JPH04255673A - Manufacture of metal hydride storage battery - Google Patents
Manufacture of metal hydride storage batteryInfo
- Publication number
- JPH04255673A JPH04255673A JP3017995A JP1799591A JPH04255673A JP H04255673 A JPH04255673 A JP H04255673A JP 3017995 A JP3017995 A JP 3017995A JP 1799591 A JP1799591 A JP 1799591A JP H04255673 A JPH04255673 A JP H04255673A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- negative electrode
- battery
- electrode
- hydrogen storage
- 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
- 229910052987 metal hydride Inorganic materials 0.000 title claims abstract description 12
- 150000004681 metal hydrides Chemical class 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 82
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 82
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 45
- 239000000956 alloy Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 7
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000004913 activation Effects 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、水素を可逆的に吸蔵及
び放出することのできる水素吸蔵合金を負極とする金属
水素化物蓄電池の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a metal hydride storage battery whose negative electrode is a hydrogen storage alloy capable of reversibly absorbing and desorbing hydrogen.
【０００２】0002
【従来の技術】従来からよく用いられているニッケル−
カドミウム蓄電池に代わる新しい密閉型アルカリ蓄電池
として、近年、高エネルギー密度化及び長寿命化が行え
る可能性があるということで、負極に水素吸蔵合金を用
いる金属水素化物蓄電池の開発が行われている。ところ
で、水素を可逆的に吸蔵及び放出する水素吸蔵合金から
なる負極と、金属酸化物を活物質とする正極とを備えた
この種金属水素化物蓄電池は、一般的に、初期容量が低
く、活性化処理を行う必要があると考えられている。[Prior art] Nickel, which has been commonly used in the past.
As a new sealed alkaline storage battery to replace cadmium storage batteries, metal hydride storage batteries that use a hydrogen storage alloy for the negative electrode have recently been developed because of their potential for higher energy density and longer life. By the way, this type of metal hydride storage battery, which is equipped with a negative electrode made of a hydrogen storage alloy that reversibly absorbs and releases hydrogen and a positive electrode whose active material is a metal oxide, generally has a low initial capacity and a low activation rate. It is believed that it is necessary to carry out a chemical treatment.
【０００３】ここで、活性化処理を行う方法として、例
えば、特開平１−２０４３７１号公報等では、水素雰囲
気下で水素の吸蔵及び放出を少なくとも１回行い、その
後、水素吸蔵合金中にいくらかの水素を残存した状態で
活性化処理工程を終了する方法が提案されている。[0003] As a method for carrying out the activation treatment, for example, in Japanese Patent Application Laid-Open No. 1-204371, hydrogen is absorbed and released at least once in a hydrogen atmosphere, and then some amount of hydrogen is absorbed into the hydrogen storage alloy. A method has been proposed in which the activation treatment step is completed with hydrogen remaining.
【０００４】また、特開昭６１−３９４６１号公報等で
は、電解液の注液前に水素雰囲気下で水素吸蔵合金に水
素ガスを吸蔵及び放出させて活性化処理し、その後、水
素雰囲気下で電解液を注液する方法が提案されている。Furthermore, in Japanese Patent Application Laid-Open No. 61-39461, an activation treatment is performed by occluding and releasing hydrogen gas in a hydrogen storage alloy in a hydrogen atmosphere before pouring an electrolyte solution, and then an activation treatment is performed in a hydrogen atmosphere. A method of injecting electrolyte has been proposed.
【０００５】しかしながら、上記いずれの方法において
も、電池組立て後、最大電池容量を得るまでに数サイク
ル〜数十サイクルの充放電処理を行う必要がある。これ
は、初期においては水素吸蔵合金の可逆性が低く、負極
容量が十分に発揮されず正極容量に比べて小さくなるか
らである。このため、放電時、負極が先に過放電状態と
なり、負極側から酸素ガスが発生して、水素吸蔵合金を
酸化し水素吸蔵合金電極の表面に強固な酸化被膜ができ
るために水素吸蔵合金電極の特性が低下する。However, in any of the above methods, after the battery is assembled, it is necessary to perform several to several tens of cycles of charging and discharging before the maximum battery capacity is obtained. This is because the reversibility of the hydrogen storage alloy is low in the initial stage, and the negative electrode capacity is not fully exhibited and becomes smaller than the positive electrode capacity. Therefore, during discharging, the negative electrode becomes over-discharged first, and oxygen gas is generated from the negative electrode side, which oxidizes the hydrogen storage alloy and forms a strong oxide film on the surface of the hydrogen storage alloy electrode. properties deteriorate.
【０００６】また、初期において水素吸蔵合金電極に水
素を多く吸蔵させておくと負極が速く満充電状態となり
、過充電特性やサイクル寿命を低下させる。さらに、注
液時や組立時に空気中の酸素と水素吸蔵合金が反応しや
すい状態となるため、水素吸蔵合金の酸化が速まり、水
素吸蔵合金電極表面に酸化被膜ができ電池特性が低下す
るという問題が生じる。[0006] Furthermore, if a large amount of hydrogen is stored in the hydrogen storage alloy electrode at the initial stage, the negative electrode will quickly reach a fully charged state, reducing overcharging characteristics and cycle life. Furthermore, during injection and assembly, the oxygen in the air and the hydrogen storage alloy tend to react, which accelerates the oxidation of the hydrogen storage alloy and forms an oxide film on the surface of the hydrogen storage alloy electrode, reducing battery characteristics. A problem arises.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上記の如き
問題を解決し、初回の活性化処理時から、最大電池容量
を得ることができ、過充電特性及びサイクル特性の良好
な金属水素化物蓄電池の製造方法を提供するものである
。[Problems to be Solved by the Invention] The present invention solves the above problems and provides a metal hydride that can obtain maximum battery capacity from the initial activation treatment and has good overcharge characteristics and cycle characteristics. A method for manufacturing a storage battery is provided.
【０００８】[0008]
【課題を解決するための手段】本発明の金属水素化物蓄
電池の製造方法は、水素吸蔵合金電極からなる負極に、
水素雰囲気下で水素を吸蔵させた後、負極の公称容量の
１％以下に相当する量の水素を含んだ状態まで水素を放
出させた状態にして、電池に組み立てることを特徴とす
るものである。[Means for Solving the Problems] The method for manufacturing a metal hydride storage battery of the present invention includes a negative electrode made of a hydrogen storage alloy electrode,
After storing hydrogen in a hydrogen atmosphere, hydrogen is released until it contains hydrogen in an amount equivalent to 1% or less of the nominal capacity of the negative electrode, and then assembled into a battery. .
【０００９】ここで、水素吸蔵合金電極からなる負極の
電位は、参照電極（Ｈｇ／ＨｇＯ）に対して−０．９Ｖ
以上−０．７Ｖ以下とすることが好ましい。Here, the potential of the negative electrode made of a hydrogen storage alloy electrode is -0.9V with respect to the reference electrode (Hg/HgO).
It is preferable that the voltage is -0.7 V or more.
【００１０】0010
【作用】本発明の製造方法によれば、水素吸蔵合金電極
の水素吸蔵量を負極の公称容量の１％以下にすることに
よって、過充電時において、負極が正極より速く満充電
状態にならないため、正極から発生する酸素ガスを負極
で十分に消費することができる。したがって、酸素ガス
発生によって電池内圧が上昇し、弁作動することで電解
液が漏れ、電池重量が減少して電極特性が低下するとい
ったこともなくなり、酸素ガスによる水素吸蔵合金電極
の酸化も抑制することができる。[Function] According to the manufacturing method of the present invention, by setting the hydrogen storage capacity of the hydrogen storage alloy electrode to 1% or less of the nominal capacity of the negative electrode, the negative electrode does not become fully charged faster than the positive electrode during overcharging. , oxygen gas generated from the positive electrode can be sufficiently consumed at the negative electrode. Therefore, the internal pressure of the battery increases due to the generation of oxygen gas, the electrolyte leaks due to valve operation, the weight of the battery decreases, and the electrode characteristics deteriorate. This also prevents the oxidation of the hydrogen storage alloy electrode due to oxygen gas. be able to.
【００１１】また、水素吸蔵合金は、水素を吸蔵及び放
出させると反応性が増し活性化する。この活性化処理時
に負極の公称容量の１％以下まで水素吸蔵量を減少させ
ると、水素吸蔵合金はそのほとんどが活性化される。そ
のため負極容量は十分に発揮され、この水素吸蔵合金を
負極として電池に組んだときに、サイクル初期から十分
に高い電池容量が得ることができる。[0011] Furthermore, when hydrogen storage alloys are allowed to store and release hydrogen, their reactivity increases and they become activated. When the hydrogen storage amount is reduced to 1% or less of the nominal capacity of the negative electrode during this activation treatment, most of the hydrogen storage alloy is activated. Therefore, the negative electrode capacity is fully exhibited, and when this hydrogen storage alloy is used as a negative electrode in a battery, a sufficiently high battery capacity can be obtained from the beginning of the cycle.
【００１２】0012
【実施例】本発明の一実施例を以下に説明する。[Example] An example of the present invention will be described below.
【００１３】市販のミッシュメタルＭｍ（Ｌａ、Ｃｅ、
Ｎｄ、Ｐｒなどの希土類元素の混合物）、Ｎｉ、Ｃｏ及
びＡｌを一定の元素比、Ｍｍ：Ｎｉ：ＣＯ：Ａｌが１：
３：１．５：０．５になるように秤量して混合する。Commercially available misch metal Mm (La, Ce,
A mixture of rare earth elements such as Nd and Pr), Ni, Co and Al in a constant element ratio, Mm:Ni:CO:Al being 1:
Weigh and mix so that the ratio is 3:1.5:0.5.
【００１４】次に、この混合物をアルゴンアーク溶解炉
により加熱溶解させ、ＭｍＮｉ３Ｃ ｏ１．５Ａｌ０．
５ の組成を有する合金を製造した。Next, this mixture was heated and melted in an argon arc melting furnace to form MmNi3C o1.5Al0.
An alloy having a composition of 5 was produced.
【００１５】次いで、この合金を通常の機械的な粉砕に
よって、５０μｍ以下の微粉末とした。[0015] Next, this alloy was made into a fine powder of 50 μm or less by ordinary mechanical pulverization.
【００１６】この微粉末に結着剤としてのポリテトラフ
ルオロエチレン（ＰＴＦＥ）ディスパージョンを添加し
、均一に混合し、水を加えてペースト状にする。A polytetrafluoroethylene (PTFE) dispersion as a binder is added to this fine powder, mixed uniformly, and water is added to form a paste.
【００１７】このペーストを、ニッケルメッキを施した
パンチングメタル集電体の両面に圧着して水素吸蔵合金
負極を作製した。[0017] This paste was pressed onto both sides of a nickel-plated punched metal current collector to produce a hydrogen storage alloy negative electrode.
【００１８】この水素吸蔵合金からなる負極と、公知の
焼結式ニッケル正極とを、不織布から成るセパレータを
介して渦巻状に巻取って電極体を作製し、電池缶に挿入
した。この上部を開放状態にしたままの電池缶を耐圧ガ
スケースに入れ、水素ガスを導入し、１０ｋｇ／ｃｍ２
の圧力に保った。この状態で、水素吸蔵合金１ｇ当り１
００ ｃｃの水素を吸蔵させた。[0018] The negative electrode made of this hydrogen storage alloy and the known sintered nickel positive electrode were spirally wound with a separator made of nonwoven fabric interposed therebetween to prepare an electrode body, and the electrode body was inserted into a battery can. Place the battery can with the top open in a pressure-resistant gas case, and introduce hydrogen gas to a pressure of 10 kg/cm2.
pressure was maintained. In this state, 1 g of hydrogen storage alloy
00 cc of hydrogen was absorbed.
【００１９】その後、耐圧ガスケースを８０℃に加温し
、真空ポンプで真空度２ｔｏｒｒまで吸引し、水素を放
出させた。この状態では、水素吸蔵合金電極の水素吸蔵
量は負極の公称容量の１％以下である。[0019] Thereafter, the pressure-resistant gas case was heated to 80°C and suctioned to a vacuum level of 2 torr using a vacuum pump to release hydrogen. In this state, the hydrogen storage capacity of the hydrogen storage alloy electrode is 1% or less of the nominal capacity of the negative electrode.
【００２０】次に、耐圧ガスケース内より電池缶を取り
出し、電池缶に電解液を注液した。尚、電解液には３０
ｗｔ％の水酸化カリウム水溶液を用いる。Next, the battery can was taken out from inside the pressure-resistant gas case, and electrolyte was poured into the battery can. In addition, the electrolyte contains 30
A wt% potassium hydroxide aqueous solution is used.
【００２１】電解液注液後、電池缶の封口を行い完全に
密閉し、金属水素化物蓄電池を作製した。このように作
製した金属水素化物蓄電池を電池Ａとする。After injecting the electrolyte, the battery can was sealed and completely sealed to produce a metal hydride storage battery. The metal hydride storage battery produced in this manner is referred to as battery A.
【００２２】次に、真空ポンプでの真空度を１０ｔｏｒ
ｒで行う以外は、電池Ａと同一条件で、電池Ｂを作製し
た。
この場合の水素吸蔵合金電極の水素吸蔵量は負極の公称
容量の約３％に相当する。Next, the degree of vacuum in the vacuum pump is set to 10 torr.
Battery B was produced under the same conditions as Battery A, except that the battery B was used under the same conditions as Battery A. In this case, the hydrogen storage capacity of the hydrogen storage alloy electrode corresponds to about 3% of the nominal capacity of the negative electrode.
【００２３】また、真空ポンプでの真空度を２０ｔｏｒ
ｒで行う以外は、電池Ａと同一条件で、電池Ｃを作製し
た。
この場合の水素吸蔵合金電極の水素吸蔵量は負極の公称
容量の約１０％に相当する。[0023] Also, the degree of vacuum in the vacuum pump is set to 20 torr.
Battery C was produced under the same conditions as Battery A, except that the battery was run at r. In this case, the hydrogen storage capacity of the hydrogen storage alloy electrode corresponds to about 10% of the nominal capacity of the negative electrode.
【００２４】さらにまた、耐圧ガスケース内に電池缶を
入れず水素を吸蔵及び放出（活性化処理）しない以外は
電池Ａと同一条件で、電池Ｄを作製した。Furthermore, Battery D was produced under the same conditions as Battery A, except that the battery can was not placed in the pressure-resistant gas case and hydrogen was not absorbed and released (activated).
【００２５】これらの電池Ａ乃至Ｄについて、それぞれ
サイクル特性の評価を行った。サイクル特性の測定条件
は、２５℃の雰囲気下で０．３Ｃの電流で４時間充電し
た後、０．３Ｃの電流で電池電圧が１．０Ｖに達するま
で放電するものであり、サイクル特性は、この条件で充
放電を繰り返して測定を行った。The cycle characteristics of these batteries A to D were evaluated. The measurement conditions for cycle characteristics were to charge for 4 hours with a current of 0.3C in an atmosphere of 25°C, and then discharge with a current of 0.3C until the battery voltage reached 1.0V.The cycle characteristics were as follows. Measurements were performed by repeating charging and discharging under these conditions.
【００２６】図１に、電池Ａ乃至電池Ｄの初期から１０
サイクルまでのサイクル数と放電容量の関係を示す。FIG. 1 shows battery A to battery D starting from the beginning.
The relationship between the number of cycles and discharge capacity is shown.
【００２７】図１より、明らかなように、水素を吸蔵及
び放出させる活性化処理工程を行った電池Ａ、Ｂ及びＣ
は、電池Ｄに比べ初期から、放電容量が公称容量の１０
０％となることが判る。これは、活性化処理することに
より負極の活性化が行われ、負極の電極性能が初期から
十分発揮されているからである。これに対して、活性化
処理を行わなかった電池Ｄは、負極の活性化が十分でな
いために、数サイクル後に容量が回復しているが、公称
容量の１００％の放電容量は出ていない。As is clear from FIG. 1, batteries A, B, and C were subjected to the activation treatment step for occluding and desorbing hydrogen.
Compared to battery D, the discharge capacity was 10% of the nominal capacity from the beginning.
It turns out that it is 0%. This is because the negative electrode is activated by the activation treatment, and the electrode performance of the negative electrode is fully exhibited from the beginning. On the other hand, in battery D, which was not subjected to the activation treatment, the negative electrode was not sufficiently activated, so the capacity recovered after several cycles, but the discharge capacity was not 100% of the nominal capacity.
【００２８】次に、電池Ａ乃至電池Ｄ各々に使用した負
極を水酸化カリウム（３０％）水溶液中に浸漬後、０．
１Ｃの電流で放電させ、参照電極（Ｈｇ／ＨｇＯ）との
電位差を調べ図２に示した。ここで、−０．５Ｖに達す
るまでは、負極中の水素吸蔵合金の放電反応が行われる
が、−０．５Ｖより卑な電位では極板内では前記放電反
応は行われず不可逆的な酸化反応が起こるため、−０．
５Ｖに到達するまでの放電容量を放電可能量とした。Next, the negative electrodes used in each of Batteries A to D were immersed in a potassium hydroxide (30%) aqueous solution.
It was discharged with a current of 1 C, and the potential difference with the reference electrode (Hg/HgO) was investigated and is shown in FIG. Here, until reaching -0.5V, a discharge reaction of the hydrogen storage alloy in the negative electrode takes place, but at a potential less noble than -0.5V, the above-mentioned discharge reaction does not take place in the electrode plate, resulting in an irreversible oxidation reaction. occurs, -0.
The discharge capacity until reaching 5V was defined as the dischargeable amount.
【００２９】図２より、電気化学的に放電可能量を電池
Ａ、Ｂ、及びＣについて各々求めると、電池Ａは公称容
量の１％以下の放電容量をもち、電池Ｂは公称容量の３
％の放電容量をもち、電池Ｃは公称容量の１０％の放電
容量をもつことが判る。From FIG. 2, when the electrochemical discharge capacity is determined for batteries A, B, and C, battery A has a discharge capacity of 1% or less of the nominal capacity, and battery B has a discharge capacity of 3% of the nominal capacity.
It can be seen that battery C has a discharge capacity of 10% of its nominal capacity.
【００３０】次に、図３に電池Ａ乃至電池Ｄの１０００
サイクルまでのサイクル数と放電容量の関係を示す。Next, FIG. 3 shows 1000 cells of batteries A to D.
The relationship between the number of cycles and discharge capacity is shown.
【００３１】図３より真空度２ｔｏｒｒで水素の放出を
行い負極の公称容量の１％以下の放電容量を持つ電池Ａ
は、水素を吸蔵及び放出した後の水素吸蔵量が多く負極
の公称容量の３％及び１０％の放電容量を持つ電池Ｂ及
びＣに比べ、充電時に負極が満充電になるのが遅いため
、負極からのガス発生が見られず、負極で行う正極から
発生するガスの消費が良好になるためサイクル寿命が向
上している。From FIG. 3, battery A releases hydrogen at a vacuum level of 2 torr and has a discharge capacity of 1% or less of the nominal capacity of the negative electrode.
Compared to Batteries B and C, which have a large amount of hydrogen storage after storing and desorbing hydrogen, and have a discharge capacity of 3% and 10% of the negative electrode's nominal capacity, the negative electrode is slower to reach full charge during charging. No gas is generated from the negative electrode, and the gas generated from the positive electrode is better consumed by the negative electrode, resulting in an improved cycle life.
【００３２】以上より、電池Ａは、サイクル初期から公
称容量の１００％の放電容量を持ち、かつサイクル寿命
も長く優れた電池であることが判る。From the above, it can be seen that Battery A is an excellent battery having a discharge capacity of 100% of the nominal capacity from the beginning of the cycle and a long cycle life.
【００３３】次に、水素吸蔵合金の水素の放出量を規制
して水素吸蔵量が負極の公称容量の１％以下でかつ負極
板の電位が参照電極（Ｈｇ／ＨｇＯ）に対して、それぞ
れ−０．５、−０．７、−０．８、−０．９及び−０．
９３Ｖの電位差を持つ負極を用い、電池Ａと同一条件で
それぞれ電池Ｅ、Ｆ、Ｇ、Ｈ及びＩを作製した。この時
の電位測定温度は２０℃で行った。Next, the amount of hydrogen released from the hydrogen storage alloy is regulated so that the amount of hydrogen storage is 1% or less of the nominal capacity of the negative electrode and the potential of the negative electrode plate is - with respect to the reference electrode (Hg/HgO). 0.5, -0.7, -0.8, -0.9 and -0.
Batteries E, F, G, H, and I were produced under the same conditions as Battery A using negative electrodes with a potential difference of 93V. The potential measurement temperature at this time was 20°C.
【００３４】図４に、電池Ｅ乃至電池Ｉの１０００サイ
クルまでのサイクル数と放電容量の関係を示す。FIG. 4 shows the relationship between the number of cycles up to 1000 cycles and the discharge capacity of batteries E to I.
【００３５】図４から判るように、電池Ｅ、Ｆ及びＧは
サイクル性能が良好である。このことは、水素吸蔵合金
電極の電位が−０．７Ｖより貴な電位であると酸化電位
となり水素吸蔵合金の劣化が進行するためである。した
がって、サイクル数が進行するにつれて放電容量は低下
している。また、水素吸蔵合金電極の電位が−０．９Ｖ
未満であると水素吸蔵合金が平衡圧状態の電位となるた
め、水素の吸蔵及び放出量が低下するために、この水素
吸蔵合金を負極とする電池はサイクル寿命の低下を引き
起こす。このため、水素吸蔵合金の電位を−０．９Ｖ以
上−０．７Ｖ以下にすることが好ましい。As can be seen from FIG. 4, batteries E, F, and G have good cycle performance. This is because if the potential of the hydrogen storage alloy electrode is nobler than -0.7V, it becomes an oxidation potential and the deterioration of the hydrogen storage alloy progresses. Therefore, as the number of cycles progresses, the discharge capacity decreases. In addition, the potential of the hydrogen storage alloy electrode is -0.9V
If the hydrogen storage alloy is less than 100%, the potential of the hydrogen storage alloy is at an equilibrium pressure state, and the amount of hydrogen storage and release decreases, resulting in a reduction in the cycle life of a battery using this hydrogen storage alloy as a negative electrode. For this reason, it is preferable that the potential of the hydrogen storage alloy is -0.9V or more and -0.7V or less.
【００３６】[0036]
【発明の効果】以上より、水素吸蔵合金電極からなる負
極を活性化処理して水素吸蔵量を公称容量の１％以下に
した負極を用いた電池は、初期充放電時より公称容量の
１００％の放電容量が得られ、サイクル寿命が向上され
、その工業的価値は極めて大である。[Effects of the Invention] As described above, a battery using a negative electrode made of a hydrogen-absorbing alloy electrode which has been activated to reduce the amount of hydrogen storage to 1% or less of the nominal capacity can achieve 100% of the nominal capacity from the initial charge/discharge. The discharge capacity is obtained, the cycle life is improved, and its industrial value is extremely large.
【図１】電池Ａ乃至Ｄの１０サイクルまでの放電容量と
サイクル数の関係を示す図である。FIG. 1 is a diagram showing the relationship between discharge capacity and cycle number up to 10 cycles for batteries A to D.
【図２】電池Ａ乃至Ｄの電池組立て時の水素吸蔵合金電
極容量を示す図である。FIG. 2 is a diagram showing the capacity of hydrogen storage alloy electrodes when batteries A to D are assembled.
【図３】電池Ａ乃至Ｄの１０００サイクルまでの放電容
量とサイクル数の関係を示す図である。FIG. 3 is a diagram showing the relationship between discharge capacity and cycle number up to 1000 cycles for batteries A to D.
【図４】電池Ｅ乃至Ｉの１０００サイクルまでの放電容
量とサイクル数の関係を示す図である。FIG. 4 is a diagram showing the relationship between discharge capacity and cycle number up to 1000 cycles for batteries E to I.
Claims (2)
る金属水素化物蓄電池の製造方法において、この水素吸
蔵合金電極を水素雰囲気下で水素を吸蔵させた後、負極
の公称容量の１％以下に相当する量の水素を含んだ状態
まで水素を放出させた状態にして、電池に組み立てるこ
とを特徴とする金属水素化物蓄電池の製造方法。Claim 1: In a method for manufacturing a metal hydride storage battery using a negative electrode made of a hydrogen storage alloy electrode, after the hydrogen storage alloy electrode is allowed to store hydrogen in a hydrogen atmosphere, the hydrogen storage battery has a hydrogen storage capacity equivalent to 1% or less of the nominal capacity of the negative electrode. A method for manufacturing a metal hydride storage battery, which comprises assembling the metal hydride storage battery into a battery after releasing hydrogen to a state containing a certain amount of hydrogen.
電位が参照電極（Ｈｇ／ＨｇＯ）に対して−０．９Ｖ以
上−０．７Ｖ以下であることを特徴とする請求項１記載
の金属水素化物蓄電池の製造方法。2. The metal hydrogen according to claim 1, wherein the potential of the negative electrode made of the hydrogen storage alloy electrode is −0.9 V or more and −0.7 V or less with respect to a reference electrode (Hg/HgO). Method for manufacturing a compound storage battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3017995A JPH04255673A (en) | 1991-02-08 | 1991-02-08 | Manufacture of metal hydride storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3017995A JPH04255673A (en) | 1991-02-08 | 1991-02-08 | Manufacture of metal hydride storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04255673A true JPH04255673A (en) | 1992-09-10 |
Family
ID=11959309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3017995A Pending JPH04255673A (en) | 1991-02-08 | 1991-02-08 | Manufacture of metal hydride storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04255673A (en) |
-
1991
- 1991-02-08 JP JP3017995A patent/JPH04255673A/en active Pending
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