JPH0642376B2 - Metal-hydrogen secondary battery - Google Patents
Metal-hydrogen secondary batteryInfo
- Publication number
- JPH0642376B2 JPH0642376B2 JP60246673A JP24667385A JPH0642376B2 JP H0642376 B2 JPH0642376 B2 JP H0642376B2 JP 60246673 A JP60246673 A JP 60246673A JP 24667385 A JP24667385 A JP 24667385A JP H0642376 B2 JPH0642376 B2 JP H0642376B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- electrode
- microporous film
- hydrogen
- negative 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 - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 (イ)産業上の利用分野 本発明は水素を吸蔵及び放出することのできる水素吸蔵
合金を備えた負極と、水酸化ニツケルなどの金属酸化物
を活物質とする正極を備えた金属−水素二次電池に関す
る。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a negative electrode provided with a hydrogen storage alloy capable of storing and releasing hydrogen, and a positive electrode using a metal oxide such as nickel hydroxide as an active material. And a metal-hydrogen secondary battery provided with.
(ロ)従来の技術 従来からよく用いられる二次電池としては鉛電池及びニ
ツケル−カドミウム電池があるが、近年これら電池より
軽量で且つ高容量となる可能性があるということで、特
に低圧で負極活物質である水素を可逆的に吸蔵及び放出
する水素吸蔵合金を備えた電極を負極に用い、水酸化ニ
ツケルからなる正極活物質を備えた電極を正極に用いた
金属ー水素二次電池が注目されている。一般にこの種蓄
電池は特公昭５８−４６８２７号公報に於いて示される
ように、水素吸蔵合金を備えた水素吸蔵電極と、正極と
の間にセパレータを介して構成されており、充電時や保
存時に正極から発生する酸素ガスは、充電状態の負極、
すなわち水素吸蔵電極中の水素吸蔵合金に吸蔵した水素
と反応して消費される構成となっている。ところが、酸
素は水素吸蔵合金中の水素と反応して水になると共に、
水素吸蔵合金と直接反応して水素吸蔵合金の組成を化学
的に変化させ、この化学的変化によって水素吸蔵合金は
水素吸蔵能力を失うため、負極の容量が低下し長期にわ
たって高容量を維持することができず、特に保存特性が
悪かった。(B) Conventional technology There are lead batteries and nickel-cadmium batteries as rechargeable batteries that have been often used in the past.However, since these batteries are lighter in weight and have a higher capacity than these batteries in recent years, especially at low voltage A metal-hydrogen secondary battery that uses an electrode with a hydrogen storage alloy that reversibly absorbs and desorbs hydrogen, which is the active material, as the negative electrode and an electrode with a positive electrode active material made of nickel hydroxide as the positive electrode Has been done. Generally, as shown in Japanese Patent Publication No. 58-46827, this type of storage battery is constituted by a separator between a hydrogen storage electrode provided with a hydrogen storage alloy and a positive electrode, and is used during charging or storage. Oxygen gas generated from the positive electrode is the charged negative electrode,
That is, the hydrogen storage alloy in the hydrogen storage electrode is consumed by reacting with the stored hydrogen. However, oxygen reacts with hydrogen in the hydrogen storage alloy to form water, and
The composition of the hydrogen storage alloy is chemically changed by directly reacting with the hydrogen storage alloy, and the hydrogen storage alloy loses its hydrogen storage capacity due to this chemical change, so the capacity of the negative electrode decreases and the high capacity is maintained for a long time. Was not possible, and especially the storage characteristics were poor.
(ハ)発明が解決しようとする問題点 本発明は水素吸蔵合金を主体とする負極を備えた金属ー
水素二次電池の容量の低下を抑制し保存特性の改良及び
サイクル寿命の向上を図ったものである。(C) Problems to be Solved by the Invention The present invention aims to improve the storage characteristics and the cycle life by suppressing the decrease in the capacity of the metal-hydrogen secondary battery having the negative electrode mainly composed of the hydrogen storage alloy. It is a thing.
(ニ)問題点を解決するための手段 上記目的を達成するための本発明に係る金属ー水素二次
電池は、水素吸蔵合金を主体とする負極と、正極とを備
え、少なくとも一方の電極に近傍する位置にガス透過性
の小さい合成樹脂製の微孔性フィルムを配したものであ
る。(D) Means for Solving the Problems The metal-hydrogen secondary battery according to the present invention for achieving the above object comprises a negative electrode mainly composed of a hydrogen storage alloy, and a positive electrode, and at least one of the electrodes. A microporous film made of synthetic resin having a small gas permeability is arranged in the vicinity thereof.
(ホ)作用 水素吸蔵合金を主体とする負極と金属酸化物を活物質と
する正極の少なくとも一方の電極に近接した位置にガス
透過性の小さい合成樹脂製の微孔性フイルムを配すと、
充電時及び保存時に於いて正極から発生する酸素が負極
に到達することを抑制でき、負極の水素吸蔵合金が酸素
と反応することによる容量低下を抑えることができる。(E) Action When a microporous film made of a synthetic resin having a small gas permeability is arranged at a position close to at least one electrode of a negative electrode mainly composed of a hydrogen storage alloy and a positive electrode having a metal oxide as an active material,
Oxygen generated from the positive electrode can be prevented from reaching the negative electrode during charging and storage, and the reduction in capacity due to the reaction of the hydrogen storage alloy of the negative electrode with oxygen can be suppressed.
(ヘ)実施例 水素吸蔵能力を有するＬａＮｉ５を機械的に粉砕して微
粉化し、このＬａＮｉ５粉末に小さなせん断力で粒子が
簡単に繊維化し塑性変形するポリテトラフルオロエチレ
ン粉末を、ＬａＮｉ５粉末の重量に対して１〜５％添加
して混合機で均一に混合すると共にポリテトラフルオロ
エチレンを繊維化する。次いでこうして得られたポリテ
トラフルオロエチレンが繊維化した混合物に水を加えて
ペースト状とした後、ニツケルメツキを施したパンチン
グメタルからなる集電体の両面に貼り付けて水素吸蔵電
極を得る。第１図に示すようにこの水素吸蔵電極(1)を
ポリプロピレン微孔性フイルム(2)で包み、放電容量が
１２００mAHの焼結式ニツケル正極(3)と前記微孔性フイ
ルム(2)で包んだ水素吸蔵電極(1)との間にセパレータ
(4)を介して巻回して渦巻電極体を構成し、電池外装缶
にこの電極体を挿入した後アルカリ電解液を注入し封口
を行なって本発明のニツケル−水素二次電池(A)を作製
した。(F) Example micronized mechanically grinding the LaNi 5 having a hydrogen storage capacity, the polytetrafluoroethylene powder particles with a small shear force to the LaNi 5 powder is easily fibrillated plastic deformation, LaNi 5 powder 1 to 5% with respect to the weight of the above, and uniformly mixed with a mixer, and polytetrafluoroethylene is made into fibers. Then, water is added to the thus obtained mixture of polytetrafluoroethylene to form a fiber to form a paste, and the mixture is attached to both sides of a nickel-plated current collector made of punching metal to obtain a hydrogen storage electrode. As shown in Fig. 1, this hydrogen storage electrode (1) is wrapped with a polypropylene microporous film (2), and a sintered nickel positive electrode (3) with a discharge capacity of 1200 mAH and the microporous film (2). Separator between the hydrogen storage electrode (1)
(4) to form a spirally wound electrode body, insert the electrode body into the battery outer can and then inject the alkaline electrolyte to seal the nickel-hydrogen secondary battery (A) of the present invention. It was made.
また前記電池(A)に於いてニツケル正極をポリプロピレ
ン微孔性フイルムで包み、水素吸蔵電極はポリプロピレ
ン微孔性フイルムで包まないで同様にして本発明電池
(B)、前記電池(A)に於いてニツケル正極及び水素吸蔵電
極の何れもポリプロピレン微孔性フイルムで包んで同様
にして本発明電池(C)、比較として前記電池(A)に於いて
ニツケル正極及び水素吸蔵電極の何れもポリプロピレン
微孔性フイルムで包まないで比較電池(D)を夫々作製し
た。Further, in the battery (A), the nickel positive electrode was wrapped with a polypropylene microporous film, and the hydrogen storage electrode was not wrapped with a polypropylene microporous film.
(B), in the battery (A), both the nickel positive electrode and the hydrogen storage electrode were wrapped with a polypropylene microporous film in the same manner as the battery (C) of the present invention, and in the battery (A) as a comparison, nickel was used. A comparative battery (D) was prepared by wrapping neither the positive electrode nor the hydrogen storage electrode with the polypropylene microporous film.
これら電池(A)乃至(D)を１２０mAで１６時間充電し、次
いで２４０mAで電池電圧が１．０Ｖになるまで放電する
充放電サイクルを数回行なって初期活性化を完了した
後、１２０mAで１６時間充電して放置し、放置時間と残
存容量との関係を調べ、この結果を初期容量を夫々１０
０として第２図に示した。尚、残存容量は一定期間放置
後に２４０mAで放電して測定した。また第３図は前記放
置を１ケ月行なった後電池(A)乃至(D)を夫々前記充放電
サイクルによって充放電を繰り返し行なって測定したサ
イクル特性図である。Charge these batteries (A) to (D) at 120mA for 16 hours, then discharge the batteries at 240mA until the battery voltage reaches 1.0V. After charging for an hour and leaving it for a while, the relationship between the leaving time and the remaining capacity is investigated, and this result is used as the initial capacity of 10
It is shown as 0 in FIG. The remaining capacity was measured by discharging at 240 mA after standing for a certain period. Further, FIG. 3 is a cycle characteristic diagram measured by repeating charging / discharging of the batteries (A) to (D) by the charging / discharging cycle after leaving them for one month.
これらの図面から明らかなように本発明電池(A)乃至(C)
は比較電池(D)に比べて放置による容量の低下が小さく
抑えられ、また放置後のサイクル寿命が長く優れたもの
であることがわかる。As apparent from these drawings, the batteries of the present invention (A) to (C)
It can be seen that, compared with the comparative battery (D), the decrease in capacity due to leaving is suppressed to a small extent, and the cycle life after leaving is long and excellent.
負極に用いた水素吸蔵電極は、従来から用いられてきた
カドミウム負極とは異なり満充電時には極めて活性であ
り、酸素と接触すると非常に速い速度で反応して酸化す
る。そしてこの酸化に於いて酸素は水素吸蔵合金に吸蔵
された水素と反応して水になると共に、水素吸蔵合金と
反応して水素吸蔵合金をしばしば組成の異なる他の物質
に変化させる。つまり、上記実施例に於いては放置した
間にＬａＮｉ５がＬａ２Ｏ３、Ｌａ（ＯＨ）３やＮｉ、
ＮｉＯ、Ｎｉ（ＯＨ）２に変化することにより水素吸蔵
能力を失い、以後充放電を繰り返してもＬａＮｉ５に戻
ることはない。比較電池(D)では正極から充電時及び放
置時に発生した酸素が容易に負極に到達するため容量の
低下が大きく、また負極中の水素吸蔵合金の組成変化も
多く生じるため、放置後は充放電サイクルの経過に伴う
容量低下も大きくなっている。これに対して本発明電池
(A)では負極に近接して配した微孔性フイルムにより酸
素ガスが負極に到達することを妨げ、また本発明電池
(B)では正極に近接して配した微孔性フイルムにより酸
素がセパレータ中に滞留するのを防いでいるものと考え
られ、何れも比較電池より優れた特性を示している。特
に本発明電池(C)では正極と負極の両方に夫々近接して
微孔性フイルムを配しており酸素と負極の反応がより一
層抑えられたと考えられ、本発明電池(A)及び(B)より放
置時の容量の低下が小さく、また放置後のサイクル特性
も良好になっている。Unlike the cadmium negative electrode that has been used conventionally, the hydrogen storage electrode used for the negative electrode is extremely active when fully charged, and when it contacts oxygen, it reacts and oxidizes at a very fast rate. Then, in this oxidation, oxygen reacts with hydrogen stored in the hydrogen storage alloy to become water, and also reacts with the hydrogen storage alloy to change the hydrogen storage alloy into another substance often having a different composition. That is, in the above-described embodiment, LaNi 5 was replaced with La 2 O 3 , La (OH) 3 and Ni while being left standing.
The hydrogen storage capacity is lost by changing to NiO or Ni (OH) 2 and does not return to LaNi 5 even after repeating charging and discharging. In the comparative battery (D), oxygen generated during charging and leaving from the positive electrode easily reaches the negative electrode, resulting in a large decrease in capacity, and because the composition of the hydrogen storage alloy in the negative electrode also changes a lot, charging and discharging after standing. The decrease in capacity with the progress of cycles is also increasing. On the other hand, the battery of the present invention
In (A), the microporous film disposed close to the negative electrode prevents oxygen gas from reaching the negative electrode,
In (B), it is considered that the microporous film disposed close to the positive electrode prevents oxygen from staying in the separator, and each of them shows superior characteristics to the comparative battery. Especially in the present invention battery (C), it is considered that the reaction between oxygen and the negative electrode was further suppressed by disposing the microporous film in close proximity to both the positive electrode and the negative electrode, and the present invention batteries (A) and (B ), The decrease in capacity after leaving is small, and the cycle characteristics after leaving are also good.
尚、実施例では水素吸蔵合金にＬａＮｉ５を用いたが、
他の水素吸蔵合金を用いた場合にも同様の効果が得られ
る。またガス透過性の小さい微孔性フイルムは孔径が５
μｍ以下なら使用可能であり、親水性のフイルムである
ことが好ましいが、疎水性のフイルムであっても表面処
理を行ない親水性を付与すると使用可能である。Although LaNi 5 was used as the hydrogen storage alloy in the examples,
Similar effects can be obtained when other hydrogen storage alloys are used. A microporous film having a small gas permeability has a pore size of 5
If it is less than or equal to μm, it can be used, and it is preferably a hydrophilic film, but even a hydrophobic film can be used if surface treatment is performed to impart hydrophilicity.
(ト)発明の効果 本発明の金属ー水素二次電池は、水素吸蔵合金を主体と
する負極と金属酸化物を活物質とする正極とを備え、少
なくとも一方の電極に近接する位置にガス透過性の小さ
い合成樹脂製の微孔性フイルムを配したものであり、前
記合成樹脂製の微孔性フイルムによって充電時及び放置
時に正極から発生する酸素ガスが負極に到達するのを抑
制することができ、負極が電池内で酸素と反応すること
による放置時の容量低下の抑制及びサイクル寿命の向上
を行なうことができる。(G) Effect of the Invention A metal-hydrogen secondary battery of the present invention includes a negative electrode mainly composed of a hydrogen storage alloy and a positive electrode mainly composed of a metal oxide, and has gas permeation at a position close to at least one electrode. A synthetic resin microporous film having a small property is arranged, and the synthetic resin microporous film can prevent oxygen gas generated from the positive electrode from reaching the negative electrode during charging and during standing. Therefore, it is possible to suppress a decrease in capacity when left standing due to the negative electrode reacting with oxygen in the battery and to improve cycle life.
第１図は本発明電池の正負極、セパレータ及び微孔性フ
イルムの配置を示す図面、第２図は電池の放置日数と残
存容量との関係を示す保存特性図、第３図は１ケ月放置
後のサイクル特性図である。 (1)……水素吸蔵電極、(2)……微孔性フイルム、(3)…
…ニツケル正極、(4)……セパレータ。FIG. 1 is a drawing showing the arrangement of the positive and negative electrodes, separator and microporous film of the battery of the present invention, FIG. 2 is a storage characteristic diagram showing the relationship between the number of days left of the battery and the remaining capacity, and FIG. 3 is left for one month. It is a subsequent cycle characteristic diagram. (1) …… Hydrogen storage electrode, (2) …… Microporous film, (3)…
… Nickel positive electrode, (4) …… Separator.
Claims (2)
を備え、少なくとも一方の電極に近傍する位置にガス透
過性の小さい合成樹脂製の微孔性フィルムを配したこと
を特徴とする金属−水素二次電池。1. A negative electrode mainly composed of a hydrogen storage alloy, and a positive electrode, wherein a microporous film made of synthetic resin having a small gas permeability is arranged at a position near at least one of the electrodes. Metal-hydrogen secondary battery.
性フィルムである特許請求の範囲第１項記載の金属−水
素二次電池。2. The metal-hydrogen secondary battery according to claim 1, wherein the microporous film is a polypropylene microporous film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60246673A JPH0642376B2 (en) | 1985-11-01 | 1985-11-01 | Metal-hydrogen secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60246673A JPH0642376B2 (en) | 1985-11-01 | 1985-11-01 | Metal-hydrogen secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62108468A JPS62108468A (en) | 1987-05-19 |
| JPH0642376B2 true JPH0642376B2 (en) | 1994-06-01 |
Family
ID=17151911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60246673A Expired - Lifetime JPH0642376B2 (en) | 1985-11-01 | 1985-11-01 | Metal-hydrogen secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0642376B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0821378B2 (en) * | 1984-06-22 | 1996-03-04 | 松下電器産業株式会社 | Nickel-hydrogen storage battery |
-
1985
- 1985-11-01 JP JP60246673A patent/JPH0642376B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62108468A (en) | 1987-05-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |