JP2001185138A - Positive electrode active material for alkaline storage battery and manufacturing method therefor - Google Patents
Positive electrode active material for alkaline storage battery and manufacturing method thereforInfo
- Publication number
- JP2001185138A JP2001185138A JP36962599A JP36962599A JP2001185138A JP 2001185138 A JP2001185138 A JP 2001185138A JP 36962599 A JP36962599 A JP 36962599A JP 36962599 A JP36962599 A JP 36962599A JP 2001185138 A JP2001185138 A JP 2001185138A
- Authority
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- Japan
- Prior art keywords
- active material
- positive electrode
- nickel
- storage battery
- electrode active
- 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.)
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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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、アルカリ蓄電池用
正極活物質及びその製法に関する。The present invention relates to a positive electrode active material for an alkaline storage battery and a method for producing the same.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
アルカリ蓄電池用ペースト式ニッケル極の活物質利用率
の向上を目的として、水酸化ニッケルと一酸化コバルト
との混合物に、Ｋ2 Ｓ2 Ｏ8 、Ｎａ2 Ｓ 2 Ｏ8 、（ＮＨ
4 ）2 Ｓ2 Ｏ8 、Ｈ2 Ｏ2 等の酸化剤を添加したり、水
酸化ニッケルとコバルトイオンとを含む溶液に、Ｋ2 Ｓ
2 Ｏ8 、Ｎａ2 Ｓ2 Ｏ8 、（ＮＨ 4 ）2 Ｓ2 Ｏ8 、Ｈ2
Ｏ2 等の酸化剤を添加して、水酸化ニッケル粒子表面を
導電性の高いβ−ＣｏＯＯＨで被覆したりすることが、
提案されている（国際公開公報ＷＯ ９３／０８６１
１）。2. Description of the Related Art
Active material utilization rate of paste-type nickel electrode for alkaline storage battery
Nickel hydroxide and cobalt monoxide to improve
To the mixture withTwo STwoO8 , NaTwo S TwoO8 , (NH
Four)TwoSTwoO8 , HTwoOTwoAdd an oxidizing agent such as
In a solution containing nickel oxide and cobalt ions, KTwo S
TwoO8 , NaTwo STwoO8 , (NH Four)TwoSTwoO8 , HTwo
OTwoAdd an oxidizing agent such as
Or coating with a highly conductive β-CoOOH,
Has been proposed (WO 93/0861).
1).
【０００３】しかしながら、本発明者らが検討した結
果、Ｋ2 Ｓ2 Ｏ8 等を酸化剤として用いる従来の方法で
は、β−ＣｏＯＯＨを水酸化ニッケル粒子の表面に均一
に分散させることができないために、活物質利用率を十
分に高めることは困難であることが分かった。However, as a result of investigations by the present inventors, β-CoOOH cannot be uniformly dispersed on the surface of nickel hydroxide particles by the conventional method using K 2 S 2 O 8 or the like as an oxidizing agent. In addition, it was found that it was difficult to sufficiently increase the active material utilization rate.
【０００４】また、特に亜鉛を負極活物質に用いる密閉
型アルカリ亜鉛蓄電池では、粒子表面を導電性の高いβ
−ＣｏＯＯＨで被覆していない水酸化ニッケル粒子を正
極活物質として用いた場合、以下の問題が生じる。In particular, in a sealed alkaline zinc storage battery using zinc as a negative electrode active material, a highly conductive β
-When nickel hydroxide particles not coated with CoOOH are used as the positive electrode active material, the following problems occur.
【０００５】正極に導電剤として添加するコバルト化合
物は、アルカリ水溶液中に浸漬した場合、ＨＣｏＯ2 -
として溶出し、これが負極（亜鉛極）にＣｏとして析出
するため、亜鉛の水素過電圧が低下して水素ガスが発生
し（自己放電）、電池内圧が上昇する。これは、Ｃｏの
水素過電圧が低いために、式〔１〕に示す亜鉛の自己放
電及び式〔２〕に示す水素ガス発生反応が起こるからで
ある。[0005] Cobalt compounds to be added as a conductive agent to the positive electrode, when immersed in an alkaline aqueous solution, HCoO 2 -
, And this is precipitated as Co on the negative electrode (zinc electrode), so that the hydrogen overvoltage of zinc decreases and hydrogen gas is generated (self-discharge), and the internal pressure of the battery increases. This is because the self-discharge of zinc represented by the formula [1] and the hydrogen gas generation reaction represented by the formula [2] occur because the hydrogen overvoltage of Co is low.
【０００６】 Ｚｎ＋２ＯＨ- →Ｚｎ（ＯＨ）2 ＋２ｅ- ……〔１〕 ２Ｈ2 Ｏ＋２ｅ- →Ｈ2 ＋２ＯＨ- ……〔２〕[0006] Zn + 2OH - → Zn (OH ) 2 + 2e - ...... [1] 2H 2 O + 2e - → H 2 + 2OH - ...... [2]
【０００７】上記の問題を解決するためには、アルカリ
水溶液を注液する前に、コバルト化合物を予め酸化して
オキシ水酸化コバルトに変化させることが必要である。
オキシ水酸化コバルトは、アルカリ水溶液に溶解しない
ので、負極に析出することがないからである。In order to solve the above problems, it is necessary to oxidize the cobalt compound in advance to convert it to cobalt oxyhydroxide before injecting the alkaline aqueous solution.
This is because cobalt oxyhydroxide does not dissolve in the alkaline aqueous solution, and thus does not precipitate on the negative electrode.
【０００８】従って、本発明は、β−ＣｏＯＯＨが水酸
化ニッケル粒子の表面に均一に分散して存在するために
粒子表面の導電性が極めて高いアルカリ蓄電池用正極活
物質及びその製法を提供することを目的とする。Accordingly, the present invention provides a positive electrode active material for an alkaline storage battery having extremely high conductivity on the surface of β-CoOOH since the β-CoOOH is uniformly dispersed on the surface of the nickel hydroxide particles, and a method for producing the same. With the goal.
【０００９】[0009]
【課題を解決するための手段】上記の目的を達成するた
めの本発明に係るアルカリ蓄電池用正極活物質の製法
（本発明方法）は、固溶元素としてマンガンを含有する
水酸化ニッケル粒子の表面にオキシ水酸化コバルト層を
形成して成るアルカリ蓄電池用正極活物質を製造するに
あたり、前記水酸化ニッケル粒子の表面に水酸化コバル
ト層を形成して複合体粒子を作製し、次いで、前記水酸
化コバルト層を酸化して前記オキシ水酸化コバルト層に
変えるべく、前記複合体粒子を、次亜塩素酸塩又は次亜
臭素酸塩を含有するアルカリ水溶液と混合することを特
徴とする。In order to achieve the above-mentioned object, a method for producing a cathode active material for an alkaline storage battery according to the present invention (the method of the present invention) comprises the steps of: preparing a surface of nickel hydroxide particles containing manganese as a solid solution element; In producing a positive electrode active material for an alkaline storage battery formed by forming a cobalt oxyhydroxide layer on the surface of the nickel hydroxide particles, a cobalt hydroxide layer is formed on the surface of the nickel hydroxide particles to form composite particles. The composite particles are mixed with an alkaline aqueous solution containing hypochlorite or hypobromite in order to oxidize the cobalt layer to convert it to the cobalt oxyhydroxide layer.
【００１０】本発明方法においては、水酸化ニッケル粒
子として、マンガンを固溶元素として含有する水酸化ニ
ッケル粒子を使用する。マンガンを固溶元素として含有
する水酸化ニッケル粒子は、マンガンを固溶元素として
含有しない水酸化ニッケル粒子に比べて酸素過電圧が大
きいので、充電受け入れ性が良い。マンガンを固溶元素
として含有する水酸化ニッケル粒子は、例えば、マンガ
ン塩及びニッケル塩を溶かした水溶液に、アルカリを添
加することにより、共沈物として得ることができる（ア
ルカリ共沈法）。マンガンの固溶量は、使用するマンガ
ン塩の量を加減することにより調整することができる。
水酸化ニッケル粒子としては、マンガンの固溶量が、ニ
ッケルとマンガンとの総量に基づいて、１５〜５０重量
％のものを使用することが好ましい。マンガンの固溶量
が１５重量％未満の場合は、酸素過電圧が充分に増大せ
ず活物質利用率が低下する傾向がある。一方、マンガン
の固溶量が５０重量％を越えた場合は、水酸化ニッケル
の充填量の減少の影響が大きくなり、放電容量（電池容
量）が減少する傾向がある。In the method of the present invention, nickel hydroxide particles containing manganese as a solid solution element are used as the nickel hydroxide particles. Nickel hydroxide particles containing manganese as a solid solution element have a higher oxygen overvoltage than nickel hydroxide particles not containing manganese as a solid solution element, and thus have good charge acceptability. Nickel hydroxide particles containing manganese as a solid solution element can be obtained as a coprecipitate, for example, by adding an alkali to an aqueous solution in which a manganese salt and a nickel salt are dissolved (alkali coprecipitation method). The manganese solid solution amount can be adjusted by adjusting the amount of the manganese salt used.
As the nickel hydroxide particles, those having a solid solution amount of manganese of 15 to 50% by weight based on the total amount of nickel and manganese are preferably used. When the solid solution amount of manganese is less than 15% by weight, the oxygen overpotential does not sufficiently increase and the active material utilization rate tends to decrease. On the other hand, when the solid solution amount of manganese exceeds 50% by weight, the effect of the decrease in the filling amount of nickel hydroxide increases, and the discharge capacity (battery capacity) tends to decrease.
【００１１】水酸化ニッケル粒子としては、固溶元素と
して、さらに、コバルト、亜鉛、カルシウム、アルミニ
ウム、イットリウム、イッテルビウム、エルビウム及び
ガドリニウムよりなる群から選ばれた少なくとも１種の
元素Ｍを含有するものを使用することが好ましい。これ
らの元素Ｍを含有せしめることにより、充電受け入れ性
のいっそう良い正極活物質が得られる。元素Ｍの固溶量
は、ニッケルと元素Ｍとの総量に基づいて、５重量％以
下が好ましい。元素Ｍの固溶量が５重量％を越えた場合
は、水酸化ニッケルの充填量の減少の影響が大きくな
り、放電容量が減少する。The nickel hydroxide particles include those containing at least one element M selected from the group consisting of cobalt, zinc, calcium, aluminum, yttrium, ytterbium, erbium and gadolinium as a solid solution element. It is preferred to use. By incorporating these elements M, a positive electrode active material having better charge acceptability can be obtained. The solid solution amount of the element M is preferably 5% by weight or less based on the total amount of nickel and the element M. When the amount of the solid solution of the element M exceeds 5% by weight, the effect of the decrease in the filling amount of nickel hydroxide increases, and the discharge capacity decreases.
【００１２】本発明方法においては、水酸化ニッケル粒
子の表面に先ず水酸化コバルト層を形成して複合体粒子
を作製する。In the method of the present invention, a composite particle is prepared by first forming a cobalt hydroxide layer on the surface of the nickel hydroxide particles.
【００１３】水酸化コバルト層を先ず形成することとし
ているのは、水酸化コバルト（β−Ｃｏ（ＯＨ）2 ）を
水酸化ニッケル粒子の表面に均一に分散して存在させる
ことにより、次の工程での酸化剤の添加によりオキシ水
酸化コバルト（β−ＣｏＯＯＨ）が水酸化ニッケル粒子
の表面に均一に分散して生成するようにするためであ
る。The first step of forming the cobalt hydroxide layer is that cobalt hydroxide (β-Co (OH) 2 ) is uniformly dispersed on the surface of the nickel hydroxide particles, so that the next step is performed. The reason for this is that the addition of the oxidizing agent causes the cobalt oxyhydroxide (β-CoOOH) to be uniformly dispersed and generated on the surface of the nickel hydroxide particles.
【００１４】上記複合体粒子は、例えば、コバルト塩の
水溶液に水酸化ニッケル粉末を投入し、アルカリ水溶液
を添加することにより、沈殿物として得ることができ
る。The composite particles can be obtained as a precipitate, for example, by adding nickel hydroxide powder to an aqueous solution of a cobalt salt and adding an aqueous alkali solution.
【００１５】本発明方法においては、次いで、上記複合
体粒子の表面の水酸化コバルト層を酸化してオキシ水酸
化コバルト層に変えるべく、上記複合体粒子粉末を、次
亜塩素酸ナトリウム（ＮａＣｌＯ）、次亜塩素酸カルシ
ウム（Ｃａ（ＣｌＯ）2 ）等の次亜塩素酸塩、又は、次
亜臭素酸ナトリウム（ＮａＢｒＯ）、次亜臭素酸カルシ
ウム（Ｃａ（ＢｒＯ）2 ）等の次亜臭素酸塩を含有する
アルカリ水溶液と混合する。酸化剤として、次亜塩素酸
塩又は次亜臭素酸塩を使用することとしているのは、次
亜塩素酸塩及び次亜臭素酸塩は、Ｋ2 Ｓ2 Ｏ8 、Ｎａ2
Ｓ2 Ｏ8 、（ＮＨ4 ）2 Ｓ2 Ｏ8 、Ｈ2 Ｏ2 に比べて酸
化力が弱く、このため水酸化ニッケル粒子の表面にβ−
ＣｏＯＯＨを均一に分散して生成させることができるか
らである。In the method of the present invention, the composite particle powder is then subjected to sodium hypochlorite (NaClO) so as to oxidize the cobalt hydroxide layer on the surface of the composite particle into a cobalt oxyhydroxide layer. Hypochlorite such as calcium hypochlorite (Ca (ClO) 2 ) or hypobromite such as sodium hypobromite (NaBrO) or calcium hypobromite (Ca (BrO) 2 ) Mix with an aqueous alkaline solution containing a salt. The hypochlorite or hypobromite is used as the oxidizing agent because the hypochlorite and hypobromite are K 2 S 2 O 8 , Na 2
S 2 O 8 , (NH 4 ) 2 S 2 O 8 , has a weaker oxidizing power than H 2 O 2 , so that the surface of the nickel hydroxide particles has β-
This is because CoOOH can be uniformly dispersed and generated.
【００１６】アルカリ水溶液としては、３０〜７０°Ｃ
に保持した２０〜４０重量％水酸化ナトリウム水溶液を
使用することが好ましい。上記の酸化処理を３０°Ｃよ
り低温で行った場合及び２０重量％未満の水酸化ナトリ
ウム水溶液を使用して行った場合は、酸化反応が進行し
にくくなるため、一方、上記の酸化処理を７０°Ｃより
高温で行った場合及び４０重量％を越える水酸化ナトリ
ウム水溶液を使用して行った場合は、酸化反応が急激に
進行し、その結果、先の工程において水酸化ニッケル粒
子の表面に均一に分散して生成させたコバルト化合物の
一部が脱落し、水酸化ニッケル粒子の表面に生成するβ
−ＣｏＯＯＨの均一分散性が低下するため、いずれの場
合も得られる正極活物質の粒子表面の導電性が低下して
活物質利用率が低下する傾向がある。The aqueous alkaline solution is 30 to 70 ° C.
It is preferable to use an aqueous solution of 20 to 40% by weight of sodium hydroxide held in water. When the above-mentioned oxidation treatment is performed at a temperature lower than 30 ° C. or when an aqueous solution of sodium hydroxide of less than 20% by weight is used, the oxidation reaction hardly proceeds. When carried out at a temperature higher than 0 ° C. and when using an aqueous solution of sodium hydroxide exceeding 40% by weight, the oxidation reaction proceeds rapidly, and as a result, the surface of the nickel hydroxide particles is uniformly formed in the previous step. Β part of the cobalt compound formed by dispersing in the nickel hydroxide particles
Since the uniform dispersibility of -CoOOH is reduced, the conductivity of the particle surface of the obtained positive electrode active material is reduced in any case, and the active material utilization tends to be reduced.
【００１７】マンガンを固溶元素として含有する水酸化
ニッケル粒子に対するオキシ水酸化コバルト層の比率
は、コバルト元素換算で、２〜１０重量％とすることが
好ましい。同比率が２重量％未満の場合は、導電剤とし
てのオキシ水酸化コバルト量が少ないために、活物質利
用率が低下する。一方、同比率が１０重量％を越えた場
合は、水酸化ニッケルの充填量の減少の影響が大きくな
り、放電容量が減少する。オキシ水酸化コバルト層の比
率は、水酸化コバルト層を形成する先の工程において、
使用するコバルト塩の量を加減することにより調整する
ことができる。The ratio of the cobalt oxyhydroxide layer to the nickel hydroxide particles containing manganese as a solid solution element is preferably 2 to 10% by weight in terms of cobalt element. When the ratio is less than 2% by weight, the active material utilization rate decreases because the amount of cobalt oxyhydroxide as the conductive agent is small. On the other hand, when the ratio exceeds 10% by weight, the effect of the decrease in the amount of nickel hydroxide charged becomes large, and the discharge capacity decreases. The ratio of the cobalt oxyhydroxide layer is, in the previous step of forming the cobalt hydroxide layer,
It can be adjusted by adjusting the amount of the cobalt salt used.
【００１８】本発明方法により作製した正極活物質は粒
子表面の導電性が良い。したがって、これを使用するこ
とにより活物質利用率の高いペースト式ニッケル極を得
ることが可能になる。また、上記ペースト式ニッケル極
を密閉型ニッケル・亜鉛蓄電池の正極として使用するこ
とにより、負極での自己放電が少ない、信頼性の高い密
閉型電池を得ることが可能になる。The positive electrode active material produced by the method of the present invention has good conductivity on the particle surface. Therefore, by using this, it is possible to obtain a paste-type nickel electrode having a high active material utilization rate. In addition, by using the paste-type nickel electrode as the positive electrode of the sealed nickel-zinc storage battery, it is possible to obtain a highly reliable sealed battery with less self-discharge at the negative electrode.
【００１９】[0019]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例に何ら限定されるも
のではなく、その要旨を変更しない範囲において適宜変
更して実施することが可能なものである。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples, and may be carried out by appropriately changing the scope of the invention without changing its gist. Is possible.
【００２０】（実験１）本発明方法により作製した正極
活物質を使用したアルカリ蓄電池と比較方法により作製
した正極活物質を使用したアルカリ蓄電池について、活
物質利用率及び放電容量を調べた。(Experiment 1) The active material utilization rate and the discharge capacity of an alkaline storage battery using the positive electrode active material manufactured by the method of the present invention and an alkaline storage battery using the positive electrode active material manufactured by the comparative method were examined.
【００２１】（実施例１） ステップ１：水酸化ニッケル粒子の作製 硫酸マンガン（ＭｎＳＯ4 ）４０．４ｇ及び硫酸ニッケ
ル（ＮｉＳＯ4 ）１５４．８ｇを水に溶かした水溶液５
０００ｍｌに、１０重量％アンモニア水と１０重量％水
酸化ナトリウム水溶液との重量比１：１の混液を滴下し
てｐＨを１０．５±０．５に調整し、ｐＨが一定になっ
た後、１時間攪拌混合した。次いで、沈殿物をろ別し、
水洗し、８０°Ｃで乾燥して、固溶元素としてマンガン
を含有する水酸化ニッケル粒子粉末を作製した。この水
酸化ニッケル粒子のマンガン固溶量を原子吸光法により
調べたところ、ニッケルとマンガンの総量に基づいて２
０重量％であった。(Example 1) Step 1: Preparation of nickel hydroxide particles An aqueous solution 5 in which 40.4 g of manganese sulfate (MnSO 4 ) and 154.8 g of nickel sulfate (NiSO 4 ) are dissolved in water
A mixture of 10% by weight of aqueous ammonia and a 10% by weight of aqueous sodium hydroxide in a weight ratio of 1: 1 was dropped into 000 ml to adjust the pH to 10.5 ± 0.5, and after the pH became constant, Stir and mix for 1 hour. Then, the precipitate is filtered off,
After washing with water and drying at 80 ° C., nickel hydroxide particles containing manganese as a solid solution element were produced. The amount of manganese dissolved in the nickel hydroxide particles was determined by atomic absorption spectroscopy.
It was 0% by weight.
【００２２】ステップ２：複合体粒子の作製 硫酸コバルト（ＣｏＳＯ4 ）１３．１ｇを水に溶かした
水溶液１０００ｍｌに、ステップ１で作製した水酸化ニ
ッケル粒子粉末１００ｇを投入し、３０重量％水酸化ナ
トリウム水溶液を滴下してｐＨを９±０．５に調整し、
ｐＨが一定になった後、１時間攪拌混合した。次いで、
沈殿物をろ別し、水洗し、８０°Ｃで乾燥して、水酸化
ニッケル粒子の表面に水酸化コバルト層を形成して成る
複合体粒子を作製した。Step 2: Preparation of Composite Particles To 1000 ml of an aqueous solution of 13.1 g of cobalt sulfate (CoSO 4 ) dissolved in water, 100 g of the nickel hydroxide particle powder prepared in Step 1 is added, and 30% by weight of sodium hydroxide The pH is adjusted to 9 ± 0.5 by dropping the aqueous solution,
After the pH became constant, the mixture was stirred and mixed for 1 hour. Then
The precipitate was separated by filtration, washed with water, and dried at 80 ° C. to produce composite particles having a cobalt hydroxide layer formed on the surface of nickel hydroxide particles.
【００２３】ステップ３：正極活物質の作製 ３０重量％水酸化ナトリウム水溶液１０００ｍｌに、１
２重量％次亜塩素酸ナトリウム水溶液６２ｇを投入し、
５０°Ｃに加熱した後、ステップ２で作製した複合体粉
末１００ｇを投入し、１時間攪拌混合し、ろ過し、ろ物
を水洗し、８０°Ｃで乾燥して、水酸化ニッケル粒子の
表面にオキシ水酸化コバルト層を形成して成る正極活物
質を作製した。この正極活物質のマンガン固溶量を原子
吸光法により調べたところ、ニッケルとマンガンの総量
に基づいて２０重量％であった。また、水酸化ニッケル
粒子に対するオキシ水酸化コバルト層のコバルト原子換
算での比率を原子吸光法により調べたところ、５重量％
であった。Step 3: Preparation of Positive Electrode Active Material
62 g of a 2% by weight aqueous solution of sodium hypochlorite is added,
After heating to 50 ° C., 100 g of the composite powder prepared in Step 2 was added, and the mixture was stirred and mixed for 1 hour, filtered, washed with water, and dried at 80 ° C. to obtain a surface of nickel hydroxide particles. A positive electrode active material was formed by forming a cobalt oxyhydroxide layer on the substrate. When the manganese solid solution amount of this positive electrode active material was examined by an atomic absorption method, it was 20% by weight based on the total amount of nickel and manganese. When the ratio of the cobalt oxyhydroxide layer to the nickel hydroxide particles in terms of cobalt atoms was determined by an atomic absorption method, the ratio was 5% by weight.
Met.
【００２４】〔非焼結式ニッケル極の作製〕上記の正極
活物質１００ｇとペースト化剤としての１重量％メチル
セルロース水溶液４０ｇとを混練してペーストを調製
し、このペーストを発泡ニッケル（多孔度９５％、平均
孔径２００μｍ）からなる多孔性基板に充填し、乾燥
し、加圧成形して、縦４０ｍｍ、横６５ｍｍ、厚み０．
６ｍｍの本発明電極を作製した。[Preparation of Non-Sintered Nickel Electrode] A paste was prepared by kneading 100 g of the above-mentioned positive electrode active material and 40 g of a 1% by weight aqueous solution of methylcellulose as a pasting agent. %, Average pore size of 200 μm), dried, pressed and molded to a height of 40 mm, a width of 65 mm and a thickness of 0.1 mm.
A 6 mm electrode of the present invention was produced.
【００２５】〔密閉型ニッケル・亜鉛蓄電池の作製〕酸
化亜鉛と金属亜鉛と酸化インジウムとの重量比率４０：
２０：１の混合物２５０ｇと、ペースト化剤としての６
０重量％ＰＴＦＥ（ポリテトラフルオロエチレン）水分
散液１５ｇとを混合してペーストを調製し、このペース
トを厚さ０．１ｍｍの真鍮製のパンチングメタルに貼り
あわせ、圧延した後、６０°Ｃで乾燥して、縦４２ｍ
ｍ、横１００ｍｍ、厚み０．６ｍｍの亜鉛極を作製し
た。次いで、上記の本発明電極（正極）、上記の亜鉛極
（負極）、ポリアミド不織布（セパレータ）、３０重量
％水酸化カリウム水溶液（アルカリ電解液）、金属製の
電池缶、金属製の電池蓋などを用いて、ＡＡサイズの密
閉型ニッケル・亜鉛蓄電池（電池容量：約１０００ｍＡ
ｈ）Ａ１（本発明電池）を作製した。なお、負極と正極
の容量比を４：１とした。[Production of sealed nickel-zinc storage battery] A weight ratio of zinc oxide, metallic zinc and indium oxide of 40:
250 g of a 20: 1 mixture with 6 as a pasting agent
A paste was prepared by mixing 15 g of an aqueous dispersion of 0% by weight of PTFE (polytetrafluoroethylene), and the paste was attached to a 0.1 mm-thick brass punching metal, rolled, and then heated at 60 ° C. Dry, length 42m
A zinc electrode having a length of 100 mm, a width of 100 mm and a thickness of 0.6 mm was prepared. Then, the above-mentioned electrode of the present invention (positive electrode), the above-mentioned zinc electrode (negative electrode), polyamide nonwoven fabric (separator), 30% by weight potassium hydroxide aqueous solution (alkaline electrolyte), metal battery can, metal battery lid, etc. AA-size sealed nickel-zinc storage battery (battery capacity: about 1000 mA)
h) A1 (battery of the present invention) was prepared. The capacity ratio between the negative electrode and the positive electrode was set to 4: 1.
【００２６】（実施例２）ステップ３において、酸化剤
として１２重量％次亜塩素酸ナトリウム水溶液６２ｇに
代えて、５重量％次亜臭素酸ナトリウム水溶液を２３．
４ｇ使用したこと以外は実施例１と同様にして、正極の
みが本発明電池Ａ１と異なる密閉型ニッケル・亜鉛蓄電
池Ａ２（本発明電池）を作製した。Example 2 In step 3, a 5% by weight aqueous solution of sodium hypobromite was used instead of 62 g of a 12% by weight aqueous solution of sodium hypochlorite as an oxidizing agent.
A sealed nickel-zinc storage battery A2 (battery of the present invention) was prepared in the same manner as in Example 1 except that 4 g of the battery was used, and only the positive electrode was different from the battery A1 of the present invention.
【００２７】（比較例１）ステップ３を行わず、ステッ
プ２で作製した複合体粒子をそのまま非焼結式ニッケル
極の作製において正極活物質として使用したこと以外は
実施例１と同様にして、正極のみが本発明電池Ａ１と異
なる密閉型ニッケル・亜鉛蓄電池Ｘ（比較電池）を作製
した。Comparative Example 1 The procedure of Example 1 was repeated, except that Step 3 was not performed, and the composite particles produced in Step 2 were used as a positive electrode active material in producing a non-sintered nickel electrode. A sealed nickel-zinc storage battery X (comparative battery) in which only the positive electrode was different from the battery A1 of the present invention was produced.
【００２８】（比較例２）ステップ３において、酸化剤
として１２重量％次亜塩素酸ナトリウム水溶液６２ｇに
代えて、Ｋ2 Ｓ2 Ｏ8 を２．７ｇ使用したこと以外は実
施例１と同様にして、正極のみが本発明電池Ａ１と異な
る密閉型ニッケル・亜鉛蓄電池Ｙ１（比較電池）を作製
した。Comparative Example 2 In the same manner as in Example 1 except that 2.7 g of K 2 S 2 O 8 was used in Step 3 instead of 62 g of a 12% by weight aqueous solution of sodium hypochlorite as an oxidizing agent. Thus, a sealed nickel-zinc storage battery Y1 (comparative battery) in which only the positive electrode was different from the battery A1 of the present invention was produced.
【００２９】（比較例３）ステップ１において、硫酸マ
ンガンを使用せず、且つステップ３において、１２重量
％次亜塩素酸ナトリウム水溶液６２ｇに代えて、Ｋ2 Ｓ
2 Ｏ8 を２．７ｇ使用したこと以外は実施例１と同様に
して、正極のみが本発明電池Ａ１と異なる密閉型ニッケ
ル・亜鉛蓄電池Ｙ２（比較電池）を作製した。(Comparative Example 3) In step 1, manganese sulfate was not used, and in step 3, instead of 62 g of a 12% by weight aqueous solution of sodium hypochlorite, K 2 S was used.
A sealed nickel-zinc storage battery Y2 (comparative battery) having a positive electrode different from that of the battery A1 of the present invention was produced in the same manner as in Example 1 except that 2.7 g of 2 O 8 was used.
【００３０】（比較例４）固溶元素としてマンガンを２
０重量％含有する水酸化ニッケル粒子粉末と、粒径１μ
ｍ、比表面積７０ｃｍ2 ／ｇの一酸化コバルト粉末と
を、比重１．２５の水酸化カリウム水溶液中にて、重量
比９４．５：５．５で混合した後、ろ過し、水洗し、ろ
物を２重量％ＣＭＣ水溶液と混合してペーストを調製
し、このペーストを発泡ニッケルからなる多孔性基板の
孔内に充填し、乾燥し、加圧成形して、電極を作製し
た。次いで、この電極を、比重１．２５の水酸化カリウ
ム水溶液に浸漬し、Ｋ2 Ｓ2 Ｏ8 ０．４ｇを添加し、さ
らにＫ2 Ｓ2 Ｏ8 を酸素ガスが発生するまで追加で添加
して、一酸化コバルトをオキシ水酸化ニッケルに変えた
後、水洗し、乾燥して、比較電極を作製した。次いで、
この比較電極を正極として使用して、正極のみが本発明
電池Ａ１と異なる密閉型ニッケル・亜鉛蓄電池Ｚ１（比
較電池）を作製した。(Comparative Example 4) Manganese as a solid solution element
Nickel hydroxide particle powder containing 0% by weight and a particle diameter of 1 μm
m, and a specific surface area of 70 cm 2 / g of cobalt monoxide powder were mixed at a weight ratio of 94.5: 5.5 in an aqueous potassium hydroxide solution having a specific gravity of 1.25, followed by filtration, washing with water, and filtration. The product was mixed with a 2% by weight aqueous solution of CMC to prepare a paste, and the paste was filled in the pores of a porous substrate made of foamed nickel, dried, and pressed to form an electrode. Next, this electrode was immersed in an aqueous solution of potassium hydroxide having a specific gravity of 1.25, 0.4 g of K 2 S 2 O 8 was added, and K 2 S 2 O 8 was further added until oxygen gas was generated. Then, after changing cobalt monoxide to nickel oxyhydroxide, it was washed with water and dried to prepare a comparative electrode. Then
Using this comparative electrode as a positive electrode, a sealed nickel-zinc storage battery Z1 (comparative battery) in which only the positive electrode was different from the battery A1 of the present invention was produced.
【００３１】（比較例５）固溶元素としてマンガンを２
０重量％含有する水酸化ニッケル粒子粉末に代えて、マ
ンガンを含有しない水酸化ニッケル粒子粉末を使用した
こと以外は比較例４と同様にして、正極のみが本発明電
池Ａ１と異なる密閉型ニッケル・亜鉛蓄電池Ｚ２（比較
電池）を作製した。(Comparative Example 5) Manganese as a solid solution element
In the same manner as in Comparative Example 4 except that the nickel hydroxide particle powder containing no manganese was used instead of the nickel hydroxide particle powder containing 0% by weight, a sealed nickel alloy having only the positive electrode different from the battery A1 of the present invention was used. A zinc storage battery Z2 (comparative battery) was produced.
【００３２】〈活物質利用率及び放電容量〉各電池につ
いて、２５°Ｃにて１００ｍＡで１２時間充電した後、
２５°Ｃにて１Ａで１．０Ｖまで放電する工程を１サイ
クルとする充放電を１０サイクル行い、各電池の正極
（ペースト式ニッケル極）の１０サイクル目の活物質利
用率及び１０サイクル目の放電容量を調べた。活物質利
用率は下式に基づき算出した。なお、以下の実験におけ
る活物質利用率も下式に基づき算出した値である。<Active Material Utilization and Discharge Capacity> After charging each battery at 25 ° C. and 100 mA for 12 hours,
10 cycles of charging / discharging were performed in which the step of discharging to 1.0 V at 1 A at 25 ° C. was 1 cycle, and the active material utilization rate at the 10th cycle of the positive electrode (paste nickel electrode) of each battery and the 10th cycle The discharge capacity was examined. The active material utilization was calculated based on the following equation. The active material utilization in the following experiments is also a value calculated based on the following equation.
【００３３】活物質利用率（％）＝｛放電容量（ｍＡ
ｈ）／〔使用した水酸化ニッケル量（ｇ）×２８８（ｍ
Ａｈ／ｇ）〕｝×１００Active material utilization rate (%) = ｛discharge capacity (mA)
h) / [amount of nickel hydroxide used (g) × 288 (m
Ah / g)]｝ × 100
【００３４】結果を表１に示す。但し、表１中の１０サ
イクル目の活物質利用率及び１０サイクル目の放電容量
は、それぞれ本発明電池Ａ１の１０サイクル目の活物質
利用率及び１０サイクル目の放電容量を１００としたと
きの指数である。Table 1 shows the results. However, the active material utilization rate at the 10th cycle and the discharge capacity at the 10th cycle in Table 1 are assuming that the active material utilization rate at the 10th cycle and the discharge capacity at the 10th cycle of the battery A1 of the present invention are 100, respectively. It is an index.
【００３５】[0035]
【表１】 [Table 1]
【００３６】表１より、本発明方法によれば、比較方法
に比べて、活物質利用率の高い正極活物質が得られるこ
とが分かる。比較電池Ｘで、液漏れが生じたのは、負極
で亜鉛が自己放電して、水素ガスが多量に発生したため
である。Table 1 shows that the method of the present invention can provide a positive electrode active material having a higher active material utilization rate than the comparative method. In the comparative battery X, the liquid leakage occurred because zinc was self-discharged at the negative electrode, and a large amount of hydrogen gas was generated.
【００３７】（実験２）水酸化ニッケル粒子中のマンガ
ンの固溶量の好適な範囲を調べた。(Experiment 2) A suitable range of the amount of manganese dissolved in the nickel hydroxide particles was examined.
【００３８】ステップ１における硫酸マンガンの使用量
を、２０．２ｇ、３０．３ｇ、１０１ｇ又は１２１ｇと
したこと以外は実施例１と同様にして、順に、密閉型ニ
ッケル・亜鉛蓄電池Ａ３、Ａ４、Ａ５及びＡ６を作製し
た。水酸化ニッケル粒子のマンガン固溶量を原子吸光法
により調べたところ、ニッケルとマンガンの総量に基づ
いて、順に、１０重量％、１５重量％、５０重量％及び
６０重量％であった。In the same manner as in Example 1 except that the amount of manganese sulfate used in Step 1 was 20.2 g, 30.3 g, 101 g, or 121 g, the sealed nickel-zinc storage batteries A3, A4, A5 And A6. When the manganese solid solution amount of the nickel hydroxide particles was examined by an atomic absorption method, they were 10% by weight, 15% by weight, 50% by weight and 60% by weight based on the total amount of nickel and manganese.
【００３９】各電池について、実験１で行ったものと同
じ条件の充放電を１０サイクル行い、各電池の正極の１
０サイクル目の活物質利用率及び１０サイクル目の放電
容量を調べた。結果を表２に示す。表２には、本発明電
池Ａ１についての結果も表１より転記して示してある。For each battery, 10 cycles of charge / discharge under the same conditions as those performed in Experiment 1 were performed, and 1
The active material utilization rate at the 0th cycle and the discharge capacity at the 10th cycle were examined. Table 2 shows the results. In Table 2, the results for the battery A1 of the present invention are also transcribed from Table 1.
【００４０】[0040]
【表２】 [Table 2]
【００４１】表２に示すように、活物質利用率はマンガ
ン固溶量が多くなるほど高くなるが、放電容量はマンガ
ン固溶量が少な過ぎる場合及び多過ぎる場合のいずれの
場合も減少する。マンガン固溶量が少な過ぎる場合に放
電容量が減少するのは、活物質利用率が低いためであ
り、一方マンガン固溶量が多過ぎる場合に放電容量が減
少するのは、水酸化ニッケルの充填量の減少の影響が大
きいからである。表２より、マンガンの固溶量が、ニッ
ケルとマンガンとの総量に基づいて、１５〜５０重量％
の水酸化ニッケル粒子を使用することが好ましいことが
分かる。As shown in Table 2, the active material utilization rate increases as the manganese solid solution amount increases, but the discharge capacity decreases when the manganese solid solution amount is too small or too large. When the manganese solid solution amount is too small, the discharge capacity decreases because the utilization rate of the active material is low. On the other hand, when the manganese solid solution amount is too large, the discharge capacity decreases because of the nickel hydroxide filling. This is because the effect of the decrease in the amount is large. From Table 2, the solid solution amount of manganese is 15 to 50% by weight based on the total amount of nickel and manganese.
It is understood that it is preferable to use nickel hydroxide particles.
【００４２】（実験３）酸化処理に使用するアルカリ水
溶液の好適な濃度範囲を調べた。(Experiment 3) A suitable concentration range of the aqueous alkali solution used for the oxidation treatment was examined.
【００４３】ステップ３において、３０重量％水酸化ナ
トリウム水溶液に代えて、１５重量％、２０重量％、４
０重量％又は４５重量％の水酸化ナトリウム水溶液を使
用したこと以外は実施例１と同様にして、順に、密閉型
ニッケル・亜鉛蓄電池Ａ７、Ａ８、Ａ９及びＡ１０を作
製した。In step 3, 15% by weight, 20% by weight, 4%
Sealed nickel-zinc batteries A7, A8, A9 and A10 were produced in the same manner as in Example 1 except that an aqueous solution of 0% by weight or 45% by weight of sodium hydroxide was used.
【００４４】各電池について、実験１で行ったものと同
じ条件の充放電を１０サイクル行い、各電池の正極の１
０サイクル目の活物質利用率及び１０サイクル目の放電
容量を調べた。結果を表３に示す。表３には、本発明電
池Ａ１についての結果も表１より転記して示してある。For each battery, 10 cycles of charging and discharging under the same conditions as those performed in Experiment 1 were performed, and the positive electrode 1
The active material utilization rate at the 0th cycle and the discharge capacity at the 10th cycle were examined. Table 3 shows the results. Table 3 also shows the results of the battery A1 of the present invention, transcribed from Table 1.
【００４５】[0045]
【表３】 [Table 3]
【００４６】表３より、酸化処理のアルカリ水溶液とし
て水酸化ナトリウム水溶液を使用する場合は、２０〜４
０重量％水酸化ナトリウム水溶液を使用することが好ま
しいことが分かる。As shown in Table 3, when an aqueous solution of sodium hydroxide is used as the aqueous alkali solution for the oxidation treatment, 20 to 4
It can be seen that it is preferable to use a 0% by weight aqueous sodium hydroxide solution.
【００４７】（実験４）酸化処理に使用するアルカリ水
溶液の好適な温度範囲を調べた。(Experiment 4) A suitable temperature range of the aqueous alkali solution used for the oxidation treatment was examined.
【００４８】ステップ３における酸化処理時の３０重量
％水酸化ナトリウム水溶液の温度を、５０°Ｃに代え
て、２５°Ｃ、３０°Ｃ、７０°Ｃ又は７５°Ｃとした
こと以外は実施例１と同様にして、順に、密閉型ニッケ
ル・亜鉛蓄電池Ａ１１、Ａ１２、Ａ１３及びＡ１４を作
製した。Example 3 except that the temperature of the 30% by weight aqueous sodium hydroxide solution during the oxidation treatment in Step 3 was changed to 25 ° C., 30 ° C., 70 ° C. or 75 ° C. instead of 50 ° C. In the same manner as in Example 1, sealed nickel-zinc storage batteries A11, A12, A13, and A14 were produced in this order.
【００４９】各電池について、実験１で行ったものと同
じ条件の充放電を１０サイクル行い、各電池の正極の１
０サイクル目の活物質利用率を調べた。結果を表４に示
す。表４には、本発明電池Ａ１についての結果も表１よ
り転記して示してある。For each battery, 10 cycles of charging and discharging under the same conditions as those performed in Experiment 1 were performed, and the positive electrode 1
The active material utilization rate at the 0th cycle was examined. Table 4 shows the results. In Table 4, the results for the battery A1 of the present invention are also transcribed from Table 1.
【００５０】[0050]
【表４】 [Table 4]
【００５１】表４より、酸化処理のアルカリ水溶液とし
て水酸化ナトリウム水溶液を使用する場合は、３０〜７
０°Ｃに保持した水酸化ナトリウム水溶液を使用するこ
とが好ましいことが分かる。As shown in Table 4, when an aqueous solution of sodium hydroxide is used as the aqueous alkali solution for the oxidation treatment, 30 to 7
It can be seen that it is preferable to use an aqueous solution of sodium hydroxide maintained at 0 ° C.
【００５２】実験３及び４の結果より、酸化処理のアル
カリ水溶液として水酸化ナトリウム水溶液を使用する場
合は、３０〜７０°Ｃに保持した２０〜４０重量％水酸
化ナトリウム水溶液を使用することが好ましいことが分
かる。From the results of Experiments 3 and 4, when using an aqueous sodium hydroxide solution as the alkaline aqueous solution for the oxidation treatment, it is preferable to use a 20 to 40% by weight aqueous sodium hydroxide solution maintained at 30 to 70 ° C. You can see that.
【００５３】（実験５）水酸化ニッケル粒子に対するオ
キシ水酸化コバルト層の比率の好適な範囲を調べた。(Experiment 5) A suitable range of the ratio of the cobalt oxyhydroxide layer to the nickel hydroxide particles was examined.
【００５４】ステップ２における硫酸コバルトの使用量
を、２．６ｇ、５．２ｇ、２６．４ｇ又は３９．３ｇと
したこと以外は実施例１と同様にして、順に、密閉型ニ
ッケル・亜鉛蓄電池Ａ１５、Ａ１６、Ａ１７及びＡ１８
を作製した。水酸化ニッケル粒子に対するオキシ水酸化
コバルト層のコバルト原子換算での比率を原子吸光法に
より調べたところ、順に、１重量％、２重量％、１０重
量％及び１５重量％であった。The procedure of Example 1 was repeated, except that the amount of cobalt sulfate used in Step 2 was changed to 2.6 g, 5.2 g, 26.4 g or 39.3 g. , A16, A17 and A18
Was prepared. When the ratio of the cobalt oxyhydroxide layer to the nickel hydroxide particles in terms of cobalt atoms was examined by an atomic absorption method, they were 1% by weight, 2% by weight, 10% by weight and 15% by weight, respectively.
【００５５】各電池について、実験１で行ったものと同
じ条件の充放電を１０サイクル行い、各電池の正極の１
０サイクル目の活物質利用率及び１０サイクル目の放電
容量を調べた。結果を表５に示す。表５には、本発明電
池Ａ１についての結果も表１より転記して示してある。For each battery, 10 cycles of charge / discharge under the same conditions as those performed in Experiment 1 were performed, and the positive electrode 1
The active material utilization rate at the 0th cycle and the discharge capacity at the 10th cycle were examined. Table 5 shows the results. In Table 5, the results for the battery A1 of the present invention are also transcribed from Table 1.
【００５６】[0056]
【表５】 [Table 5]
【００５７】表５より、水酸化ニッケル粒子に対してオ
キシ水酸化コバルト層をコバルト原子換算で２〜１０重
量％形成することが好ましいことが分かる。Table 5 shows that the cobalt oxyhydroxide layer is preferably formed in an amount of 2 to 10% by weight in terms of cobalt atoms with respect to the nickel hydroxide particles.
【００５８】（実験６）固溶元素として、マンガン以外
に、コバルト、亜鉛、カルシウム、アルミニウム、イッ
トリウム、イッテルビウム、エルビウム及びガドリニウ
ムよりなる群から選ばれた少なくとも１種の元素Ｍを含
有する水酸化ニッケル粒子を使用して、密閉型ニッケル
・亜鉛蓄電池を作製し、各電池の正極の活物質利用率及
び放電容量を調べた。(Experiment 6) Nickel hydroxide containing, as a solid solution element, at least one element M selected from the group consisting of cobalt, zinc, calcium, aluminum, yttrium, ytterbium, erbium and gadolinium, in addition to manganese. Using the particles, sealed nickel-zinc storage batteries were fabricated, and the active material utilization and discharge capacity of the positive electrode of each battery were examined.
【００５９】ステップ１において、硫酸マンガン（Ｍｎ
ＳＯ4 ）４０．４ｇ及び硫酸ニッケル（ＮｉＳＯ4 ）１
５４．８ｇとともに、硫酸コバルト（ＣｏＳＯ4 ）１．
５５ｇ、硫酸亜鉛（ＺｎＳＯ4 ）１．４６ｇ、硝酸カル
シウム（Ｃａ（ＮＯ3 ）2 ）２．４１ｇ、硫酸アルミニ
ウム（Ａｌ2 （ＳＯ4 ）3 ) ３．７４ｇ、硫酸イットリ
ウム（Ｙ2 （ＳＯ4 ）3 ) １．５５ｇ、硫酸イッテルビ
ウム（Ｙｂ2 （ＳＯ4）3 ) １．０８ｇ、硫酸エルビウ
ム（Ｅｒ2 （ＳＯ4 ）3 ) １．１０ｇ、硫酸ガドリニウ
ム（Ｇｄ2 （ＳＯ4 ）3 ) １．１３ｇ、又は、硫酸亜鉛
（ＺｎＳＯ4 ）１．４６ｇ及び硫酸コバルト１．５５ｇ
を、水に溶かした水溶液を使用したこと以外は実施例１
と同様にして、順に、密閉型ニッケル・亜鉛蓄電池Ｂ１
〜Ｂ９を作製した。各電池に使用した水酸化ニッケル粒
子の元素Ｍの固溶量を調べたところ、電池Ｂ１〜Ｂ８に
ついては、ニッケルと元素Ｍとの総量に基づいて、１重
量％であり、また電池Ｂ９については、ニッケルと元素
Ｍとの総量に基づいて、２重量％（亜鉛１重量％、コバ
ルト１重量％）であった。コバルト、亜鉛及びカルシウ
ムの固溶量は原子吸光法により、またアルミニウム、イ
ットリウム、イッテルビウム、エルビウム及びガドリニ
ウムの固溶量は発光分析法（ＩＣＰ）により、それぞれ
求めた。In step 1, manganese sulfate (Mn)
SO 4 ) 40.4 g and nickel sulfate (NiSO 4 ) 1
With 54.8 g of cobalt sulfate (CoSO 4 ) 1.
55 g, zinc sulfate (ZnSO 4 ) 1.46 g, calcium nitrate (Ca (NO 3 ) 2 ) 2.41 g, aluminum sulfate (Al 2 (SO 4 ) 3 ) 3.74 g, yttrium sulfate (Y 2 (SO 4 )) 3 ) 1.55 g, ytterbium sulfate (Yb 2 (SO 4 ) 3 ) 1.08 g, erbium sulfate (Er 2 (SO 4 ) 3 ) 1.10 g, gadolinium sulfate (Gd 2 (SO 4 ) 3 ) 1.13 g Or 1.46 g of zinc sulfate (ZnSO 4 ) and 1.55 g of cobalt sulfate
Example 1 except that an aqueous solution dissolved in water was used.
In the same manner as described above, the sealed nickel-zinc storage battery B1
To B9. When the solid solution amount of the element M in the nickel hydroxide particles used for each battery was examined, it was 1% by weight for the batteries B1 to B8 based on the total amount of nickel and the element M, and for the battery B9. , 2% by weight (1% by weight of zinc, 1% by weight of cobalt) based on the total amount of nickel and element M. The solid solution amounts of cobalt, zinc and calcium were determined by atomic absorption spectrometry, and the solid solution amounts of aluminum, yttrium, ytterbium, erbium and gadolinium were determined by emission spectrometry (ICP).
【００６０】各電池について、実験１で行ったものと同
じ条件の充放電を１０サイクル行い、各電池の正極の１
０サイクル目の活物質利用率及び１０サイクル目の放電
容量を調べた。結果を表６に示す。表６には、本発明電
池Ａ１についての結果も表１より転記して示してある。For each battery, 10 cycles of charge / discharge under the same conditions as those performed in Experiment 1 were performed, and the positive electrode 1
The active material utilization rate at the 0th cycle and the discharge capacity at the 10th cycle were examined. Table 6 shows the results. In Table 6, the results for the battery A1 of the present invention are also transcribed from Table 1.
【００６１】[0061]
【表６】 [Table 6]
【００６２】表６より、水酸化ニッケル粒子として、マ
ンガン以外に、特定の元素Ｍを固溶元素としてさらに含
有する水酸化ニッケル粒子を使用することが好ましいこ
とが分かる。Table 6 shows that it is preferable to use, as the nickel hydroxide particles, nickel hydroxide particles further containing a specific element M as a solid solution element in addition to manganese.
【００６３】（実験７）水酸化ニッケル粒子中の元素Ｍ
の好適な固溶量を調べた。(Experiment 7) Element M in nickel hydroxide particles
Was examined for a suitable solid solution amount.
【００６４】ステップ１において、硫酸マンガン（Ｍｎ
ＳＯ4 ）４０．４ｇ及び硫酸ニッケル（ＮｉＳＯ4 ）１
５４．８ｇとともに、硫酸亜鉛を０．３７ｇ、０．７３
ｇ、７．３ｇ又は１０．９５ｇを、水に溶かした水溶液
を使用したこと以外は実施例１と同様にして、順に、密
閉型ニッケル・亜鉛蓄電池Ｃ１〜Ｃ４を作製した。各電
池に使用した水酸化ニッケル粒子中の亜鉛の固溶量を原
子吸光法により調べたところ、ニッケルと元素Ｍとの総
量に基づいて、順に、０．２５重量％、０．５重量％、
５重量％及び７．５重量％であった。In step 1, manganese sulfate (Mn)
SO 4 ) 40.4 g and nickel sulfate (NiSO 4 ) 1
With 54.8 g, 0.37 g of zinc sulfate, 0.73 g
g, 7.3 g or 10.95 g of the sealed nickel-zinc storage batteries C1 to C4 were produced in the same manner as in Example 1 except that an aqueous solution in which water was dissolved was used. The amount of zinc dissolved in the nickel hydroxide particles used in each battery was examined by atomic absorption spectrometry. Based on the total amount of nickel and the element M, 0.25% by weight, 0.5% by weight,
5% and 7.5% by weight.
【００６５】各電池について、実験１で行ったものと同
じ条件の充放電を１０サイクル行い、各電池の正極の１
０サイクル目の活物質利用率及び１０サイクル目の放電
容量を調べた。結果を表７に示す。表７には、電池Ｂ２
についての結果も表６より転記して示してある。For each battery, 10 cycles of charge / discharge under the same conditions as those performed in Experiment 1 were performed, and the positive electrode 1
The active material utilization rate at the 0th cycle and the discharge capacity at the 10th cycle were examined. Table 7 shows the results. Table 7 shows that the battery B2
Are also transcribed from Table 6 and shown.
【００６６】[0066]
【表７】 [Table 7]
【００６７】表７より、亜鉛の固溶量としては、５重量
％以下が好ましいことが分かる。他の元素Ｍの固溶量に
ついても、概ね５重量％以下が好ましいことを確認し
た。From Table 7, it can be seen that the solid solution amount of zinc is preferably 5% by weight or less. It was also confirmed that the solid solution amount of the other element M was preferably about 5% by weight or less.
【００６８】[0068]
【発明の効果】本発明方法によれば、粒子表面の導電性
が極めて良い正極活物質を作製することができる。ま
た、本発明方法により作製した正極活物質を使用するこ
とにより、活物質利用率の極めて高いペースト式ニッケ
ル極を作製することができる。さらに、本発明方法によ
り作製した正極活物質を、亜鉛極を負極とする密閉型ニ
ッケル・亜鉛蓄電池の正極活物質として使用することに
より、負極での水素ガスの発生が少ない、信頼性の高い
密閉型電池を作製することができる。According to the method of the present invention, it is possible to prepare a positive electrode active material having extremely good conductivity on the particle surface. Further, by using the positive electrode active material produced by the method of the present invention, a paste-type nickel electrode having an extremely high active material utilization rate can be produced. Furthermore, by using the positive electrode active material produced by the method of the present invention as a positive electrode active material of a sealed nickel-zinc storage battery having a zinc electrode as a negative electrode, generation of hydrogen gas at the negative electrode is small, and a highly reliable sealed Type battery can be manufactured.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 矢野 睦 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 伊藤 靖彦 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 Ｆターム(参考） 5H003 AA02 BA01 BA02 BA03 BA07 BB02 BB04 BC01 BC05 BD01 BD04 5H016 AA02 BB02 BB05 BB06 BB09 EE05 5H028 AA02 BB01 BB03 BB04 BB05 BB06 CC17 EE01 EE05 EE06 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Mutsumi Yano 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Yasuhiko Ito 2-chome, Keihanhondori, Moriguchi-shi, Osaka No.5 Sanyo Electric Co., Ltd. F-term (reference) 5H003 AA02 BA01 BA02 BA03 BA07 BB02 BB04 BC01 BC05 BD01 BD04 5H016 AA02 BB02 BB05 BB06 BB09 EE05 5H028 AA02 BB01 BB03 BB04 BB05 BB06 CC17 EE01 EE05 EE06
Claims (8)
ニッケル粒子の表面にオキシ水酸化コバルト層を形成し
て成るアルカリ蓄電池用正極活物質を製造するにあた
り、前記水酸化ニッケル粒子の表面に水酸化コバルト層
を形成して複合体粒子を作製し、次いで、前記水酸化コ
バルト層を酸化して前記オキシ水酸化コバルト層に変え
るべく、前記複合体粒子を、次亜塩素酸塩又は次亜臭素
酸塩を含有するアルカリ水溶液と混合することを特徴と
するアルカリ蓄電池用正極活物質の製法。1. A method for producing a positive electrode active material for an alkaline storage battery, comprising forming a cobalt oxyhydroxide layer on the surface of nickel hydroxide particles containing manganese as a solid solution element, wherein the surface of the nickel hydroxide particles is water. To form a cobalt oxide layer to produce composite particles, and then oxidize the cobalt hydroxide layer to convert it to the cobalt oxyhydroxide layer, the composite particles are treated with hypochlorite or hypobromite. A method for producing a positive electrode active material for an alkaline storage battery, which is mixed with an aqueous alkali solution containing an acid salt.
としてマンガンをニッケルとマンガンとの総量に基づい
て１５〜５０重量％含有する水酸化ニッケル粒子を使用
する請求項１記載のアルカリ蓄電池用正極活物質の製
法。2. The positive electrode for an alkaline storage battery according to claim 1, wherein the nickel hydroxide particles comprise nickel hydroxide particles containing manganese as a solid solution element in an amount of 15 to 50% by weight based on the total amount of nickel and manganese. Active material manufacturing method.
Ｃに保持した２０〜４０重量％水酸化ナトリウム水溶液
を使用する請求項１記載のアルカリ蓄電池用正極活物質
の製法。3. The method according to claim 1, wherein the aqueous alkaline solution is 30 to 70 °.
The method for producing a positive electrode active material for an alkaline storage battery according to claim 1, wherein a 20 to 40% by weight aqueous sodium hydroxide solution held at C is used.
シ水酸化コバルト層を、コバルト元素換算で、２〜１０
重量％形成する請求項１記載のアルカリ蓄電池用正極活
物質の製法。4. A method according to claim 1, wherein said cobalt oxyhydroxide layer is applied to said nickel hydroxide particles in an amount of 2 to 10 in terms of cobalt element.
The method for producing a positive electrode active material for an alkaline storage battery according to claim 1, wherein the positive electrode active material is formed in a percentage by weight.
として、さらに、コバルト、亜鉛、カルシウム、アルミ
ニウム、イットリウム、イッテルビウム、エルビウム及
びガドリニウムよりなる群から選ばれた少なくとも１種
の元素Ｍを、ニッケルと元素Ｍとの総量に基づいて、５
重量％以下含有する水酸化ニッケル粒子を使用する請求
項１記載のアルカリ蓄電池用正極活物質の製法。5. The nickel hydroxide particles further comprise, as a solid solution element, at least one element M selected from the group consisting of cobalt, zinc, calcium, aluminum, yttrium, ytterbium, erbium and gadolinium. 5 based on the total amount of
2. The method for producing a positive electrode active material for an alkaline storage battery according to claim 1, wherein nickel hydroxide particles having a content of not more than 10% by weight are used.
り製造したアルカリ蓄電池用正極活物質。6. A positive electrode active material for an alkaline storage battery produced by the method according to claim 1.
質を備えるアルカリ蓄電池用ペースト式ニッケル極。7. A paste-type nickel electrode for an alkaline storage battery, comprising the positive electrode active material for an alkaline storage battery according to claim 6.
式ニッケル極を備える密閉型ニッケル・亜鉛蓄電池。8. A sealed nickel-zinc storage battery comprising the paste-type nickel electrode for an alkaline storage battery according to claim 7.
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| JP36962599A JP2001185138A (en) | 1999-12-27 | 1999-12-27 | Positive electrode active material for alkaline storage battery and manufacturing method therefor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36962599A JP2001185138A (en) | 1999-12-27 | 1999-12-27 | Positive electrode active material for alkaline storage battery and manufacturing method therefor |
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| Publication Number | Publication Date |
|---|---|
| JP2001185138A true JP2001185138A (en) | 2001-07-06 |
Family
ID=18494913
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|---|---|---|---|
| JP36962599A Pending JP2001185138A (en) | 1999-12-27 | 1999-12-27 | Positive electrode active material for alkaline storage battery and manufacturing method therefor |
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| Country | Link |
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Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20070417 |