JPH02186559A - Hydrogen storage alloy electrode for alkaline storage battery - Google Patents
Hydrogen storage alloy electrode for alkaline storage batteryInfo
- Publication number
- JPH02186559A JPH02186559A JP1006536A JP653689A JPH02186559A JP H02186559 A JPH02186559 A JP H02186559A JP 1006536 A JP1006536 A JP 1006536A JP 653689 A JP653689 A JP 653689A JP H02186559 A JPH02186559 A JP H02186559A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- storage alloy
- rare earth
- alloy
- weight
- 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
- 239000000956 alloy Substances 0.000 title claims abstract description 88
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 88
- 239000001257 hydrogen Substances 0.000 title claims abstract description 68
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 68
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 32
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims description 30
- -1 and M is Co Inorganic materials 0.000 claims 3
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 6
- 229910052777 Praseodymium Inorganic materials 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は、アルカリ蓄電池の負極として用いられる水素
吸蔵合金電極に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a hydrogen storage alloy electrode used as a negative electrode of an alkaline storage battery.
（ロ）従来の技術
従来より使用されている電池としては、ニアケル−カド
ミウム蓄電池の如きアルカリ蓄電池、あるいは鉛蓄電池
等が挙げられるが、近年これらの電池よりも軽量且つ高
容量で高エネルギー密度となる可能性のある水素吸蔵合
金電極を備えた金属酸化物−水素アルカリ蓄電池が注目
されている。(b) Conventional technology Conventionally used batteries include alkaline storage batteries such as near-cadmium storage batteries, lead storage batteries, etc., but in recent years, batteries have become lighter, higher in capacity, and have higher energy density than these batteries. Metal oxide-hydrogen alkaline storage batteries with potential hydrogen storage alloy electrodes are attracting attention.
この電池に用いられる水素吸蔵合金として、例えば特公
昭５９−４９６７１号公報に開示された如く、ＬａＮｉ
５や、その改良であるＬａＮｉ４Ｃ。As a hydrogen storage alloy used in this battery, for example, as disclosed in Japanese Patent Publication No. 59-49671, LaNi
5 and its improvement LaNi4C.
Ｌ ａ Ｎ Ｉ ４．ａＦ ｅ ｏ、 ２等の水素吸蔵
合金が用いられ、ＬａＳ ＣｅＳ Ｐｒ％Ｎｄ、Ｓｍな
どのランタン系の混合物であるＭｍを用いた水素吸蔵合
金（例えば特開昭６２−２０２４５号公報）が開発され
ている。L a N I 4. Hydrogen storage alloys such as aFeO, 2, etc. are used, and hydrogen storage alloys using Mm, which is a lanthanum-based mixture such as LaS CeS Pr%Nd, Sm, have been developed (for example, Japanese Patent Application Laid-Open No. 62-20245). ing.
ここでＭｍ系水素吸蔵合金は、Ｌａ系水素吸蔵合金に比
べ平衡圧が高いため、平衡圧を低くした多元素系のＭｍ
系水素吸蔵合金が提案されている。また特開昭６２−２
７１３４８号公報には、Ｍｍ系水素吸蔵合金電極におい
て、Ｌ ａの含有量として２０％以上が電極の容量の関
係上好ましい事が記載されている。Here, Mm-based hydrogen storage alloys have a higher equilibrium pressure than La-based hydrogen storage alloys, so multi-element Mm-based alloys with lower equilibrium pressures
Hydrogen storage alloys have been proposed. Also, JP-A-62-2
Publication No. 71348 describes that in a Mm-based hydrogen storage alloy electrode, the content of La is preferably 20% or more in view of the capacity of the electrode.
更に、例えば特開昭６２−１１．９８６３号公報には、
Ｍｍ系水素吸蔵合金が開示されており、組成としてはＬ
ａが２５〜３５重量％、Ｃｅが４０〜５０重量％、Ｎｄ
が５〜１５重量％、Ｐｒが２〜ｌＯ重量％、その他の希
土類元素と他種金属が１〜５重量％であることが記載さ
れている。Furthermore, for example, in JP-A-62-11.9863,
A Mm-based hydrogen storage alloy is disclosed, and its composition is L
a is 25-35% by weight, Ce is 40-50% by weight, Nd
It is described that Pr is 5 to 15% by weight, Pr is 2 to 10% by weight, and other rare earth elements and other metals are 1 to 5% by weight.
しかし、この種の水素吸蔵合金は、Ｎｄ、ＰｒＳｍの含
有量が少ないので、アルカリ電解液中で充放電を繰り返
した時に、水素吸蔵合金が微粉化したり、あるいは合金
表面が不活性化して電極容量が低下し、遂にはサイクル
寿命となってしまうという傾向がある。However, this type of hydrogen storage alloy has a low content of Nd and PrSm, so when it is repeatedly charged and discharged in an alkaline electrolyte, the hydrogen storage alloy becomes fine powder, or the alloy surface becomes inactive, resulting in electrode capacity. There is a tendency for the cycle life to decrease and eventually reach the end of its cycle life.
（ハ）発明が解決しようとする課題
本発明は、前記問題点に鑑みてなされたものであって、
負極に用いる水素吸蔵合金の耐食性を向上させ、かかる
電極を用いたアルカリ蓄電池のサイクル特性の向上を計
るものである。(c) Problems to be solved by the invention The present invention has been made in view of the above problems, and includes:
The purpose is to improve the corrosion resistance of the hydrogen storage alloy used in the negative electrode, and to improve the cycle characteristics of alkaline storage batteries using such an electrode.
（ニ）課題を解決するための手段
本発明の第１のアルカリ蓄電池用水素吸蔵合金電極は、
水素吸蔵合金中の全希土類元素の総重量に対して、Ｎｄ
の含有量が３０重量％以上であることを特徴とするもの
である。(d) Means for solving the problems The first hydrogen storage alloy electrode for alkaline storage batteries of the present invention includes:
With respect to the total weight of all rare earth elements in the hydrogen storage alloy, Nd
The content thereof is 30% by weight or more.
また、本発明の第２のアルカリ蓄電池用水素吸蔵合金電
極は、水素吸蔵合金中の全希土類元素の総重量に対して
、Ｐｒの含有量が２０重量％以上であることを特徴とす
るものである。Further, the second hydrogen storage alloy electrode for alkaline storage batteries of the present invention is characterized in that the content of Pr is 20% by weight or more based on the total weight of all rare earth elements in the hydrogen storage alloy. be.
更に、本発明の第３のアルカリ蓄電池用水素吸蔵合金電
極は、水素吸蔵合金中の全希土類元素の総重量に対して
、Ｓｍの含有量が１０重量％以上であることを特徴とす
るものである。Furthermore, the third hydrogen storage alloy electrode for alkaline storage batteries of the present invention is characterized in that the Sm content is 10% by weight or more based on the total weight of all rare earth elements in the hydrogen storage alloy. be.
そして、前記水素吸蔵合金としては、組成式が、ＡＮｉ
ｘＭｙ（組成式中、Ａｉ、１ｔＮｄ、Ｐｒ、Ｓｍのうち
のいずれが１種を含む希土類元素、ＭはＣｏ、Ａｌ、Ｃ
ｕＳＦｅ、Ｍｎ、Ｃｒ、Ｚｎ、ＴＩ、Ｚｒよりなる群よ
り選ばれた少なくとも１種の元素）で表わされ、３５≦
ｘ＋ｙ ≦６．０であるものが好適である。The hydrogen storage alloy has a compositional formula of ANi
xMy (in the composition formula, a rare earth element containing one of Ai, 1tNd, Pr, and Sm, M is Co, Al, and C
uSFe, Mn, Cr, Zn, TI, Zr), 35≦
It is preferable that x+y≦6.0.
（ホ）作 用
第１の本発明電極の如く、水素吸蔵合金中の希土類元素
の総重量に対してＮｄの含有量が３０重量％以上、また
第２の本発明電極の如＜Ｐｒの含有量が２０重量％以上
、更に第３の本発明電極の々Ｄ＜ Ｓｍの含有量が１０
重量％以上とすることで、水素吸蔵合金表面の不活性化
が抑制され、且つ合金の耐食性が向上して、合金の微粉
化に伴なう電極容量低下を抑制することが可能となる。(E) Function As in the first electrode of the present invention, the content of Nd is 30% by weight or more based on the total weight of rare earth elements in the hydrogen storage alloy, and as in the electrode of the second present invention, the content of <Pr is The content of the third invention electrode is 20% by weight or more, and the content of D<Sm is 10% by weight or more.
When the content is at least % by weight, inactivation of the surface of the hydrogen storage alloy is suppressed, and the corrosion resistance of the alloy is improved, making it possible to suppress a decrease in electrode capacity due to pulverization of the alloy.
その結果、長期サイクルに亘って高容量を維持すること
ができ、サイクル特性に優れたアルカリ蓄電池が提供で
きる。As a result, it is possible to provide an alkaline storage battery that can maintain high capacity over long cycles and has excellent cycle characteristics.
（へ）実施例 以下に、本発明と比較例との対比に言及し、詳述する。(f) Example Below, the comparison between the present invention and a comparative example will be mentioned and explained in detail.
［第１実験例］
先づ、Ｎｄを含有せる種々の水素吸蔵合金について検討
する。[First Experimental Example] First, various hydrogen storage alloys containing Nd will be studied.
希土類混合物Ａ（Ｎｄ：６０重量％、Ｌａ：１０重量％
、Ｃｅ：２５重量％、Ｐｒ：４重量％、Ｓｍ：１重量％
）Ｎｉ（純度９９％以」−）及び組成式中のＭとしての
Ｃ０１Ａ！、Ｃｕ、Ｆｅ、Ｍｎを用い、第１表に示す組
成を有する水素吸蔵合金電極を得た。そして、これらの
水素吸蔵合金電極を備えた電池を、第１表に示す如く、
それぞれ本発明電池Ａ、Ｂ、Ｃ，Ｄ、Ｅとした。Rare earth mixture A (Nd: 60% by weight, La: 10% by weight
, Ce: 25% by weight, Pr: 4% by weight, Sm: 1% by weight
)Ni (purity 99% or more''-) and C01A as M in the composition formula! , Cu, Fe, and Mn to obtain hydrogen storage alloy electrodes having the compositions shown in Table 1. As shown in Table 1, batteries equipped with these hydrogen storage alloy electrodes are as follows:
These were designated as inventive batteries A, B, C, D, and E, respectively.
第 １ 表
この時用いた水素吸蔵合金電極の作製方法は、各元素を
第１表に示す組成比で夫々秤量して混合し、次いでアル
ゴン雰囲気下でアーク溶解炉に入れ、加熱溶解して合金
化し、冷却する。次に、この合金を機械的に５０μｍ以
下に粉砕して、水素吸蔵合金粉末を得た。これらの各種
水素吸蔵合金粉末９０重量％及び結着剤としてのフッ素
払（脂末］０重量％を、それぞれ混合し、フッ素樹脂を
繊維化させる。そしてこの混合物をニッケル網で包み込
み、３ｔｏｎ／ｃｍ’で加圧成型して、水素吸蔵合金電
極とした。この水素吸蔵合金電極に用いた水素吸蔵合金
粉末の使用量は、それぞれ１，５ｇである。このように
して得た水素吸蔵合金電極を負極とし、焼結式ニッケル
正極と組み合せ、電解液としての水酸化カリウム水溶液
を用いて、密閉型ニッケルー水素アルカリ蓄電池（Ａ−
Ｅ）を作製した。Table 1 The method for producing the hydrogen storage alloy electrode used at this time was to weigh and mix each element in the composition ratio shown in Table 1, then place it in an arc melting furnace under an argon atmosphere, and heat and melt it to form an alloy. and cool. Next, this alloy was mechanically crushed to a size of 50 μm or less to obtain a hydrogen storage alloy powder. 90% by weight of these various hydrogen-absorbing alloy powders and 0% by weight of fluoride removal (fat powder) as a binder are mixed, respectively, and the fluororesin is made into fibers.Then, this mixture is wrapped in a nickel net, and 3 ton/cm ' to make a hydrogen storage alloy electrode.The amount of hydrogen storage alloy powder used in this hydrogen storage alloy electrode was 1.5g each.The hydrogen storage alloy electrode obtained in this way was A sealed nickel-hydrogen alkaline storage battery (A-
E) was produced.
方、比較例として、市販のミツシュメタルＭｍ（Ｎｄ：
１４重量％、Ｌａ：３０重量％、Ｃｅ：５０重量％、Ｐ
ｒ：４重量％、Ｓｍ：１重量％、残渣、１重量％）を希
土類混合物Ａとして水素吸蔵合金を得た事を除いて他は
、前記本発明電池と同様にして、比較電池ａ、ｂｓ Ｃ
，ｄ、ｅを作製した。On the other hand, as a comparative example, commercially available Mitshu Metal Mm (Nd:
14% by weight, La: 30% by weight, Ce: 50% by weight, P
Comparative batteries a and bs were prepared in the same manner as the batteries of the present invention, except that a hydrogen storage alloy was obtained using rare earth mixture A (r: 4% by weight, Sm: 1% by weight, residue: 1% by weight). C
, d, and e were prepared.
この比較電池ａ、ｂ、ｃ、ｄ、ｅに用いた水素吸蔵合金
組成を、第２表に示す。Table 2 shows the hydrogen storage alloy compositions used in the comparative batteries a, b, c, d, and e.
第 ２ 表
これらの本発明電池Ａ−Ｅ及び比較電池ａ−ｅを用い、
電池のサイクル寿命を調べた。この時のサイクル条件は
、電池を２０ｍＡの電流で５時間充電した後、４０ｍＡ
の電流で電池電圧が１．０Ｖになる迄放電するというも
のであり、電池の容量が初期容量の５０％となったサイ
クル数をサイクル寿命とした。Table 2 Using these inventive batteries A-E and comparative batteries a-e,
The cycle life of the battery was investigated. The cycle conditions at this time were to charge the battery with a current of 20mA for 5 hours, then charge the battery with a current of 40mA.
The battery was discharged at a current of 1.0 V until the battery voltage reached 1.0 V, and the cycle life was defined as the number of cycles at which the battery capacity became 50% of its initial capacity.
この結果を、第１表、第２表に合わせて示す。The results are shown in Tables 1 and 2.
これより、本発明電池Ａ−Ｅは、比較電池ａ〜ｅに比べ
、添加元素Ｍが同じである場合（Ｎｉ、Ｃｏ、ＡＩ、Ｃ
ｕ、Ｆｅ、Ｍｎ等）、充放電サイクル寿命が著しく向上
していることが理解される。これは、水素吸蔵合金中に
おける、希土類元素のＮｄ含有量の差に起因すると考え
られる。From this, it can be seen that the batteries A-E of the present invention have the same additive element M (Ni, Co, AI, C
u, Fe, Mn, etc.), it is understood that the charge/discharge cycle life is significantly improved. This is considered to be due to the difference in the Nd content of the rare earth element in the hydrogen storage alloy.
［第２実験例］
次に、Ｎｄの含有量を変化させた場合について検討する
。[Second Experimental Example] Next, the case where the Nd content is changed will be considered.
ここで用いた水素吸蔵合金は、
ＡＮ １２ｃＯ２□Ａｌｏ ｓ （Ａ 希土類元素）
の組成を有するものであり、希土類元素Ａとして、第３
表に示す如く、Ｎｄ、Ｌａ、Ｃｅ、Ｐｒ、Ｓｍが含有さ
れている。尚、合金組成の合計が１００とならないもの
があるのは、残渣を含んでいるためである。The hydrogen storage alloy used here is AN12cO2□Alos (A rare earth element)
It has a composition of
As shown in the table, Nd, La, Ce, Pr, and Sm are contained. The reason why some alloy compositions do not add up to 100 is because they contain residues.
第 ３ 表
これらの電池す、Ｆ、Ｇ、Ｈ，１，Ｊを用い、電池のサ
イクル寿命を調べた。この時のサイクル条件は、前記第
１実験例に準じた。Table 3 Using these batteries F, G, H, 1, and J, the cycle life of the batteries was investigated. The cycle conditions at this time were similar to those in the first experimental example.
この結果を、第３表に示すと共に、第１図に図示する。The results are shown in Table 3 and illustrated in FIG.
これより、Ｎｄの含有量が３０重量％未満になると、Ｎ
ｄ以外の希土類元素である、Ｌａ、Ｃｅの含有量が多く
なる。このＬａ、Ｃｅは、Ｎｄに比べて、アルカリ電解
液中で腐食され易いので、水素吸蔵合金が腐食、不活性
化したり、微粉化するので、電池のサイクル寿命が短か
くなると考えられる。しかしながら、Ｎｄの添加量を３
０重量％以上とすることにより、上述の問題点が解消さ
れ、電池のサイクル寿命が向上する。From this, when the Nd content is less than 30% by weight, Nd
The content of rare earth elements other than d, such as La and Ce, increases. Since La and Ce are more easily corroded in an alkaline electrolyte than Nd, the hydrogen storage alloy is corroded, inactivated, or pulverized, which is thought to shorten the cycle life of the battery. However, the amount of Nd added was
By setting the content to 0% by weight or more, the above-mentioned problems are solved and the cycle life of the battery is improved.
［第３実験例］
水素吸蔵合金中のＰｒの含有量を変化させた場合につい
て検討する。[Third Experimental Example] A case will be considered in which the content of Pr in the hydrogen storage alloy is changed.
ここで用いた水素吸蔵合金は、
ＡＮ ｉ ２ＣＯ２２ＡＩＯ８（Ａ ’希土類元素）の
組成を有するものであり、希土類元素として、第４表に
示す如く、Ｐｒ、Ｌａ、Ｃｅ、Ｎｄ、Ｓｍが含有されて
いる。尚、合金組成の合計が］００とならないものがあ
るのは、残渣を含んでいるためである。The hydrogen storage alloy used here has a composition of AN i 2 CO 2 2 AIO 8 (A' rare earth element), and contains Pr, La, Ce, Nd, and Sm as rare earth elements as shown in Table 4. There is. It should be noted that the reason why the sum of the alloy compositions is not 00 in some cases is because they contain residues.
第 ４ 表
これらの電池す、に、Ｌ、Ｍ、Ｎを用い、電池のサイク
ル寿命を調べた。この時のサイクル条件は、前記第］実
験例に準じた。Table 4 Using these batteries, L, M, and N, the cycle life of the batteries was investigated. The cycle conditions at this time were in accordance with the above-mentioned Experimental Example.
この結果を第４表に示す。The results are shown in Table 4.
これより、Ｐｒの含有量が２０重量％未満、たとえば１
０重量％、４重量％になると、電池のサイクル特性が悪
くなる。しかしながら、Ｐｒの含有量を２０重量％以上
に設定することにより、１ ］
Ｐｒがアルカリ電解液中で腐食され難いことに起因して
、水素吸蔵合金の耐食性が向上し、合金の不活性化を抑
制することができる。その結果、電池のサイクル寿命が
向上する。From this, the content of Pr is less than 20% by weight, for example 1
When the amount is 0% or 4% by weight, the cycle characteristics of the battery deteriorate. However, by setting the Pr content to 20% by weight or more, 1] Due to the fact that Pr is difficult to corrode in an alkaline electrolyte, the corrosion resistance of the hydrogen storage alloy is improved and the inactivation of the alloy is improved. Can be suppressed. As a result, the cycle life of the battery is improved.
［第４実験例コ
次に、水素吸蔵合金中のＳｍの含有量を変化させた場合
について検討する。[Fourth Experimental Example Next, the case where the Sm content in the hydrogen storage alloy is changed will be considered.
ここで用いた水素吸蔵合金は、
ＡＮ Ｉ ２ＣＯ２ｚＡｊ２ｏ ｍ （Ａ ’希土類元
素）の組成を有するものであり、希土類元素として、第
５表に示す如く、Ｓｍ、Ｌａ、Ｃｅ、Ｎｄ、Ｐｒが含有
されている。尚、合金組成の合計が１００とならないも
のがあるのは、残渣を含んでいるためである。The hydrogen storage alloy used here has a composition of AN I 2 CO 2 z A j 2 o m (A' rare earth element), and contains Sm, La, Ce, Nd, and Pr as rare earth elements, as shown in Table 5. ing. The reason why some alloy compositions do not add up to 100 is because they contain residues.
第 ５ 表
これらの電池Ｋ、０、Ｐ、Ｑを用い、電池のサイクル寿
命を調べた。この時のサイクル条件は、前記第１実験例
に準じた。Table 5 Using these batteries K, 0, P, and Q, the cycle life of the batteries was investigated. The cycle conditions at this time were similar to those in the first experimental example.
この結果を、第５表に示す。The results are shown in Table 5.
これよりＳｍの含有量が１０重量％以上になると、Ｓｍ
がアルカリ電解液中で腐食され難いことに起因して水素
吸蔵合金の耐食性が向上し、合金の不活性化を抑制する
ことができる。その結果、電池のサイクル寿命が向上す
る。From this, when the Sm content becomes 10% by weight or more, Sm
Because it is difficult to corrode in an alkaline electrolyte, the corrosion resistance of the hydrogen storage alloy is improved, and deactivation of the alloy can be suppressed. As a result, the cycle life of the battery is improved.
［第５実験例］
水素吸蔵合金の合金組成において、ＡＢ５型合金より化
学量論比がずれた場合について検討する。[Fifth Experimental Example] In the alloy composition of the hydrogen storage alloy, a case where the stoichiometric ratio deviates from that of the AB5 type alloy will be considered.
前記第１実験例に同一の希土類元素の混合物及び市販の
Ｍｍを用い、第６表に示す合金組成を有する水素吸蔵合
金電極を作製した。そして前記第１実験例と同様にして
各種電池を得た。Using the same mixture of rare earth elements and commercially available Mm as in the first experimental example, a hydrogen storage alloy electrode having the alloy composition shown in Table 6 was produced. Various batteries were obtained in the same manner as in the first experimental example.
以下余白
第 ６
表
これらの本発明電池Ｒ，Ｓ、１３、Ｔ、及び比較電池ｒ
、ｓ、ｂ、ｔを用い、電池のサイクル寿命を調べた。こ
の時のサイクル条件は、前記第１実験例に準じた。Table 6: These inventive batteries R, S, 13, T, and comparative battery r
, s, b, and t were used to examine the cycle life of the battery. The cycle conditions at this time were similar to those in the first experimental example.
この結果を、第６表及び第２図に示す。The results are shown in Table 6 and FIG.
この結果より、ＡＢ、型合金よりも化学量論比がずれた
水素吸蔵合金を使用する電池ｒ、ｓ、ｔは、サイクル寿
命が短かくなることがわかる。しかしながら、Ｎｄを多
く含有した合金を有する本発明電池Ｒ，Ｓ、Ｔは、その
低下の割合が極めて小さく抑えられ、合金組成が化学量
論比からすノまた場合であっても、優れたサイクル特性
が発揮される。From this result, it can be seen that batteries r, s, and t that use a hydrogen storage alloy whose stoichiometric ratio is different from that of the AB type alloy have a shorter cycle life. However, in the batteries R, S, and T of the present invention, which have alloys containing a large amount of Nd, the rate of decrease is suppressed to an extremely low level, and even when the alloy composition is different from the stoichiometric ratio, the batteries R, S, and T of the present invention have excellent cycle performance. Characteristics are demonstrated.
尚、希土類元素中のＮｄの含有量が６０重量％の場合に
ついて例示したが、前記傾向は、Ｎｄの含有量が３０重
量％以」二において観察された。Although the case where the Nd content in the rare earth element was 60% by weight was exemplified, the above-mentioned tendency was observed when the Nd content was 30% by weight or more.
また、Ｐ ｒを２０重量％以上含有させた場合及びＳｍ
を１０重量％以」二含有させた場合においても、やはり
同様の傾向が観察された。その結果、本発明の構成とす
ることにより、この種水素吸蔵合金を用いたアルカリ蓄
電池のサイクル寿命の低下が抑制できる。In addition, when Pr is contained in an amount of 20% by weight or more and Sm
A similar tendency was also observed when the content of 10% by weight or more. As a result, with the configuration of the present invention, it is possible to suppress a decrease in the cycle life of an alkaline storage battery using this type of hydrogen storage alloy.
（ト）発明の効果
上述した如く、少なくとも希土類元素を含む水素吸蔵合
金を電極とするアルカリ蓄電池において、前記希土類元
素の総重量に対して、Ｎｄ、Ｐｒ或いはＳｍの含有量を
、それぞれ３０重量％以上、２０重量％以上、或いは１
０重量％以上と限定することにより、１１ｊ記合金のア
ルカリ電解液中における耐食性が向上し、サイクル特性
に優れたアルカリ蓄電池が得られるので、その工業的価
値は極めて大きい。(g) Effects of the invention As described above, in an alkaline storage battery using a hydrogen storage alloy containing at least a rare earth element as an electrode, the content of Nd, Pr, or Sm is 30% by weight each with respect to the total weight of the rare earth element. or more, 20% by weight or more, or 1
By limiting the amount to 0% by weight or more, the corrosion resistance of the alloy No. 11j in an alkaline electrolyte is improved, and an alkaline storage battery with excellent cycle characteristics can be obtained, so its industrial value is extremely large.
第１図は水素吸蔵合金中のＮｃｌの含有量と電池のサイ
クル寿命との関係を示す図、第２図は水素吸蔵合金を化
学量論比からずらしたときの電池のサイクル寿命を示す
図である。
Ｂ、Ｆ、Ｇ、Ｈ，Ｉ、Ｊ、Ｒ，Ｓ、Ｔ・・本発明電池、
ｂ、ｒ、ｓ、ｔ・・・比較電池。Figure 1 is a diagram showing the relationship between the Ncl content in the hydrogen storage alloy and the cycle life of the battery, and Figure 2 is a diagram showing the cycle life of the battery when the hydrogen storage alloy is shifted from the stoichiometric ratio. be. B, F, G, H, I, J, R, S, T...battery of the present invention, b, r, s, t... comparative battery.
Claims (1)
り、前記希土類元素の総重量に対して、Ｎｄが３０重量
％以上含有されていることを特徴とするアルカリ蓄電池
用水素吸蔵合金電極。 ［２］前記水素吸蔵合金は、組成式ＡＮｉｘＭｙ（組成
式中、ＡはＮｄ、或いはＮｄとその他の希土類元素との
混合物、ＭはＣｏ、Ａｌ、Ｃｕ、Ｆｅ、Ｍｎ、Ｃｒ、Ｚ
ｎ、Ｔｉ、Ｚｒよりなる群より選ばれた少なくとも１種
の元素）で表わされ、３．５≦ｘ＋ｙ≦６．０であるこ
とを特徴とする請求項［１］記載の水素吸蔵合金電極。 ［３］少なくとも希土類元素を含む水素吸蔵合金よりな
り、前記希土類元素の総重量に対して、Ｐｒが２０重量
％以上含有されていることを特徴とするアルカリ蓄電池
用水素吸蔵合金電極。 ［４］前記水素吸蔵合金は、組成式ＡＮｉｘＭｙ（組成
式中、ＡはＰｒ、或いはＰｒとその他の希土類元素との
混合物、ＭはＣｏ、Ａｌ、Ｃｕ、Ｆｅ、Ｍｎ、Ｃｒ、Ｚ
ｎ、Ｔｉ、Ｚｒよりなる群より選ばれた少なくとも１種
の元素）で表わされ、３．５≦ｘ＋ｙ≦６．０であるこ
とを特徴とする請求項［３］記載の水素吸蔵合金電極。 ［５］少なくとも希土類元素を含む水素吸蔵合金よりな
り、前記希土類元素の総重量に対して、Ｓｍが１０重量
％以上含有されていることを特徴とするアルカリ蓄電池
用水素吸蔵合金電極。 ［６］前記水素吸蔵合金は、組成式ＡＮｉｘＭｙ（組成
式中、ＡはＳｍ、或いはＳｍとその他の希土類元素との
混合物、ＭはＣｏ、Ａｌ、Ｃｕ、Ｆｅ、Ｍｎ、Ｃｒ、Ｚ
ｎ、Ｔｉ、Ｚｒよりなる群より選ばれた少なくとも１種
の元素）で表わされ、３．５≦ｘ＋ｙ≦６．０であるこ
とを特徴とする請求項［５］記載の水素吸蔵合金電極。[Scope of Claims] [1] Hydrogen storage for an alkaline storage battery, characterized in that it is made of a hydrogen storage alloy containing at least a rare earth element, and contains 30% by weight or more of Nd based on the total weight of the rare earth element. Alloy electrode. [2] The hydrogen storage alloy has a composition formula ANixMy (in the composition formula, A is Nd or a mixture of Nd and other rare earth elements, and M is Co, Al, Cu, Fe, Mn, Cr, Z
At least one element selected from the group consisting of n, Ti, and Zr), and 3.5≦x+y≦6.0, the hydrogen storage alloy electrode according to claim . [3] A hydrogen storage alloy electrode for an alkaline storage battery, which is made of a hydrogen storage alloy containing at least a rare earth element, and contains 20% by weight or more of Pr based on the total weight of the rare earth element. [4] The hydrogen storage alloy has a composition formula ANixMy (in the composition formula, A is Pr or a mixture of Pr and other rare earth elements, and M is Co, Al, Cu, Fe, Mn, Cr, Z
At least one element selected from the group consisting of n, Ti, and Zr), and 3.5≦x+y≦6.0, the hydrogen storage alloy electrode according to claim . [5] A hydrogen storage alloy electrode for an alkaline storage battery, which is made of a hydrogen storage alloy containing at least a rare earth element, and contains 10% by weight or more of Sm based on the total weight of the rare earth element. [6] The hydrogen storage alloy has a composition formula ANixMy (in the composition formula, A is Sm or a mixture of Sm and other rare earth elements, and M is Co, Al, Cu, Fe, Mn, Cr, Z
At least one element selected from the group consisting of n, Ti, and Zr), and 3.5≦x+y≦6.0, the hydrogen storage alloy electrode according to claim [5]. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1006536A JPH02186559A (en) | 1989-01-13 | 1989-01-13 | Hydrogen storage alloy electrode for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1006536A JPH02186559A (en) | 1989-01-13 | 1989-01-13 | Hydrogen storage alloy electrode for alkaline storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02186559A true JPH02186559A (en) | 1990-07-20 |
Family
ID=11641072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1006536A Pending JPH02186559A (en) | 1989-01-13 | 1989-01-13 | Hydrogen storage alloy electrode for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02186559A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0608646A1 (en) * | 1992-12-04 | 1994-08-03 | Saft | Hydridable material for nickel-hydride accumulator negative electrode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6089066A (en) * | 1983-10-21 | 1985-05-18 | エヌ・ベ−・フイリツプス・フル−イランペンフアブリケン | Electrochemical cell |
| JPS60109183A (en) * | 1983-11-17 | 1985-06-14 | Matsushita Electric Ind Co Ltd | Sealed type nickel-hydrogen storage battery |
| JPS61168870A (en) * | 1985-01-19 | 1986-07-30 | Sanyo Electric Co Ltd | Metal-hydrogen alkaline storage battery |
| JPS61285658A (en) * | 1985-06-12 | 1986-12-16 | Matsushita Electric Ind Co Ltd | Manufacture of hydrogen occlusion electrode |
-
1989
- 1989-01-13 JP JP1006536A patent/JPH02186559A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6089066A (en) * | 1983-10-21 | 1985-05-18 | エヌ・ベ−・フイリツプス・フル−イランペンフアブリケン | Electrochemical cell |
| JPS60109183A (en) * | 1983-11-17 | 1985-06-14 | Matsushita Electric Ind Co Ltd | Sealed type nickel-hydrogen storage battery |
| JPS61168870A (en) * | 1985-01-19 | 1986-07-30 | Sanyo Electric Co Ltd | Metal-hydrogen alkaline storage battery |
| JPS61285658A (en) * | 1985-06-12 | 1986-12-16 | Matsushita Electric Ind Co Ltd | Manufacture of hydrogen occlusion electrode |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0608646A1 (en) * | 1992-12-04 | 1994-08-03 | Saft | Hydridable material for nickel-hydride accumulator negative electrode |
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