JPS6222370A - Nickel-hydrogen alkaline storage battery - Google Patents
Nickel-hydrogen alkaline storage batteryInfo
- Publication number
- JPS6222370A JPS6222370A JP60161401A JP16140185A JPS6222370A JP S6222370 A JPS6222370 A JP S6222370A JP 60161401 A JP60161401 A JP 60161401A JP 16140185 A JP16140185 A JP 16140185A JP S6222370 A JPS6222370 A JP S6222370A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- alloy
- hydrogen
- negative electrode
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/242—Hydrogen storage electrodes
-
- 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
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、水素を可逆的に吸蔵・放出する合金からなる
水素吸蔵電極を負極とし、酸化ニッケル電極を正極とす
るニッケル−水素蓄電池に関するものて、とくにその負
極の改良に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a nickel-hydrogen storage battery in which the negative electrode is a hydrogen storage electrode made of an alloy that reversibly stores and releases hydrogen, and the positive electrode is a nickel oxide electrode. Especially regarding the improvement of the negative electrode.
従来の技術
可逆的に水素を吸蔵・放出する合金（水素吸蔵合金と云
う）を用いる水素吸蔵電極を負極とするアルカリ蓄電池
において、このアルカリ蓄電池の充・放電サイクルによ
って、負極を構成する水素吸蔵合金又は水素化物が細分
化し、電極支持体から脱落したり、膨張や亀裂をおこし
、電池性能の低下がおこる。この現象はとくに開放型ア
ルカリ蓄電池に顕著に現われる。そこで、水素吸蔵合金
粉末の表面に銅（Ｃｕ）を被覆する事によって上記の問
題点を解決しようとする試みが提案されている（特開昭
５０−１１１５４６号）。すなわち、水素吸蔵合金粉末
の表面に銅の無電解メッキを施こす事により、合金自体
を保護すると共に合金自体の機械的強度と電気伝導性の
増大を図っている蓄電池陰極が提案されており、この水
素吸蔵電極を負極とし、セパレータを介して公知のニッ
ケル正極と組合わせてアルカリ蓄電池が考えられている
。Conventional technology In an alkaline storage battery whose negative electrode is a hydrogen storage electrode that uses an alloy that reversibly stores and releases hydrogen (referred to as a hydrogen storage alloy), the hydrogen storage alloy constituting the negative electrode is Alternatively, the hydride may become fragmented and fall off the electrode support, causing expansion or cracking, resulting in a decrease in battery performance. This phenomenon is particularly noticeable in open-type alkaline storage batteries. Therefore, an attempt has been proposed to solve the above problems by coating the surface of hydrogen storage alloy powder with copper (Cu) (Japanese Patent Laid-Open No. 111546/1983). In other words, a storage battery cathode has been proposed in which electroless copper plating is applied to the surface of hydrogen-absorbing alloy powder to protect the alloy itself and to increase the mechanical strength and electrical conductivity of the alloy itself. An alkaline storage battery is being considered in which this hydrogen storage electrode is used as a negative electrode and is combined with a known nickel positive electrode via a separator.
発明が解決しようとする問題点
前記、銅を被覆した合金を負極に用いると、無焼結及び
焼結電極いずれにおいても、電極自体の機械的強度と導
電性は良くなシ、電池性能は向上すると考えられる。し
かし、ニッケル−水素アルカリ蓄電池の電解液は２０〜
３０％のＫＯＨ溶液を用いているために、放電末期、あ
るいは過放電領域に入ると銅が酸化されてＣｕ ２０と
なり逆に充電状態において溶解析出する。この現象をく
シかえずことによって、セパレータ内に銅（Ｃｕ）が析
出して、短絡現象の原因となる。とくに高温サイクル寿
命においては顕著に現れる。酸化水銀（Ｈｑ／Ｈｇ（１
）標準電極に対して一〇、４ｖよシ貴な電位、すなわち
酸化電位にするとＣｕ２０−ＣｕＯ２−となって溶解す
る。充電時にはまたＣｕまで還元されるのでＣｕが析出
する。したがって、水素吸蔵合金を被覆している金属に
よって高温度でのサイクル寿命に大きな影響を及ぼす事
が判明した。これに対して貴金属、ニッケル及びそれら
の合金は耐アルカリ性に強く、高温度におけるサイクル
寿命も長いが貴金属（銀、金、白金など）は高価なので
、コストの点から採用困難である。したがって、Ｎｉお
よびＮｉ基合金が無電解メッキの容易性などの点からも
最適な金属と云える。Ｃｏは無電解メッキが可能である
がＣｕと同様な性質を有している。しかしＮｉ−Ｃｏ基
合金にすれば耐食性も出て来るので利用可能となる。Problems to be Solved by the Invention As mentioned above, if a copper-coated alloy is used for the negative electrode, the mechanical strength and conductivity of the electrode itself will be poor in both unsintered and sintered electrodes, but the battery performance will improve. It is thought that then. However, the electrolyte of nickel-hydrogen alkaline storage batteries is 20~
Since a 30% KOH solution is used, at the end of discharge or in the overdischarge region, copper is oxidized and becomes Cu 20, which is dissolved and deposited in the charged state. By not changing this phenomenon, copper (Cu) is deposited within the separator, causing a short circuit phenomenon. This is especially noticeable during high-temperature cycle life. Mercury oxide (Hq/Hg(1
) When the potential is 10.4 V higher than the standard electrode, that is, the oxidation potential, it becomes Cu20-CuO2- and dissolves. During charging, it is reduced to Cu again, so Cu is deposited. Therefore, it has been found that the metal coating the hydrogen storage alloy has a significant effect on the cycle life at high temperatures. On the other hand, noble metals, nickel, and alloys thereof have strong alkali resistance and a long cycle life at high temperatures, but noble metals (silver, gold, platinum, etc.) are expensive, so it is difficult to employ them from the viewpoint of cost. Therefore, Ni and Ni-based alloys can be said to be the most suitable metals from the viewpoint of ease of electroless plating. Although Co can be electrolessly plated, it has properties similar to Cu. However, if a Ni-Co-based alloy is used, it will have corrosion resistance and can be used.
問題点を解決するための手段
本発明は酸化ニッケル正極と、水素を可逆的に吸蔵・放
出する少なくともニッケルを含む水素吸蔵合金又は水素
化物からなる負極と、アルカリ電解液を備え、前記負極
がニッケル又はニッケル基合金のいずれかによって部分
的に被覆され、水素を吸蔵・放出しうる電気化学的特性
を保持した水素吸蔵合金又は水素化物からなるニッケル
・水素アルカリ蓄電池である。Means for Solving the Problems The present invention comprises a nickel oxide positive electrode, a negative electrode made of a hydrogen storage alloy or hydride containing at least nickel that reversibly stores and releases hydrogen, and an alkaline electrolyte, wherein the negative electrode is made of nickel. or a nickel-hydrogen alkaline storage battery made of a hydrogen storage alloy or hydride that is partially coated with either a nickel-based alloy and retains electrochemical properties capable of storing and releasing hydrogen.
さらに本発明は前記負極において、ニッケル又はニッケ
ル基合金によって部分的に被覆した水素吸蔵合金、又は
水素化物粒子と結着剤を含有したペースト型電極、およ
びニッケル又はニッケル基合金によって部分的に被覆し
た水素吸蔵合金又は水素化物粒子単独かあるいはこれに
粘結剤を配し、８６０〜１，０００ ’Ｃの温度で焼結
した焼結型電極を負極に用いたニッケル−水素アルカリ
蓄電池である。Furthermore, in the negative electrode, the present invention provides a hydrogen storage alloy partially coated with nickel or a nickel-based alloy, or a paste-type electrode containing hydride particles and a binder, and a hydrogen storage alloy partially coated with nickel or a nickel-based alloy. This is a nickel-hydrogen alkaline storage battery using a sintered electrode made of hydrogen storage alloy or hydride particles alone or with a binder arranged thereon and sintered at a temperature of 860 to 1,000'C as the negative electrode.
作 用
ニッケル又はニッケル基合金（たとえばＮｉ−Ｃｏ、Ｎ
１−Ｃｏ−Ｂ、Ｎ１−Ｆｅ−Ｐ など）を無電解メッキ
法などで表面を被覆した少なくともニッケルを含む水素
吸蔵合金粉末又は水素化物粉末を負極に用いたアルカリ
蓄電池は、高温サイクル寿命の伸長が可能となる。その
理由は、ニッケルを含む水素吸蔵合金（水素化物）であ
るために同種類のニッケル、ニッケル基合金による表面
被覆（メッキ処理）が均一に、密着性よく円滑に進むと
共に、電池を構成した時に充・放電のくシかえしによる
電解液中への溶解も非常に少なくなシ、微少短絡による
容量低下もなくなるからである。しかも、電極自体の機
械的強度も保持しているために、さらに長寿命化が期待
できる。Function Nickel or nickel-based alloys (e.g. Ni-Co, N
Alkaline storage batteries that use a hydrogen storage alloy powder or hydride powder containing at least nickel, whose surface is coated with nickel (such as 1-Co-B, N1-Fe-P, etc.) by electroless plating, have a longer high-temperature cycle life. becomes possible. The reason for this is that since it is a hydrogen storage alloy (hydride) containing nickel, the surface coating (plating treatment) with the same type of nickel or nickel-based alloy proceeds uniformly and smoothly with good adhesion, and when the battery is constructed. This is because dissolution into the electrolyte due to recombination during charging and discharging is extremely small, and there is no reduction in capacity due to minute short circuits. Moreover, since the electrode itself maintains its mechanical strength, it can be expected to have a longer lifespan.
一方、この電極体を高温で焼結して焼結型電極を構成す
るとニッケル粒子間の結合力が強く、またニッケルを含
む水素吸蔵合金であるために、被覆金属との密着性もよ
く、長期のサイクル寿命において十分耐えるだけの強度
を保持する作用を有している。On the other hand, if this electrode body is sintered at high temperature to form a sintered electrode, the bonding force between the nickel particles will be strong, and since it is a hydrogen storage alloy containing nickel, it will have good adhesion with the coating metal and will last for a long time. It has the effect of maintaining sufficient strength to withstand the cycle life of .
実施例１ 以下、本発明の詳細を実施例で説明する。Example 1 Hereinafter, the details of the present invention will be explained with reference to Examples.
市販のＭｍ （ミツシュメタル；重量比でＬａ：６０．
Ｃｅ ： ２５． Ｎｄ ： ７． Ｐｒその他８
）、Ｎｉ（純度９９チ以上）、Ｃｏ（純度９９％以上）
の各試料を一定の組成比に秤量し、水冷銅るつぼ内に入
れ、アーク溶解炉によって加熱させ、ＭｍＮｉ５Ｃｏ□
合金を製造した。この合金を粉砕機で４００メツシユ以
下で細かく粉砕し、負極合金試料とした。つぎに、この
合金試料の一部を水素化した試料も合わせて作った。こ
れらの試料の表面にニッケル、ニッケル基合金（Ｎｉ−
Ｃｏ−Ｐ系）を無電解メッキし、ニッケルおよびニッケ
ル基合金の被覆膜を部分的に形成させる。その時の無電
解メッキの条件はつぎの通りである。Commercially available Mm (Mitushmetal; weight ratio La: 60.
Ce: 25. Nd: 7. PrOther 8
), Ni (purity of 99% or more), Co (purity of 99% or more)
Each sample was weighed to a certain composition ratio, placed in a water-cooled copper crucible, and heated in an arc melting furnace to form MmNi5Co□
An alloy was produced. This alloy was finely ground to 400 mesh or less using a grinder to obtain a negative electrode alloy sample. Next, a partially hydrogenated sample of this alloy sample was also made. Nickel and nickel-based alloys (Ni-
Electroless plating of Co--P based alloy is applied to partially form a coating film of nickel and nickel-based alloy. The conditions for electroless plating at that time were as follows.
このものは−見、合金粒子の表面に均質な金属被覆膜を
形成しているが、まだ多くの穴９割れ目が存在している
。この穴２割れ目があるために部分的な被覆膜を形成し
ていることになる。この穴。In this case, a homogeneous metal coating film was formed on the surface of the alloy particles, but there were still many holes and cracks. Due to the presence of these two holes, a partial coating film is formed. This hole.
割れ目を通して水素の吸蔵・放出が行なわれているもの
と考えられる。It is thought that hydrogen is absorbed and released through the cracks.
従来例との比較のために、同じ水素吸蔵合金粉末を用い
て、同様に銅の無電解メッキを施した電極を作った。こ
の時の無電解メッキの条件はつぎの通シである。For comparison with the conventional example, an electrode was made using the same hydrogen storage alloy powder and electrolessly plated with copper in the same manner. The conditions for electroless plating at this time are as follows.
この様にして製造した２種の合金粉末、すなわちニッケ
ル被覆形成を施した粉末（、）と銅被覆形成を施した粉
末（ｂ）にポリビニルアルコールのような結着剤をよく
混練して電極支持体（穴開き板；別名パンチングメタル
）の両側に塗着し、加圧、乾燥後リードを取り付けて負
極とし、公知の酸化ニッケル正極とをセパレータを介し
て構成し、アルカリ性電解液を入れてアルカリ蓄電池と
した。この蓄電池の構成を第１図に示す。金属被覆した
合金又は水素化物を含む水素吸蔵電極からなる負極１、
酸化ニッケルからなる正極２９両極の間にセパレータ３
が配され電解液４の中に浸されている。The two types of alloy powders produced in this way, namely the powder with nickel coating (2) and the powder with copper coating (b), are thoroughly kneaded with a binder such as polyvinyl alcohol to support the electrode. It is applied to both sides of the body (perforated plate; also known as punching metal), pressurized, dried, and then a lead is attached to form a negative electrode.A well-known nickel oxide positive electrode is connected via a separator, and an alkaline electrolyte is added to make the alkaline electrode. It was used as a storage battery. The configuration of this storage battery is shown in FIG. a negative electrode 1 consisting of a metal-coated alloy or hydrogen storage electrode containing a hydride;
A separator 3 is placed between the positive electrode 29 and both electrodes made of nickel oxide.
is arranged and immersed in the electrolytic solution 4.
６は電槽、６は蓋、７は注液口、８と９は負極と正極の
リード端子である。6 is a battery container, 6 is a lid, 7 is a liquid inlet, and 8 and 9 are negative and positive electrode lead terminals.
実施例１における負極の大きさは４０ ｗ Ｘ ５０箇
、厚さ１．２ｆｉとした。負極容量の比較を行なうため
に、正極容量は負極容量より大きくし、負極律則で容量
規制を行なった。充電・放電電流はともに４００ ｍＡ
とした。また充電時間は放電時間の約１．３倍とし、終
止電圧は１．Ｏｖとした。The size of the negative electrode in Example 1 was 40 w x 50 pieces, and the thickness was 1.2 fi. In order to compare the negative electrode capacity, the positive electrode capacity was made larger than the negative electrode capacity, and the capacity was regulated using the negative electrode rule. Both charging and discharging currents are 400 mA
And so. The charging time is approximately 1.3 times the discharging time, and the final voltage is 1.3 times the discharging time. It was Ov.
ａ粉末°を用いた本発明の蓄電池をＡとし、ｂ粉末を用
また従来の蓄電池をＢとして４５℃の温度でサイクル寿
命試験を行なった。第２図に本発明の蓄電池Ａと従来型
蓄電池Ｂのサイクル寿命特性の比較を示す。但し、６０
サイクル毎に一度過放電状態（※印で示す）まで電位を
持って行き、やや過酷な条件に取り入れた試験結果であ
る。加速試験も含めて、実用の場合には過放電特性も重
要な因子であるので、との様な試験においてサイクル寿
命の比較を行なった。A cycle life test was carried out at a temperature of 45°C, with A being a storage battery of the present invention using A powder and B being a conventional storage battery using B powder. FIG. 2 shows a comparison of the cycle life characteristics of storage battery A of the present invention and conventional storage battery B. However, 60
These are test results in which the potential was brought to an overdischarge state (indicated by *) once every cycle, and the battery was subjected to somewhat harsh conditions. Since overdischarge characteristics are also an important factor in practical use, including accelerated tests, cycle life was compared in tests such as .
従来型蓄電池Ｂは１００サイクル目よシ容量低下が大き
くなり、２００サイクル目ではｏ、ｓＡｈ。In conventional storage battery B, the capacity decrease becomes larger at the 100th cycle, and at the 200th cycle, the capacity decreases to o, sAh.
２６％程の容量低下を起こしている。これに対して本発
明の蓄電池Ａは２００サイクル目において・も０．１５
Ａｈ、７．５％程の容量低下にとどまっており、Ｂの約
３倍以上の耐久性を持っている。The capacity has decreased by about 26%. On the other hand, in the storage battery A of the present invention, at the 200th cycle, the value was 0.15.
Ah, the capacity drop is only about 7.5%, and the durability is more than three times that of B.
２００サイクル目で電極を調べた所、電池Ｂの電極は膨
張が大きく、銅の被覆膜が少しふやけて、密着性が悪く
なっており、電極自体の抵抗が大きくなっている。この
現象は電子顕微鏡による観察で明らかであった。これに
対して、電池Ａの電極は、膨張も少なく、合金とニッケ
ルの被覆膜との密着性もよく、顕微鏡観察によっても膜
のふくれも少ない。また電池Ｂの電極では、電解液中へ
の銅の溶解と、セパレータ内への銅析出現象があり、微
少短絡現象も見られた。電池Ａの電極ではこれらの現象
は見られなかった。ここでは水素吸蔵合金についてのべ
たが、水素化した合金についても同様な試験を行なった
が、殆ど同じ傾向を示した。When the electrodes were examined at the 200th cycle, it was found that the electrodes of battery B had expanded significantly, the copper coating had slightly softened, the adhesion had deteriorated, and the resistance of the electrode itself had increased. This phenomenon was clearly observed by electron microscopy. On the other hand, the electrode of battery A has little expansion, good adhesion between the alloy and the nickel coating film, and even microscopic observation shows that the film does not bulge. Further, in the electrode of battery B, dissolution of copper into the electrolyte and precipitation of copper into the separator were observed, and a slight short circuit phenomenon was also observed. These phenomena were not observed in the electrode of battery A. Although we have discussed hydrogen storage alloys here, similar tests were conducted on hydrogenated alloys, and almost the same trends were shown.
実施例２
実施例１と同じ組成の水素吸蔵合金（水素化物）を用い
て焼結・型電極を作り比較した。すなわち、ニッケルに
よって部分的に被覆した水素吸蔵合金を粘結剤と共に発
泡状メタル内に充てんし、加圧・乾燥した後、９６０℃
の温度で焼結した焼結型電極を負極とし、実施例１で用
いたのと同じニッケル−水素アルカリ蓄電池を構成し、
実施例１と同じ試験条件でサイクル寿命試験を行なった
。従来型電池の電極は実施例１で作った銅被覆合金粉末
（ｂ）を用いて同様な焼結型電極を作った。Example 2 A sintered molded electrode was made using a hydrogen storage alloy (hydride) having the same composition as in Example 1 and compared. That is, a hydrogen storage alloy partially coated with nickel is filled into a foamed metal together with a binder, and after being pressurized and dried, it is heated to 960°C.
A sintered type electrode sintered at a temperature of is used as a negative electrode to constitute the same nickel-hydrogen alkaline storage battery as used in Example 1,
A cycle life test was conducted under the same test conditions as in Example 1. For the electrode of a conventional battery, a similar sintered electrode was made using the copper-coated alloy powder (b) made in Example 1.
第３図に本発明の蓄電池Ａ′と従来型蓄電池Ｂ′のサイ
クル寿命特性の比較を示す。FIG. 3 shows a comparison of the cycle life characteristics of the storage battery A' of the present invention and the conventional storage battery B'.
従来型蓄電池Ｂ′は２００サイクル目より容量低下が大
きくなり、４００サイクル目では０ 、５Ａｈ 。For conventional storage battery B', the capacity decrease becomes larger from the 200th cycle, and at the 400th cycle, the capacity decreases to 0.5Ah.
２５チ程の容量低下を起こしている。これに対して本願
型蓄電池Ａは４００サイクル目においても０．２Ａｈ、
１０％程の容量低下にとどまっている。The capacity has decreased by about 25 inches. On the other hand, the storage battery A according to the present application has 0.2Ah even at the 400th cycle.
The capacity drop remains at about 10%.
約２．６倍の耐久性を持っている。焼結型電極は、前者
のペース型電極と比較して耐久性において優れているが
、ＡとＢ、ＡＩ とＢ′電池の比較においては同じ傾向
を示す。It has about 2.6 times the durability. The sintered electrode is superior in durability compared to the former pace-type electrode, but comparisons of batteries A and B, and AI and B' show the same tendency.
Ａ′とＢ′電池の容量において差が認められるのは、実
施例１で述べた理由と殆ど同じである。The difference in capacity between batteries A' and B' is observed for almost the same reason as stated in Example 1.
すなわち、電極自体の膨張の差異、電解液への銅の溶解
Φ析出の差異によるものである。この様に本発明の電池
では高温サイクル寿命、耐久性、過放電特性に強い事が
わかる。That is, this is due to differences in the expansion of the electrodes themselves and differences in the dissolution and Φ precipitation of copper in the electrolyte. Thus, it can be seen that the battery of the present invention has a high temperature cycle life, durability, and strong overdischarge characteristics.
無電解メッキの場合は合金よシも水素化物化しておく方
が表面が活性となシ、メッキしゃすい。In the case of electroless plating, it is better to hydride the alloy as well as the surface to make it more active and easier to plate.
したがって水素化物化した合金を無電解メッキする方が
好ましい。Therefore, it is preferable to electrolessly plate the hydride alloy.
実施例では焼結温度を９６０℃としたが、８５０〜１０
００℃が最適である。８５０℃以下では焼結する時の強
度が弱く大きな効果が出ない。逆に１ｏｏｏ℃以上では
過焼結して表面積を小さくし容量を著しく、小さくする
ので、８５０〜１０００℃が最適である。また他の焼結
方法としてホットプレスする事によって、加圧と焼結を
同時に行なう事が出来る。その場合表面積、多孔度がや
や小さくなるが、機械的強度は増大する。In the example, the sintering temperature was 960°C, but it was set at 850-10°C.
00°C is optimal. If the temperature is below 850°C, the strength during sintering will be weak and no great effect will be produced. On the other hand, if it exceeds 100°C, it will oversinter, reducing the surface area and significantly reducing the capacity, so 850 to 1000°C is optimal. Another sintering method is hot pressing, which allows pressing and sintering to be performed at the same time. In that case, the surface area and porosity will become slightly smaller, but the mechanical strength will increase.
水素吸蔵合金又は水素化物の表面に被覆するニッケル及
びニッケル基合金の量は全体の６〜３０ｗｔ％が好まし
い。５ｗｔ％以下では被覆膜の形成が均質に密着できな
く、大きな穴（ピンホール）がある状態なので効果が少
ない。また、３０ｗｔ％以上になると単位容積当りの容
量が小さくなると共に、粒径が大きくなシ合金の充てん
密度（容量）が減少し、電気容量が小さくなる。実用的
な面から６〜３０ｗｔ％がよいと云える。The amount of nickel and nickel-based alloy coated on the surface of the hydrogen storage alloy or hydride is preferably 6 to 30 wt% of the total amount. If it is less than 5 wt%, the coating film cannot be uniformly adhered, and there are large holes (pinholes), resulting in little effect. Moreover, when it becomes 30 wt% or more, the capacity per unit volume becomes small, and the packing density (capacity) of the Si alloy having a large particle size decreases, and the electric capacity becomes small. From a practical standpoint, it can be said that 6 to 30 wt% is good.
水素吸蔵合金としてはＭｒｒｈＮ ｉ ａ Ｃｏ ３を
用いて述べたが他の希土類−ニッケル系でも同じである
。Although MrrhNiaCo3 has been described as the hydrogen storage alloy, the same applies to other rare earth-nickel based alloys.
また、Ｔ １２ Ｎ ｉのようなチタン−ニッケル系で
もよい。最初の出発物質として水素吸蔵合金を用いても
、水素化物を用いてもよい。中でもニッケルを含有する
水素吸蔵合金が最も効果が大きい。Alternatively, a titanium-nickel type material such as T12Ni may be used. A hydrogen storage alloy or a hydride may be used as the initial starting material. Among them, hydrogen storage alloys containing nickel are the most effective.
また、実施例１で作った合金粉末を用いて単２サイズの
密閉型アルカリ蓄電池を作って４６℃における容量試験
を行なった。Furthermore, a AA size sealed alkaline storage battery was made using the alloy powder made in Example 1, and a capacity test was conducted at 46°C.
本発明の蓄電池では初期２．０Ａｈの容量を示し、充・
放電２０ｏサイクル後も２．０Ａｈの容量を示 ′した
。これに対し、従来型蓄電池では初期に２．ＯＡｈの容
量を示したが、充拳放電２ｏ００サイクル後では１．ｅ
Ａｈの容量に低下した。充・放電流はいずれも０．２０
相当の４００ ｍＡとした。負極容量は正極容量より大
きくし、正極律則になるように容量を規制して行なった
。本発明の蓄電池では２００サイクルの充・放電を行な
っても正極律則であるが、従来型蓄電池では負極律則で
容量が低下している。電池内で微少短絡を発生しており
、負極の容量が低下している。The storage battery of the present invention has an initial capacity of 2.0Ah, and
Even after 20o discharge cycles, it still showed a capacity of 2.0Ah. In contrast, with conventional storage batteries, 2. The capacity of OAh was shown, but after 2000 cycles of charging and discharging, it was 1. e
The capacity decreased to Ah. Both charging and discharging currents are 0.20
It was set to a corresponding 400 mA. The negative electrode capacity was made larger than the positive electrode capacity, and the capacity was regulated to comply with the positive electrode rule. In the storage battery of the present invention, even after 200 cycles of charging and discharging, the capacity is reduced according to the positive electrode rule, but in the conventional storage battery, the capacity decreases due to the negative electrode rule. A slight short circuit has occurred within the battery, reducing the capacity of the negative electrode.
この様に、本発明では開放型蓄電池でも、密閉型蓄電池
においても高温サイクル寿命が優れている。In this manner, the present invention provides excellent high-temperature cycle life for both open storage batteries and sealed storage batteries.
発明の効果
以上のように本発明によれば、機械的強度、耐久性があ
り、しかも高温サイクル寿命にすぐれ、過放電時の容量
低下の少ないニッケル−水素アルカリ蓄電池が得られる
。Effects of the Invention As described above, according to the present invention, a nickel-hydrogen alkaline storage battery can be obtained which has mechanical strength and durability, has excellent high-temperature cycle life, and exhibits little capacity loss during overdischarge.
第１図は本発明の実施例における水素吸蔵合金を負極と
するニッケル−水素アルカリ蓄電池の構成を示す断面略
図、第２図はペースト型水素吸蔵電極を負極とするニッ
ケル−水素アルカリ蓄電池のサイクル寿命を従来型蓄電
池と比較した図、第３図は焼結型水素吸蔵電極を負極と
するニッケル−水素アルカリ蓄電池のサイクル寿命を従
来型蓄電池と比較した図である。
１・・・・・・負極、２・・・・・・正極、３・・・・
・・セパレータ。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名ぺ
派 Ｖ解ζ４鴨くFig. 1 is a schematic cross-sectional view showing the structure of a nickel-hydrogen alkaline storage battery using a hydrogen storage alloy as a negative electrode according to an embodiment of the present invention, and Fig. 2 shows the cycle life of a nickel-hydrogen alkaline storage battery using a paste-type hydrogen storage electrode as a negative electrode. FIG. 3 is a diagram comparing the cycle life of a nickel-hydrogen alkaline storage battery with a sintered hydrogen storage electrode as a negative electrode with that of a conventional storage battery. 1...Negative electrode, 2...Positive electrode, 3...
...Separator. Name of agent Patent attorney Toshio Nakao and 1 other person V solution ζ4 Kamoku
Claims (4)
する少なくともニッケルを含む水素吸蔵合金又は水素化
物からなる負極と、アルカリ電解液を備え、前記負極が
ニッケル又はニッケル基合金のいずれかによって部分的
に被覆され、水素を吸蔵・放出しうる電気化学的特性を
保持する水素吸蔵合金又は水素化物からなることを特徴
とするニッケル−水素アルカリ蓄電池。(1) A nickel oxide positive electrode, a negative electrode made of a hydrogen storage alloy or hydride containing at least nickel that reversibly absorbs and releases hydrogen, and an alkaline electrolyte, wherein the negative electrode is made of either nickel or a nickel-based alloy. A nickel-hydrogen alkaline storage battery comprising a partially coated hydrogen storage alloy or hydride that maintains electrochemical properties capable of absorbing and desorbing hydrogen.
分的に被覆した水素吸蔵合金又は水素化物粒子と結着剤
を含有したペースト型電極である特許請求の範囲第１項
記載のニッケル−水素アルカリ蓄電池。(2) The nickel-hydrogen alkaline storage battery according to claim 1, wherein the negative electrode is a paste-type electrode containing hydrogen storage alloy or hydride particles partially coated with nickel or a nickel-based alloy and a binder. .
分的に被覆した水素吸蔵合金又は水素化物粒子単独か、
あるいはこれに粘結剤を配し、８５０〜１，０００℃の
温度で焼結したことを特徴とする特許請求の範囲第１項
記載のニッケル−水素アルカリ蓄電池。(3) Whether the negative electrode is a hydrogen storage alloy partially coated with nickel or a nickel-based alloy or hydride particles alone;
Alternatively, the nickel-hydrogen alkaline storage battery according to claim 1, wherein a binder is applied thereto and sintered at a temperature of 850 to 1,000°C.
によって部分的に被覆された金属部分が全体の水素吸蔵
合金又は水素化物に対して５〜３０ｗｔ％であることを
特徴とする特許請求の範囲第１項記載のニッケル−水素
アルカリ蓄電池。(4) Claims characterized in that the metal portion of the negative electrode partially coated with either nickel or nickel-based alloy is 5 to 30 wt% based on the entire hydrogen storage alloy or hydride. The nickel-hydrogen alkaline storage battery according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60161401A JPS6222370A (en) | 1985-07-22 | 1985-07-22 | Nickel-hydrogen alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60161401A JPS6222370A (en) | 1985-07-22 | 1985-07-22 | Nickel-hydrogen alkaline storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6222370A true JPS6222370A (en) | 1987-01-30 |
Family
ID=15734389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60161401A Pending JPS6222370A (en) | 1985-07-22 | 1985-07-22 | Nickel-hydrogen alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6222370A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0279369A (en) * | 1988-09-14 | 1990-03-19 | Sanyo Electric Co Ltd | Hydrogen storage alloy electrode |
| CN1060697C (en) * | 1995-02-24 | 2001-01-17 | 北京有色金属研究总院 | Composition and method for chemical copper plating of rare-earth containing nickle-based hydrogen storage alloy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6119063A (en) * | 1984-07-05 | 1986-01-27 | Sanyo Electric Co Ltd | Hydrogen occlusion electrode |
| JPS61168866A (en) * | 1985-01-19 | 1986-07-30 | Sharp Corp | Hydrogen occlusion electrode |
-
1985
- 1985-07-22 JP JP60161401A patent/JPS6222370A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6119063A (en) * | 1984-07-05 | 1986-01-27 | Sanyo Electric Co Ltd | Hydrogen occlusion electrode |
| JPS61168866A (en) * | 1985-01-19 | 1986-07-30 | Sharp Corp | Hydrogen occlusion electrode |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0279369A (en) * | 1988-09-14 | 1990-03-19 | Sanyo Electric Co Ltd | Hydrogen storage alloy electrode |
| CN1060697C (en) * | 1995-02-24 | 2001-01-17 | 北京有色金属研究总院 | Composition and method for chemical copper plating of rare-earth containing nickle-based hydrogen storage alloy |
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