JP2009199748A - Cylindrical alkaline dry cell - Google Patents

Cylindrical alkaline dry cell Download PDF

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JP2009199748A
JP2009199748A JP2008037212A JP2008037212A JP2009199748A JP 2009199748 A JP2009199748 A JP 2009199748A JP 2008037212 A JP2008037212 A JP 2008037212A JP 2008037212 A JP2008037212 A JP 2008037212A JP 2009199748 A JP2009199748 A JP 2009199748A
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positive electrode
electrode mixture
battery case
cylindrical
cross
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Yasushi Sumihiro
泰史 住廣
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Panasonic Corp
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Panasonic Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a cylindrical alkaline dry cell with high reaction efficiency and good discharge performance. <P>SOLUTION: The cylindrical alkaline dry cell comprises: a bottomed tubular cell case; a columnar positive electrode mixture that contacts an internal surface of the cell case and has a hollow portion; a gel-like negative electrode disposed in the hollow portion of the positive electrode mixture; a separator disposed between the positive electrode mixture and the gel-like negative electrode; and an electrolyte, wherein the positive electrode mixture is shaped to allow a cavity to be formed between the positive electrode mixture and the cell case. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、円筒形アルカリ乾電池に関し、特にアルカリ乾電池に用いられる正極合剤に関する。   The present invention relates to a cylindrical alkaline dry battery, and more particularly to a positive electrode mixture used for an alkaline dry battery.

一般に、円筒形アルカリ乾電池は、正極端子を兼ねる電池ケースの中に前記電池ケースの内面に密着して中空円筒形の正極合剤が配置され、その中空部にセパレータを介してゲル状負極が配置されたインサイドアウト型の構造を有する。
近年、円筒形アルカリ乾電池では、高性能化が要求される一方で、コストパフォーマンスを追求した廉価仕様の需要も高まっている。活物質量を減らして、できるだけ反応効率を向上させることが検討されている。
In general, a cylindrical alkaline dry battery has a hollow cylindrical positive electrode mixture placed in contact with the inner surface of the battery case in a battery case that also serves as a positive electrode terminal, and a gelled negative electrode is placed in the hollow portion via a separator. It has an inside-out type structure.
In recent years, while cylindrical alkaline batteries are required to have high performance, demand for low-priced specifications pursuing cost performance is also increasing. It has been studied to reduce the amount of active material and improve the reaction efficiency as much as possible.

例えば、特許文献1では、アルカリ乾電池のゲル状負極にポリスチレンビーズのような合成樹脂粉末を添加することが提案されている。これにより、ゲル状負極の充填高さを高くして、正極合剤とゲル状負極との対向面積を増大させることができる。しかし、負極活物質である亜鉛粒子間の電子伝導ネットワークが崩壊し、ゲル状負極の電子伝導性が低下し、反応効率が低下しやすい。
特開昭60−091562号公報 特開平7−326247号公報
For example, Patent Document 1 proposes adding a synthetic resin powder such as polystyrene beads to a gelled negative electrode of an alkaline battery. Thereby, the filling height of a gel-like negative electrode can be made high, and the opposing area of a positive electrode mixture and a gel-like negative electrode can be increased. However, the electron conduction network between the zinc particles as the negative electrode active material is collapsed, the electron conductivity of the gelled negative electrode is lowered, and the reaction efficiency is likely to be lowered.
Japanese Patent Laid-Open No. 60-091562 JP 7-326247 A

また、特許文献2では、中空円筒形の正極合剤において、中空部(内周側)の、軸方向に垂直な断面形状を多角形状とし、正極合剤の内周側に配される円筒状セパレータと、正極合剤との間に空隙を形成することが提案されている。これにより、正極合剤とゲル状負極との間に形成された空隙に電解液を充填することが可能となり、正極合剤とゲル状負極との対向面積を増大させることができる。しかし、正極合剤およびゲル状負極のセパレータ近傍において反応効率が低下しやすい。   Further, in Patent Document 2, in a hollow cylindrical positive electrode mixture, the hollow portion (inner peripheral side) has a polygonal cross-sectional shape perpendicular to the axial direction, and is arranged on the inner peripheral side of the positive electrode mixture. It has been proposed to form a gap between the separator and the positive electrode mixture. Thereby, it becomes possible to fill the space formed between the positive electrode mixture and the gelled negative electrode with the electrolytic solution, and the facing area between the positive electrode mixture and the gelled negative electrode can be increased. However, the reaction efficiency tends to decrease in the vicinity of the separator of the positive electrode mixture and the gelled negative electrode.

本発明は、上記従来の問題を解決するために、反応効率が高く、放電性能に優れた円筒形アルカリ乾電池を提供することを目的とする。   In order to solve the above-described conventional problems, an object of the present invention is to provide a cylindrical alkaline dry battery having high reaction efficiency and excellent discharge performance.

本発明の円筒形アルカリ乾電池は、有底円筒形の電池ケースと、前記電池ケースの内面に接し、中空部を有する柱状の正極合剤と、前記正極合剤の中空部内に配されたゲル状負極と、前記正極合剤と前記ゲル状負極との間に配されるセパレータと、電解液と、を具備し、前記正極合剤は、前記電池ケースとの間に空隙を形成するような形状を有することを特徴とする。   The cylindrical alkaline dry battery of the present invention includes a bottomed cylindrical battery case, a columnar positive electrode mixture having a hollow portion in contact with the inner surface of the battery case, and a gel-like material disposed in the hollow portion of the positive electrode mixture. A negative electrode, a separator disposed between the positive electrode mixture and the gelled negative electrode, and an electrolytic solution, wherein the positive electrode mixture forms a gap with the battery case It is characterized by having.

前記正極合剤は、中空円筒形における外周部の一部に切欠部を設けたような形状を有するのが好ましい。
前記切欠部は、前記正極合剤の軸方向に沿って延びているのが好ましい。
前記正極合剤の外周部における軸方向に垂直な前記切欠部の断面形状は、V字形、U字形、または矩形であるのが好ましい。
前記正極合剤の軸方向に垂直な断面形状は、前記電池ケースと接する円弧、および前記空隙部に露出する線分を含むのが好ましい。
前記正極合剤の軸方向に垂直な断面形状は、正多角形であるのが好ましい。
The positive electrode mixture preferably has a shape in which a notch is provided in a part of the outer peripheral portion of the hollow cylindrical shape.
It is preferable that the notch extends along the axial direction of the positive electrode mixture.
The cross-sectional shape of the notch perpendicular to the axial direction at the outer periphery of the positive electrode mixture is preferably V-shaped, U-shaped, or rectangular.
The cross-sectional shape perpendicular to the axial direction of the positive electrode mixture preferably includes an arc in contact with the battery case and a line segment exposed in the gap.
The cross-sectional shape perpendicular to the axial direction of the positive electrode mixture is preferably a regular polygon.

本発明によれば、反応効率が高く、放電性能に優れたアルカリ乾電池が得られる。活物質量が少ない場合でも、良好な放電性能が得られるため、アルカリ乾電池の低コスト化および放電性能向上の両立が可能である。   According to the present invention, an alkaline dry battery having high reaction efficiency and excellent discharge performance can be obtained. Even when the amount of the active material is small, good discharge performance can be obtained. Therefore, it is possible to reduce the cost of the alkaline dry battery and improve the discharge performance.

本発明は、有底円筒形の電池ケースと、前記電池ケースの内面に接し、中空部を有する柱状の正極合剤と、前記正極合剤の中空部内に配されたゲル状負極と、前記正極合剤と前記ゲル状負極との間に配されるセパレータと、電解液と、を具備し、前記正極合剤は、前記電池ケースとの間に空隙を形成するような形状を有する円筒形アルカリ乾電池に関する。
さらに換言すると、空隙は、有底円筒形の内面が平滑な電池ケースと、中空円筒形でない(電池ケースと対向する部分の一部が、電池ケース内面に対応しない形状である)正極合剤とにより形成される。正極合剤には、例えば、中空円筒形(中空部を有する円柱形)の正極合剤において電池ケースと対向する外周部に切欠部を設けたものや、正極合剤の軸方向と垂直な断面形状が多角形のものが用いられる。
The present invention includes a bottomed cylindrical battery case, a columnar positive electrode mixture having a hollow portion in contact with the inner surface of the battery case, a gelled negative electrode disposed in the hollow portion of the positive electrode mixture, and the positive electrode A cylindrical alkali having a separator disposed between the mixture and the gelled negative electrode, and an electrolyte, the positive electrode mixture having a shape that forms a gap with the battery case It relates to dry batteries.
In other words, the void is a battery case with a smooth bottomed cylindrical inner surface and a positive electrode mixture that is not hollow cylindrical (a part of the portion facing the battery case does not correspond to the inner surface of the battery case). It is formed by. The positive electrode mixture includes, for example, a hollow cylindrical (columnar shape having a hollow portion) positive electrode mixture provided with a notch in the outer peripheral portion facing the battery case, or a cross section perpendicular to the axial direction of the positive electrode mixture. A polygonal shape is used.

一般に、アルカリ乾電池は、セパレータ近傍の反応効率が高く、従来の中空円筒形の正極合剤における電池ケース側の外周部はゲル状負極から離れており、反応効率(活物質利用率)が低い。また、負極の集電面積(負極集電体におけるゲル状負極に挿入される部分の表面積に相当)と比較して正極の集電面積(電池ケース内面における正極合剤と接触する部分の面積に相当)は過剰である。
これに対して、本発明における正極合剤は、従来の中空円筒形の正極合剤の外周部(活物質利用率が低い部分)を切り欠いたような形状を有する。すなわち、正極合剤の外周部の一部を切り欠いて、正極合剤の電池ケースの筒状側部との接触面積が減少したとしても、反応効率が低い部分と過剰な正極の集電面積の一部を失うに留まる。このため、放電性能の大幅な低下を招くことなく、活物質量を減らすことができ、コスト低減できる。
さらに、正極合剤の軸方向の充填高さを増大させて、正極合剤のゲル状負極との対向面積を増大させることにより、反応効率とともに放電性能を向上させることができる。
Generally, the alkaline dry battery has a high reaction efficiency in the vicinity of the separator, and the outer peripheral part on the battery case side in the conventional hollow cylindrical positive electrode mixture is separated from the gelled negative electrode, and the reaction efficiency (active material utilization rate) is low. In addition, compared with the current collection area of the negative electrode (corresponding to the surface area of the portion inserted into the gelled negative electrode in the negative electrode current collector), the current collection area of the positive electrode (the area of the portion in contact with the positive electrode mixture on the inner surface of the battery case) Equivalent) is excessive.
On the other hand, the positive electrode mixture in the present invention has a shape in which the outer peripheral portion (portion where the active material utilization rate is low) of a conventional hollow cylindrical positive electrode mixture is notched. That is, even if the contact area of the positive electrode mixture with the cylindrical side portion of the battery case is reduced by cutting out a part of the outer periphery of the positive electrode mixture, the current collection area of the portion with low reaction efficiency and the excess positive electrode Stay losing some of it. For this reason, the amount of active material can be reduced and the cost can be reduced without significantly reducing the discharge performance.
Furthermore, by increasing the filling height in the axial direction of the positive electrode mixture and increasing the area of the positive electrode mixture facing the gelled negative electrode, the discharge performance can be improved along with the reaction efficiency.

以下、本発明の円筒形アルカリ乾電池の一実施形態を、図1を参照しながら説明する。図1は、本発明の円筒形アルカリ乾電池の一部を断面とする正面図である。
ニッケルめっき鋼板からなる有底円筒形の電池ケース1内に、正極合剤2が複数個挿入されている。正極合剤2は、例えば、正極活物質と、導電材として黒鉛粉末と、アルカリ電解液との混合物からなる。正極活物質には、例えば、二酸化マンガン、オキシ水酸化ニッケル、またはそれらの混合物が用いられる。電池ケース1の平滑な内面には、黒鉛塗装膜(図示しない)が形成されている。
Hereinafter, one embodiment of a cylindrical alkaline battery of the present invention will be described with reference to FIG. FIG. 1 is a front view of a cross section of a part of a cylindrical alkaline battery of the present invention.
A plurality of positive electrode mixtures 2 are inserted into a bottomed cylindrical battery case 1 made of a nickel-plated steel plate. The positive electrode mixture 2 is made of, for example, a mixture of a positive electrode active material, graphite powder as a conductive material, and an alkaline electrolyte. As the positive electrode active material, for example, manganese dioxide, nickel oxyhydroxide, or a mixture thereof is used. A graphite coating film (not shown) is formed on the smooth inner surface of the battery case 1.

正極合剤2の中空部には、セパレ−タ4を介して、ゲル状負極3が充填されている。ゲル状負極3は、例えば、ポリアクリル酸ナトリウム等のゲル化剤と、アルカリ電解液、負極活物質の混合物からなる。負極活物質には、例えば、亜鉛粉末または亜鉛合金粉末が用いられる。亜鉛合金は、例えばBi、In、またはAlを含む。セパレータ4には、例えば、ポリビニルアルコール繊維およびレーヨン繊維を主体として混抄した不織布が用いられる。電解液には、例えば、水酸化カリウム水溶液または水酸化ナトリウム水溶液が用いられる。   The hollow portion of the positive electrode mixture 2 is filled with a gelled negative electrode 3 via a separator 4. The gelled negative electrode 3 is made of, for example, a mixture of a gelling agent such as sodium polyacrylate, an alkaline electrolyte, and a negative electrode active material. For the negative electrode active material, for example, zinc powder or zinc alloy powder is used. The zinc alloy contains, for example, Bi, In, or Al. For the separator 4, for example, a nonwoven fabric mainly composed of polyvinyl alcohol fiber and rayon fiber is used. For example, an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution is used as the electrolytic solution.

電池ケース1の開口部は、組立封口体9により封口されている。組立封口体9は、樹脂製封口体5、負極端子を兼ねる底板7、および負極集電体6からなる。負極集電体6はゲル状負極3内に挿入されている。負極集電体6の胴部は封口体5の中央部に設けられた貫通孔に挿入され、負極集電体6の頭部は底板7に溶接されている。電池ケース1の開口端部は、封口体5の外周端部を介して底板7の周縁部にかしめつけられている。電池ケース1の外表面には外装ラベル8が被覆されている。   The opening of the battery case 1 is sealed by an assembly sealing body 9. The assembly sealing body 9 includes a resin sealing body 5, a bottom plate 7 that also serves as a negative electrode terminal, and a negative electrode current collector 6. The negative electrode current collector 6 is inserted into the gelled negative electrode 3. The body of the negative electrode current collector 6 is inserted into a through hole provided in the center of the sealing body 5, and the head of the negative electrode current collector 6 is welded to the bottom plate 7. The opening end portion of the battery case 1 is caulked to the peripheral edge portion of the bottom plate 7 via the outer peripheral end portion of the sealing body 5. The outer surface of the battery case 1 is covered with an exterior label 8.

ここで、図2は、図1の円筒形アルカリ乾電池の横断面図(円筒形アルカリ乾電池の軸方向に垂直な断面図)である。図2に示すように、正極合剤2は、中空円筒形の正極合剤の外周部の一部を、同じ幅で、等間隔で、6箇所切り欠いたような形状を有する。切欠部は軸方向に沿って延びている。このため、正極合剤の成形および電池ケースへの挿入が容易である。切欠部の正極合剤2の軸方向に垂直な断面形状は線形状である。切欠部により、正極合剤2と電池ケース1との間に空隙部2aが形成されている。正極合剤2の筒状側部の切欠部以外の部分は、電池ケース1の筒状側部の内面に接している。また、正極合剤2の底部は、電池ケース1の内底面に接している。   Here, FIG. 2 is a cross-sectional view of the cylindrical alkaline battery of FIG. 1 (cross-sectional view perpendicular to the axial direction of the cylindrical alkaline battery). As shown in FIG. 2, the positive electrode mixture 2 has a shape in which a part of the outer peripheral portion of the hollow cylindrical positive electrode mixture is cut out at the same width and at six equal intervals. The notch extends along the axial direction. For this reason, it is easy to mold the positive electrode mixture and insert it into the battery case. The cross-sectional shape perpendicular to the axial direction of the positive electrode mixture 2 at the notch is a linear shape. A gap 2 a is formed between the positive electrode mixture 2 and the battery case 1 by the notch. Portions other than the cutout portion of the cylindrical side portion of the positive electrode mixture 2 are in contact with the inner surface of the cylindrical side portion of the battery case 1. The bottom of the positive electrode mixture 2 is in contact with the inner bottom surface of the battery case 1.

正極合剤2の外周部における軸方向に垂直な断面形状は、六角形における各頂点が円弧状であるような形状を有する。より具体的には、電池ケース1と接する6つの円弧と、空隙部2aに露出する6つの線分を含み、6つの円弧と6つの線分とが交互に配置されるような形状を有する。すなわち、電池ケース1の筒状側部と対向する正極合剤の側部は、電池ケース1と接する6つの曲面部と、空隙部2aに露出する6つの平面部とからなり、6つの曲面部と6つの平面部とは交互に配置されている。
図2に示す正極合剤はエッジ部がないため、電池ケース挿入時において正極合剤が欠けることや割れたりすることが抑制される。材料ロスやばらつきが少なく、生産性が向上する。また、重量バランスが良好である。
図2中の円弧の部分に対応する中心角の角度θは、例えば5°〜40°である。図2では、切欠部が6つあり、6つの円弧と6つの線分とが交互に形成されているが、切欠部の数や円弧および線分の数は、これに限定されない。
The cross-sectional shape perpendicular to the axial direction in the outer peripheral portion of the positive electrode mixture 2 has a shape such that each vertex in the hexagon is an arc shape. More specifically, it includes six arcs in contact with the battery case 1 and six line segments exposed to the gap 2a, and has a shape in which the six arcs and the six line segments are alternately arranged. That is, the side portion of the positive electrode mixture that faces the cylindrical side portion of the battery case 1 includes six curved surface portions that are in contact with the battery case 1 and six flat surface portions that are exposed in the gap 2a. And the six plane portions are alternately arranged.
Since the positive electrode mixture shown in FIG. 2 does not have an edge portion, the positive electrode mixture is prevented from being chipped or cracked when the battery case is inserted. Productivity is improved with less material loss and variation. Also, the weight balance is good.
The angle θ of the central angle corresponding to the arc portion in FIG. 2 is, for example, 5 ° to 40 °. In FIG. 2, there are six notches, and six arcs and six line segments are alternately formed. However, the number of notches and the number of arcs and line segments are not limited thereto.

上記以外に、正極合剤の外周部における軸方向に垂直な断面形状が多角形である正極合剤を用いてもよい。正極合剤の断面形状が正多角形であるのが好ましい。生産性に優れ、正極合剤の成型品の管理が容易である。電池ケースへの挿入が容易であり、重量バランスが良好である。多角形の頂点が、電池ケースの内面に接していればよい。これにより、電池ケース内で正極合剤が確実に固定され、電池ケースの正極合剤との十分な接触状態が確保される。また、正極合剤の底部は電池ケースの内底面に接しているため、正極合剤の電池ケースとの良好な接触状態が確保される。   In addition to the above, a positive electrode mixture having a polygonal cross-sectional shape perpendicular to the axial direction in the outer peripheral portion of the positive electrode mixture may be used. The cross-sectional shape of the positive electrode mixture is preferably a regular polygon. Excellent productivity and easy management of molded product of positive electrode mixture. It can be easily inserted into the battery case and has a good weight balance. The vertex of a polygon should just touch the inner surface of a battery case. Thereby, the positive electrode mixture is reliably fixed in the battery case, and a sufficient contact state with the positive electrode mixture of the battery case is ensured. Further, since the bottom of the positive electrode mixture is in contact with the inner bottom surface of the battery case, a good contact state with the battery case of the positive electrode mixture is ensured.

例えば、図3に示すような正極合剤の外周部の軸方向に垂直な断面形状が8角形の正極合剤12、または図4に示すような正極合剤の外周部の軸方向に垂直な断面形状が12角形の正極合剤22が挙げられる。電池ケース1と正極合剤12との間には、空隙部12aが形成され、正極合剤12の8角形の断面形状における8個の頂点が、それぞれ電池ケース1の筒状側部の内面と接している。電池ケース1と正極合剤22との間には、空隙部22aが形成され、正極合剤12の12角形の断面形状における12個の頂点が、それぞれ電池ケース1の筒状側部の内面と接している。断面形状が多角形の正極合剤は、電池ケースに収納する際、再度加圧成形するため、電池作製時には、正極合剤の角部の先端(断面形状である多角形の頂点)は電池ケースの内面に対応する形状となる。   For example, the cross-sectional shape perpendicular to the axial direction of the outer periphery of the positive electrode mixture as shown in FIG. 3 is an octagonal positive electrode mixture 12, or the positive electrode mixture as shown in FIG. The positive electrode mixture 22 whose cross-sectional shape is a dodecagon is mentioned. A gap 12a is formed between the battery case 1 and the positive electrode mixture 12, and the eight vertices in the octagonal cross-sectional shape of the positive electrode mixture 12 are the inner surfaces of the cylindrical side portions of the battery case 1, respectively. It touches. A gap 22 a is formed between the battery case 1 and the positive electrode mixture 22, and twelve vertices in the dodecagonal cross-sectional shape of the positive electrode mixture 12 are respectively connected to the inner surface of the cylindrical side portion of the battery case 1. It touches. The positive electrode mixture having a polygonal cross-sectional shape is pressure-molded again when it is housed in the battery case. Therefore, at the time of manufacturing the battery, the tip of the corner of the positive electrode mixture (the apex of the polygon that is the cross-sectional shape) is the battery case. It becomes a shape corresponding to the inner surface.

上記のように切欠部の断面形状が線形である正極合剤3以外に、図5に示すような切欠部により形成される正極合剤の軸方向に垂直な断面形状が矩形である正極合剤32、図6に示すような切欠部により形成される正極合剤の軸方向に垂直な断面形状がV字形である正極合剤42、図7に示すような切欠部により形成される正極合剤の軸方向に垂直な断面形状がU字形である正極合剤52が挙げられる。電池ケース1と正極合剤32との間には、空隙部32aが形成されている。電池ケース1と正極合剤42との間には、空隙部42aが形成されている。電池ケース1と正極合剤52との間には、空隙部52aが形成されている。
正極合剤の最外周部(正極合剤の外周部における電池ケースとの接触部)から正極合剤の内周部までの距離に対する空隙部(切欠部)の深さの割合は、例えば60%程度以下である。
In addition to the positive electrode mixture 3 in which the cross-sectional shape of the notch is linear as described above, the positive electrode mixture in which the cross-sectional shape perpendicular to the axial direction of the positive electrode mixture formed by the notch as shown in FIG. 5 is rectangular. 32, a positive electrode mixture 42 having a V-shaped cross section perpendicular to the axial direction of the positive electrode mixture formed by the notch as shown in FIG. 6, and a positive electrode mixture formed by the notch as shown in FIG. And a positive electrode mixture 52 having a U-shaped cross-section perpendicular to the axial direction. A gap 32 a is formed between the battery case 1 and the positive electrode mixture 32. A gap 42 a is formed between the battery case 1 and the positive electrode mixture 42. A gap 52 a is formed between the battery case 1 and the positive electrode mixture 52.
The ratio of the depth of the gap (notch) to the distance from the outermost peripheral part of the positive electrode mixture (the contact part with the battery case in the outer peripheral part of the positive electrode mixture) to the inner peripheral part of the positive electrode mixture is, for example, 60% Less than or equal to

以下に、本発明の実施例を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
《実施例1》
(1)正極合剤の作製
正極活物質として電解二酸化マンガン粉末(平均粒径:45μm)、導電材として黒鉛粉末(平均粒径:15μm)、電解液として33重量%の水酸化カリウム水溶液、およびバインダーとしてポリエチレン粉末(平均粒径:20μm)を、重量比94:6:2:0.4の割合で混合した。この混合物をミキサ−で均一に撹拌・混合して一定粒度に整粒した。得られた粒状物を所定の金型を用いて加圧成形し、図2と同じ形状の正極合剤2を得た。図2中の正極合剤の筒状側部では、平面部と曲面部とが交互に配置され、平面部(空隙部を形成する部分)は等間隔で6箇所設けられた。
Examples of the present invention will be described in detail below, but the present invention is not limited to these examples.
Example 1
(1) Preparation of positive electrode mixture Electrolytic manganese dioxide powder (average particle size: 45 μm) as a positive electrode active material, graphite powder (average particle size: 15 μm) as a conductive material, 33 wt% potassium hydroxide aqueous solution as an electrolyte, and Polyethylene powder (average particle size: 20 μm) as a binder was mixed in a weight ratio of 94: 6: 2: 0.4. This mixture was uniformly stirred and mixed by a mixer to adjust the particle size to a constant particle size. The obtained granular material was pressure-molded using a predetermined mold to obtain a positive electrode mixture 2 having the same shape as in FIG. In the cylindrical side portion of the positive electrode mixture in FIG. 2, the flat surface portions and the curved surface portions are alternately arranged, and the flat surface portions (portions forming the void portions) are provided at six equal intervals.

(2)アルカリ乾電池の作製
上記で得られた正極合剤2を用いて図1に示す単3形アルカリ一次電池を以下のように作製した。図1は本発明の一実施例に係るアルカリ乾電池の一部を断面にした正面図である。
内面に黒鉛塗装膜が形成された、ニッケルめっき鋼板からなる有底円筒形の電池ケース1(外径:14.0mm、内径:13.7mm、高さ:51.8mm)内に、正極合剤2を複数個挿入した後、電池ケース1内において再加圧することにより、電池ケース1の内面に正極合剤2(高さ:40.5mm、内径:8.8mm)を密着させた。このとき、電池ケース1と正極合剤2との間には、空隙部2aが形成された。図2の円弧部分に対応する中心角θは23°であり、円弧部分における外径は13.7mmであった。そして、この正極合剤2の内側に、ポリビニルアルコール繊維およびレーヨン繊維を主体として混抄した、厚さ90μmの不織布からなるセパレ−タ4(不織布を円筒状に3重に巻いて構成)を配した後、電池ケース1内に、電解液として33重量%の水酸化カリウム水溶液を注液した。
(2) Production of Alkaline Dry Battery Using the positive electrode mixture 2 obtained above, an AA alkaline primary battery shown in FIG. 1 was produced as follows. FIG. 1 is a front view of a cross section of a part of an alkaline battery according to an embodiment of the present invention.
Inside the bottomed cylindrical battery case 1 (outer diameter: 14.0 mm, inner diameter: 13.7 mm, height: 51.8 mm) made of nickel-plated steel sheet with a graphite coating film formed on the inner surface, the positive electrode mixture After a plurality of 2 were inserted, the positive electrode mixture 2 (height: 40.5 mm, inner diameter: 8.8 mm) was brought into close contact with the inner surface of the battery case 1 by repressurization in the battery case 1. At this time, a gap 2 a was formed between the battery case 1 and the positive electrode mixture 2. The central angle θ corresponding to the arc portion in FIG. 2 was 23 °, and the outer diameter of the arc portion was 13.7 mm. A separator 4 made of a nonwoven fabric having a thickness of 90 μm and composed mainly of polyvinyl alcohol fiber and rayon fiber was arranged inside the positive electrode mixture 2 (constituted by winding the nonwoven fabric in a triple cylinder). Thereafter, a 33 wt% aqueous potassium hydroxide solution was injected into the battery case 1 as an electrolytic solution.

注液した後、セパレータ4の内側にゲル状負極3を充填した。ゲル状負極3には、負極活物質として亜鉛粉末(平均粒径:150μm)、電解液として33重量%の水酸化カリウム水溶液、およびゲル化剤としてポリアクリル酸ナトリウムを、重量比190:100:2の割合で混合したものを用いた。
樹脂製封口体5の中央部に設けられた貫通孔に負極集電体6の胴部を挿入し、負極集電体6の頭部を底板7に溶接し、組立封口体9を得た。電池ケース1の開口部を組立封口体9で封口した。このとき、負極集電体6をゲル状負極3に差し込み、電池ケース1の開口端部を、封口体5の外周部を介して底板7の周縁部にかしめつけた。次いで、電池ケース1の外表面に外装ラベル8を被覆した。このようにして、アルカリ乾電池を作製した。
After the injection, the gelled negative electrode 3 was filled inside the separator 4. In the gelled negative electrode 3, zinc powder (average particle size: 150 μm) as a negative electrode active material, 33 wt% potassium hydroxide aqueous solution as an electrolytic solution, and sodium polyacrylate as a gelling agent, a weight ratio of 190: 100: What was mixed in the ratio of 2 was used.
The body of the negative electrode current collector 6 was inserted into a through-hole provided in the center of the resin sealing body 5, and the head of the negative electrode current collector 6 was welded to the bottom plate 7 to obtain an assembly sealing body 9. The opening of the battery case 1 was sealed with the assembly sealing body 9. At this time, the negative electrode current collector 6 was inserted into the gelled negative electrode 3, and the opening end portion of the battery case 1 was caulked to the peripheral edge portion of the bottom plate 7 through the outer peripheral portion of the sealing body 5. Next, the exterior label 8 was coated on the outer surface of the battery case 1. In this manner, an alkaline battery was produced.

《実施例2》
実施例1と同じ粒状物を所定の金型を用いて加圧成形し、図3と同じ断面形状が正8角形の正極合剤12を得た。上記以外は、実施例1と同様の方法によりアルカリ乾電池を作製した。電池ケース1と正極合剤12との間には、空隙部12aが形成された。正極合剤12は、内径(中空部の径)8.55mmおよび高さ43.0mmであった。
Example 2
The same granular material as in Example 1 was pressure-molded using a predetermined mold to obtain a positive electrode mixture 12 having the same cross-sectional shape as in FIG. Except for the above, an alkaline dry battery was produced in the same manner as in Example 1. A gap 12 a was formed between the battery case 1 and the positive electrode mixture 12. The positive electrode mixture 12 had an inner diameter (hollow part diameter) of 8.55 mm and a height of 43.0 mm.

《実施例3》
実施例1と同じ粒状物を所定の金型を用いて加圧成形し、図4と同じ断面形状が正12角形の正極合剤22を得た。上記以外は、実施例1と同様の方法によりアルカリ乾電池を作製した。電池ケース1と正極合剤22との間には、空隙部22aが形成された。正極合剤22は、内径(中空部の径)8.8mmおよび高さ40.5mmであった。
Example 3
The same granular material as in Example 1 was pressure-molded using a predetermined mold to obtain a positive electrode mixture 22 having a regular dodecagonal cross-section as in FIG. Except for the above, an alkaline dry battery was produced in the same manner as in Example 1. A gap 22 a was formed between the battery case 1 and the positive electrode mixture 22. The positive electrode mixture 22 had an inner diameter (hollow part diameter) of 8.8 mm and a height of 40.5 mm.

《比較例1》
実施例1と同じ粒状物を所定の金型を用いて加圧成形し、図8に示す従来のアルカリ乾電池に用いられる中空円筒状の正極合剤62を得た。これ以外は、実施例1と同様の方法によりアルカリ乾電池を作製した。図8の正極合剤62の側部全体が、電池ケース1の内面に接した。正極合剤62は、外径13.7mm、内径9.0mm、および高さ42.6mmであった。
<< Comparative Example 1 >>
The same granular material as in Example 1 was pressure-molded using a predetermined mold to obtain a hollow cylindrical positive electrode mixture 62 used in the conventional alkaline dry battery shown in FIG. Except for this, an alkaline dry battery was produced in the same manner as in Example 1. The entire side part of the positive electrode mixture 62 in FIG. 8 was in contact with the inner surface of the battery case 1. The positive electrode mixture 62 had an outer diameter of 13.7 mm, an inner diameter of 9.0 mm, and a height of 42.6 mm.

《比較例2》
以下の方法により、比較例1よりも活物質量の少ない廉価仕様のアルカリ乾電池を作製した。実施例1と同じ粒状物を所定の金型を用いて加圧成形し、従来のアルカリ乾電池に用いられる中空円筒状の正極合剤を得た。上記以外は、実施例1と同様の方法によりアルカリ乾電池を作製した。正極合剤は、外径13.7mm、内径9.0mm、および高さ38.7mmであった。
<< Comparative Example 2 >>
A low-priced alkaline dry battery having a smaller amount of active material than Comparative Example 1 was produced by the following method. The same granular material as in Example 1 was pressure-molded using a predetermined mold to obtain a hollow cylindrical positive electrode mixture used in a conventional alkaline dry battery. Except for the above, an alkaline dry battery was produced in the same manner as in Example 1. The positive electrode mixture had an outer diameter of 13.7 mm, an inner diameter of 9.0 mm, and a height of 38.7 mm.

《比較例3》
実施例1と同じ粒状物を所定の金型を用いて加圧成形し、図9に示す形状の正極合剤72を得た。正極合剤72の中空部における軸方向に垂直な断面形状を正6角形とした。上記以外は、実施例1と同様の方法によりアルカリ乾電池を作製した。このとき、セパレータと正極合剤72との間に空隙部72aが形成された。正極合剤72は、高さ40.5mmであった。
<< Comparative Example 3 >>
The same granular material as in Example 1 was pressure-molded using a predetermined mold to obtain a positive electrode mixture 72 having the shape shown in FIG. The cross-sectional shape perpendicular to the axial direction in the hollow portion of the positive electrode mixture 72 was a regular hexagon. Except for the above, an alkaline dry battery was produced in the same manner as in Example 1. At this time, a gap 72 a was formed between the separator and the positive electrode mixture 72. The positive electrode mixture 72 had a height of 40.5 mm.

[評価]
上記で作製した各電池について、20℃±2℃の恒温環境の中で、1日毎に250mAで1時間放電するサイクルを繰り返す間欠放電を、閉路電圧が0.9Vに達するまで行った。試験結果を表1に示す。なお、比較例3の正極合剤の内径の値は、正極合剤における軸方向に垂直な断面における円の中心からセパレータとの接触部までの寸法を示す。
[Evaluation]
About each battery produced above, the intermittent discharge which repeats the cycle discharged at 250 mA for 1 hour every day in a constant temperature environment of 20 ° C. ± 2 ° C. was performed until the closed circuit voltage reached 0.9V. The test results are shown in Table 1. In addition, the value of the internal diameter of the positive electrode mixture of the comparative example 3 shows the dimension from the center of the circle | round | yen in the cross section perpendicular | vertical to the axial direction in a positive electrode mixture to the contact part with a separator.

Figure 2009199748
Figure 2009199748

高性能仕様の比較例1の電池では、廉価仕様の比較例2の電池よりも、活物質量が多いため、放電性能が向上するが、活物質の増量によりコストが増大した。
本発明の実施例1〜3は、従来の廉価仕様の比較例2および3の電池と活物質量が同じであるが、実施例1〜3の電池は、比較例2および3の電池より優れた放電性能を示すことがわかった。このように、本発明の実施例1〜3の電池では、活物質量を増やさずに、放電性能を向上させることができ、コスト低減と放電性能の向上とを両立することが可能であることが確かめられた。
The battery of Comparative Example 1 with a high performance specification has a higher amount of active material than the battery of Comparative Example 2 with a low price specification, so that the discharge performance is improved, but the cost is increased by increasing the amount of active material.
Examples 1 to 3 of the present invention have the same amount of active material as the batteries of Comparative Examples 2 and 3 of the conventional inexpensive specification, but the batteries of Examples 1 to 3 are superior to the batteries of Comparative Examples 2 and 3. It was found that the discharge performance was high. Thus, in the batteries of Examples 1 to 3 of the present invention, the discharge performance can be improved without increasing the amount of the active material, and it is possible to achieve both cost reduction and improvement of the discharge performance. Was confirmed.

本発明のアルカリ乾電池は、携帯機器等の電子機器の電源として好適に用いられる。   The alkaline dry battery of the present invention is suitably used as a power source for electronic devices such as portable devices.

本発明における一実施形態の円筒形アルカリ乾電池の一部を断面にした正面図である。It is the front view which made a part of cylindrical alkaline dry battery of one embodiment in the present invention a section. 図1の円筒形アルカリ乾電池の横断面図である。It is a cross-sectional view of the cylindrical alkaline battery of FIG. 本発明の円筒形アルカリ乾電池における正極合剤の断面形状が正8角形である場合の横断面図である。It is a cross-sectional view in case the cross-sectional shape of the positive mix in the cylindrical alkaline dry battery of this invention is a regular octagon. 本発明の円筒形アルカリ乾電池における正極合剤の断面形状が正12角形である場合の横断面図である。It is a cross-sectional view when the cross-sectional shape of the positive electrode mixture in the cylindrical alkaline dry battery of the present invention is a regular dodecagon. 本発明の円筒形アルカリ乾電池における正極合剤の切欠部の断面形状が矩形である場合の横断面図である。It is a cross-sectional view in case the cross-sectional shape of the notch part of the positive mix in the cylindrical alkaline dry battery of this invention is a rectangle. 本発明の円筒形アルカリ乾電池における正極合剤の切欠部の断面形状がV字形である場合の横断面図である。It is a cross-sectional view in case the cross-sectional shape of the notch part of the positive mix in the cylindrical alkaline dry battery of this invention is V shape. 本発明の円筒形アルカリ乾電池における正極合剤の切欠部の断面形状がU字形である場合の横断面図である。It is a cross-sectional view in case the cross-sectional shape of the notch part of the positive mix in the cylindrical alkaline dry battery of this invention is U shape. 従来の比較例1のアルカリ乾電池の横断面図である。It is a cross-sectional view of a conventional alkaline dry battery of Comparative Example 1. 従来の比較例3のアルカリ乾電池の横断面図である。It is a cross-sectional view of a conventional alkaline dry battery of Comparative Example 3.

符号の説明Explanation of symbols

1 電池ケース
2、12、22、32、42、52、62、72 正極合剤
2a、12a、22a、32a、42a、52a、62a、72a 空隙部
3 ゲル状負極
4 セパレータ
5 樹脂封口体
6 負極集電体
7 底板
8 外装ラベル
9 組立封口体
DESCRIPTION OF SYMBOLS 1 Battery case 2, 12, 22, 32, 42, 52, 62, 72 Positive electrode mixture 2a, 12a, 22a, 32a, 42a, 52a, 62a, 72a Air gap part 3 Gel-like negative electrode 4 Separator 5 Resin sealing body 6 Negative electrode Current collector 7 Bottom plate 8 Exterior label 9 Assembly sealant

Claims (6)

有底円筒形の電池ケースと、
前記電池ケースの内面に接し、中空部を有する柱状の正極合剤と、
前記正極合剤の中空部内に配されたゲル状負極と、
前記正極合剤と前記ゲル状負極との間に配されるセパレータと、
電解液と、を具備し、
前記正極合剤は、前記電池ケースとの間に空隙を形成するような形状を有することを特徴とする円筒形アルカリ乾電池。
A bottomed cylindrical battery case;
A columnar positive electrode mixture in contact with the inner surface of the battery case and having a hollow portion;
A gelled negative electrode disposed in the hollow part of the positive electrode mixture;
A separator disposed between the positive electrode mixture and the gelled negative electrode;
An electrolyte solution,
The positive electrode mixture has a shape that forms a gap between the battery case and the cylindrical alkaline dry battery.
前記正極合剤は、中空円筒形における外周部の一部に切欠部を設けたような形状を有する請求項1記載の円筒形アルカリ乾電池。   The cylindrical alkaline dry battery according to claim 1, wherein the positive electrode mixture has a shape in which a cutout portion is provided in a part of an outer peripheral portion of a hollow cylindrical shape. 前記切欠部は、前記正極合剤の軸方向に沿って延びている請求項2記載の円筒形アルカリ乾電池。   The cylindrical alkaline battery according to claim 2, wherein the notch extends along an axial direction of the positive electrode mixture. 前記正極合剤の軸方向に垂直な前記切欠部の断面形状は、V字形、U字形、または矩形である請求項2記載の円筒形アルカリ乾電池。   3. The cylindrical alkaline battery according to claim 2, wherein a cross-sectional shape of the notch perpendicular to the axial direction of the positive electrode mixture is V-shaped, U-shaped, or rectangular. 前記正極合剤の軸方向に垂直な断面形状は、前記電池ケースと接する円弧、および前記空隙に露出する線分を含む請求項1記載の円筒形アルカリ乾電池。   The cylindrical alkaline dry battery according to claim 1, wherein a cross-sectional shape perpendicular to the axial direction of the positive electrode mixture includes an arc in contact with the battery case and a line segment exposed in the gap. 前記正極合剤の軸方向に垂直な断面形状は、正多角形である請求項1記載の円筒形アルカリ乾電池。   The cylindrical alkaline dry battery according to claim 1, wherein a cross-sectional shape perpendicular to the axial direction of the positive electrode mixture is a regular polygon.
JP2008037212A 2008-02-19 2008-02-19 Cylindrical alkaline dry cell Withdrawn JP2009199748A (en)

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