JPH1012199A - Alkaline battery - Google Patents
Alkaline batteryInfo
- Publication number
- JPH1012199A JPH1012199A JP8161602A JP16160296A JPH1012199A JP H1012199 A JPH1012199 A JP H1012199A JP 8161602 A JP8161602 A JP 8161602A JP 16160296 A JP16160296 A JP 16160296A JP H1012199 A JPH1012199 A JP H1012199A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- plating layer
- tin alloy
- container
- alkaline 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.)
- Pending
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、端子を兼ねた正極
容器に改良を加えて超重負荷特性等を向上させたアルカ
リ電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkaline battery having an improved ultra-heavy load characteristic by improving a positive electrode container also serving as a terminal.
【０００２】[0002]
【従来の技術】従来のアルカリ電池の正極容器は、鋼板
の両面に予めニッケルメッキを施したものをプレス加工
するか、または鋼板を絞り加工した後ニッケルメッキを
施し、しかる後それぞれ内面に黒鉛を主成分とする導電
膜を形成したものを使用していた。2. Description of the Related Art A conventional positive electrode container of an alkaline battery is prepared by pressing a steel plate having both surfaces subjected to nickel plating in advance, or by subjecting a steel plate to a drawing process and then performing a nickel plating process. What used the conductive film formed as a main component was used.
【０００３】このうち、前者すなわち、鋼板に予めニッ
ケルメッキを施してからプレス加工した場合は、プレス
加工によりニッケル表面にひび割れが生じて鉄の地肌が
露出するので、その分ニッケルメッキの表面積が少なく
なり、そのため接触抵抗が上昇する。一方、後者すなわ
ち、鋼板を絞り加工してからニッケルメッキする場合
は、容器内面側のメッキのつきが悪く、例えば外面側に
３μｍの厚さでニッケルメッキを施すと内面側は０．５
μｍ程度の厚さとなる。このため、正極合剤との接触が
悪くなり、接触抵抗が高くなって短絡電流の低下とな
り、長期貯蔵では性能の劣化を招いて水素ガスの発生量
も増加する。[0003] In the former case, that is, in the case where a steel plate is preliminarily subjected to nickel plating and then pressed, the surface of the nickel plating is reduced by a corresponding amount since cracks occur on the nickel surface due to the pressing and the surface of iron is exposed. Therefore, the contact resistance increases. On the other hand, in the latter case, when the steel plate is drawn and then nickel-plated, the plating on the inner surface side of the container is poor. For example, when the outer surface side is nickel-plated with a thickness of 3 μm, the inner surface becomes 0.5%.
The thickness is about μm. For this reason, the contact with the positive electrode mixture deteriorates, the contact resistance increases, the short-circuit current decreases, and the performance deteriorates during long-term storage, and the amount of generated hydrogen gas increases.
【０００４】[0004]
【発明が解決しようとする課題】このような問題点を解
決するために、前記したように正極容器内面には黒鉛を
主成分とする導電膜が形成されているが、近年、ノート
型パソコン，ＣＤプレーヤ，ＭＤプレーヤ，液晶テレビ
等の携帯用ＡＶ機器、携帯電話などのように、超重負
荷、重負荷の用途がアルカリ電池に要求されており、こ
れらの用途に対しては上記の方法では不十分となった。
また、高容量化のために正極合剤中の黒鉛の添加率を８
％以下とし、正極作用物質の二酸化マンガンを増量した
場合には、缶内面と正極合剤との接触抵抗が高くなるの
で、これに対してもさらなる改善が必要であることがわ
かった。In order to solve such a problem, a conductive film mainly composed of graphite is formed on the inner surface of the positive electrode container as described above. Ultra-heavy loads and heavy loads are required for alkaline batteries, such as portable AV equipment such as CD players, MD players, and liquid crystal televisions, and mobile phones. It was enough.
In order to increase the capacity, the addition ratio of graphite in the positive electrode mixture was reduced to 8%.
% Or less, and when the amount of manganese dioxide as the positive electrode active substance was increased, the contact resistance between the inner surface of the can and the positive electrode mixture became high, so that it was found that further improvement was necessary.
【０００５】本発明は上記状況に対処してなされたもの
で、超重負荷、重負荷の用途に対し、または高容量化に
対して優れた特性を有し、また貯蔵特性にも優れたアル
カリ電池を提供することを目的としたものである。The present invention has been made in view of the above circumstances, and has excellent characteristics for use under an extremely heavy load, a heavy load, or for increasing a capacity, and has excellent storage characteristics. The purpose is to provide.
【０００６】[0006]
【課題を解決するための手段】本発明は、アルカリ電池
の端子兼容器に改良を加えることによって上記目的を達
成したものであって、すなわち本発明は、発電要素を内
填する端子兼容器として、一方の面にニッケルメッキ層
およびニッケル−スズ合金メッキ層を順次施し、他方の
面にニッケルメッキ層を施した冷間圧延鋼板材を、前者
の面が内面になるようにプレス絞り加工し、次に内面の
ニッケル−スズ合金メッキ層の上に黒鉛を主成分とする
導電膜を形成してなる缶を用いたことを特徴とするアル
カリ電池に関する。SUMMARY OF THE INVENTION The present invention has achieved the above object by improving the terminal / container of an alkaline battery. That is, the present invention provides a terminal / container in which a power generating element is inserted. A nickel-plated layer and a nickel-tin alloy-plated layer are sequentially applied to one surface, and a cold-rolled steel sheet material applied with a nickel-plated layer to the other surface is press-drawn so that the former surface is an inner surface, Next, the present invention relates to an alkaline battery using a can formed by forming a conductive film mainly containing graphite on a nickel-tin alloy plating layer on an inner surface.
【０００７】本発明では、冷間圧延鋼板材の容器内面に
なる側にニッケルメッキとその上にさらにニッケル−ス
ズ合金メッキを施してあるので、非常に硬いメッキ層と
なっており、プレス絞り加工時は表面のニッケル−スズ
合金メッキ層が硬いためにひび割れを生じ、凸凹面を形
成して正極合剤との接触向上に寄与する。また、ひび割
れしたニッケル−スズ合金メッキ層の下にはニッケルメ
ッキ層があるので、鉄の地肌は露出しない。したがっ
て、接触抵抗が大きくなることはなく、短絡電流の向上
を図ることができる。In the present invention, since the cold-rolled steel sheet material is nickel-plated on the side to be the inner surface of the container and further plated with nickel-tin alloy, a very hard plating layer is formed. In some cases, the nickel-tin alloy plating layer on the surface is hard, causing cracks, forming an uneven surface, and contributing to improved contact with the positive electrode mixture. Further, since the nickel plating layer is provided below the cracked nickel-tin alloy plating layer, the iron background is not exposed. Therefore, the contact resistance does not increase and the short-circuit current can be improved.
【０００８】ニッケル−スズ合金メッキ層が電解液に直
接接している場合にはスズが溶解して開路電圧の低下と
水素ガスの発生が起こるが、本発明ではニッケル−スズ
合金メッキ層の上に黒鉛を主成分とする導電膜が形成さ
れているので、これを防ぐことができ、短絡電流がさら
に向上する。When the nickel-tin alloy plating layer is in direct contact with the electrolytic solution, tin dissolves and lowers the open-circuit voltage and generates hydrogen gas. Since the conductive film mainly composed of graphite is formed, this can be prevented, and the short-circuit current is further improved.
【０００９】[0009]
【発明の実施の形態】本発明の実施形態を図面を参照し
て説明する。図１は本発明の一実施例を示すアルカリ電
池（ＪＩＳ規格ＬＲ６形（単３形））の断面図である。
この図において、１は正極端子を兼ねる有底円筒形の金
属缶、２は正極合剤、３はセパレータ、４はゲル状負
極、５は負極集電棒、６は絶縁ガスケット、７はリング
状金属板、８は金属封口板、９はラベルジャケットであ
る。Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view of an alkaline battery (JIS standard LR6 type (AA) type) showing one embodiment of the present invention.
In this figure, 1 is a cylindrical metal can with a bottom also serving as a positive electrode terminal, 2 is a positive electrode mixture, 3 is a separator, 4 is a gelled negative electrode, 5 is a negative electrode current collector rod, 6 is an insulating gasket, 7 is a ring-shaped metal. Reference numeral 8 denotes a metal sealing plate, and 9 denotes a label jacket.
【００１０】図２は図１における正極端子を兼ねる有底
円筒形の金属缶１の断面構造を示すもので、図中１０は
ニッケルメッキ層、１１は鋼板、１２はニッケルメッキ
層、１３はニッケル−スズ合金メッキ層、１４は黒鉛を
主成分とする導電膜層である。図２に示すように、金属
缶１は、鋼板１１の外面側にニッケルメッキ層１０が形
成され、内面側にニッケルメッキ層１２、ニッケル−ス
ズ合金メッキ層１３および黒鉛を主成分とする導電膜層
１４が形成されている。FIG. 2 shows a sectional structure of a bottomed cylindrical metal can 1 also serving as a positive electrode terminal in FIG. 1, in which 10 is a nickel plating layer, 11 is a steel plate, 12 is a nickel plating layer, and 13 is a nickel plating layer. A tin alloy plating layer 14 is a conductive layer mainly composed of graphite; As shown in FIG. 2, the metal can 1 has a nickel plating layer 10 formed on the outer surface side of a steel plate 11, and a nickel plating layer 12, a nickel-tin alloy plating layer 13 and a conductive film mainly composed of graphite on the inner surface side. A layer 14 is formed.
【００１１】金属缶１は次のようにして製作する。すな
わち、鋼板１１にメッキ加工したものを有底の円筒形に
プレス絞り加工する。メッキは金属缶内面素地側にニッ
ケルメッキを厚さ１〜２μｍ施し、その上にニッケル−
スズ合金メッキを１〜２μｍ施す。金属缶外面素地側に
はニッケルメッキを２〜３μｍ施す。これを金属缶にプ
レス絞り加工した後、金属缶内面（開口部のガスケット
と接する箇所を除いた部分）に、黒鉛を主成分とする導
電膜を形成する。The metal can 1 is manufactured as follows. That is, the steel plate 11 is plated and pressed into a bottomed cylindrical shape. Nickel plating is applied to the inner surface of the metal can with a thickness of 1 to 2 μm.
Apply a tin alloy plating of 1-2 μm. The outer surface of the metal can is nickel-plated with a thickness of 2 to 3 μm. After this is press-drawn into a metal can, a conductive film containing graphite as a main component is formed on the inner surface of the metal can (excluding the portion of the opening that is in contact with the gasket).
【００１２】導電膜の塗布方法は、黒鉛を主成分とする
導電塗料をメチルエチルケトン（ＭＥＫ）等の低沸点有
機溶媒で希釈し、スプレーガンにより霧状に金属缶内面
に塗布する。その時開口部のガスケットと接する部分に
は塗布しないようにする。塗布後、乾燥機で溶剤を蒸発
させる。残った導電膜の厚さは１〜１０μｍが望まし
い。As a method for applying the conductive film, a conductive paint containing graphite as a main component is diluted with a low-boiling organic solvent such as methyl ethyl ketone (MEK) and applied to the inner surface of the metal can in the form of a mist using a spray gun. At this time, do not apply to the portion of the opening that is in contact with the gasket. After the application, the solvent is evaporated by a dryer. Desirably, the thickness of the remaining conductive film is 1 to 10 μm.
【００１３】この金属缶１内には、円筒状に加圧成形し
た正極合剤２が充填されている。正極合剤２は、二酸化
マンガン粉末と黒鉛粉末とを混合し、これを金属缶１内
に収容し、所定の圧力で中空円筒状に加圧成形したもの
である。放電容量の高容量化のために、正極合剤２中の
黒鉛添加率は８％とした（黒鉛添加率＝［黒鉛粉末重
量］／［二酸化マンガン重量＋黒鉛粉末重量］）。The metal can 1 is filled with a positive electrode mixture 2 formed into a cylindrical shape under pressure. The positive electrode mixture 2 is obtained by mixing a manganese dioxide powder and a graphite powder, storing the manganese dioxide powder in a metal can 1, and press-molding the mixture into a hollow cylinder at a predetermined pressure. In order to increase the discharge capacity, the graphite addition ratio in the positive electrode mixture 2 was set to 8% (graphite addition ratio = [weight of graphite powder] / [weight of manganese dioxide + weight of graphite powder]).
【００１４】また、正極合剤２の中空部には、ビニロン
繊維30％，レーヨン繊維30％，マーセル化パルプ30％，
ポリビニルアルコール繊維10％の不織布からなる有底円
筒状のセパレータ３を介してゲル状負極４が充填されて
いる。ゲル状負極４内には真鍮製の負極集電棒５が、そ
の上端部をゲル状負極４より突出するように挿着されて
いる。負極集電棒５の突出部外周面および金属缶１の上
部内周面には二重環状のポリアミド樹脂からなる絶縁ガ
スケット６が配設されている。また、絶縁ガスケット６
の二重環状部の間にはリング状の金属板７が配設され、
かつ金属板７には負極端子を兼ねる帽子形の金属封口板
８が集電棒５の頭部に当接するように配設されている。
そして金属缶１の開口縁を内方に屈曲させることによ
り、ガスケット６および金属封口板８で金属缶１内を密
封口している。Further, in the hollow portion of the positive electrode mixture 2, 30% vinylon fiber, 30% rayon fiber, 30% mercerized pulp,
The gelled negative electrode 4 is filled via a bottomed cylindrical separator 3 made of a nonwoven fabric of 10% polyvinyl alcohol fiber. A negative electrode current collector rod 5 made of brass is inserted into the gelled negative electrode 4 so that its upper end protrudes from the gelled negative electrode 4. An insulating gasket 6 made of a double annular polyamide resin is provided on the outer peripheral surface of the protruding portion of the negative electrode current collecting rod 5 and the upper inner peripheral surface of the metal can 1. Also, the insulating gasket 6
A ring-shaped metal plate 7 is disposed between the double annular portions of
In addition, a hat-shaped metal sealing plate 8 also serving as a negative electrode terminal is disposed on the metal plate 7 so as to contact the head of the current collecting rod 5.
By bending the opening edge of the metal can 1 inward, the inside of the metal can 1 is sealed with the gasket 6 and the metal sealing plate 8.
【００１５】上記した本発明の実施例と比較するため
に、以下の比較例に示すアルカリ電池を組み立てた。い
ずれも金属缶１以外は同じ構造のＪＩＳ規格ＬＲ６形
（単３形）アルカリ電池である。For comparison with the above-mentioned embodiment of the present invention, alkaline batteries shown in the following comparative examples were assembled. Both are JIS standard LR6 type (AA) alkaline batteries having the same structure except for the metal can 1.
【００１６】（比較例１）発電要素を内填する端子兼容
器として、冷間圧延鋼板材の内面側にニッケルメッキ層
とその上にニッケル−スズ合金メッキ層を施し、外面側
にニッケルメッキ層を施したものを、プレス絞り加工し
て缶としたものを用いた。(Comparative Example 1) As a terminal / container in which a power generating element is to be filled, a nickel plating layer is formed on the inner surface of a cold-rolled steel sheet and a nickel-tin alloy plating layer is formed thereon, and a nickel plating layer is formed on the outer surface. Was subjected to press drawing and used as a can.
【００１７】（比較例２）発電要素を内填する端子兼容
器として、冷間圧延鋼板材の内面側にニッケルメッキ層
を施し、外面側にニッケルメッキ層を施したものを、プ
レス絞り加工して缶とし、その缶内面に黒鉛を主成分と
する導電膜を形成したものを用いた。(Comparative Example 2) As a terminal / container in which a power generation element is to be filled, a cold-rolled steel sheet material having a nickel plating layer applied to the inner surface side and a nickel plating layer applied to the outer surface side is subjected to press drawing. A can having a conductive film containing graphite as a main component was formed on the inner surface of the can.
【００１８】（比較例３）発電要素を内填する端子兼容
器として、冷間圧延鋼板材をプレス絞り加工して缶とし
た後、その内外両面にニッケルメッキを施し、内面にさ
らに黒鉛を主成分とする導電膜を形成したものを用い
た。(Comparative Example 3) A cold-rolled steel sheet was press-drawn to form a can as a terminal / container in which a power generating element was to be filled, and then nickel plating was applied to both inner and outer surfaces, and graphite was further applied to the inner surface. A conductive film formed as a component was used.
【００１９】上記の各アルカリ電池について、６０℃で
１０日間および６０日間貯蔵した後の、開路電圧（ｎ＝
１００個の平均値）、短絡電流（ｎ＝１００個の平均
値）おび水素ガス量（ｎ＝１００個の平均値）を調べ
た。水素ガス量は電池を水中で分解し、電池内部のガス
を捕集して測定した。結果を表１に示す。For each of the above alkaline batteries, the open circuit voltage (n =
100 average values), short circuit current (n = 100 average values), and hydrogen gas amount (n = 100 average values) were examined. The amount of hydrogen gas was measured by decomposing the battery in water and collecting gas inside the battery. Table 1 shows the results.
【００２０】[0020]
【表１】 [Table 1]
【００２１】表１に示されるように、実施例１と比較例
１とを比較すると、６０℃６０日貯蔵で、開路電圧の劣
化に著しい差が認められ、また６０℃６０日貯蔵後の水
素ガス量にも著しい差が認められる。また、短絡電流に
ついても著しい差が見られる。したがって、本発明にお
いて缶の内面に導電膜を形成したことの効果が確認でき
る。また、実施例１と比較例２および各例３を比較する
と、ニッケル−スズ合金メッキ層による短絡電流の向上
が確認できる。As shown in Table 1, when Example 1 and Comparative Example 1 were compared, there was a remarkable difference in the deterioration of the open-circuit voltage when stored at 60 ° C. for 60 days. A remarkable difference is also observed in the gas amount. Also, there is a remarkable difference in the short-circuit current. Therefore, the effect of forming the conductive film on the inner surface of the can in the present invention can be confirmed. In addition, when Example 1 is compared with Comparative Example 2 and Example 3, it can be confirmed that the nickel-tin alloy plating layer improves short-circuit current.
【００２２】[0022]
【発明の効果】以上説明したように、本発明は発電要素
を内填する端子兼容器を改良することによって、高容量
特性、高重負荷特性に優れ、また貯蔵特性にも優れたア
ルカリ電池を提供することができる。As described above, according to the present invention, by improving a terminal / container in which a power generating element is inserted, an alkaline battery excellent in high capacity characteristics, high heavy load characteristics and storage characteristics is provided. Can be provided.
【図１】本発明の実施例であるアルカリ電池の断面図。FIG. 1 is a sectional view of an alkaline battery according to an embodiment of the present invention.
【図２】図１のアルカリ電池の端子兼容器の断面構造を
示す図。FIG. 2 is a diagram showing a cross-sectional structure of a terminal / container of the alkaline battery of FIG. 1;
１…正極端子を兼ねる有底円筒形の金属缶、２…正極合
剤、３…セパレータ、４…ゲル状負極、５…負極集電
棒、６…絶縁ガスケット、７…リング状金属板、８…金
属封口板、９…ラベルジャケット、１０，１２…ニッケ
ルメッキ層、１１…鋼板、１３…ニッケル−スズ合金メ
ッキ層、１４…黒鉛を主成分とする導電膜層。DESCRIPTION OF SYMBOLS 1 ... Bottom cylindrical metal can also serving as a positive electrode terminal, 2 ... Positive electrode mixture, 3 ... Separator, 4 ... Gel negative electrode, 5 ... Negative electrode current collecting rod, 6 ... Insulating gasket, 7 ... Ring metal plate, 8 ... Metal sealing plate, 9: label jacket, 10, 12, nickel plating layer, 11: steel plate, 13: nickel-tin alloy plating layer, 14: conductive film layer mainly composed of graphite.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 飯塚 一雄 東京都品川区南品川三丁目４番10号 東芝 電池株式会社内 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Kazuo Iizuka 3-4-10 Minamishinagawa, Shinagawa-ku, Tokyo Toshiba Battery Corporation
Claims (2)
一方の面にニッケルメッキ層およびニッケル−スズ合金
メッキ層を順次施し、他方の面にニッケルメッキ層を施
した冷間圧延鋼板材を、前者の面が内面になるようにプ
レス絞り加工し、次に内面のニッケル−スズ合金メッキ
層の上に黒鉛を主成分とする導電膜を形成してなる缶を
用いたことを特徴とするアルカリ電池。1. A terminal / container in which a power generating element is filled,
A cold-rolled steel sheet having a nickel plating layer and a nickel-tin alloy plating layer sequentially applied to one surface and a nickel plating layer applied to the other surface is press-drawn so that the former surface is an inner surface. An alkaline battery using a can formed by forming a conductive film containing graphite as a main component on a nickel-tin alloy plating layer on an inner surface thereof.
が８％以下である請求項１記載のアルカリ電池。2. The alkaline battery according to claim 1, wherein the graphite addition rate in the positive electrode mixture as a power generating element is 8% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8161602A JPH1012199A (en) | 1996-06-21 | 1996-06-21 | Alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8161602A JPH1012199A (en) | 1996-06-21 | 1996-06-21 | Alkaline battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1012199A true JPH1012199A (en) | 1998-01-16 |
Family
ID=15738285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8161602A Pending JPH1012199A (en) | 1996-06-21 | 1996-06-21 | Alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1012199A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000005437A1 (en) * | 1998-07-24 | 2000-02-03 | Toyo Kohan Co., Ltd. | Surface-treated steel sheet for battery case, method of production thereof, battery case formed by the steel sheet and battery using the case |
| US6852445B1 (en) * | 1998-11-12 | 2005-02-08 | Hille & Mueller Gmbh | Battery sheath made of a formed cold-rolled sheet and method for producing battery sheaths |
-
1996
- 1996-06-21 JP JP8161602A patent/JPH1012199A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000005437A1 (en) * | 1998-07-24 | 2000-02-03 | Toyo Kohan Co., Ltd. | Surface-treated steel sheet for battery case, method of production thereof, battery case formed by the steel sheet and battery using the case |
| US6852445B1 (en) * | 1998-11-12 | 2005-02-08 | Hille & Mueller Gmbh | Battery sheath made of a formed cold-rolled sheet and method for producing battery sheaths |
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