JP2001006665A - Sealed alkaline storage battery - Google Patents
Sealed alkaline storage batteryInfo
- Publication number
- JP2001006665A JP2001006665A JP11175801A JP17580199A JP2001006665A JP 2001006665 A JP2001006665 A JP 2001006665A JP 11175801 A JP11175801 A JP 11175801A JP 17580199 A JP17580199 A JP 17580199A JP 2001006665 A JP2001006665 A JP 2001006665A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- manganese
- battery
- negative electrode
- storage battery
- 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.)
- Granted
Links
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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、放電スタートの密
閉型アルカリ蓄電池に関するものである。放電スタート
の蓄電池とは、予め充電することなく初回の放電を行う
ことができる蓄電池のことである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealed alkaline storage battery with a discharge start. The discharge-started storage battery is a storage battery that can be discharged for the first time without being charged in advance.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
亜鉛を負極活物質とする密閉型アルカリ蓄電池用の正極
活物質としては、二酸化マンガンが提案されている（特
公昭４５−３５７０号公報参照）。また、亜鉛を負極活
物質とするアルカリ蓄電池の正極活物質として、酸化ニ
ッケルと二酸化マンガンを混合したものが提案されてい
る（特公昭４９−１１４７４１号公報参照）。2. Description of the Related Art
Manganese dioxide has been proposed as a positive electrode active material for a sealed alkaline storage battery using zinc as a negative electrode active material (see Japanese Patent Publication No. 45-3570). A mixture of nickel oxide and manganese dioxide has been proposed as a positive electrode active material of an alkaline storage battery using zinc as a negative electrode active material (see Japanese Patent Publication No. 49-114471).
【０００３】しかしながら、二酸化マンガンは充放電サ
イクルにおける可逆性が悪く、初回の放電を行った後充
電しても当初の二酸化マンガンに戻らないので、充放電
サイクルにおいて放電容量が急激に低下する。また、二
酸化マンガンの酸素過電圧が低いために、充電時に正極
側で酸素ガス（水の電気分解による）が発生して電池内
圧が上昇し、それに伴い電池外装部材の接合部における
密着性が低下して、電解液が外部に漏出しやすい。ま
た、酸化ニッケルと二酸化マンガンとの混合物を蓄電池
に用いた場合、活物質である酸化ニッケルの酸素過電圧
が低いために、二酸化マンガンを単独で使用した場合と
同様に、電池内圧が上昇しやすく漏液が起こりやすい。However, manganese dioxide has poor reversibility in the charge / discharge cycle, and does not return to the original manganese dioxide even if charged after the first discharge, so that the discharge capacity sharply decreases in the charge / discharge cycle. In addition, since the oxygen overvoltage of manganese dioxide is low, oxygen gas (due to electrolysis of water) is generated on the positive electrode side during charging, and the internal pressure of the battery increases, and accordingly, the adhesion at the junction of the battery exterior member decreases. Therefore, the electrolyte is easily leaked to the outside. Also, when a mixture of nickel oxide and manganese dioxide is used for a storage battery, the internal pressure of the battery is likely to rise, as in the case of using manganese dioxide alone, because the oxygen overvoltage of nickel oxide, which is the active material, is low. Liquid is likely to occur.
【０００４】このような問題を解消し得る正極活物質と
して、本出願人はマンガンを固溶したγ型オキシ水酸化
ニッケルを提案している（特開平１０−２１４６２１号
公報参照）。マンガンを固溶したγ型オキシ水酸化ニッ
ケルを正極活物質として用いることにより、充放電サイ
クルの長期に渡って電解液が外部に漏出しにくい、信頼
性の高い放電スタートの密閉型アルカリ蓄電池を得るこ
とができる。しかしながら、このような密閉型アルカリ
蓄電池においては、さらに放電容量を高めることが求め
られている。As a positive electrode active material that can solve such a problem, the present applicant has proposed γ-type nickel oxyhydroxide in which manganese is dissolved (see JP-A-10-214621). By using γ-type nickel oxyhydroxide in which manganese is dissolved as a positive electrode active material, it is possible to obtain a highly reliable discharge-starting sealed alkaline storage battery in which the electrolyte is unlikely to leak out for a long period of the charge / discharge cycle. be able to. However, such a sealed alkaline storage battery is required to further increase the discharge capacity.
【０００５】本発明の目的は、充放電サイクルの長期に
渡って電解液が外部に漏出しにくく、かつ放電容量の高
い放電スタートの密閉型アルカリ蓄電池を提供すること
にある。An object of the present invention is to provide a sealed alkaline storage battery having a high discharge capacity and a low discharge capacity, in which the electrolyte is unlikely to leak out to the outside over a long charge / discharge cycle.
【０００６】[0006]
【課題を解決するための手段】本発明の密閉型アルカリ
蓄電池は、電池缶と、該電池缶と電気的に接触するよう
に電池缶内に配置される、γ型オキシ水酸化ニッケルか
らなる正極活物質を成形した中空状の正極と、正極の内
側に配置される、亜鉛を負極活物質とした負極と、正極
と負極の間に配置されるセパレータと、負極内に挿入さ
れた状態で配置される負極集電体と、正極、負極、及び
セパレータ内に含浸される電解液とを備える密閉型アル
カリ蓄電池であり、γ型オキシ水酸化ニッケルがマンガ
ンを固溶しており、かつ正極成形体の密度が２．５〜
３．５ｇ／ｃｍ3 であることを特徴としている。A sealed alkaline storage battery according to the present invention comprises a battery can and a positive electrode made of γ-type nickel oxyhydroxide disposed in the battery can so as to make electrical contact with the battery can. A hollow positive electrode formed by molding an active material, a negative electrode having zinc as a negative electrode active material disposed inside the positive electrode, a separator disposed between the positive electrode and the negative electrode, and disposed in a state inserted in the negative electrode Negative electrode current collector, a positive electrode, a negative electrode, and a sealed alkaline storage battery comprising an electrolytic solution impregnated in a separator, γ-type nickel oxyhydroxide has a solid solution of manganese, and a positive electrode molded body Density of 2.5 ~
It is characterized by a weight of 3.5 g / cm 3 .
【０００７】本発明においては、正極成形体の密度が
２．５〜３．５ｇ／ｃｍ3 に規定されている。正極成形
体の密度が２．５ｇ／ｃｍ3 より小さいと、正極成形体
の強度が弱くなり、電池缶内へ正極成形体を挿入する際
にクラックが生じて挿入が困難となる。また、正極成形
体の密度が３．５ｇ／ｃｍ3 より大きくなると、正極成
形体内部への電解液の浸透が困難になるため、充放電サ
イクルを経過するに伴い、放電容量の低下を生じる。正
極成形体の密度は、成形時のプレス圧を調整することに
より変化させることができる。正極成形体の密度は、正
極成形体の寸法から体積を算出するとともに、正極成形
体の重量を測定して、以下の式により求めることができ
る。In the present invention, the density of the positive electrode molded body is specified to be 2.5 to 3.5 g / cm 3 . If the density of the positive electrode molded article is less than 2.5 g / cm 3 , the strength of the positive electrode molded article will be weak, and cracks will occur when inserting the positive electrode molded article into the battery can, making insertion difficult. On the other hand, when the density of the positive electrode molded body is higher than 3.5 g / cm 3 , it becomes difficult for the electrolyte solution to penetrate into the inside of the positive electrode molded body, so that the discharge capacity decreases as the charge / discharge cycle progresses. The density of the positive electrode molded body can be changed by adjusting the press pressure during molding. The density of the positive electrode molded body can be obtained by calculating the volume from the dimensions of the positive electrode molded body, measuring the weight of the positive electrode molded body, and using the following formula.
【０００８】正極成形体の密度＝（正極成形体の重量）
／（正極成形体の体積） 本発明において正極活物質として用いるγ型オキシ水酸
化ニッケルは、好ましくは、マンガン（Ｍｎ）を５〜５
０重量％固溶している。マンガンの固溶量は以下の式に
より定義される。[0008] Density of molded positive electrode = (weight of molded positive electrode)
/ (Volume of positive electrode molded body) The γ-type nickel oxyhydroxide used as the positive electrode active material in the present invention preferably contains manganese (Mn) of 5 to 5%.
0% by weight solid solution. The solid solution amount of manganese is defined by the following equation.
【０００９】マンガンの固溶量（重量％）＝（γ型オキ
シ水酸化ニッケル中のマンガン量）／（γ型オキシ水酸
化ニッケル中のニッケル及びマンガンの合計量）×１０
０ マンガンの固溶量が５重量％未満になると、充放電サイ
クルの経過に伴い、オキシ水酸化ニッケルの放電生成物
である水酸化ニッケルの結晶構造が、α型からβ型へ変
化するため、酸素過電圧（酸素発生電位−充電電位）が
低下し、充電時に正極側で酸素が発生しやすくなる傾向
にある。一方、固溶量が５０重量％を超えると、正極活
物質であるγ型オキシ水酸化ニッケルの量が減少するた
め、十分な放電容量を得ることが困難になる。マンガン
の固溶量は、マンガンの原料とニッケル原料の混合割合
を変化させることにより、調整することができる。Amount of solid solution of manganese (% by weight) = (amount of manganese in γ-type nickel oxyhydroxide) / (total amount of nickel and manganese in γ-type nickel oxyhydroxide) × 10
0 When the solid solution amount of manganese is less than 5% by weight, the crystal structure of nickel hydroxide, which is a discharge product of nickel oxyhydroxide, changes from α-form to β-form with the progress of the charge / discharge cycle. Oxygen overvoltage (oxygen generation potential-charge potential) decreases, and oxygen tends to be generated on the positive electrode side during charging. On the other hand, when the amount of solid solution exceeds 50% by weight, the amount of γ-type nickel oxyhydroxide, which is a positive electrode active material, decreases, and it becomes difficult to obtain a sufficient discharge capacity. The solid solution amount of manganese can be adjusted by changing the mixing ratio of the manganese raw material and the nickel raw material.
【００１０】本発明におけるγ型オキシ水酸化ニッケル
中のニッケル原子の価数は、初回放電前において、すな
わち満充電状態で、３．４〜３．８価であることが好ま
しい。ニッケル原子の価数が３．４未満になると、十分
な放電容量が得られにくく、また酸素過電圧が低いため
充電時に電解液の漏れが発生する場合がある。また、一
般にオキシ水酸化ニッケルにおいては、ニッケル原子の
価数が３．８価よりも大きなものは存在しない。従っ
て、満充填状態の後にさらに充電を続けても、水が分解
して酸素ガスが発生するだけであり、ニッケル原子の価
数が３．８価を超えることはない。The valence of the nickel atom in the γ-type nickel oxyhydroxide in the present invention is preferably 3.4 to 3.8 before the first discharge, that is, in a fully charged state. If the valence of the nickel atom is less than 3.4, it is difficult to obtain a sufficient discharge capacity, and the electrolyte may leak during charging due to a low oxygen overvoltage. In general, there is no nickel oxyhydroxide having a valence of nickel atom larger than 3.8. Therefore, even if the charging is further continued after the fully charged state, only the water is decomposed and oxygen gas is generated, and the valence of the nickel atom does not exceed 3.8.
【００１１】本発明において用いるγ型オキシ水酸化ニ
ッケルは、例えば水酸化ニッケルを次亜塩素酸ナトリウ
ム（ＮａＣｌＯ）等の酸化剤で酸化することにより得ら
れる。またニッケルの価数は、反応させる酸化剤の添加
量により調整することができる。The γ-type nickel oxyhydroxide used in the present invention is obtained, for example, by oxidizing nickel hydroxide with an oxidizing agent such as sodium hypochlorite (NaClO). The valence of nickel can be adjusted by the amount of the oxidizing agent to be reacted.
【００１２】本発明において用いるγ型オキシ水酸化ニ
ッケルには、マンガン以外に、さらにアルミニウム（Ａ
ｌ）、コバルト（Ｃｏ）、イットリウム（Ｙ）、イッテ
ルビウム（Ｙｂ）、エルビウム（Ｅｒ）及びガドリニウ
ム（Ｇｄ）よりなる群から選ばれた少なくとも１種の元
素が固溶されていてもよい。これらの元素が固溶したγ
型オキシ水酸化ニッケルを用いることにより、正極の酸
素過電圧をさらに高めることができる。これらの元素の
固溶量としては、０．５〜５重量％程度が好ましい。な
お、この固溶量は以下の式により定義される。The γ-type nickel oxyhydroxide used in the present invention further includes aluminum (A) in addition to manganese.
l), at least one element selected from the group consisting of cobalt (Co), yttrium (Y), ytterbium (Yb), erbium (Er), and gadolinium (Gd) may be dissolved. Γ in which these elements are dissolved
By using the nickel oxyhydroxide, the oxygen overvoltage of the positive electrode can be further increased. The solid solution amount of these elements is preferably about 0.5 to 5% by weight. The solid solution amount is defined by the following equation.
【００１３】他の元素の固溶量（重量％）＝（γ型オキ
シ水酸化ニッケル中の他の元素の量）／（γ型オキシ水
酸化ニッケル中のニッケル及び他の元素の合計量）×１
００ また、本発明においては、正極、負極、セパレータ、負
極集電体、及び電解液が、電池缶内の容積の７５体積％
以上を占めることが好ましい。これにより、電池缶内に
おける活物質の充填量を高めることができ、放電容量の
高い密閉型アルカリ蓄電池とすることができる。また、
このような放電容量の高い密閉型アルカリ蓄電池におい
て、電池内圧の上昇を抑制し、充放電を繰り返した際に
電解液が外部へ漏出するのを防止することができる。Solid solution amount of other elements (% by weight) = (amount of other elements in γ-type nickel oxyhydroxide) / (total amount of nickel and other elements in γ-type nickel oxyhydroxide) × 1
Further, in the present invention, the positive electrode, the negative electrode, the separator, the negative electrode current collector, and the electrolyte are 75% by volume of the volume in the battery can.
It is preferable to occupy the above. Thereby, the filling amount of the active material in the battery can can be increased, and a sealed alkaline storage battery having a high discharge capacity can be obtained. Also,
In such a sealed alkaline storage battery having a high discharge capacity, it is possible to suppress an increase in the internal pressure of the battery and to prevent the electrolyte from leaking out when charging and discharging are repeated.
【００１４】[0014]
【発明の実施の形態】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、本発明は下記の実施例に何ら
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。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples at all, and may be modified as appropriate without departing from the scope of the invention. It can be implemented by
【００１５】〔実験１〕この実験１では、正極活物質で
あるγ型オキシ水酸化ニッケルを成形した正極の密度と
クラック発生率、初期容量、充放電サイクル経過に伴う
放電容量、及び漏液電池発生数の関係を調べた。[Experiment 1] In Experiment 1, the density and crack generation rate, the initial capacity, the discharge capacity of the positive electrode formed from γ-type nickel oxyhydroxide, which is the positive electrode active material, as the charge / discharge cycle progressed, and the leakage battery The relationship between the number of occurrences was examined.
【００１６】（実施例１） 〔正極の作製〕 ステップ１：水酸化ニッケルの作製 １．４Ｍの硫酸ニッケル水溶液５００ｍｌ、０．３７Ｍ
の硫酸マンガン水溶液５００ｍｌ、及び３０重量％アン
モニア水溶液１．９Ｌを１時間混合した。この溶液に、
温度を３０℃に保持しながら、１０重量％の水酸化ナト
リウム水溶液を滴下して攪拌し、反応溶液のｐＨを１
１．０の一定値となるように保持して８時間反応させ
た。そして、この生成物をろ過、水洗し、６０℃で乾燥
してマンガンを固溶させたα型の水酸化ニッケルを作製
した。この際、α型水酸化ニッケル内のマンガン固溶量
をＩＣＰ（発光分析法）により定量分析した結果、２０
重量％であった。(Example 1) [Preparation of positive electrode] Step 1: Preparation of nickel hydroxide 500 ml of a 1.4 M nickel sulfate aqueous solution, 0.37 M
Of manganese sulfate aqueous solution and 1.9 L of 30% by weight aqueous ammonia solution were mixed for 1 hour. In this solution,
While maintaining the temperature at 30 ° C., a 10% by weight aqueous solution of sodium hydroxide was added dropwise and stirred to adjust the pH of the reaction solution to 1
The reaction was carried out for 8 hours while maintaining a constant value of 1.0. Then, this product was filtered, washed with water, and dried at 60 ° C. to produce α-type nickel hydroxide in which manganese was dissolved. At this time, the manganese solid solution amount in the α-type nickel hydroxide was quantitatively analyzed by ICP (emission spectrometry),
% By weight.
【００１７】ステップ２：酸化処理 酸化剤である１０重量％の次亜塩素酸ナトリウム１４５
０ｍｌと４０重量％水酸化ナトリウム水溶液５００ｍｌ
とを混合した水溶液を用意し、この水溶液を８０℃に加
熱した。この水溶液中に、上記ステップ１で作製したマ
ンガンを固溶したα型水酸化ニッケル粉末を１００ｇ攪
拌しながら投入し、１時間反応させた。その後、ろ過、
水洗し、６０℃で乾燥して、活物質であるマンガンを固
溶したγ型オキシ水酸化ニッケルを作製した。得られた
生成物について、マンガンの固溶量をＩＣＰにより定量
分析した結果、ステップ１で作製したα型水酸化ニッケ
ル中の固溶量と同量で、２０重量％であった。また、鉄
の２価／３価酸化還元滴定測定法により、生成物のニッ
ケル原子の価数を測定した結果、３．５であった。Step 2: Oxidation Treatment 10% by weight sodium hypochlorite 145 as an oxidizing agent
0 ml and a 40% by weight aqueous solution of sodium hydroxide 500 ml
Was prepared, and this aqueous solution was heated to 80 ° C. Into this aqueous solution, 100 g of the α-type nickel hydroxide powder in which manganese prepared in Step 1 was dissolved was added with stirring, and reacted for 1 hour. Then filtration,
After washing with water and drying at 60 ° C., γ-type nickel oxyhydroxide in which manganese as an active material was dissolved was prepared. As a result of quantitative analysis of the amount of manganese dissolved in the obtained product by ICP, the amount was 20% by weight, the same as the amount of solid solution in the α-type nickel hydroxide prepared in Step 1. The valence of the nickel atom in the product was measured by a divalent / trivalent redox titration measurement method of iron to be 3.5.
【００１８】なお、上記の例では、酸化剤として、次亜
塩素酸ナトリウム（ＮａＣｌＯ）を使用しているが、他
に過硫酸ナトリウム（Ｎａ2 Ｓ2 Ｏ8 ）を酸化剤として
用いた場合でも、同様の処理が行えることを確認した。In the above example, sodium hypochlorite (NaClO) is used as the oxidizing agent. However, even when sodium persulfate (Na 2 S 2 O 8 ) is used as the oxidizing agent, It was confirmed that similar processing could be performed.
【００１９】ステップ３：電極の作製 上記ステップ２で得られたγ型オキシ水酸化ニッケル粉
末１００重量部と黒鉛粉末１０重量部と３０重量％水酸
化カリウム水溶液１０重量部とを、らいかい機で３０分
間混合し、得られた正極合剤２．９ｇをプレス圧３．７
ｔｏｎ／ｃｍ2で加圧成形して、外径１３．３ｍｍ、内
径９ｍｍ、高さ１３ｍｍの円筒中空状の正極成形体ａ１
を作製した。電極ａ１の体積は０．９７８ｃｍ3 であ
り、正極Ａ１の重量は２．９ｇであったので、正極成形
体ａ１の密度は３．０ｇ／ｃｍ3 となる。なお、電池の
作製においては、この円筒中空状の正極成形体を３個直
列に重ねて、全体として１個の円筒中空状正極として使
用した。Step 3: Preparation of electrode 100 parts by weight of the γ-type nickel oxyhydroxide powder, 10 parts by weight of graphite powder, and 10 parts by weight of a 30% by weight aqueous solution of potassium hydroxide obtained in the above step 2 were used with a grinder. After mixing for 30 minutes, 2.9 g of the obtained positive electrode mixture was pressed at a pressing pressure of 3.7.
ton / cm 2 , and formed into a hollow cylindrical positive electrode molded article a1 having an outer diameter of 13.3 mm, an inner diameter of 9 mm, and a height of 13 mm.
Was prepared. Volume of the electrode a1 is 0.978cm 3, the weight of the positive electrode A1 was 2.9 g, the density of the positive electrode green body a1 becomes 3.0 g / cm 3. In the production of the battery, three cylindrical hollow positive electrode molded bodies were stacked in series and used as one cylindrical hollow positive electrode as a whole.
【００２０】〔負極の作製〕負極活物質としての亜鉛粉
末６５重量部と、酸化亜鉛（ＺｎＯ）を飽和量含む４０
重量％水酸化カリウム水溶液３４重量部と、ゲル化剤と
してのアクリル酸樹脂（日本純薬社製、商品名「ジュン
ロンＰＷ１５０」）１重量部とを混合して、ゲル状の負
極を作製した。[Production of Negative Electrode] 65 parts by weight of zinc powder as a negative electrode active material and 40 parts of zinc oxide (ZnO) containing a saturated amount.
A gelled negative electrode was prepared by mixing 34 parts by weight of a potassium hydroxide aqueous solution by weight and 1 part by weight of an acrylic resin (trade name “Junron PW150” manufactured by Nippon Pure Chemical Co., Ltd.) as a gelling agent.
【００２１】〔電池の作製〕上記の正極及び負極を用い
て、通称「インサイドアウト型」と呼ばれている構造
（電池缶側が正極側、電池蓋側が負極側：「アウトサイ
ド・正極型」とも呼ばれる）で、ＡＡサイズの密閉型ア
ルカリ蓄電池（本発明電池）Ａ１を作製した。なお、放
電容量を正極容量で規定するために、正極と負極との電
気化学的な容量を１：１．２とした（以下の電池も全て
これと同じ容量比にした）。また、負極、正極、セパレ
ータ、負極集電体、及び電解液からなる発電要素体が占
める体積を、電池缶内の容積に対して、８０体積％とし
た（以下の電池も全てこれと同じ充填率にした）。[Preparation of Battery] Using the above-described positive electrode and negative electrode, a structure commonly called “inside-out type” (the battery can side is the positive electrode side, the battery lid side is the negative electrode side: both “outside / positive type”) AA size sealed alkaline storage battery (battery of the present invention) A1 was manufactured. In addition, in order to define the discharge capacity by the positive electrode capacity, the electrochemical capacity between the positive electrode and the negative electrode was set to 1: 1.2 (all the following batteries had the same capacity ratio). Further, the volume occupied by the power generating element body composed of the negative electrode, the positive electrode, the separator, the negative electrode current collector, and the electrolyte was set to 80% by volume with respect to the volume in the battery can (the following batteries were all the same filling). Rate).
【００２２】図１は、作製した密閉型アルカリ蓄電池を
示す部分断面図である。図示の密閉型アルカリ蓄電池
は、有底円筒状の正極缶（正極外部端子）１、負極蓋
（負極外部端子）２、絶縁パッキング３、真鍮製の負極
集電棒４、円筒中空状の正極（ニッケル極）５、ビニロ
ンを主材とする円筒フィルム状のセパレータ６、ゲル状
負極（亜鉛極）７などからなる。FIG. 1 is a partial sectional view showing the manufactured sealed alkaline storage battery. The illustrated sealed alkaline storage battery includes a cylindrical bottomed positive electrode can (positive electrode external terminal) 1, a negative electrode cover (negative electrode external terminal) 2, an insulating packing 3, a negative electrode current collector rod 4 made of brass, and a cylindrical positive electrode (nickel negative electrode). Electrode 5, a cylindrical film-shaped separator 6 mainly composed of vinylon, a gelled negative electrode (zinc electrode) 7, and the like.
【００２３】正極缶１には、正極缶１の円筒部の内周面
に当接させて正極５が収納されており、該円筒中空状の
正極５の内周面には、セパレータ６が外周面を当接させ
て設けられており、セパレータ６の内側には、ゲル状の
負極７が充填されている。負極７の中央部には、正極缶
１と負極蓋２とを電気的に絶縁する絶縁パッキング３に
より一端を支持された負極集電棒（負極集電体）４が挿
入されている。正極缶１の開口部は、負極蓋２により閉
蓋されている。電池内部の密閉は、正極缶１の開口部に
絶縁パッキング３を嵌め込み、その上に負極蓋２を載置
した後、正極缶１の閉口端を内側にかしめることにより
なされている。本実施例の密閉型アルカリ蓄電池におい
て、電極缶は、正極缶１、負極蓋２及び絶縁パッキング
３から構成される。A positive electrode 5 is housed in the positive electrode can 1 in contact with the inner peripheral surface of the cylindrical portion of the positive electrode can 1, and a separator 6 has an outer peripheral surface on the inner peripheral surface of the cylindrical hollow positive electrode 5. The separator 6 is filled with a gelled negative electrode 7 inside the separator 6. A negative electrode current collector rod (negative electrode current collector) 4 whose one end is supported by an insulating packing 3 that electrically insulates the positive electrode can 1 and the negative electrode lid 2 is inserted into the center of the negative electrode 7. The opening of the positive electrode can 1 is closed by a negative electrode lid 2. The inside of the battery is sealed by inserting an insulating packing 3 into the opening of the positive electrode can 1, placing the negative electrode cover 2 thereon, and caulking the closed end of the positive electrode can 1 inside. In the sealed alkaline storage battery according to the present embodiment, the electrode can includes a positive electrode can 1, a negative electrode lid 2, and an insulating packing 3.
【００２４】なお、上記実施例の密閉型アルカリ蓄電池
においては中空状正極として円筒状の正極を用いている
が、本発明はこれに限定されるものではなく、例えば、
角筒状などの中空状正極であってもよい。Although the sealed alkaline storage battery of the above embodiment uses a cylindrical positive electrode as the hollow positive electrode, the present invention is not limited to this.
It may be a hollow positive electrode such as a rectangular tube.
【００２５】（実施例２）上記〔正極の作製〕のステッ
プ３において、正極成形体を作製する際の正極合剤の重
量及びプレス圧を表１に示すように変化させて、円筒中
空状の正極成形体ａ２〜ａ７を作製した。正極成形体の
外径、内径及び高さは、正極成形体ａ１と同じ寸法とし
た。(Example 2) In step 3 of [Preparation of positive electrode], the weight of the positive electrode mixture and the pressing pressure at the time of preparing the positive electrode molded body were changed as shown in Table 1 to obtain a hollow cylindrical member. Positive electrode molded bodies a2 to a7 were produced. The outer diameter, the inner diameter, and the height of the positive electrode molded body were the same dimensions as the positive electrode molded body a1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】次に、正極成形体ａ２〜ａ７を用い、上記
実施例２と同様にして、電池Ａ２〜Ａ７を作製した。 （比較例１）二酸化マンガン粉末９０．５重量部と、黒
鉛粉末４．５重量部と、４０重量％水酸化カリウム水溶
液５重量部とを混合し、得られた正極合剤を用いて、密
度３．０５ｇ／ｃｍ3 の正極成形体を作製した。この正
極成形体を使用したこと以外は、上記実施例１と同様に
して比較電池Ｘを作製した。Next, batteries A2 to A7 were produced in the same manner as in Example 2 above, using the molded positive electrodes a2 to a7. (Comparative Example 1) 90.5 parts by weight of manganese dioxide powder, 4.5 parts by weight of graphite powder, and 5 parts by weight of a 40% by weight aqueous potassium hydroxide solution were mixed, and the density was determined using the obtained positive electrode mixture. A positive electrode compact of 3.05 g / cm 3 was produced. A comparative battery X was produced in the same manner as in Example 1 except that this positive electrode molded body was used.
【００２８】〔各電池の充放電サイクルにおける放電容
量及び漏液電池発生個数〕上記電池Ａ１〜Ａ７及び比較
電池Ｘについて、１００ｍＡの電流で電池電圧が１Ｖに
なるまで放電した後、１００ｍＡの電流で電池電圧が
１．９５Ｖ（比較電池Ｘについては１．６５Ｖ）に達す
るまで充電を行う工程を１サイクルとする充放電サイク
ル試験を行った。そして、各電池の５サイクル目及び２
０サイクル目における放電容量及び漏液電池発生数を調
べた。各電池それぞれ１０個について、放電容量及び漏
液電池発生数を調べた。[Discharge Capacity and Number of Generated Leakage Batteries in Charge / Discharge Cycle of Each Battery] The batteries A1 to A7 and the comparative battery X were discharged at a current of 100 mA until the battery voltage became 1 V, and then discharged at a current of 100 mA. A charge / discharge cycle test was performed in which the charging process was performed as one cycle until the battery voltage reached 1.95 V (1.65 V for the comparative battery X). Then, the fifth cycle of each battery and the second cycle
The discharge capacity and the number of liquid leakage batteries generated at the 0th cycle were examined. For each of the 10 batteries, the discharge capacity and the number of leaked batteries generated were examined.
【００２９】この結果を表２に示す。表２中の５サイク
ル目及び２０サイクル目の放電容量は、各電池の１サイ
クル目の放電容量を１００とした指数であり、電解液が
漏出しなかった電池の放電容量の平均値である。また、
表２中の漏液電池発生数は２０サイクル目の測定値であ
り、充放電サイクル試験を行った電池の個数（１０）を
分母とし、分数の分子が「電解液が漏出した漏液電池の
個数」を表している。Table 2 shows the results. The discharge capacity at the 5th cycle and the 20th cycle in Table 2 is an index with the discharge capacity at the 1st cycle of each battery being 100, and is an average value of the discharge capacity of the battery in which the electrolyte did not leak. Also,
The number of leaked batteries in Table 2 is a measured value at the 20th cycle. The number of batteries (10) subjected to the charge / discharge cycle test is used as a denominator, and the numerator of the fraction is “ Number ".
【００３０】また、表２には、正極成形体を電池缶内に
挿入する際に生じたクラックの発生率を併せて示してい
る。クラック発生率は、以下の式で定義される。 クラック発生率（％）＝（クラックが生じた正極成形体
の個数）／（作製した正極成形体の個数）×１００Table 2 also shows the rate of occurrence of cracks generated when the positive electrode molded body was inserted into the battery can. The crack occurrence rate is defined by the following equation. Crack generation rate (%) = (number of positive electrode molded articles having cracks) / (number of produced positive electrode molded articles) × 100
【００３１】[0031]
【表２】 [Table 2]
【００３２】正極成形体の密度が２．５〜３．５ｇ／ｃ
ｍ3 である電池Ａ１及びＡ３〜Ａ６においては、充放電
サイクルを経過しても放電容量の低下が小さく、電解液
が外部に漏出していないことがわかる。正極成形体の密
度が本発明の範囲よりも低い電池Ａ２においては、正極
成形体を電池缶内に挿入する際のクラック発生率が大き
く、電池の作製が困難であることがわかる。また、正極
成形体密度が３．７ｇ／ｃｍ3 である電池Ａ７において
は、放電容量が若干低くなっていることがわかる。ま
た、電池Ｘでは、正極活物質として、二酸化マンガンを
使用しているため、充放電サイクルの経過に伴い放電容
量が減少していることがわかる。以上の結果から、正極
成形体の密度としては、２．５〜３．５ｇ／ｃｍ3 であ
ることが好ましいことがわかる。The density of the molded positive electrode is 2.5 to 3.5 g / c.
It can be seen that in the batteries A1 and A3 to A6 of m 3 , the decrease in the discharge capacity is small even after the lapse of the charge / discharge cycle, and the electrolyte does not leak to the outside. In the battery A2 in which the density of the positive electrode molded product is lower than the range of the present invention, the crack generation rate when the positive electrode molded product is inserted into the battery can is large, and it can be seen that the production of the battery is difficult. In addition, it can be seen that in the battery A7 having a positive electrode molded body density of 3.7 g / cm 3 , the discharge capacity is slightly lower. In addition, in the battery X, since manganese dioxide is used as the positive electrode active material, it can be seen that the discharge capacity decreases as the charge / discharge cycle progresses. From the above results, it is understood that the density of the positive electrode molded body is preferably 2.5 to 3.5 g / cm 3 .
【００３３】〔実験２〕この実験２では、正極活物質に
固溶されるマンガンの含有量と、充放電サイクル経過に
伴う放電容量及び漏液電池発生数との関係を調べた。[Experiment 2] In Experiment 2, the relationship between the content of manganese dissolved in the positive electrode active material, the discharge capacity with the passage of charge / discharge cycles, and the number of leaked batteries was examined.
【００３４】上記〔実験１〕の（実施例１）のステップ
１において、硫酸ニッケル水溶液に同時に添加する硫酸
マンガン水溶液の濃度を表３に示すように変化させ、マ
ンガンを固溶した水酸化ニッケルを作製した。なお、表
３には本発明電池Ａ１の条件もあわせて示す。得られた
水酸化ニッケルを〔実験１〕のステップ２と同様の方法
で酸化処理し、γ型オキシ水酸化ニッケルを作製した。
得られたγ型オキシ水酸化ニッケルのマンガン含有量を
ＩＣＰにより測定し、マンガン固溶量を表３に示した。In step 1 of (Example 1) of [Experiment 1], the concentration of the aqueous solution of manganese sulfate simultaneously added to the aqueous solution of nickel sulfate was changed as shown in Table 3, and nickel hydroxide in which manganese was dissolved was used. Produced. Table 3 also shows the conditions of the battery A1 of the present invention. The obtained nickel hydroxide was oxidized by the same method as in Step 2 of [Experiment 1] to prepare γ-type nickel oxyhydroxide.
The manganese content of the obtained γ-type nickel oxyhydroxide was measured by ICP, and the manganese solid solution amount is shown in Table 3.
【００３５】次に、これらのγ型オキシ水酸化ニッケル
を用いて、上記〔実験１〕の（実施例１）と同様にして
正極成形体を作製し、この正極成形体を用いて電池Ｂ１
〜Ｂ７を作製した。なお、正極成形体の密度は、すべて
３．０ｇ／ｃｍ3 であった。Next, using these γ-type nickel oxyhydroxides, a molded positive electrode was produced in the same manner as in (Example 1) of [Experiment 1].
To B7. In addition, the density of all the positive electrode molded bodies was 3.0 g / cm 3 .
【００３６】[0036]
【表３】 [Table 3]
【００３７】上記電池Ａ１及び電池Ｂ１〜Ｂ７につい
て、上記〔実験１〕と同じ条件で充放電サイクル試験を
行い、その際の１サイクル目、５サイクル目及び２０サ
イクル目の放電容量、及び漏液電池発生数を調べた。各
電池それぞれ１０個について放電容量及び漏液電池発生
数を調べた。The battery A1 and the batteries B1 to B7 were subjected to a charge / discharge cycle test under the same conditions as in [Experiment 1]. The discharge capacities at the first, fifth, and 20th cycles, The number of batteries generated was examined. The discharge capacity and the number of occurrences of leaked batteries were examined for each of 10 batteries.
【００３８】得られた結果を表４に示す。各電池の１サ
イクル目の放電容量は、電池Ａ１の１サイクル目の放電
容量を１００とした指数で示している。また５サイクル
目及び２０サイクル目の放電容量は、各電池の１サイク
ル目の放電容量を１００とした指数で示しており、電解
液が漏出しなかった電池の放電容量の平均値である。ま
た、漏液電池発生数は２０サイクル目の測定値である。
表４には、正極成形体を電池缶内に挿入した際のクラッ
ク発生率も併せて示している。Table 4 shows the obtained results. The discharge capacity of the first cycle of each battery is indicated by an index with the discharge capacity of the first cycle of the battery A1 as 100. The discharge capacity at the 5th cycle and the 20th cycle is indicated by an index when the discharge capacity at the first cycle of each battery is set to 100, and is an average value of the discharge capacity of the batteries in which the electrolyte did not leak. The number of occurrences of the liquid leakage battery is a measured value at the 20th cycle.
Table 4 also shows the crack occurrence rate when the positive electrode molded body was inserted into the battery can.
【００３９】[0039]
【表４】 [Table 4]
【００４０】表４に示す結果から明らかなように、電池
Ａ１及び電池Ｂ２〜Ｂ６においては、初期の放電容量が
高く、充放電サイクルを経過しても放電容量は維持され
ており、漏液電池は認められなかった。As is evident from the results shown in Table 4, in the battery A1 and the batteries B2 to B6, the initial discharge capacity was high, and the discharge capacity was maintained even after the charge / discharge cycle. Was not found.
【００４１】一方、電池Ｂ１においては、充放電サイク
ルを経過しても放電容量は維持されるが、漏液電池発生
数が高くなっている。これは、γ型オキシ水酸化ニッケ
ル内のマンガン固溶量が少ないため、酸素過電圧の上昇
が不十分であったためと考えられる。また、電池Ｂ７に
おいては、マンガンの固溶量が多いため、充放電サイク
ルを経過しても放電容量は維持されるが、初期の段階か
ら十分な放電容量が得られていない。以上のことから、
マンガン固溶量としては、５〜５０重量％が好ましいこ
とがわかる。On the other hand, in the battery B1, the discharge capacity is maintained even after the charging / discharging cycle, but the number of occurrences of the liquid leakage battery is high. This is presumably because the amount of manganese solid solution in the γ-type nickel oxyhydroxide was small and the oxygen overvoltage was insufficiently increased. Further, in the battery B7, since the manganese has a large amount of solid solution, the discharge capacity is maintained even after the charge / discharge cycle, but a sufficient discharge capacity has not been obtained from the initial stage. From the above,
It is understood that the manganese solid solution amount is preferably 5 to 50% by weight.
【００４２】〔実験３〕この実験３では、正極活物質で
あるγ型オキシ水酸化ニッケルのニッケル原子の価数と
放電容量及び漏液電池発生数の関係を調べた。[Experiment 3] In Experiment 3, the relationship between the valence of nickel atoms of γ-type nickel oxyhydroxide, which is a positive electrode active material, the discharge capacity, and the number of liquid leakage batteries was examined.
【００４３】上記〔実験１〕の（実施例１）のステップ
２で、酸化剤である１０重量％次亜塩素酸ナトリウム水
溶液の量を、１４５０ｍｌから、１３５０ｍｌ、１４０
０ｍｌ、１６００ｍｌと変化させて正極活物質を作製し
た。得られたγ型オキシ水酸化ニッケルのニッケルの価
数は、鉄の２価／３価酸化還元滴定法により測定した結
果、それぞれ３．３、３．４、３．８であった。In step 2 of (Example 1) of [Experiment 1], the amount of the 10% by weight aqueous solution of sodium hypochlorite as the oxidizing agent was changed from 1450 ml to 1350 ml,
The positive electrode active material was prepared by changing the amount to 0 ml and 1600 ml. The valence of nickel in the obtained γ-type nickel oxyhydroxide was 3.3, 3.4, and 3.8, respectively, as measured by a divalent / trivalent redox titration method of iron.
【００４４】次いで、上記の正極活物質を用いて、上記
（実施例１）と同様にして正極成形体を作製し、電池Ｃ
１〜Ｃ３を作製した。なお、得られた正極成形体の密度
は、いずれも３．０ｇ／ｃｍ3 であった。Next, using the above-mentioned positive electrode active material, a molded positive electrode was produced in the same manner as in the above (Example 1).
1 to C3 were produced. In addition, the density of each of the obtained positive electrode molded bodies was 3.0 g / cm 3 .
【００４５】上記電池Ａ及び電池Ｃ１〜Ｃ３について、
上記〔実験１〕と同じ条件で充放電サイクル試験を行
い、その際の１サイクル目及び２０サイクル目の放電容
量、及び漏液電池発生率を調べた。With respect to the battery A and the batteries C1 to C3,
A charge-discharge cycle test was performed under the same conditions as in [Experiment 1], and the discharge capacity at the first cycle and the 20th cycle and the leakage battery generation rate were examined.
【００４６】その結果を表５に示す。表５中の１サイク
ル目の放電容量は、電池Ａ１の１サイクル目の放電容量
を１００とした指数で示しており、また、２０サイクル
目の放電容量は、各電池の１サイクル目の放電容量を１
００とした指数で示しており、電解液が漏出しなかった
電池の放電容量の平均値である。また、正極成形体を電
池缶内に導入した際のクラック発生率を表５に併せて示
す。Table 5 shows the results. The discharge capacity at the first cycle in Table 5 is indicated by an index when the discharge capacity at the first cycle of the battery A1 is set to 100, and the discharge capacity at the 20th cycle is the discharge capacity at the first cycle of each battery. 1
The index is set to 00, and is an average value of the discharge capacity of the battery in which the electrolyte did not leak. Table 5 also shows the crack occurrence rate when the positive electrode molded body was introduced into the battery can.
【００４７】[0047]
【表５】 [Table 5]
【００４８】表５に示すように、電池Ａ１及び電池Ｃ２
及びＣ３においては、充放電サイクル経過に伴う放電容
量が高く、電解液の漏出は認められなかった。しかしな
がら、電池Ｃ１においては、初期の放電容量が低くなっ
ていた。これは、正極活物質中のニッケル原子の価数が
低いため、十分な電池容量が得られなかったことによる
ものと考えられる。従って、正極活物質としてのγ型オ
キシ水酸化ニッケル中のニッケル原子の価数は、３．４
〜３．８の範囲内が好ましいことがわかる。As shown in Table 5, the batteries A1 and C2
In C3 and C3, the discharge capacity with the passage of the charge / discharge cycle was high, and no leakage of the electrolytic solution was observed. However, in the battery C1, the initial discharge capacity was low. This is considered to be due to the fact that a sufficient battery capacity was not obtained because the valence of nickel atoms in the positive electrode active material was low. Therefore, the valence of the nickel atom in the γ-type nickel oxyhydroxide as the positive electrode active material is 3.4.
It can be seen that the range of ~ 3.8 is preferable.
【００４９】〔実験４〕この実験４では、マンガン以外
の元素のγ型オキシ水酸化ニッケルへの固溶と、初期容
量、充放電サイクル経過に伴う放電容量、及び漏液電池
発生率の関係を調べた。[Experiment 4] In Experiment 4, the relationship between the solid solution of elements other than manganese in γ-type nickel oxyhydroxide, the initial capacity, the discharge capacity with the progress of the charge / discharge cycle, and the rate of occurrence of the liquid leakage battery was measured. Examined.
【００５０】（実施例３）〔実験１〕の〔正極の作製〕
において、硫酸ニッケル水溶液及び硫酸マンガン水溶液
と同時に０．００４９Ｍの硫酸エルビウム水溶液５００
ｍｌを添加したこと以外は、〔実験１〕と同様にして、
電池Ｄ１を作製した。このときのエルビウム及びマンガ
ンの固溶量をＩＣＰ（発光分析）により定量した結果、
エルビウムの固溶量は１重量％、マンガンの固溶量は２
０重量％であった。(Example 3) [Production of positive electrode] in [Experiment 1]
, An aqueous solution of 0.0049 M erbium sulfate at the same time as an aqueous solution of nickel sulfate and an aqueous solution of manganese sulfate
except that ml was added, in the same manner as in [Experiment 1].
Battery D1 was made. As a result of quantifying the solid solution amounts of erbium and manganese at this time by ICP (emission analysis),
The amount of erbium is 1% by weight, and the amount of manganese is 2
It was 0% by weight.
【００５１】（実施例４）〔実験１〕の〔正極の作製〕
において、硫酸ニッケル水溶液及び硫酸マンガン水溶液
と同時に０．００４８Ｍの硫酸イッテルビウム水溶液５
００ｍｌを添加したこと以外は、〔実験１〕と同様にし
て、電池Ｄ２を作製した。このときのイッテルビウム及
びマンガンの固溶量をＩＣＰ（発光分析）により定量し
た結果、イッテルビウムの固溶量は１重量％、マンガン
の固溶量は２０重量％であった。(Example 4) [Preparation of positive electrode] in [Experiment 1]
And a 0.0048 M aqueous ytterbium sulfate solution at the same time as the aqueous nickel sulfate solution and the aqueous manganese sulfate solution.
A battery D2 was made in the same manner as in [Experiment 1] except that 00 ml was added. At this time, the amount of solid solution of ytterbium and manganese was determined by ICP (emission analysis). As a result, the amount of solid solution of ytterbium was 1% by weight, and the amount of solid solution of manganese was 20% by weight.
【００５２】（実施例５）〔実験１〕の〔正極の作製〕
において、硫酸ニッケル水溶液及び硫酸マンガン水溶液
と同時に０．００９２Ｍの硫酸イットリウム水溶液５０
０ｍｌを添加したこと以外は、〔実験１〕と同様にし
て、電池Ｄ３を作製した。このときのイットリウム及び
マンガンの固溶量をＩＣＰ（発光分析）により定量した
結果、イットリウムの固溶量は１重量％、マンガンの固
溶量は２０重量％であった。(Example 5) [Production of positive electrode] in [Experiment 1]
At the same time as the aqueous nickel sulfate solution and the aqueous manganese sulfate solution,
A battery D3 was made in the same manner as in [Experiment 1] except that 0 ml was added. As a result of quantifying the amount of yttrium and manganese dissolved at this time by ICP (emission spectroscopy), the amount of yttrium was 1% by weight and the amount of manganese was 20% by weight.
【００５３】（実施例６）〔実験１〕の〔正極の作製〕
において、硫酸ニッケル水溶液及び硫酸マンガン水溶液
と同時に０．００５２Ｍの硫酸ガドリニウム水溶液５０
０ｍｌを添加したこと以外は、〔実験１〕と同様にし
て、電池Ｄ４を作製した。このときのガドリニウム及び
マンガンの固溶量をＩＣＰ（発光分析）により定量した
結果、ガドリニウムの固溶量は１重量％、マンガンの固
溶量は２０重量％であった。(Example 6) [Preparation of positive electrode] in [Experiment 1]
At the same time as the aqueous nickel sulfate solution and the aqueous manganese sulfate solution,
A battery D4 was made in the same manner as in [Experiment 1] except that 0 ml was added. As a result of quantifying the solid solution amounts of gadolinium and manganese at this time by ICP (emission analysis), the solid solution amount of gadolinium was 1% by weight, and the solid solution amount of manganese was 20% by weight.
【００５４】（実施例７）〔実験１〕の〔正極の作製〕
において、硫酸ニッケル水溶液及び硫酸マンガン水溶液
と同時に０．０３０Ｍの硫酸アルミニウム水溶液５００
ｍｌを添加したこと以外は、〔実験１〕と同様にして、
電池Ｄ５を作製した。このときのアルミニウム及びマン
ガンの固溶量をＩＣＰ（発光分析）により定量した結
果、アルミニウムの固溶量は１重量％、マンガンの固溶
量は２０重量％であった。(Example 7) [Production of positive electrode] in [Experiment 1]
, A nickel sulfate aqueous solution and a manganese sulfate aqueous solution simultaneously with a 0.030 M aluminum sulfate aqueous solution 500
except that ml was added, in the same manner as in [Experiment 1].
Battery D5 was made. As a result of quantifying the solid solution amount of aluminum and manganese at this time by ICP (emission analysis), the solid solution amount of aluminum was 1% by weight, and the solid solution amount of manganese was 20% by weight.
【００５５】（実施例８）〔実験１〕の〔正極の作製〕
において、硫酸ニッケル水溶液及び硫酸マンガン水溶液
と同時に０．００１４Ｍの硫酸コバルト水溶液５００ｍ
ｌを添加したこと以外は、〔実験１〕と同様にして、電
池Ｄ６を作製した。このときのコバルト及びマンガンの
固溶量をＩＣＰ（発光分析）により定量した結果、コバ
ルトの固溶量は１重量％、マンガンの固溶量は２０重量
％であった。(Example 8) [Production of positive electrode] in [Experiment 1]
500m of 0.0014M cobalt sulfate aqueous solution at the same time as nickel sulfate aqueous solution and manganese sulfate aqueous solution
A battery D6 was made in the same manner as in [Experiment 1] except that 1 was added. At this time, the amount of solid solution of cobalt and manganese was determined by ICP (emission analysis). As a result, the amount of solid solution of cobalt was 1% by weight, and the amount of solid solution of manganese was 20% by weight.
【００５６】（実施例９）〔実験１〕の〔正極の作製〕
において、硫酸ニッケル水溶液及び硫酸マンガン水溶液
と同時に０．００２５Ｍの硫酸エルビウム水溶液５００
ｍｌ及び０．００４６Ｍの硫酸イットリウム５００ｍｌ
を添加したこと以外は、〔実験１〕と同様にして、電池
Ｄ７を作製した。このときのエルビウム、イットリウム
及びマンガンの固溶量をＩＣＰ（発光分析）により定量
した結果、エルビウム及びイットリウムの固溶量はそれ
ぞれ０．５重量％、マンガンの固溶量は２０重量％であ
った。(Example 9) [Preparation of positive electrode] in [Experiment 1]
, A nickel sulfate aqueous solution and a manganese sulfate aqueous solution at the same time as a 0.0025 M erbium sulfate aqueous solution 500
ml and 500 ml of 0.0046M yttrium sulfate
A battery D7 was made in the same manner as in [Experiment 1] except that was added. As a result of quantifying the amount of erbium, yttrium and manganese dissolved at this time by ICP (emission analysis), the amount of erbium and yttrium was 0.5% by weight and the amount of manganese was 20% by weight, respectively. .
【００５７】上記実施例３〜９において、得られたγ型
オキシ水酸化ニッケルのニッケル原子の価数はいずれも
３．５であり、これらを用いて得られた正極成形体の密
度はいずれも３．０ｇ／ｃｍ3 であった。上記の固溶元
素の異なる７種の電池Ｄ１〜Ｄ７について、〔実験１〕
と同様の条件にて充放電サイクル試験を行い、その際の
５サイクル目及び２０サイクル目の放電容量、及び漏液
電池発生率を調べた。放電容量は、各電池の１サイクル
目の放電容量を１００とした指数であり、電解液が漏出
しなかった電池の放電容量の平均値である。結果を表６
に示す。In Examples 3 to 9 described above, the valence of nickel atoms of the obtained γ-type nickel oxyhydroxide is 3.5, and the density of the positive electrode molded article obtained by using any of these is 3.5. It was 3.0 g / cm 3 . Regarding the seven types of batteries D1 to D7 having different solid solution elements, [Experiment 1]
A charge / discharge cycle test was performed under the same conditions as those described above, and the discharge capacity at the 5th cycle and the 20th cycle and the leakage battery generation rate at that time were examined. The discharge capacity is an index with the discharge capacity of the first cycle of each battery as 100, and is an average value of the discharge capacity of the battery in which the electrolyte did not leak. Table 6 shows the results
Shown in
【００５８】[0058]
【表６】 [Table 6]
【００５９】表６に示すように、正極活物質であるγ型
オキシ水酸化ニッケルに、マンガン以外の元素として、
エルビウム、イッテルビウム、イットリウム、ガドリニ
ウム、アルミニウム及びコバルトから選ばれる１種以上
の元素が固溶された場合においても、充放電サイクルの
長期にわたり、放電容量の低下が小さく、電解液の外部
への漏出が認められないことがわかる。As shown in Table 6, γ-type nickel oxyhydroxide as a positive electrode active material was
Even when one or more elements selected from erbium, ytterbium, yttrium, gadolinium, aluminum, and cobalt are dissolved, the decrease in discharge capacity is small over a long charge-discharge cycle, and leakage of the electrolyte to the outside is prevented. It turns out that it is not recognized.
【００６０】[0060]
【発明の効果】以上のように、本発明によれば、充放電
サイクルの長期にわたって電解液が外部に漏出しにく
く、かつ放電容量の高い放電スタートの密閉型アルカリ
蓄電池とすることができる。As described above, according to the present invention, it is possible to obtain a sealed alkaline storage battery having a high discharge capacity and a low discharge capacity, in which the electrolyte does not easily leak to the outside over a long charge / discharge cycle.
【図１】本発明に従う一実施例の密閉型アルカリ蓄電池
を示す部分断面図。FIG. 1 is a partial sectional view showing a sealed alkaline storage battery of one embodiment according to the present invention.
１…正極缶 ２…負極蓋 ３…絶縁パッキング ４…負極集電棒 ５…正極 ６…セパレータ ７…ゲル状負極 DESCRIPTION OF SYMBOLS 1 ... Positive electrode can 2 ... Negative electrode cover 3 ... Insulating packing 4 ... Negative current collector rod 5 ... Positive electrode 6 ... Separator 7 ... Gelled negative electrode
───────────────────────────────────────────────────── フロントページの続き (72)発明者 木本 衛 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 AA04 BA00 BB02 BB04 BD00 BD04 5H016 AA01 BB00 EE05 HH08 5H028 AA01 BB00 CC17 EE01 EE05 FF02 HH03 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Mamoru Kimoto 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Yasuhiko Ito 2-chome Keihanhondori, Moriguchi-shi, Osaka No.5-5 Sanyo Electric Co., Ltd. F term (reference) 5H003 AA04 BA00 BB02 BB04 BD00 BD04 5H016 AA01 BB00 EE05 HH08 5H028 AA01 BB00 CC17 EE01 EE05 FF02 HH03
Claims (5)
るように前記電池缶内に配置される、γ型オキシ水酸化
ニッケルからなる正極活物質を成形した中空状の正極
と、前記正極の内側に配置される、亜鉛を負極活物質と
した負極と、前記正極と前記負極の間に配置されるセパ
レータと、前記負極内に挿入された状態で配置される負
極集電体と、前記正極、前記負極、及び前記セパレータ
内に含浸される電解液とを備える密閉型アルカリ蓄電池
であって、 前記γ型オキシ水酸化ニッケルがマンガンを固溶してお
り、かつ前記正極成形体の密度が２．５〜３．５ｇ／ｃ
ｍ3 であることを特徴とする密閉型アルカリ蓄電池。1. A battery can, a hollow positive electrode formed of a positive electrode active material made of γ-type nickel oxyhydroxide, which is disposed in the battery can so as to be in electrical contact with the battery can; A negative electrode having zinc as a negative electrode active material, disposed inside the positive electrode, a separator disposed between the positive electrode and the negative electrode, and a negative electrode current collector disposed in a state inserted into the negative electrode, A sealed alkaline storage battery comprising the positive electrode, the negative electrode, and an electrolyte impregnated in the separator, wherein the γ-type nickel oxyhydroxide has manganese as a solid solution, and a density of the positive electrode molded body. Is 2.5 to 3.5 g / c
m 3 is a sealed alkaline storage battery.
％であることを特徴とする請求項１に記載の密閉型アル
カリ蓄電池。2. The sealed alkaline storage battery according to claim 1, wherein the solid solution amount of the manganese is 5 to 50% by weight.
ケル中のニッケル原子の価数が３．４〜３．８価である
請求項１または２に記載の密閉型アルカリ蓄電池。3. The sealed alkaline storage battery according to claim 1, wherein the valence of the nickel atom in the γ-type nickel oxyhydroxide before the first discharge is 3.4 to 3.8.
ガン以外に、さらにアルミニウム（Ａｌ）、コバルト
（Ｃｏ）、イットリウム（Ｙ）、イッテルビウム（Ｙ
ｂ）、エルビウム（Ｅｒ）及びガドリニウム（Ｇｄ）よ
りなる群から選ばれた少なくとも１種の元素が固溶して
いる請求項１、２または３に記載の密閉型アルカリ蓄電
池。4. The γ-type nickel oxyhydroxide may further contain aluminum (Al), cobalt (Co), yttrium (Y), ytterbium (Y) in addition to manganese.
4. The sealed alkaline storage battery according to claim 1, wherein at least one element selected from the group consisting of b), erbium (Er), and gadolinium (Gd) is dissolved.
徴とする請求項１〜４のいずれか１項に記載の密閉型ア
ルカリ蓄電池。5. The sealed alkaline storage battery according to claim 1, wherein the positive electrode molded body has a cylindrical shape.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336250C (en) * | 2002-08-30 | 2007-09-05 | 东芝电池株式会社 | Nickel based compound positive electrode material primary cell |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0676819A (en) * | 1992-08-31 | 1994-03-18 | Sanyo Electric Co Ltd | Electrode plate for cylindrical battery and manufacture thereof |
| JPH10125318A (en) * | 1996-10-24 | 1998-05-15 | Matsushita Electric Ind Co Ltd | Positive active material and positive electrode for alkaline storage battery |
| JPH10149821A (en) * | 1996-09-20 | 1998-06-02 | Matsushita Electric Ind Co Ltd | Positive electrode for alkaline storage battery |
| JPH10214621A (en) * | 1997-01-30 | 1998-08-11 | Sanyo Electric Co Ltd | Sealed alkaline storage battery |
| JPH10270040A (en) * | 1997-03-25 | 1998-10-09 | Sanyo Electric Co Ltd | Non-sintered nickel electrode for alkaline storage battery |
| JPH10289714A (en) * | 1997-04-14 | 1998-10-27 | Matsushita Electric Ind Co Ltd | Nickel-hydrogen storage battery |
| JPH10334913A (en) * | 1997-05-30 | 1998-12-18 | Matsushita Electric Ind Co Ltd | Alkaline storage battery and its manufacture |
| JPH10334910A (en) * | 1997-05-29 | 1998-12-18 | Toshiba Battery Co Ltd | Manufacture of positive electrode mix for alkaline battery |
-
1999
- 1999-06-22 JP JP17580199A patent/JP3728143B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0676819A (en) * | 1992-08-31 | 1994-03-18 | Sanyo Electric Co Ltd | Electrode plate for cylindrical battery and manufacture thereof |
| JPH10149821A (en) * | 1996-09-20 | 1998-06-02 | Matsushita Electric Ind Co Ltd | Positive electrode for alkaline storage battery |
| JPH10125318A (en) * | 1996-10-24 | 1998-05-15 | Matsushita Electric Ind Co Ltd | Positive active material and positive electrode for alkaline storage battery |
| JPH10214621A (en) * | 1997-01-30 | 1998-08-11 | Sanyo Electric Co Ltd | Sealed alkaline storage battery |
| JPH10270040A (en) * | 1997-03-25 | 1998-10-09 | Sanyo Electric Co Ltd | Non-sintered nickel electrode for alkaline storage battery |
| JPH10289714A (en) * | 1997-04-14 | 1998-10-27 | Matsushita Electric Ind Co Ltd | Nickel-hydrogen storage battery |
| JPH10334910A (en) * | 1997-05-29 | 1998-12-18 | Toshiba Battery Co Ltd | Manufacture of positive electrode mix for alkaline battery |
| JPH10334913A (en) * | 1997-05-30 | 1998-12-18 | Matsushita Electric Ind Co Ltd | Alkaline storage battery and its manufacture |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336250C (en) * | 2002-08-30 | 2007-09-05 | 东芝电池株式会社 | Nickel based compound positive electrode material primary cell |
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