JPH11265702A - Alkaline-manganese battery - Google Patents
Alkaline-manganese batteryInfo
- Publication number
- JPH11265702A JPH11265702A JP6708598A JP6708598A JPH11265702A JP H11265702 A JPH11265702 A JP H11265702A JP 6708598 A JP6708598 A JP 6708598A JP 6708598 A JP6708598 A JP 6708598A JP H11265702 A JPH11265702 A JP H11265702A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- electrode case
- conductive
- case
- graphite
- 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
-
- Y02E60/12—
Landscapes
- Sealing Battery Cases Or Jackets (AREA)
- Primary Cells (AREA)
- Connection Of Batteries Or Terminals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、二酸化マンガンと
炭素材を主構成材料とした正極合剤を、金属製正極ケー
ス内に密着させて収納したアルカリマンガン電池、特に
正極ケースの内面に形成されて正極合剤に接する導電性
被膜の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkaline manganese battery in which a positive electrode mixture containing manganese dioxide and a carbon material as main constituents is tightly housed in a metal positive electrode case, and particularly formed on the inner surface of the positive electrode case. And improvement of the conductive film in contact with the positive electrode mixture.
【０００２】[0002]
【従来の技術】アルカリマンガン電池は、正極端子を兼
ねる正極ケースの中に、正極ケースに密着して円筒状の
正極合剤が配置され、その中央にセパレータを介してゲ
ル状負極が配置された構造を有する。そして、正極合剤
は、あらかじめ成型されたものを正極ケースに挿入した
後、ケース内において加圧することにより、正極ケース
との密着を良くするとともに正極合剤の充填量の増加を
図っている。このような構成のアルカリマンガン電池に
おいて、正極ケースと正極合剤が直接接する構成である
と、電池の保存中に正極合剤などによる酸化作用によ
り、正極ケースの表面に薄い酸化被膜が形成され、ケー
スと正極合剤との電気的接触状態が悪くなり、電池の保
存性能が低下するという問題が生じる。そこで、従来か
ら正極ケースの内面にカーボン等の導電性被膜をあらか
じめ形成し、この被膜を介して正極ケースと正極合剤間
の電気的接触状態を良好にする試みがなされている（例
えば、特開昭６０−２４００５６号公報）。2. Description of the Related Art In an alkaline manganese battery, a cylindrical positive electrode mixture is disposed in close contact with a positive electrode case in a positive electrode case also serving as a positive electrode terminal, and a gel negative electrode is disposed at the center of the mixture through a separator. Having a structure. The positive electrode mixture is inserted into a positive electrode case after being molded in advance, and then pressurized in the case to improve the adhesion to the positive electrode case and increase the filling amount of the positive electrode mixture. In the alkaline manganese battery having such a configuration, if the positive electrode case and the positive electrode mixture are in direct contact with each other, a thin oxide film is formed on the surface of the positive electrode case due to the oxidizing action of the positive electrode mixture and the like during storage of the battery, A problem arises in that the electrical contact between the case and the positive electrode mixture deteriorates, and the storage performance of the battery decreases. Therefore, conventionally, an attempt has been made to previously form a conductive film of carbon or the like on the inner surface of the positive electrode case and to improve the electrical contact state between the positive electrode case and the positive electrode mixture through this film (for example, JP-A-60-240056).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、あらか
じめ前述の導電性被膜を形成した正極ケースに、円筒状
に成型された正極合剤を挿入し、加圧すると、正極合剤
が圧縮されると同時に導電性被膜が剥離するという現象
が発生する。そうすると、電池保存中に導電性被膜が剥
離した正極ケースの内面に酸化被膜が形成され、特に強
負荷放電の電池性能が低下するという問題が生じる。こ
の問題は、特に正極ケース内壁にあらかじめ形成された
導電性被膜と正極ケースとの密着強度が十分でない場合
に顕著である。本発明は、このような従来の問題点を解
決するもので、正極ケースと正極合剤間の電気的接触状
態を良好にし、特に保存後の強負荷特性が向上したアル
カリマンガン電池を提供することを目的とする。However, when the positive electrode mixture formed into a cylindrical shape is inserted into the positive electrode case on which the above-mentioned conductive film has been formed in advance, and then the positive electrode mixture is compressed, the positive electrode mixture is simultaneously compressed. A phenomenon occurs in which the conductive coating peels off. Then, an oxide film is formed on the inner surface of the positive electrode case from which the conductive film has been peeled off during storage of the battery, which causes a problem that the battery performance particularly under heavy load discharge is reduced. This problem is remarkable particularly when the adhesive strength between the conductive film formed in advance on the inner wall of the positive electrode case and the positive electrode case is not sufficient. The present invention is to solve such a conventional problem, and to provide an alkaline manganese battery in which the electrical contact state between the positive electrode case and the positive electrode mixture is improved, and in particular, the heavy load characteristics after storage are improved. With the goal.
【０００４】[0004]
【課題を解決するための手段】本発明は、上記目的を達
成するために、二酸化マンガンと炭素材を主構成材料と
して円筒状に成型された正極合剤を、金属製正極ケース
内に密着させて収納したアルカリマンガン電池におい
て、正極ケース内壁に形成された導電性被膜として、バ
インダーとしての１０〜２０wt％のポリビニルブチラー
ルと、９０〜８０wt％の導電性炭素材とからなる被膜を
用いることを特徴とする。ここにおいて、導電性炭素材
は、黒鉛とカーボンブラックからなり、その配合比が黒
鉛６０〜７５wt％、カーボンブラック４０〜２５wt％で
あることが好ましい。According to the present invention, in order to achieve the above object, a cylindrical positive electrode mixture composed mainly of manganese dioxide and a carbon material is brought into close contact with a metal positive electrode case. In the alkaline manganese battery housed in the positive electrode case, as the conductive film formed on the inner wall of the positive electrode case, a film composed of 10 to 20% by weight of polyvinyl butyral as a binder and 90 to 80% by weight of a conductive carbon material is used. And Here, the conductive carbon material is preferably composed of graphite and carbon black, and the compounding ratio thereof is preferably 60 to 75% by weight of graphite and 40 to 25% by weight of carbon black.
【０００５】[0005]
【発明の実施の形態】本発明は、正極ケース内壁に形成
する導電性被膜をポリビニルブチラールと導電性炭素材
とから構成し、導電性被膜の固形分中のバインダーの割
合を１０〜２０wt％と適切にして、正極ケース内壁との
密着性を向上するものである。導電性被膜の正極ケース
との密着性を向上させるには、導電性被膜の固形分中の
バインダーの量を増加すればよいが、そうすると被膜自
体の導電性が低下する。本発明は、バインダーとして金
属製正極ケースとの密着性に優れているポリビニルブチ
ラールを用いることにより、被膜自体の導電性を損なう
ことなく正極ケースとの密着性を向上する。また、導電
性炭素材として、黒鉛とカーボンブラックを併用し、そ
れらの配合比率を黒鉛６０〜７５wt％、カーボンブラッ
ク４０〜２５wt％に規制することによって、導電性被膜
自体の電気抵抗の増加を抑制することができる。BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a conductive film formed on the inner wall of a positive electrode case is composed of polyvinyl butyral and a conductive carbon material, and a ratio of a binder to a solid content of the conductive film is 10 to 20% by weight. In a proper manner, the adhesion to the inner wall of the positive electrode case is improved. In order to improve the adhesion of the conductive film to the positive electrode case, the amount of the binder in the solid content of the conductive film may be increased, but then the conductivity of the film itself decreases. The present invention improves the adhesion to the positive electrode case without impairing the conductivity of the coating itself by using polyvinyl butyral having excellent adhesion to the metal positive electrode case as a binder. In addition, graphite and carbon black are used in combination as conductive carbon materials, and the compounding ratio thereof is restricted to 60 to 75 wt% of graphite and 40 to 25 wt% of carbon black, thereby suppressing an increase in electric resistance of the conductive coating itself. can do.
【０００６】本発明によると、導電性被膜を形成した正
極ケース内に、円筒状に成型された正極合剤を挿入し再
加圧した際、正極合剤に接している側の被膜表層部分が
多少削り取られても、正極ケース内壁自体からの導電性
被膜の剥離を抑制することができる。従って、酸化力の
ある正極二酸化マンガンや電解液によって正極ケースの
内壁表面に酸化被膜が形成されることは殆どなく、特に
保存中の強負荷放電の電池性能を向上させることができ
る。なお、導電性炭素材として黒鉛とカーボンブラック
を併用することによる前記のような効果が生じる理由は
定かではないが次のように考えられる。すなわち、層状
に結晶構造の発達した黒鉛は、層の面方向の導電性は優
れているが、層間方向の導電性が悪い。一方、カーボン
ブラックは、黒鉛ほど結晶構造が発達していないため、
導電性に方向性がさほどない。このような黒鉛とカーボ
ンブラックの配合比率が適切な範囲において両者の併用
の相乗効果により、導電性被膜の膜厚方向の導電性が向
上したものと推定される。本発明による導電性被膜の好
ましい厚さは、約３〜７μｍである。According to the present invention, when a positive electrode mixture formed into a cylindrical shape is inserted into a positive electrode case having a conductive film formed thereon and repressurized, the surface layer portion of the coating in contact with the positive electrode mixture is reduced. Even if it is slightly removed, the peeling of the conductive film from the inner wall of the positive electrode case itself can be suppressed. Therefore, the oxide film is hardly formed on the inner wall surface of the positive electrode case by the positive electrode manganese dioxide or the electrolytic solution having the oxidizing power, and the battery performance of heavy load discharge during storage can be particularly improved. The reason why the above-mentioned effect is produced by using graphite and carbon black together as the conductive carbon material is not clear, but is considered as follows. That is, graphite having a layered crystal structure has excellent conductivity in the plane direction of the layer, but poor conductivity in the interlayer direction. On the other hand, carbon black has a less developed crystal structure than graphite,
There is not much directionality in conductivity. It is presumed that the conductivity in the thickness direction of the conductive film is improved due to the synergistic effect of the combined use of the graphite and the carbon black in the appropriate range of the mixing ratio of the graphite and the carbon black. The preferred thickness of the conductive coating according to the present invention is about 3-7 μm.
【０００７】図１は本発明の一実施例におけるアルカリ
乾電池ＬＲ６の一部を断面にした正面図である。この電
池は、以下のようにして製造される。１はニッケルめっ
きされた鋼からなる正極ケースを表す。この正極ケース
１の内面には、図２に示されるように、導電性被膜２が
形成されている。まず、正極ケース１の内部に、二酸化
マンガンと黒鉛を主構成材とする短筒状の正極合剤成型
体の複数個が挿入され、ケース内において再加圧するこ
とによりケース１の内面に密着される。こうしてケース
内に充填された正極合剤３の内側にセパレータ４および
絶縁キャップ５を挿入した後、セパレータの内側にゲル
状負極６が注入される。ゲル状負極６は、ゲル化剤のポ
リアクリル酸ソーダ、アルカリ電解液および負極活物質
の亜鉛粉末からなる。次に、樹脂製封口体７、負極端子
を兼ねる底板８および絶縁ワッシャ９と一体化された負
極集電体１０をゲル状負極６中に差し込み、正極ケース
１の開口端部を樹脂製封口体７の端部を介して底板８の
周縁部にかしめつけて正極ケース１の開口部を密閉す
る。次いで、正極ケース１の外表面に外装ラベル１１を
被覆する。こうしてアルカリ乾電池が完成する。FIG. 1 is a front view in which a part of an alkaline dry battery LR6 according to an embodiment of the present invention is sectioned. This battery is manufactured as follows. Reference numeral 1 denotes a positive electrode case made of nickel-plated steel. As shown in FIG. 2, a conductive coating 2 is formed on the inner surface of the positive electrode case 1. First, a plurality of short cylindrical positive electrode mixture moldings mainly composed of manganese dioxide and graphite are inserted into the inside of the positive electrode case 1, and are closely adhered to the inner surface of the case 1 by repressurizing the inside of the case. You. After inserting the separator 4 and the insulating cap 5 inside the positive electrode mixture 3 filled in the case in this way, the gelled negative electrode 6 is injected inside the separator. The gelled negative electrode 6 is composed of sodium polyacrylate as a gelling agent, an alkaline electrolyte, and zinc powder as a negative electrode active material. Next, the negative electrode current collector 10 integrated with the resin sealing member 7, the bottom plate 8 also serving as the negative electrode terminal, and the insulating washer 9 is inserted into the gelled negative electrode 6, and the opening end of the positive electrode case 1 is closed with the resin sealing member. The opening of the positive electrode case 1 is sealed by caulking the peripheral edge of the bottom plate 8 via the end of the positive electrode 7. Next, the outer label 11 is coated on the outer surface of the positive electrode case 1. Thus, an alkaline battery is completed.
【０００８】[0008]
【実施例】以下に本発明の実施例を詳細に説明する。 《実施例１》ポリビニルブチラール（以下、ＰＶＢで表
す）、導電性炭素材、およびバインダーの溶媒からなる
導電性被膜用塗料を調製し、これを正極ケースの内面に
塗布した後、正極ケース自体の電磁誘導加熱によって乾
燥し、厚さ約５μｍの導電性被膜を形成した。こうして
導電性被膜中の固形分であるＰＶＢと導電性炭素材との
配合比を表１に示すように種々変えた正極ケースを用い
て図１のようなアルカリ乾電池ＬＲ６を作製した。ここ
に用いた導電性炭素材は、黒鉛とカーボンブラックの混
合物で、その比率（重量比）は６５：３５と一定にし
た。また、導電性被膜用塗料の溶媒にはメチルエチルケ
トンとシクロヘキサノンの重量比１：１の混合物を用
い、塗料中の溶媒濃度は７０wt％とした。また、比較例
として、バインダーにポリ塩化ビニルを用い、導電材と
バインダーの固形分比率を６２．５：３７．５とした他
は上記の実施例と同様にして導電性被膜を形成しアルカ
リ乾電池（表１のＮｏ．７）を作製した。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below in detail. << Example 1 >> A coating material for a conductive film comprising polyvinyl butyral (hereinafter, referred to as PVB), a conductive carbon material, and a solvent for a binder was prepared and applied to the inner surface of the positive electrode case. Drying was performed by electromagnetic induction heating to form a conductive film having a thickness of about 5 μm. Thus, an alkaline dry battery LR6 as shown in FIG. 1 was produced using a positive electrode case in which the mixing ratio of PVB, which is the solid content in the conductive film, to the conductive carbon material was variously changed as shown in Table 1. The conductive carbon material used here was a mixture of graphite and carbon black, and the ratio (weight ratio) was fixed at 65:35. Further, a mixture of methyl ethyl ketone and cyclohexanone at a weight ratio of 1: 1 was used as a solvent for the paint for the conductive coating, and the solvent concentration in the paint was 70 wt%. As a comparative example, a conductive film was formed in the same manner as in the above example except that polyvinyl chloride was used as the binder and the solid content ratio between the conductive material and the binder was 62.5: 37.5. (No. 7 in Table 1) was produced.
【０００９】上記のそれぞれの電池について、初度およ
び６０℃１ヶ月保存後に、常温下、１５００ｍＡの定電
流で連続放電を行い、電圧が終止電圧０．９Ｖに至るま
での持続時間を測定した。表１には、各電池１０個の平
均値を示した。なお、比較例の電池の初度の持続時間を
１００として示した。For each of the above-mentioned batteries, the battery was initially discharged and stored at 60 ° C. for one month, and then continuously discharged at a constant current of 1500 mA at room temperature, and the duration until the voltage reached the final voltage of 0.9 V was measured. Table 1 shows the average value of 10 batteries. The initial duration of the battery of the comparative example was set to 100.
【００１０】[0010]
【表１】 [Table 1]
【００１１】表１から明らかなように、バインダーとし
てＰＶＢを用い導電性被膜中の固形分比率１０〜２０wt
％において、６０℃１ヶ月後の１５００ｍＡ連続放電性
能が比較例と比べて向上することが認められる。バイン
ダー量が２０％を越えると、正極ケースとの密着性は非
常に良好であるが、導電性被膜自体の電気抵抗が増大す
るため電池性能が劣化する。バインダーとしてＰＶＢを
用いた場合には、比較例のＰＶＣと同量の３７．５wt％
において、６０℃１ヶ月後の１５００ｍＡの連続放電性
能は比較例よりも劣る。これは、ＰＶＢがＰＶＣに比べ
て密着性は優れているが、比抵抗が高いためと考えられ
る。なお、バインダーＰＶＢの量が１０wt％未満になる
と、正極ケースとの密着性が低下するため導電性被膜の
剥離が発生し、保存後の電池性能が劣化する。As is apparent from Table 1, PVB is used as a binder and the solid content ratio in the conductive film is 10 to 20 wt.
%, It is recognized that the 1500 mA continuous discharge performance after one month at 60 ° C. is improved as compared with the comparative example. If the amount of the binder exceeds 20%, the adhesion to the positive electrode case is very good, but the electric resistance of the conductive film itself increases, so that the battery performance deteriorates. When PVB was used as the binder, the same amount as the PVC of the comparative example was 37.5 wt%.
, The continuous discharge performance at 1500 mA after one month at 60 ° C is inferior to the comparative example. This is presumably because PVB has better adhesion than PVC, but has higher specific resistance. When the amount of the binder PVB is less than 10% by weight, the adhesion to the positive electrode case is reduced, so that the conductive film is peeled off, and the battery performance after storage is deteriorated.
【００１２】《実施例２》次に、導電性炭素材とバイン
ダー（ＰＶＢ）の配合比率（重量比）は８５：１５と一
定にし、導電材中の黒鉛とカーボンブラックの配合比を
表２に示すように種々変えた他は上記と同様にしてアル
カリ乾電池を作製した。これらの電池について、上記と
同様の条件の下で測定した持続時間を表２に示した。Example 2 Next, the blending ratio (weight ratio) of the conductive carbon material and the binder (PVB) was fixed at 85:15, and the blending ratio of graphite and carbon black in the conductive material was as shown in Table 2. An alkaline dry battery was prepared in the same manner as described above, except that various changes were made as shown. Table 2 shows the durations of these batteries measured under the same conditions as described above.
【００１３】[0013]
【表２】 [Table 2]
【００１４】表２に示すように、導電性炭素材の配合比
率が黒鉛６０〜７５wt％、カーボンブラック４０〜２５
wt％の範囲において、それぞれ単独で用いた場合よりも
６０℃１ヶ月後の１５００ｍＡの連続放電性能が向上こ
とが確認された。なお、上記の実施例では、正極ケース
の内側面にのみ導電性被膜を形成したが、正極合剤と接
するケースの内底面部にも導電性被膜を形成するのが好
ましい。As shown in Table 2, the mixing ratio of the conductive carbon material is 60 to 75% by weight of graphite and 40 to 25% of carbon black.
In the range of wt%, it was confirmed that the continuous discharge performance of 1500 mA after one month at 60 ° C. was improved as compared with the case where each was used alone. In the above embodiment, the conductive film is formed only on the inner surface of the positive electrode case. However, it is preferable that the conductive film is also formed on the inner bottom surface of the case in contact with the positive electrode mixture.
【００１５】[0015]
【発明の効果】以上のように本発明によれば、正極ケー
スと正極合剤間の電気的接触状態を良好にし、特に保存
後の強負荷特性の向上したアルカリマンガン電池を提供
することができる。As described above, according to the present invention, it is possible to provide an alkaline manganese battery in which the electrical contact state between the positive electrode case and the positive electrode mixture is improved, and in particular, the heavy load characteristics after storage are improved. .
【図１】本発明の一実施例におけるアルカリ乾電池の一
部を断面にした正面図である。FIG. 1 is a front view showing a cross section of a part of an alkaline dry battery in one embodiment of the present invention.
【図２】同電池の要部の拡大断面図である。FIG. 2 is an enlarged sectional view of a main part of the battery.
１ 正極ケース ２ 導電性被膜 ３ 正極合剤 ４ セパレータ ５ 絶縁キャップ ６ ゲル状負極 ７ 樹脂製封口体 ８ 底板 ９ 絶縁ワッシャ １０ 負極集電体 １１ 外装ラベル DESCRIPTION OF SYMBOLS 1 Positive electrode case 2 Conductive film 3 Positive electrode mixture 4 Separator 5 Insulating cap 6 Gelled negative electrode 7 Resin sealing body 8 Bottom plate 9 Insulating washer 10 Negative electrode collector 11 Outer label
フロントページの続き (72)発明者 大倉 忠雄 滋賀県大津市栗林町５番１号 日本黒鉛工 業株式会社内 (72)発明者 成澤 博 滋賀県大津市栗林町５番１号 日本黒鉛工 業株式会社内Continuing from the front page (72) Inventor Tadao Okura 5-1 Kuribayashi-cho, Otsu-shi, Shiga Prefecture Within Japan Graphite Industries Co., Ltd. (72) Inventor Hiroshi Narusawa 5-1 Kuribayashi-cho, Otsu-shi, Shiga Japan Graphite Works Co., Ltd. In company
Claims (2)
に形成された導電性被膜、前記正極ケース内に挿入され
て前記導電性被膜に接している筒状の正極合剤、正極合
剤の内側にセパレータを介して配された負極を具備し、
前記導電性被膜が１０〜２０wt％のポリビニルブチラー
ルと９０〜８０wt％の導電性炭素材からなることを特徴
とするアルカリマンガン電池。1. A metal positive electrode case, a conductive coating formed on the inner surface of the positive electrode case, a cylindrical positive electrode mixture inserted into the positive electrode case and in contact with the conductive coating, Equipped with a negative electrode disposed on the inside via a separator,
An alkaline manganese battery, wherein the conductive coating comprises 10 to 20% by weight of polyvinyl butyral and 90 to 80% by weight of a conductive carbon material.
ックからなり、その配合比が黒鉛６０〜７５wt％、カー
ボンブラック４０〜２５wt％である請求項１記載のアル
カリマンガン電池。2. The alkaline manganese battery according to claim 1, wherein the conductive carbon material comprises graphite and carbon black, and the compounding ratio thereof is 60 to 75% by weight of graphite and 40 to 25% by weight of carbon black.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6708598A JP3705694B2 (en) | 1998-03-17 | 1998-03-17 | Alkaline manganese battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6708598A JP3705694B2 (en) | 1998-03-17 | 1998-03-17 | Alkaline manganese battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11265702A true JPH11265702A (en) | 1999-09-28 |
| JP3705694B2 JP3705694B2 (en) | 2005-10-12 |
Family
ID=13334701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6708598A Expired - Lifetime JP3705694B2 (en) | 1998-03-17 | 1998-03-17 | Alkaline manganese battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3705694B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111628132A (en) * | 2014-05-05 | 2020-09-04 | 戴瑞米克有限责任公司 | Improved lead acid battery separator, electrode, battery and method of manufacture and use thereof |
-
1998
- 1998-03-17 JP JP6708598A patent/JP3705694B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111628132A (en) * | 2014-05-05 | 2020-09-04 | 戴瑞米克有限责任公司 | Improved lead acid battery separator, electrode, battery and method of manufacture and use thereof |
| CN111628132B (en) * | 2014-05-05 | 2023-04-07 | 戴瑞米克有限责任公司 | Improved lead acid battery separator, electrode, battery and method of manufacture and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3705694B2 (en) | 2005-10-12 |
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