable to hydrogen gas. The porosity of the MH electrode 2 is 10 to 40%, preferably 20 to 30%. This is because if it is lower than 10%, it becomes difficult for gas to permeate and the regeneration speed becomes slow, and if it exceeds 40%, the energy density of the electrode is lowered.
【００１７】〔電解液〕６は電解液であり、例えば、６
Ｎ−水酸化カリウム水溶液からなる。[Electrolytic solution] 6 is an electrolytic solution, for example, 6
It consists of an aqueous solution of N-potassium hydroxide.
【００１８】〔電解液室を兼ねた水素室〕 ７は電解液室を兼ねた水素室（以下、水素室と略称す
る）であり、ＭＨ極２に接するように備えられている。
水素室７は、ガス再生時に水素ガスを導入するためのガ
ス導入口３を有する。水素室７は、放電時又は電気化学
充電時には電解液６で満たされている。ガス再生時には
水素室７に水素ガスを加圧導入し、水素室７から電解液
を排出し、ＭＨ極２中に水素ガスを透過させることによ
り電気化学的充電と同等な再生速度で充電することがで
きる。水素室７の形成方法については、ＭＨ極２に接す
る他は、特に限定はなく、ＭＨ極２と、必要に応じて、
任意の絶縁体とで形成することができ、その形状、大き
さについても適宜選定することができる。[Hydrogen chamber also serving as electrolyte chamber] 7 is a hydrogen chamber also serving as an electrolyte chamber (hereinafter abbreviated as hydrogen chamber), and is provided so as to be in contact with the MH electrode 2.
The hydrogen chamber 7 has a gas inlet 3 for introducing hydrogen gas during gas regeneration. The hydrogen chamber 7 is filled with the electrolytic solution 6 during discharging or during electrochemical charging. At the time of gas regeneration, hydrogen gas is introduced under pressure into the hydrogen chamber 7, the electrolytic solution is discharged from the hydrogen chamber 7, and the hydrogen gas permeates into the MH electrode 2 to charge at a regeneration rate equivalent to electrochemical charging. You can The method for forming the hydrogen chamber 7 is not particularly limited except that it is in contact with the MH electrode 2, and the MH electrode 2 and, if necessary,
It can be formed of any insulator, and its shape and size can be appropriately selected.
【００１９】〔第三電極を兼ねた金属多孔質体〕５は金
属多孔体であり、ガス再生時にガス導入口３から流入す
る水素ガスが、金属多孔体５を透過して水素室７に導入
されるように備えられている。金属多孔体５は、電気化
学充電の際に第三電極として利用される。第三電極兼金
属多孔体５は特に限られたものではなく、Ｎｉ製多孔体
を用いることが出来る。Ｎｉ製多孔体としては、発泡Ｎ
ｉ、Ｎｉメッシュ、Ｎｉ繊維等を用いることが出来る。[Metallic porous body also serving as the third electrode] 5 is a metallic porous body, and hydrogen gas flowing from the gas inlet 3 at the time of gas regeneration is introduced into the hydrogen chamber 7 through the metallic porous body 5. Be prepared to be done. The metallic porous body 5 is used as a third electrode during electrochemical charging. The third electrode / metal porous body 5 is not particularly limited, and a Ni porous body can be used. As the Ni porous body, foamed N
i, Ni mesh, Ni fiber, etc. can be used.
【００２０】〔多孔性シート〕ＭＨ極の空気極側には、
ＭＨ極に接した多孔性シート１４が配置されており、ガ
ス再生時に水素室７に導入された水素ガスは、ＭＨ電極
２を透過し、更に多孔性シート１４を透過する。該多孔
体シートは、ＭＨ極を透過した水素ガスをＭＨ極表面上
に留まること無く、外部へ排出させる様に作用する。図
２に、本発明の空気ＭＨ電池のガス再生時に水素がＭＨ
極２及び多孔性シート１４を透過する様子を模式的に示
す。多孔性シート１４は特に限られたものではなく、多
孔質なものであれば材質は金属でも樹脂でも構わない
が、その孔径は５０μｍ以上であり、特に２００μｍ以
上であることが望ましい。これは、５０μｍより小さい
と水素の気泡が拡散しにくくなりＭＨ極に応力が加わり
破損の可能性が高まるからである。[Porous Sheet] On the air electrode side of the MH electrode,
The porous sheet 14 in contact with the MH electrode is arranged, and the hydrogen gas introduced into the hydrogen chamber 7 during gas regeneration passes through the MH electrode 2 and further through the porous sheet 14. The porous sheet acts so as to discharge the hydrogen gas that has permeated the MH electrode to the outside without staying on the surface of the MH electrode. FIG. 2 shows that when the gas of the air MH battery of the present invention is regenerated, hydrogen is MH.
A state of permeation through the electrode 2 and the porous sheet 14 is schematically shown. The porous sheet 14 is not particularly limited, and the material may be metal or resin as long as it is porous, but the pore diameter is preferably 50 μm or more, and particularly preferably 200 μm or more. This is because if it is less than 50 μm, hydrogen bubbles are less likely to diffuse, stress is applied to the MH pole, and the possibility of breakage increases.
【００２１】〔ガス排出口〕４はガス排出口であり、ガ
ス再生時に、多孔体シート１４を透過した水素ガスを外
部に排出するように備えられている。The [gas discharge port] 4 is a gas discharge port, and is provided so as to discharge the hydrogen gas that has permeated the porous sheet 14 to the outside when the gas is regenerated.
【００２２】〔セパレーター〕１２は空気極１とＭＨ極
２との間に備えられた空気極側セパレーターである。空
気極側セパレーター１２は親水性セパレーターであり、
特に限られたものではなく親水性で水素ガスを透過させ
なければ良い。空気極側セパレーター１２は、ＭＨ極２
を透過した水素ガスが空気極１側に透過することを防止
することにより、水素ガスにより空気極１が破損するこ
とを防止する。親水性セパレーターとしては、セルロー
ス膜、微細孔ポリマーフィルム、非多孔性ポリマーフィ
ルム、イオン交換膜等を用いることが出来る（特願平６
−６２３６２号の明細書参照）。また、空気極側セパレ
ーター１２として、水素ガスが透過しにくい親水性セパ
レーターと絶縁シートを一体化した複合膜を用いること
が出来る。[Separator] 12 is an air electrode side separator provided between the air electrode 1 and the MH electrode 2. The air electrode side separator 12 is a hydrophilic separator,
The material is not particularly limited, and may be hydrophilic and may not permeate hydrogen gas. The air electrode side separator 12 is the MH electrode 2
By preventing the hydrogen gas that has permeated the hydrogen gas from permeating to the side of the air electrode 1, the hydrogen electrode is prevented from being damaged by the hydrogen gas. As the hydrophilic separator, it is possible to use a cellulose membrane, a microporous polymer film, a non-porous polymer film, an ion exchange membrane, etc.
-62362). Further, as the air electrode side separator 12, a composite film in which a hydrophilic separator, which is hard to permeate hydrogen gas, and an insulating sheet are integrated can be used.
【００２３】１３はＭＨ極２と第三電極兼金属多孔体５
との間に備えられた第三電極側セパレーターである。第
三電極側セパレーター１３としては、例えば、親水化処
理したポリプロピレン製のものを使用できる。なお、第
三電極側セパレーター１３は、ガス再生時に水素ガスを
透過する。Reference numeral 13 denotes the MH electrode 2 and the third electrode / metal porous body 5
And a third electrode side separator provided between and. As the third electrode side separator 13, for example, a hydrophilized polypropylene product can be used. The third electrode side separator 13 allows hydrogen gas to permeate during gas regeneration.
【００２４】〔その他〕８はガス再生時に水素室７に水
素ガスを供給する水素ボンベであり、９は水素室７内の
圧力ゲージである。１０は、排出口４から排出された水
素を回収して再び水素室７へ送り込むコンプレッサーで
ある。１１は電極フレームである。[Others] 8 is a hydrogen cylinder for supplying hydrogen gas to the hydrogen chamber 7 during gas regeneration, and 9 is a pressure gauge in the hydrogen chamber 7. Reference numeral 10 denotes a compressor that collects the hydrogen discharged from the discharge port 4 and sends it to the hydrogen chamber 7 again. Reference numeral 11 is an electrode frame.
【００２５】ガス再生方法 本発明の空気−ＭＨ電池は、ＭＨ極のみを充電すれば良
い。その充電方法としては、空気極又は第三電極を用い
て充電する電気化学充電方法を採用することも、また、
水素ガスで充電するガス再生方法を採用することもでき
る。 Gas Regeneration Method In the air-MH battery of the present invention, only the MH electrode needs to be charged. As the charging method, it is also possible to adopt an electrochemical charging method of charging using an air electrode or a third electrode,
A gas regeneration method of charging with hydrogen gas can also be adopted.
【００２６】ガス再生方法においては、水素室７に外部
から水素ガスを加圧導入し、水素室７から電解液を排出
し、更に水素室７に導入した水素ガスをＭＨ極２に透過
させてＭＨ極２と反応させることによって充電する。水
素室７に水素ガスを加圧導入する際のガス圧（Ｐ）は特
に規定しないが、水素室７から電解液６を排出できる最
低圧力（Ｐ0 ）であればよく、Ｐ0 ＋Ｐが５ｋｇｆ／ｃ
ｍ2 以下であることが望ましい。この値が、５ｋｇｆ／
ｃｍ2 より高いとＭＨ極、セパレーター、空気極が破損
する可能性があるためである。In the gas regenerating method, hydrogen gas is introduced from the outside into the hydrogen chamber 7 under pressure, the electrolytic solution is discharged from the hydrogen chamber 7, and the hydrogen gas introduced into the hydrogen chamber 7 is permeated to the MH electrode 2. It is charged by reacting with the MH pole 2. The gas pressure (P) at the time of introducing the hydrogen gas under pressure into the hydrogen chamber 7 is not particularly specified, but may be the lowest pressure (P 0 ) at which the electrolytic solution 6 can be discharged from the hydrogen chamber 7, and P 0 + P is 5 kgf. / C
m 2 or less. This value is 5 kgf /
This is because if it is higher than cm 2 , the MH electrode, the separator and the air electrode may be damaged.
【００２７】[0027]
【発明の効果】本発明の空気−ＭＨ電極はガス再生時に
ＭＨ極中を水素ガスが透過することによって、ＭＨ極と
水素の反応が円滑に進行し電気化学的充電と同等な再生
が可能であり、セパレーターや支持体を配することによ
って空気極が破損しない。EFFECTS OF THE INVENTION In the air-MH electrode of the present invention, hydrogen gas permeates the MH electrode during gas regeneration, whereby the reaction between the MH electrode and hydrogen proceeds smoothly, and regeneration similar to electrochemical charging is possible. Yes, by arranging the separator and support, the air electrode is not damaged.
【００２８】[0028]
【実施例】図１に示した本発明の空気−ＭＨ電池を用い
ての充放電試験を行ったので、その結果を表１に示す。
本実施例において、空気極１はＮｉ焼結体に銀触媒を担
持したもので、ＰＴＦＥにより撥水化処理されたいる。
ＭＨ極２はＭｍＮｉ3.5 Ｃｏ0.7 Ａｌ0.8 粉末をＰＴＦ
Ｅ（ダイキン工業（株）製、ＰＴＦＥディスパージョン
Ｄ−２）で結着してシート状にしたものをエキスパンド
Ｎｉ上にポットプレスしたものである。第三電極兼金属
多孔体５は発泡Ｎｉ製である。電解液は６Ｎ−水酸化カ
リウム水溶液からなる。空気極側（親水性）セパレータ
ー１２はセルロース膜からなる。第三電極側セパレータ
ー１３は親水化処理したポリプロピレン製である。空気
極（多孔性）支持体１５はテフロン樹脂製の薄板を格子
上に張り付けたものである。EXAMPLE A charge / discharge test was conducted using the air-MH battery of the present invention shown in FIG. 1, and the results are shown in Table 1.
In this embodiment, the air electrode 1 is a Ni sintered body carrying a silver catalyst, and is made water repellent by PTFE.
MH pole 2 PTF the MmNi 3.5 Co 0.7 Al 0.8 powder
The sheet was formed by binding with E (PTFE Dispersion D-2, manufactured by Daikin Industries, Ltd.) to form a sheet, which was pot-pressed on Expanded Ni. The third electrode / metal porous body 5 is made of foamed Ni. The electrolytic solution is a 6N-potassium hydroxide aqueous solution. The air electrode side (hydrophilic) separator 12 is made of a cellulose film. The third electrode side separator 13 is made of hydrophilized polypropylene. The air electrode (porous) support 15 is a thin plate made of Teflon resin attached on a grid.
【００２９】ＭＨ極１は容量既知の焼結式Ｎｉ極との組
み合わせで容量９６０ｍＡｈであったため、ガス再生の
場合には１．２ｋｇｆ／ｃｍ2 の水素ガスを規定時間流
して行い、電気化学充電は１９２ｍＡ（０．２Ｃ）で６
時間行い、３０分の休止後、放電は１９２ｍＡでＭＨ極
の電位が−０．６Ｖ（酸化水銀電極基準）になるまで行
った。Since the MH electrode 1 had a capacity of 960 mAh in combination with a sintered Ni electrode of known capacity, 1.2 kgf / cm 2 of hydrogen gas was flowed for a specified time in the case of gas regeneration, and electrochemical charging was performed. Is 6 at 192 mA (0.2 C)
After the rest for 30 minutes, the discharge was performed at 192 mA until the potential of the MH electrode became −0.6 V (based on the mercury oxide electrode).
【００３０】[0030]
【表１】ガス再生速度 ガス再生時間（ｈ） 放電容量（ｍＡｈ） 再生割合（％） ０．５ ３８４ ４０ １ ６７２ ７０ ６ ９６０ １００ 電気化学充電 ９６０ １００ ガス再生時において空気極、ＭＨ極共に破損は見られ
ず、電気化学的充電とガス再生の両方が同等に行える電
池が得られた。[Table 1] Gas regeneration rate Gas regeneration time (h) Discharge capacity (mAh) Regeneration rate (%) 0.5 384 40 1 672 706 6 960 100 Electrochemical charging 960 100 Both air electrode and MH electrode were damaged during gas regeneration It was not found, and a battery was obtained that could perform both electrochemical charging and gas regeneration equally.
【図１】 本発明の空気−ＭＨ電池の実施例の断面図で
ある。FIG. 1 is a cross-sectional view of an example of an air-MH battery of the present invention.
【図２】 本発明の空気−ＭＨ電池のガス再生時にＭＨ
極を水素が透過する様子を模式的に示した断面図であ
る。[Fig. 2] MH during gas regeneration of the air-MH battery of the present invention
FIG. 6 is a cross-sectional view schematically showing how hydrogen permeates through the electrodes.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 上原 斎 大阪府池田市緑丘１丁目８番31号 工業 技術院大阪工業技術研究所内 (72)発明者 川瀬 哲也 愛知県刈谷市豊田町２丁目１番地 株式 会社豊田自動織機製作所内 審査官 酒井 美知子 (56)参考文献 特開 平５−290873（ＪＰ，Ａ) 特開 昭51−62339（ＪＰ，Ａ) 特開 昭47−19333（ＪＰ，Ａ) 実公 昭51−52030（ＪＰ，Ｙ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Sai Uehara 8-31 Midorigaoka, Ikeda-shi, Osaka Inside Institute of Industrial Science and Technology, Industrial Technology Institute (72) Tetsuya Kawase 2-chome, Toyota-cho, Kariya city, Aichi prefecture Michiko Sakai, Examiner, Toyota Industries Corporation (56) References JP-A-5-290873 (JP, A) JP-A-51-62339 (JP, A) JP-A-47-19333 (JP, A) Actual Public Sho 51-52030 (JP, Y2)
Claims (7)
水素吸蔵合金極を用いる空気−金属水素化物二次電池に
おいて、水素吸蔵合金極が水素ガスを透過できる多孔度
を有し、水素吸蔵合金極と接した電解液室を兼ねた水素
室を有し且つガス再生時に水素吸蔵合金極中を透過した
水素ガスを排出するための水素ガス排出口を備えたこと
を特徴とする空気−金属水素化物二次電池。 1. An air-metal hydride secondary battery in which an air electrode is used as a positive electrode and a hydrogen storage alloy electrode is used as a negative electrode, and the hydrogen storage alloy electrode has a porosity capable of transmitting hydrogen gas.
The a, transmitted through the hydrogen-absorbing alloy electrode when an organic and and gas regeneration hydrogen chamber which also serves as a electrolyte chamber in contact with the hydrogen storage alloy electrode
Air characterized by comprising a hydrogen gas outlet for discharging hydrogen gas - metal hydride rechargeable batteries.
極を兼ねた金属多孔質体を有する請求項１に記載の空気
−金属水素化物二次電池。2. The air-metal hydride secondary battery according to claim 1, wherein the hydrogen gas introducing portion of the hydrogen chamber has a metal porous body that also serves as a third electrode for charging.
した過剰な水素ガスを回収し再度水素室に導入するため
の装置を備えた請求項１に記載の空気−金属水素化物二
次電池。3. The air-metal hydride secondary battery according to claim 1, further comprising a device for recovering excess hydrogen gas that has permeated the hydrogen storage alloy electrode and reintroducing it into the hydrogen chamber during gas regeneration. .
を備えた請求項１に記載の空気−金属水素化物二次電池
において、水素吸蔵合金極と空気極との間に水素ガスを
透過させない親水性セパレーターを有する空気−金属水
素化物二次電池。4. The air-metal hydride secondary battery according to claim 1, further comprising a hydrogen storage alloy electrode provided between the hydrogen chamber and the air electrode, wherein hydrogen gas is provided between the hydrogen storage alloy electrode and the air electrode. air having a <br/> transmitted so that not hydrophilic separator - metal hydride rechargeable batteries.
を備えた請求項１に記載の空気−金属水素化物二次電池
において、水素吸蔵合金極の空気極側に多孔性シートを
配した空気−金属水素化物二次電池。5. The air-metal hydride secondary battery according to claim 1, further comprising a hydrogen storage alloy electrode between the hydrogen chamber and the air electrode, wherein a porous sheet is provided on the air electrode side of the hydrogen storage alloy electrode. Arranged air-metal hydride secondary battery.
を備えた請求項１に記載の空気−金属水素化物二次電池
において、水素吸蔵合金極と空気極との間に、水素ガス
を透過させない親水性セパレーターの空気極側を多孔体
で支持して水素ガス圧による破損を防ぐ構造を有する空
気−金属水素化物二次電池。6. The air-metal hydride secondary battery according to claim 1, further comprising a hydrogen storage alloy electrode between the hydrogen chamber and the air electrode, wherein hydrogen is provided between the hydrogen storage alloy electrode and the air electrode. gas
The air electrode side of the have a not transmit hydrophilic separator is supported by a porous body of air having a structure to prevent damage caused by the hydrogen gas pressure - metal hydride rechargeable batteries.
水素ガス圧による破損を防ぐ構造を有した請求項１に記
載の空気−金属水素化物二次電池。7. A porous support is arranged on the air side of the air electrode,
The air-metal hydride secondary battery according to claim 1, having a structure that prevents damage due to hydrogen gas pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6073487A JP2673337B2 (en) | 1994-04-12 | 1994-04-12 | Air-metal hydride secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6073487A JP2673337B2 (en) | 1994-04-12 | 1994-04-12 | Air-metal hydride secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07282861A JPH07282861A (en) | 1995-10-27 |
| JP2673337B2 true JP2673337B2 (en) | 1997-11-05 |
Family
ID=13519693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6073487A Expired - Lifetime JP2673337B2 (en) | 1994-04-12 | 1994-04-12 | Air-metal hydride secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2673337B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100470471B1 (en) | 2000-08-22 | 2005-02-05 | 히다치 막셀 가부시키가이샤 | Air - Hydrogen cell |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5152030U (en) * | 1974-10-16 | 1976-04-20 | ||
| JPS5629337B2 (en) * | 1974-11-28 | 1981-07-08 | ||
| JPH05290873A (en) * | 1992-04-14 | 1993-11-05 | Yuasa Corp | Air-hydrogen battery |
| JP3272075B2 (en) * | 1993-01-25 | 2002-04-08 | 三洋電機株式会社 | Air-hydride batteries |
-
1994
- 1994-04-12 JP JP6073487A patent/JP2673337B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07282861A (en) | 1995-10-27 |
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