JP4967229B2 - A negative electrode plate for an alkaline secondary battery and an alkaline secondary battery to which the negative electrode plate is applied. - Google Patents

A negative electrode plate for an alkaline secondary battery and an alkaline secondary battery to which the negative electrode plate is applied. Download PDF

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JP4967229B2
JP4967229B2 JP2004346329A JP2004346329A JP4967229B2 JP 4967229 B2 JP4967229 B2 JP 4967229B2 JP 2004346329 A JP2004346329 A JP 2004346329A JP 2004346329 A JP2004346329 A JP 2004346329A JP 4967229 B2 JP4967229 B2 JP 4967229B2
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electrode plate
negative electrode
substrate
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JP2006156186A (en
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学 金本
充浩 児玉
俊樹 田中
実 黒葛原
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GS Yuasa International Ltd
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Description

本発明は、捲回式極板群を備える円筒形のニッケル水素電池やニッケルカドミウム電池等に代表されるアルカリ二次電池用の負極板、およびその負極板を適用した捲回式極板群を備えるアルカリ二次電池に関するものである。   The present invention relates to a negative electrode plate for an alkaline secondary battery represented by a cylindrical nickel-metal hydride battery or a nickel cadmium battery having a wound electrode plate group, and a wound electrode plate group to which the negative electrode plate is applied. The present invention relates to an alkaline secondary battery provided.

円筒形のニッケル水素電池やニッケルカドミウム電池は、サイクル特性、耐過放電特性、耐過充電特性に優れるところから携帯形の電気機器、ハイブリッド形電気自動車（ＨＥＶ）、電動工具などの電源として用いられている。なかでも、ニッケル水素電池は、低公害であり、高エネルギー密度を有するところから広く用いられている。これらの用途においては長期間の使用に耐える電源に対する要望が強く、さらに優れたサイクル特性を有する二次電池の開発が進められている。   Cylindrical nickel metal hydride batteries and nickel cadmium batteries are used as power sources for portable electric devices, hybrid electric vehicles (HEV), electric tools, etc. because of their excellent cycle characteristics, overdischarge resistance, and overcharge resistance. ing. Among these, nickel metal hydride batteries are widely used because of their low pollution and high energy density. In these applications, there is a strong demand for a power source that can withstand long-term use, and the development of secondary batteries having excellent cycle characteristics is underway.

捲回式極板群を構成する極板は、通常、正極板、負極板共に導電性基板（穿孔金属板や金属箔）の両面に活物質層を設け、且つ、導電性基板を極板の厚さ方向に対して極板の中心に配置しているのであるが、極板群の最外周に位置する負極板の外面は正極板と対向しないので該部分に配置した活物質は、高率放電においては殆ど起電反応に寄与しない。このような従来電池の欠点に鑑み、捲回式極板群を備える二次電池において、電池のさらなる高容量化を達成するために極板群の構造の改良が提案されている。例えば、極板群の最外周に位置する負極板の導電性基板の外面を露呈させた構造の捲回式極板群が提案されている。該提案によれば、極板群の最外周に位置する負極板の外面の起電反応に殆ど寄与しない活物質を除き、起電反応に寄与する活物質量を増やすことによって、高容量化が試みられている。（例えば特許文献１、特許文献２）。
特開平１−２７９５７８号公報 特開２００１−２３６８０号公報 これらの特許文献に提案されている二次電池の捲回式極板群４の基本構造を説明するための概念図（断面図）を図９に示す。該捲回式極板群４は、矩形状の正極板５、負極板１、セパレータ６の積層体を捲回したものである。前記負極板１は、導電性基板２の両面に活物質粉末を主構成物質とする合剤層３を配置したものである。但し、正極板５の巻き終わり端部８を境にして、負極板１の正極板５と対向しない箇所には合剤層３を配置しない部分（活物質層非塗工部分）９が設けられている。 In the electrode plate constituting the wound electrode plate group, the positive electrode plate and the negative electrode plate are usually provided with active material layers on both sides of the conductive substrate (perforated metal plate or metal foil), and the conductive substrate is made of the electrode plate. Although it is arranged at the center of the electrode plate with respect to the thickness direction, the outer surface of the negative electrode plate located at the outermost periphery of the electrode plate group does not face the positive electrode plate. The discharge hardly contributes to the electromotive reaction. In view of such drawbacks of the conventional battery, in a secondary battery including a wound electrode group, an improvement in the structure of the electrode group has been proposed in order to achieve further increase in battery capacity. For example, a wound electrode group having a structure in which the outer surface of a conductive substrate of a negative electrode plate located on the outermost periphery of the electrode group is exposed. According to the proposal, the capacity can be increased by increasing the amount of the active material that contributes to the electromotive reaction, except for the active material that hardly contributes to the electromotive reaction on the outer surface of the negative electrode plate located on the outermost periphery of the electrode plate group. Has been tried. (For example, Patent Document 1 and Patent Document 2).
JP-A-1-279578 FIG. 9 is a conceptual diagram (cross-sectional view) for explaining the basic structure of the wound electrode group 4 of the secondary battery proposed in these patent documents. The wound electrode plate group 4 is obtained by winding a laminate of a rectangular positive electrode plate 5, a negative electrode plate 1, and a separator 6. In the negative electrode plate 1, a mixture layer 3 containing active material powder as a main constituent material is disposed on both surfaces of a conductive substrate 2. However, a portion (active material layer non-coating portion) 9 where the mixture layer 3 is not disposed is provided at a location not facing the positive electrode plate 5 of the negative electrode plate 1 with the winding end end portion 8 of the positive electrode plate 5 as a boundary. ing.

しかし、該構成の極板群を作製するためには、１枚の負極板に活物質塗工部分と非塗工部分を設けなければならず、そのためには間歇塗工を行うか、塗工後に一部分活物質を取り除いて活物質非塗工部分を形成する必要があった。間歇塗工においては塗工装置に複雑な機構を付与しなければならず、また、塗工後の極板の厚さが一様でないために、一枚の極板のうち厚さの大きい部分と厚さの小さい部分とに分けて二段階のプレス加工を施す必要があった。他方一部活物質を除去する方式は、活物質の除去工程が複雑であり、生産性に劣る欠点があった。   However, in order to produce the electrode plate group having such a configuration, an active material coating portion and a non-coating portion must be provided on one negative electrode plate. For that purpose, intermittent coating or coating is performed. It was necessary to remove part of the active material later to form an active material non-coated part. In intermittent coating, a complicated mechanism must be added to the coating device, and the thickness of the electrode plate after coating is not uniform. It was necessary to perform a two-stage press work separately for parts with a small thickness. On the other hand, the method of removing a part of the active material has a drawback that the process of removing the active material is complicated and the productivity is inferior.

前記特許文献１、特許文献２に記載の極板群と別の構成を有するものとして、負極板を内周部分と該内周部分に比べて厚さの小さい最外周部分とに分割し、内周部分と最外周部分とを重ね合わせて接続した捲回式極板群が示されている。（例えば特許文献３）
特開２００４−６３３２５号公報 該構成によれば、負極板を内周部分と外周部分に分割しているので、前記特許文献１、特許文献２に記載の１枚の負極板において非塗工部分を設ける構成や、負極板の厚さの異なる部分を設ける構成に比べると負極板の製造が容易である利点がある。しかし、負極板の外周部分には、起電反応に寄与しない負極活物質が存在し、負極板外周部分の正極に対向していない面（外側の面）の活物質を排除した二次電池に比べて負極活物質の利用率が低いという欠点があった。また、負極板の内周部分と最外周部分を重ね合わせ部分は活物質層同士が接触するので、該重ね合わせ部分の電気抵抗が大きく高率放電特性や急速充電を行ったときの充電受け入れ特性が劣る欠点があった。以上記述した欠点があるためか、特許文献３に提案の方法ではサイクル特性向上の効果が得られない虞があった。 The electrode plate group described in Patent Document 1 and Patent Document 2 has a different configuration, and the negative electrode plate is divided into an inner peripheral portion and an outermost peripheral portion having a thickness smaller than that of the inner peripheral portion. A wound electrode group is shown in which a peripheral portion and an outermost peripheral portion are overlapped and connected. (For example, Patent Document 3)
According to this configuration, since the negative electrode plate is divided into an inner peripheral portion and an outer peripheral portion, an uncoated portion in one negative electrode plate described in Patent Document 1 and Patent Document 2 described above. There is an advantage that the negative electrode plate can be easily manufactured as compared with the configuration in which the portions having different thicknesses of the negative electrode plate are provided. However, in the outer peripheral portion of the negative electrode plate, there is a negative electrode active material that does not contribute to the electromotive reaction, and the active material on the surface (outer surface) of the negative electrode plate outer peripheral portion not facing the positive electrode is excluded. In comparison, there was a drawback that the utilization rate of the negative electrode active material was low. In addition, since the active material layers are in contact with each other in the overlapping portion of the inner peripheral portion and the outermost peripheral portion of the negative electrode plate, the electric resistance of the overlapping portion is large, and high rate discharge characteristics and charge acceptance characteristics when performing quick charge However, there was a disadvantage that was inferior. Because of the drawbacks described above, the method proposed in Patent Document 3 may not provide the effect of improving the cycle characteristics.

本発明は、前記従来の密閉形アルカリ二次電池の欠点に鑑みてなされたものであって、捲回式極板群を備えるアルカリ二次電池（以下単に電池ともいう）であって生産性を低下させることなく、充放電サイクル特性に優れた電池を提供せんとするものである。   The present invention has been made in view of the drawbacks of the conventional sealed alkaline secondary battery, and is an alkaline secondary battery (hereinafter also simply referred to as a battery) provided with a wound electrode plate group. It is intended to provide a battery having excellent charge / discharge cycle characteristics without lowering.

本発明においては、電池の構成を以下の構成とすることによって前記課題を解決する。   In this invention, the said subject is solved by making the structure of a battery into the following structures.

本発明に係るアルカリ二次電池は、矩形状の正極板、セパレータおよび負極板を積層した捲回式極板群を備え、該捲回式極板群の最外周において負極板が正極板の外側に位置するように配置したアルカリ二次電池であって、前記負極板は、穿孔を有する金属板からなる基板の両面に活物質粉末を主構成物質とする合剤層を有し、厚さが一様であり、前記捲回式極板群の最外周側に位置する部分の基板を極板の厚さ方向の中心に対して片側に偏心させ、前記基板を偏心させることにより基板を境として厚さを大きくした負極板の合剤層を正極板に対向させたものであることを特徴とするアルカリ二次電池である。
なお、請求項１に記載の負極板のうち、前記捲回式極板群の最外周側に位置する端部のみ基板を前記極板の厚さ方向の中心に対して片側に偏心させた負極板においては、該端部以外は基板を偏心させていない極板を指す。ここでいう基板を偏心させてないとは、基板を前記極板の厚さ方向の中心に配置していることを意味する。 The alkaline secondary battery according to the present invention includes a wound electrode plate group in which a rectangular positive electrode plate, a separator, and a negative electrode plate are laminated, and the negative electrode plate is outside the positive electrode plate at the outermost periphery of the wound electrode plate group. The negative electrode plate has a mixture layer containing active material powder as a main constituent material on both sides of a substrate made of a metal plate having perforations, and has a thickness of Uniform, the substrate located at the outermost peripheral side of the wound plate group is decentered to one side with respect to the center in the thickness direction of the plate, and the substrate is decentered by decentering the substrate. The alkaline secondary battery is characterized in that the mixture layer of the negative electrode plate having an increased thickness is opposed to the positive electrode plate.
Of the negative electrode plate according to claim 1, were eccentrically to one side of the substrate only the end portion located on the outermost periphery side of the wound type electrode plate assembly with respect to the center in the thickness direction of the electrode plate negative electrode In the case of a plate, the electrode plate is not decentered except for the end portion. Here, not the substrate has eccentrically say, it means that the place of the substrate in the thickness direction of the center of the plate.

本発明に係るアルカリ二次電池用負極板は、前記基板を偏心させた部分の基板を境とした表裏２面の合剤層の厚さの比が１：９〜４：６であることが好ましい。
本発明に係るアルカリ二次電池に用いる負極板は、全体に亘って基板を偏心させたものである。 In the negative electrode plate for an alkaline secondary battery according to the present invention, the ratio of the thicknesses of the mixture layers on the front and back surfaces of the substrate where the substrate is decentered is 1: 9 to 4: 6. preferable.
The negative electrode plate used in the alkaline secondary battery according to the present invention has the substrate eccentric over the entire surface .

本発明によれば、捲回式極群を備えたアルカリ二次電池において生産性を低下させることがなく、負極板の活物質利用率を高めることによって充放電サイクル特性に優れたアルカリ二次電池の提供を可能にする。

According to the present invention , an alkaline secondary battery having excellent charge / discharge cycle characteristics by increasing the active material utilization rate of the negative electrode plate without reducing productivity in an alkaline secondary battery having a wound electrode group. Enables the provision of

本発明に係る電池は、穿孔を有する導電性基板の両面に合剤層を配置した負極板を備える。負極板の厚さは、特に限定されるものではないが、通常用いられている０．２５〜０．４０ｍｍとすることが好ましい。該厚さが０．２５ｍｍ未満では活物質充填量が少なくなる虞があり、逆に、厚さが０．４０ｍｍを超えると負極板の集電機能が低下して活物質の利用率が低下する虞がある。   The battery according to the present invention includes a negative electrode plate in which a mixture layer is disposed on both surfaces of a conductive substrate having perforations. Although the thickness of a negative electrode plate is not specifically limited, It is preferable to set it as 0.25-0.40 mm normally used. If the thickness is less than 0.25 mm, the active material filling amount may be reduced. Conversely, if the thickness exceeds 0.40 mm, the current collecting function of the negative electrode plate is lowered and the utilization rate of the active material is lowered. There is a fear.

負極板の基板には、ニッケルやニッケルメッキを施した鋼板からなる穿孔板が好適である。基板の厚さ、穿孔の形状とその大きさ、開口率は、特に限定されるものではないが、厚さは０．０３〜０．０６ｍｍが好ましい。該厚さが０．０３ｍｍ未満では抗張力が不足するために極板の製作の過程や捲回式極板群の製作の過程で基板が切断する虞があり、０．０６ｍｍを超えると活物質充填量が少なくなる虞がある。穿孔の形状は多角形、長円形、円形のいずれでも良いが、生産性の良い円形が好適である。円形の穿孔の場合、その直径が０．５〜２ｍｍが好適である。該直径が０．５ｍｍ未満のものは製造が難しく生産性が劣り、２ｍｍを超えると負極板の集電機能が低下したり、活物質が基板から脱落する虞が生じる。また、基板の開口率は３５〜６０％が好適であり、４０〜５５％がさらに好適である。該開口率が３５％未満では、基板によって、負極坂内に含まれる電解液中のイオンの移動が阻害されて、負極板の表裏両面に配置した合剤層のうち、基板を偏心させたために厚さを大きくした合剤層に含まれる活物質の利用率が低下するためか、合剤層全体に含まれる活物質の利用率が低くなる虞があり、開口率が６０％を超えると、負極板の集電機能が低下して活物質利用率が低下する虞がある。   A perforated plate made of nickel or a nickel-plated steel plate is suitable for the substrate of the negative electrode plate. The thickness of the substrate, the shape and size of the perforations, and the aperture ratio are not particularly limited, but the thickness is preferably 0.03 to 0.06 mm. If the thickness is less than 0.03 mm, the tensile strength is insufficient, so that there is a risk of the substrate being cut in the process of manufacturing the electrode plate or the wound electrode plate group. There is a risk that the amount will decrease. The shape of the perforations may be any of a polygon, an oval, and a circle, but a circle with good productivity is preferable. In the case of circular perforations, the diameter is preferably 0.5-2 mm. If the diameter is less than 0.5 mm, it is difficult to produce and the productivity is inferior. If it exceeds 2 mm, the current collecting function of the negative electrode plate may be reduced, or the active material may fall off the substrate. Further, the opening ratio of the substrate is preferably 35 to 60%, and more preferably 40 to 55%. If the aperture ratio is less than 35%, the substrate inhibits the movement of ions in the electrolyte contained in the negative electrode slope, and the thickness of the mixture layer is decentered among the mixture layers arranged on the front and back surfaces of the negative electrode plate. The utilization factor of the active material contained in the mixture layer with increased thickness may decrease, or the utilization factor of the active material contained in the entire mixture layer may be reduced. If the opening ratio exceeds 60%, the negative electrode There is a possibility that the current collecting function of the plate is lowered and the active material utilization rate is lowered.

（第１の参考例の形態）
第１の参考例の形態は、捲回式極板群の最外周側に位置する端部のみ負極板の基板を偏心させた実施形態である。図１は、本発明第１の参考例の形態に係り、プレス加工を施して極板の厚さを所定の厚さに調整した後のアルカリ二次電池用負極板１の長辺に平行な面で切断した断面を模式的に示す断面図である。図１において２は、例えばニッケルメッキを施した穿孔鋼板製の基板であり、３は、該基板の両面に担持させた水素吸蔵合金粉末やカドミウム粉末と水酸化カドミウム粉末の混合物からなる活物質粉末を主構成物質とする合剤層である。該合剤層は、前記活物質粉末の他にニッケル粉末などの導電剤粉末やスチレンブタジエンゴム（ＳＢＲ）やポリテトラフロロエチレン（ＰＴＦＥ）のような合成樹脂を結着剤として含んでもよい。 (Form of the first reference example )
The form of the first reference example is an embodiment in which the negative electrode substrate is eccentric only at the end located on the outermost peripheral side of the wound electrode group. FIG. 1 is related to the form of the first reference example of the present invention, and is parallel to the long side of the negative electrode plate 1 for an alkaline secondary battery after pressing to adjust the thickness of the electrode plate to a predetermined thickness. It is sectional drawing which shows typically the cross section cut | disconnected by the surface. In FIG. 1, 2 is a substrate made of perforated steel sheet, for example, plated with nickel, and 3 is an active material powder comprising a mixture of hydrogen storage alloy powder or cadmium powder and cadmium hydroxide powder carried on both sides of the substrate. It is a mixture layer containing as a main constituent material. In addition to the active material powder, the mixture layer may contain a conductive agent powder such as nickel powder, or a synthetic resin such as styrene butadiene rubber (SBR) or polytetrafluoroethylene (PTFE) as a binder.

図１に示すように、負極板１は、長手方向につなぎ目のない１枚ものの極板であって、且つ、一様な厚さを有する極板である。図１に示すように、極板のうち図のＸから右側の部分（負極板のうち捲回式極板群の最外周側の端部に相当）において基板２を極板の中心（厚さ方向の中心）に対して図の上側に偏心させている。該負極板は、従来の基板を偏心させていない負極板と同様、少なくとも長手方向に対して一様の厚さを有している。該第１の実施の形態に係る負極板は、従来のように負極板を複数枚に分割して、途中で繋ぎ合わせたり、極板の長手方向の途中から合剤層の厚さを変えるために極板の厚さそのものを変化させた負極板に比べて、塗工工程が簡便であり、厚さが一様であるためにプレス加工も一段階の連続プレス加工が適用できるので製造が容易である。   As shown in FIG. 1, the negative electrode plate 1 is a single electrode plate that is seamless in the longitudinal direction and has a uniform thickness. As shown in FIG. 1, the substrate 2 is positioned at the center (thickness) of the electrode plate at the portion on the right side from X in the drawing (corresponding to the outermost peripheral end of the wound electrode plate group of the negative electrode plate). It is eccentric to the upper side of the figure with respect to the direction center). The negative electrode plate has a uniform thickness at least in the longitudinal direction, similar to the negative electrode plate in which the conventional substrate is not eccentric. In the negative electrode plate according to the first embodiment, the negative electrode plate is divided into a plurality of pieces as in the prior art and joined together in the middle, or the thickness of the mixture layer is changed from the middle in the longitudinal direction of the electrode plate. Compared to the negative electrode plate with the electrode plate thickness itself being changed, the coating process is simpler and the thickness is uniform. It is.

図２は、図１に示した負極板１をセパレータ６を介して正極板５を積層させ、渦巻き状に捲回した捲回式極群４の断面の構造を模式的に示した図である。本発明においては、図２に示したように、捲回式極群の最外周（巻き終わりの周）において負極板が正極板の外側に位置するように配置し、該最外周に負極板の基板を偏心させた部分を配置し、且つ、基板を偏心させた部分の基板を境にして合剤層３の厚さが大きい面を正極板５に対向するように配置する。   FIG. 2 is a diagram schematically showing a cross-sectional structure of the wound electrode group 4 in which the negative electrode plate 1 shown in FIG. 1 is laminated with the positive electrode plate 5 via the separator 6 and wound in a spiral shape. . In the present invention, as shown in FIG. 2, the negative electrode plate is disposed outside the positive electrode plate at the outermost periphery (winding end periphery) of the wound electrode group, and the negative electrode plate is disposed at the outermost periphery. A portion where the substrate is decentered is disposed, and a surface where the thickness of the mixture layer 3 is large is disposed opposite to the positive electrode plate 5 with the substrate decentered as the boundary.

極板群の構成を、図２に示した構成とすることによって、図３に示した基板を偏心させず、基板全体を負極板の中心に配置した従来の負極板を適用した構成に比べて、負極板の厚さや大きさ、水素吸蔵合金粉末の充填量を変えることなく、正極板５に対向する負極板１の活物質の量を多くすることができる。   The configuration of the electrode plate group is the same as that shown in FIG. 2, so that the substrate shown in FIG. 3 is not decentered, and compared with a configuration using a conventional negative electrode plate in which the entire substrate is arranged at the center of the negative electrode plate. The amount of the active material of the negative electrode plate 1 facing the positive electrode plate 5 can be increased without changing the thickness and size of the negative electrode plate and the filling amount of the hydrogen storage alloy powder.

負極板１の正極板５に対向する水素吸蔵合金粉末の量を多くすると、負極板の基板を偏心させなかった電池と比較して、見かけの負極板の容量（Ｎ：単純に負極活物質の充填量から算定される負極板の容量）と正極板の容量（Ｐ）に対する比（Ｎ／Ｐ）は同じであっても、高率で充放電を行ったときに動作する（起電反応に預かる）負極活物質量から算定される負極板の容量（Ｎ'）の正極板の容量（Ｐ）に対する比率（Ｎ'／Ｐ）の値を高めることができる。   When the amount of the hydrogen storage alloy powder facing the positive electrode plate 5 of the negative electrode plate 1 is increased, the capacity of the apparent negative electrode plate (N: simply the negative electrode active material) Even if the ratio (N / P) to the capacity (P) of the negative electrode plate) and the capacity (P) of the positive electrode plate is the same, it operates when charging / discharging at a high rate (for the electromotive reaction) The value of the ratio (N ′ / P) of the capacity (N ′) of the negative electrode plate calculated from the amount of the negative electrode active material to the capacity (P) of the positive electrode plate can be increased.

アルカリ二次電池の場合は、一般に負極板の容量を正極板の容量に比べて大きくし、放電リザーブ、充電リザーブを確保している。従って、充放電サイクルの初期においては、放電容量が正極板の容量で規制されるので充電リザーブ量の大小によって放電容量に差が生じ難いが、サイクルが経過し負極板の充電リザーブ量が減少するに従って放電容量が負極板の容量で規制されるようになり、サイクルの経過とともに放電容量が低下する。前記のように、本願の発明に係る電池は、従来の電池に比べて、Ｎ'／Ｐの値を高めて大きい充電リザーブ量を確保しているために、電池の放電容量が負極板の容量で規制されるのを遅延させ、特に充電および放電を１ＩｔＡ以上のレートで行ったときの高率充放電におけるサイクル特性を高めることができる。   In the case of an alkaline secondary battery, the capacity of the negative electrode plate is generally made larger than the capacity of the positive electrode plate to ensure the discharge reserve and the charge reserve. Therefore, at the initial stage of the charge / discharge cycle, the discharge capacity is regulated by the capacity of the positive electrode plate, so that it is difficult for the discharge capacity to vary depending on the charge reserve amount, but the charge reserve amount of the negative electrode plate decreases after the cycle. Accordingly, the discharge capacity is regulated by the capacity of the negative electrode plate, and the discharge capacity decreases with the passage of the cycle. As described above, the battery according to the invention of the present application increases the value of N ′ / P and secures a large charge reserve amount as compared with the conventional battery, so that the discharge capacity of the battery is the capacity of the negative electrode plate. The cycle characteristics in high rate charge / discharge when charging and discharging are performed at a rate of 1 ItA or more can be enhanced.

前記基板２を偏心させた部分（図１においてＸより右側の部分）の長さは特に限定されるものではないが、図２に示したように、基板を偏心させた部分の長さが極板群の最外周の負極板の長さとほぼ一致させると、正極板に対向しない合剤層に含まれる活物質量を最小限にすることができるので好ましい。該基板を偏心させた部分の、基板を境にした厚さの小さい合剤層と厚さの大きい合剤層の厚さの比率は、特に限定されるものではないが、１：９〜４：６に設定するのが好ましく、１：９〜３：７に設定するのがさらに好ましい。該比率が１：９を下回ると、基板上に合剤層を担持させた後、極板にプレス加工を施す工程で、極板が変形したり、活物質（水素吸蔵合金粉末）が脱落する虞がある。該比率が４：６を上回ると負極板の活物質利用率を高める効果が得られない。   The length of the portion where the substrate 2 is eccentric (the portion on the right side of X in FIG. 1) is not particularly limited. However, as shown in FIG. 2, the length of the portion where the substrate is eccentric is extremely long. It is preferable that the length of the negative electrode plate on the outermost periphery of the plate group is substantially the same because the amount of the active material contained in the mixture layer not facing the positive electrode plate can be minimized. The ratio of the thickness of the mixture layer with a small thickness and the mixture layer with a large thickness at the part where the substrate is eccentric is not particularly limited, but is 1: 9 to 4 : 6 is preferable, and 1: 9 to 3: 7 is more preferable. When the ratio is less than 1: 9, the electrode plate is deformed or the active material (hydrogen storage alloy powder) falls off in the step of pressing the electrode plate after supporting the mixture layer on the substrate. There is a fear. If the ratio exceeds 4: 6, the effect of increasing the active material utilization of the negative electrode plate cannot be obtained.

なお、負極板のうち、基板を偏心させてない部分（図１のＸの左側の部分）は、図１に示すように、基板を極板の切断面の中心に位置させる。該部分は、両面が正極板に対向しており、基板を極板の切断面の中心に位置させることによって極板の表裏両面が均等に起電反応に寄与し、負極板の利用率を最大限高めることができるので好ましい。   Note that the portion of the negative electrode plate where the substrate is not eccentric (the portion on the left side of X in FIG. 1) positions the substrate at the center of the cut surface of the electrode plate, as shown in FIG. This part has both sides facing the positive electrode plate, and by positioning the substrate at the center of the cut surface of the electrode plate, both the front and back surfaces of the electrode plate contribute equally to the electromotive reaction, maximizing the utilization rate of the negative electrode plate It is preferable because it can be increased to the limit.

負極板の製造において、極板の一方の端部（捲回式極板群を構成したときに最外周側に位置する端部）の基板を偏心させる方法は、特に限定されるものではないが、例えば、基板を水素吸蔵合金粉末のペースト｛水素吸蔵合金粉末や結着剤を水に分散させたものにカルボキシメチルセルロース（ＣＭＣ）などの増粘剤を添加混練して糊状にしたもの｝を収容したペースト槽の中を通して基板の両面に所定量より過剰のペーストを担持させた後、所定の間隔を設けたスリットの間を通過させて余分のペーストを削ぎ落とす工程で、基板を偏芯させない部分を製造するときは基板がスリットの間隔の中心を通るように基板とスリットの位置を調整し、基板を偏芯させた部分を製造するときには、基板の位置またはスリットの位置を変えて基板がスリットの間隔の一方に偏った位置を通過するように基板とスリットの位置を調整することによって製造することができる。該方法において基板の位置またはスリットの位置を変えるときには、位置を変える時点でスリットを通過中の部分に大きな張力が加わるために、該部分で基板が切断する虞がある。   In the production of the negative electrode plate, the method of decentering the substrate at one end of the electrode plate (the end located on the outermost peripheral side when the wound electrode plate group is configured) is not particularly limited. For example, a paste of a hydrogen storage alloy powder (a paste obtained by adding a thickener such as carboxymethylcellulose (CMC) to water in which a hydrogen storage alloy powder or a binder is dispersed in water) is used as a paste. In the process of carrying excess paste over a predetermined amount on both sides of the substrate through the contained paste tank and then passing through a slit with a predetermined interval to scrape off the excess paste, the substrate is not decentered When manufacturing the part, adjust the position of the substrate and the slit so that the substrate passes through the center of the gap of the slit, and when manufacturing the part where the substrate is eccentric, change the position of the substrate or the position of the slit and The The position of the substrate and the slit so as to pass through a position offset to one Tsu City of spacing can be produced by adjusting the. In this method, when the position of the substrate or the position of the slit is changed, a large tension is applied to the portion passing through the slit at the time of changing the position, so that the substrate may be cut at the portion.

図４に示した基板２は、前記基板の切断を防ぐ効果を持たせたものであって、全体に穿孔７を設けた基板のうち、基板が偏芯を開始する部分（負極板１の厚さ方向に対して基板２の位置が変化する部分）Ｘの穿孔の数を減らして（開口率が低い、図では穿孔を無くし、開口率を０％としている。）基板の抗張力を高めている。部分Ｘにおける開口率については数値的な限定は特になく、ペーストを削ぎ落とす工程で基板を偏芯させたときに基板が切断する虞のない強度が得られるように設定すればよい。部分Ｘにおける開口率を低くした部分の幅に付いては特に限定はないが２〜５ｍｍとするのが好ましい。該幅が２ｍｍ未満では開口率を低くした部分を設けた効果が得られ難い。また、該幅が５ｍｍを超えると、活物質が脱落し易くなったり、基板によってイオンの移動が妨げられて電気的特性が低下する虞がある。   The substrate 2 shown in FIG. 4 has an effect of preventing the substrate from being cut, and is a portion of the substrate in which the perforations 7 are provided as a whole (the thickness of the negative electrode plate 1). The portion where the position of the substrate 2 changes with respect to the vertical direction) The number of perforations of X is reduced (the aperture ratio is low, the perforations are eliminated in the figure, and the aperture ratio is 0%), and the tensile strength of the substrate is increased. . The numerical aperture of the portion X is not particularly limited, and may be set so as to obtain a strength that does not cause the substrate to be cut when the substrate is decentered in the process of scraping off the paste. Although there is no particular limitation on the width of the portion where the aperture ratio in the portion X is lowered, it is preferably 2 to 5 mm. If the width is less than 2 mm, it is difficult to obtain the effect of providing a portion with a low aperture ratio. On the other hand, if the width exceeds 5 mm, the active material may easily fall off, or the movement of ions may be hindered by the substrate, resulting in a decrease in electrical characteristics.

（第２の実施の形態）
第２に実施の形態は、負極板の全体に亘って基板を偏心させた実施の形態である。図５は、本発明の第２の実施の形態に係る負極板１を長辺に平行な面で切断した断面を模式的に示す断面図である。本発明においては前記第１の参考例の形態に示した如く、負極板の一方の端部の基板の位置を偏心させる他に、図５に示した如く、極板の全体亘って基板２を偏心させることもできる。ただし、該第２の実施形態においても、前記第１の参考例形態同様に負極板の厚さが一様であり、生産性に優れた負極板である。 (Second Embodiment)
The second embodiment is an embodiment in which the substrate is eccentric over the entire negative electrode plate. FIG. 5 is a cross-sectional view schematically showing a cross section of the negative electrode plate 1 according to the second embodiment of the present invention cut along a plane parallel to the long side. In the present invention, as shown in the form of the first reference example , in addition to decentering the position of the substrate at one end of the negative electrode plate, as shown in FIG. It can also be eccentric. However, also in the second embodiment, as in the first reference example , the thickness of the negative electrode plate is uniform, and the negative electrode plate is excellent in productivity.

該負極板１を適用して捲回式極板群を構成するに際しては、負極板１の基板２を境にして合剤層３を厚くした面を内側に、合剤層３を薄くした面を外側に配置する。該構成とすることによって、極板群の最外周において負極板の合剤層の厚い面を正極板５に対向させ、起電反応に寄与する負極板の活物質量を多く確保することができる。   When the negative electrode plate 1 is applied to form a wound electrode plate group, the surface of the negative electrode plate 1 where the mixture layer 3 is thickened with the substrate 2 as a boundary, and the surface where the mixture layer 3 is thinned On the outside. With this configuration, the thick surface of the mixture layer of the negative electrode plate is opposed to the positive electrode plate 5 on the outermost periphery of the electrode plate group, and a large amount of the active material of the negative electrode plate contributing to the electromotive reaction can be secured. .

極板群の構成を該構成とすることによって、前記第１の参考例の形態と同様に、正極板に対向しない負極板の活物質量を低減し、高率で充放電を行ったときに動作する（ 起電反応に預かる） 負極活物質量から算定される負極板の容量（ Ｎ '） の正極板の容量（ Ｐ ） に対する比率（ Ｎ '／ Ｐ ） の値を高めることができ、充放電サイクル性能を高めることができる。該第２の実施の形態では、基板の両面に活物質を塗工する過程で基板の位置を変える必要がないため、第１の参考例の形態に比べてさらに負極板の製造が容易である。 When the electrode plate group is configured as described above, the amount of the active material of the negative electrode plate that does not face the positive electrode plate is reduced and charge / discharge is performed at a high rate, as in the first reference example. The ratio (N ′ / P) of the capacity of the negative electrode plate (N ′) to the capacity of the positive electrode plate (P) calculated from the amount of the negative electrode active material to be operated (deposited in the electromotive reaction) can be increased. Discharge cycle performance can be improved. In the second embodiment, since it is not necessary to change the position of the substrate in the process of applying the active material to both surfaces of the substrate, it is easier to manufacture the negative electrode plate than in the first reference example. .

該第２の実施の形態においては、負極板の基板の開口率を、前記第１の実施形態同様に基板の開口率を好ましくは３５〜６０％、さらに好ましくは４０〜５５％とすることによって負極活物質の利用率の低下を抑制して充電リザーブ量を確保できたためか、良好なサイクル性能が得られることが分かった。第２の実施の形態においては、極群の内部の周においても、負極板の基板を境にして合剤層の厚さが相違している（基板を境にして極板群の内側の合剤層の厚さが大きく、外側の合剤層の厚さが小さい。）。このように、基板を境にして合剤層の厚さを相違させた（活物質粉末の量も合剤層の厚さの比に比例して相違する）場合、厚さの大きい合剤層に含まれる活物質の利用率が低くなるのではないかと予想されたが、負極板の基板の開口率を前記のように３５〜６０％、さらに好ましくは４０〜５５％に設定することによって良好なサイクル性能が得られた。   In the second embodiment, the aperture ratio of the substrate of the negative electrode plate is preferably 35 to 60%, more preferably 40 to 55%, as in the first embodiment. It was found that good cycle performance could be obtained because the charge reserve amount could be secured by suppressing the decrease in the utilization factor of the negative electrode active material. In the second embodiment, the thickness of the mixture layer is different at the inner periphery of the electrode group with the substrate of the negative electrode plate as the boundary (the inner layer of the electrode plate group with the substrate as the boundary). The thickness of the agent layer is large, and the thickness of the outer mixture layer is small.) In this way, when the thickness of the mixture layer is made different from the substrate (the amount of the active material powder is also different in proportion to the ratio of the thickness of the mixture layer), the thick mixture layer It is expected that the utilization rate of the active material contained in the substrate will be low, but it is good by setting the aperture ratio of the substrate of the negative electrode plate to 35 to 60%, more preferably 40 to 55% as described above. Cycle performance was obtained.

該第２の実施の形態においても、負極板の基板を境にして厚さの小さい合剤層と厚さの大きい合剤層の厚さの比率は、特に限定されるものではないが、１：９〜４：６に設定するのが好ましく、１：９〜３：７に設定するのがさらに好ましい。該比率が１：９を下回ると、基板上に合剤層を担持させた後、極板にプレス加工を施す工程で、極板が変形したり、活物質粉末が脱落する虞がある。また、極板の片面に基板が露出すると、極板群を構成したときに、セパレータを介して基板が正極板の表面に近接するために、イオンの移動が阻害され、基板に面する部分において起電反応が起きにくく、活物質利用率が低下する虞がある。   Also in the second embodiment, the ratio of the thickness of the mixture layer having a small thickness and the mixture layer having a large thickness with respect to the substrate of the negative electrode plate is not particularly limited. : It is preferable to set to 9 to 4: 6, and it is more preferable to set to 1: 9 to 3: 7. When the ratio is less than 1: 9, the electrode plate may be deformed or the active material powder may fall off in the step of pressing the electrode plate after supporting the mixture layer on the substrate. In addition, when the substrate is exposed on one side of the electrode plate, when the electrode plate group is configured, the substrate is brought close to the surface of the positive electrode plate via the separator. An electromotive reaction is unlikely to occur, and the active material utilization rate may be reduced.

（第３の実施の形態）
第３に実施の形態は、負極板の全体に亘って基板を偏心させた実施の形態であって、第２の実施の形態とは別の実施の形態である。第２の実施形態においては、図５に示すように、極板を長辺に平行な線で切断したときに、基板２の極板１の厚さ方向に対する位置は変化しない。これに対して第３の実施の形態においては、負極板の全体に亘って基板を極板の厚さの中心に対して一方の側に偏心させるのであるが、図１に示したように、極板の長手方向において、基板の厚さ方向に対する位置を途中で変化させる。例えば、図１においてＸより右側（負極板のうち捲回式極板群の最外周側端部）の負極板の合剤層の厚さを１：９とし、Ｘより左側の負極板の合剤層の厚さの比を３：７とする。ただし、第３に実施の形態においても、負極板の活物質利用率を高めるために、捲回式極板群の最外周側の端部の基板の偏心の度合い（基板と極板の厚さの中心との間の距離）を他の部分より大きく設定し、且つ、極板全体に亘り、負極板の基板を境とする合剤層の厚さの比を４：６〜１：９の範囲に設定するのが好ましい。 (Third embodiment)
The third embodiment is an embodiment in which the substrate is decentered over the entire negative electrode plate, and is an embodiment different from the second embodiment. In the second embodiment, as shown in FIG. 5, when the electrode plate is cut along a line parallel to the long side, the position of the substrate 2 in the thickness direction of the electrode plate 1 does not change. On the other hand, in the third embodiment, the substrate is decentered to one side with respect to the center of the thickness of the electrode plate over the entire negative electrode plate, but as shown in FIG. In the longitudinal direction of the electrode plate, the position with respect to the thickness direction of the substrate is changed halfway. For example, in FIG. 1, the thickness of the mixture layer of the negative electrode plate on the right side of X (the outermost peripheral end of the wound electrode plate group among the negative electrode plates) is 1: 9, and the negative electrode plate on the left side of X is combined. The thickness ratio of the agent layer is set to 3: 7. However, also in the third embodiment, in order to increase the active material utilization rate of the negative electrode plate, the degree of eccentricity of the substrate at the outermost end of the wound electrode plate group (the thickness of the substrate and the electrode plate) The distance between the center of the negative electrode plate and the other part is set larger than the other part, and the ratio of the thickness of the mixture layer at the boundary of the negative electrode substrate is 4: 6 to 1: 9. It is preferable to set the range.

該第３の実施の形態においては、前記第１の参考例の形態同様、極板の厚さ方向に対して基板の位置が変化する部分Ｘ において基板の開口率を低く（例えば部分Ｘのみ穿孔を無くす）設定すると、基板の切断が抑制されるので好ましい。また、例えば前記部分Ｘ において負極板の厚さの中心を跨って基板の位置を変化させると、基板の位置の変化が大きくなって、負極板を作製する過程あるいは極板群を作製する（捲回する）過程で基板が切断される虞が高くなる。 In the third embodiment, similarly to the first reference example , the aperture ratio of the substrate is lowered in the portion X 1 where the position of the substrate changes with respect to the thickness direction of the electrode plate (for example, only the portion X is perforated). If it is set, it is preferable because cutting of the substrate is suppressed. Further, for example, when the position of the substrate is changed across the thickness center of the negative electrode plate in the portion X 1, the change in the position of the substrate becomes large, and the process of manufacturing the negative electrode plate or the electrode plate group is manufactured (捲There is a high risk that the substrate will be cut in the process of turning.

以下、負極板に水素吸蔵合金粉末を活物質とする水素吸蔵電極を用いたニッケル水素電池を例に挙げて説明するが、本発明はニッケル水素電池に限定されるものではなく例えばカドミウム電極を負極とするニッケルカドミウム電池にも適用できるものである。   Hereinafter, a nickel metal hydride battery using a hydrogen storage electrode using a hydrogen storage alloy powder as an active material for the negative electrode plate will be described as an example. However, the present invention is not limited to a nickel metal hydride battery. For example, a cadmium electrode is used as a negative electrode. The present invention can also be applied to nickel cadmium batteries.

（参考例３）
（電池の構成）
亜鉛を金属換算で亜鉛を３重量％、コバルトを１重量％固溶状態で含有する水酸化ニッケルを芯層とし該芯層９５重量％に対して５重量％のオキシ水酸化コバルトからなる表面被覆層を設けた正極活物質粉末を発泡ニッケル製基板に充填した厚さ０．７ｍｍ、長さ９６ｍｍ、幅４４ｍｍの極板を正極板とした。正極板の容量｛正極活物質充填量（ｇ）×正極活物質単位重量当たりの容量（ｍＡｈ／ｇ）｝は、２３００ｍＡｈであった。 (Reference Example 3)
(Battery configuration)
Surface coating comprising 5% by weight of cobalt oxyhydroxide having a core layer of nickel hydroxide containing 3% by weight of zinc in terms of metal and 1% by weight of cobalt in a solid solution state with respect to 95% by weight of the core layer A positive electrode plate having a thickness of 0.7 mm, a length of 96 mm, and a width of 44 mm in which a positive electrode active material powder provided with a layer was filled in a nickel foam substrate was used. The capacity of the positive electrode plate {positive electrode active material filling amount (g) × capacity per unit weight of positive electrode active material (mAh / g)} was 2300 mAh.

厚さ０．０４ｍｍ、直径が１ｍｍの円形の穿孔を有し、開口率４５％の穿孔鋼板（ニッケルメッキ品）を基板とし、該基板の両面に、Ｍｍ1.0Ｎｉ3.9Ｃｏ0.7Ｍｎ0.3Ａｌ0.2（Ｍｍはミッシュメタルを表す）の組成を有する平均粒径４０μｍの水素吸蔵合金９８．８重量％とＳＢＲ（スチレンブタジエンゴム）１重量％、ＭＣ（メチルセルロース）０．２重量％からなる活物質層を配置し、厚さが０．３４ｍｍ、長さが１３７ｍｍ、幅が４４ｍｍの極板を作成した。なお、該負極板の巻き始め側の短辺からの距離が９４ｍｍの位置（図１において、Ｘを図１の左端の辺から９４ｍｍの位置に設定した。）を境にして、基板を偏心させ、基板を境にして片側の合剤層の厚さを０．０３ｍｍ、他方の側の合剤層の厚さを０．２７ｍｍ（厚さの小さい合剤層の厚さ：厚さの大きい合剤層の厚さ＝１：９）とした。 A perforated steel sheet (nickel-plated product) having a circular perforation with a thickness of 0.04 mm and a diameter of 1 mm and having an aperture ratio of 45% is used as a substrate, and Mm 1.0 Ni 3.9 Co 0.7 Mn 0.3 Al 0.2 ( Mm represents a misch metal) and an active material layer composed of 98.8% by weight of a hydrogen storage alloy having an average particle diameter of 40 μm, 1% by weight of SBR (styrene butadiene rubber), and 0.2% by weight of MC (methyl cellulose). An electrode plate having a thickness of 0.34 mm, a length of 137 mm, and a width of 44 mm was prepared. The substrate is decentered at a position where the distance from the short side on the winding start side of the negative electrode plate is 94 mm (in FIG. 1, X is set to a position 94 mm from the left end side in FIG. 1). The thickness of the mixture layer on one side of the substrate is 0.03 mm, the thickness of the mixture layer on the other side is 0.27 mm (thickness of the mixture layer with a small thickness: The thickness of the agent layer was 1: 9).

厚さ０．１ｍｍ、坪量４０ｇ／ｍ2、幅が４６ｍｍであって親水処理を施したポリプロピレン製繊維からなる不織布をセパレータに適用した。 A non-woven fabric made of polypropylene fibers having a thickness of 0.1 mm, a basis weight of 40 g / m 2 , a width of 46 mm, and subjected to hydrophilic treatment was applied to the separator.

前記正極板、セパレータ、負極板を積層し、直径が２ｍｍの巻芯を適用し、前記負極板のうち基板を偏心させた部分が極群の巻き終わり部分になるように配置し、巻き終わり周（極板群の外周）において負極板が外側、正極板が内側になるように、また、該周において基板を偏芯させることによって形成させた合剤層の厚さが０．２７ｍｍと大きくした側が正極板に対向するように配置した。該極板群を直径（内径）１３．６ｍｍの有底円筒状の金属製電槽缶に収納し、６．８ｍｏｌ／ｌのＫＯＨと０．８ｍｏｌ／ｌのＬｉＯＨを含む水溶液からなる電解液を所定量注入し、電槽缶の開放端を排気弁およびキャップ状正極端子付きの蓋体で気密に封止してAAサイズの円筒形ニッケル水素蓄電池を作製した。なお、負極板の容量｛水素吸蔵合金粉末１ｇ当たりの容量（ｍＡｈ／ｇ）×負極板の基板を境にして正極板に対向する部位に位置する水素吸蔵合金粉末の充填量（ｇ）｝と正極板の容量｛正極活物質１ｇ当たりの容量（ｍＡｈ／ｇ）×正極活物質の充填量（ｇ）｝の比（Ｎ／Ｐ比）は、１．３０であった。該例を参考例３とする。 Laminating the positive electrode plate, the separator and the negative electrode plate, applying a winding core having a diameter of 2 mm, arranging the negative electrode plate so that the eccentric part of the substrate is the end of winding of the pole group, In the outer periphery of the electrode plate group, the thickness of the mixture layer formed by decentering the substrate in the periphery was increased to 0.27 mm so that the negative electrode plate was on the outer side and the positive electrode plate was on the inner side. It arrange | positioned so that the side might oppose a positive electrode plate. The electrode plate group is housed in a bottomed cylindrical metal battery case with a diameter (inner diameter) of 13.6 mm, and an electrolytic solution comprising an aqueous solution containing 6.8 mol / l KOH and 0.8 mol / l LiOH is prepared. A predetermined amount was injected, and the open end of the battery case was hermetically sealed with a cover with an exhaust valve and a cap-like positive electrode terminal to produce an AA size cylindrical nickel-metal hydride storage battery. Note that the capacity of the negative electrode plate {capacity per gram of hydrogen storage alloy powder (mAh / g) × filling amount of hydrogen storage alloy powder (g) located at a position facing the positive electrode plate with the substrate of the negative electrode plate as a boundary} and The ratio (N / P ratio) of the capacity of the positive electrode plate {capacity per gram of positive electrode active material (mAh / g) x positive electrode active material filling amount (g)} was 1.30. This example is referred to Reference Example 3 .

（参考例４）
前記参考例３において、負極板の基板を偏心させた部分の基板を境にして片側の合剤層の厚さを０．０６ｍｍ、他方の側の合剤層の厚さを０．２４ｍｍ（厚さの小さい合剤層の厚さ：厚さの大きい合剤層の厚さ＝２：８）とした。それ以外は、参考例３と同じ構成とした。該例を参考例４とする。該例のＮ／Ｐ比は、１．３０であった。 ( Reference Example 4)
In Reference Example 3 , the thickness of the mixture layer on one side is 0.06 mm and the thickness of the mixture layer on the other side is 0.24 mm (thickness) with the substrate of the portion where the substrate of the negative electrode plate is eccentric as a boundary. The thickness of the small mixture layer: the thickness of the large mixture layer = 2: 8). Otherwise, the configuration was the same as in Reference Example 3 . This example is referred to Reference Example 4 . The N / P ratio in this example was 1.30.

（参考例５）
前記参考例３において、負極板の基板を偏心させた部分の基板を境にして片側の合剤層の厚さを０．０９ｍｍ、他方の側の合剤層の厚さを０．２１ｍｍ（厚さの小さい合剤層の厚さ：厚さの大きい合剤層の厚さ＝３：７）とした。それ以外は、参考例３と同じ構成とした。該例を参考例５とする。該例のＮ／Ｐ比は、１．３０であった。 (Reference Example 5)
In Reference Example 3 , the thickness of the mixture layer on one side is 0.09 mm and the thickness of the mixture layer on the other side is 0.21 mm (thickness) with the substrate of the part of the negative electrode plate eccentric. The thickness of the small mixture layer: the thickness of the large mixture layer = 3: 7). Otherwise, the configuration was the same as in Reference Example 3 . This example is referred to Reference Example 5 . The N / P ratio in this example was 1.30.

（参考例６）
前記参考例３において、負極板の基板を偏心させた部分の基板を境にして片側の合剤層の厚さを０．１２ｍｍ、他方の側の合剤層の厚さを０．１８ｍｍ（厚さの小さい合剤層の厚さ：厚さの大きい合剤層の厚さ＝４：６）とした。それ以外は、参考例３と同じ構成とした。該例を参考例６とする。該例のＮ／Ｐ比は、１．３０であった。 ( Reference Example 6)
In Reference Example 3 , the thickness of the mixture layer on one side is 0.12 mm and the thickness of the mixture layer on the other side is 0.18 mm (thickness) with the substrate of the negative electrode plate being eccentric. The thickness of the small mixture layer: the thickness of the large mixture layer = 4: 6). Otherwise, the configuration was the same as in Reference Example 3 . This example is referred to as Reference Example 6 . The N / P ratio in this example was 1.30.

（比較例１）
前記参考例３において、負極板の基板を偏心させた部分を設けず、極板の長手方向の全域に亘り基板を境にして合剤層の厚さを０．１５ｍｍ（基板を境にして、一方の側の合剤層の厚さ：他方の側の合剤層の厚さ＝５：５）とした。それ以外は、参考例３と同じ構成とした。該例を比較例１とする。該例のＮ／Ｐ比は、１．３０であった。 (Comparative Example 1)
In Reference Example 3 , the negative electrode plate is not provided with an eccentric part, and the thickness of the mixture layer is 0.15 mm across the entire substrate in the longitudinal direction of the electrode plate (with the substrate as the boundary, The thickness of the mixture layer on one side: the thickness of the mixture layer on the other side = 5: 5). Otherwise, the configuration was the same as in Reference Example 3 . This example is referred to as Comparative Example 1. The N / P ratio in this example was 1.30.

（比較例２）
前記参考例３において、負極板の基板を偏心させた部分の基板を境にして片側の合剤層の厚さを０．０ｍｍ、他方の側の合剤層の厚さを０．３０ｍｍ（厚さの小さい合剤層の厚さ：厚さの大きい合剤層の厚さ＝０：１０）とした。それ以外は、参考例３と同じ構成とした。該例を比較例２とする。該例のＮ／Ｐ比は、１．３０であった。 (Comparative Example 2)
In Reference Example 3 , the thickness of the mixture layer on one side is 0.0 mm and the thickness of the mixture layer on the other side is 0.30 mm (thickness) with the substrate of the portion where the substrate of the negative electrode plate is eccentric as a boundary. The thickness of the small mixture layer: the thickness of the large mixture layer = 0: 10). Otherwise, the configuration was the same as in Reference Example 3 . This example is referred to as Comparative Example 2 . The N / P ratio in this example was 1.30.

（初期化成）
前記参考例３〜６および比較例１、比較例２に係る電池を周囲温度２０℃において初期化成を行った。初回（１サイクル目）０．０２ＩｔＡで１３時間充電した後、０．１ＩｔＡで１０時間充電した。１時間放置後放電電流０．２ＩｔＡ、放電カット電圧１．０Ｖとして放電した。２〜１０サイクル目まで０．１ＩｔＡで１６時間充電後１時間放置し、放電電流０．２ＩｔＡ、放電カット電圧を１．０Ｖとし、該充放電を１サイクルとして繰り返し充放電を行った。 (Initialization)
The batteries according to Reference Examples 3 to 6 and Comparative Examples 1 and 2 were initialized at an ambient temperature of 20 ° C. The first charge (first cycle) was charged with 0.02 ItA for 13 hours, and then charged with 0.1 ItA for 10 hours. After being left for 1 hour, the battery was discharged with a discharge current of 0.2 ItA and a discharge cut voltage of 1.0 V. From the 2nd to the 10th cycle, the battery was charged with 0.1 ItA for 16 hours and then left for 1 hour, the discharge current was 0.2 ItA, the discharge cut voltage was 1.0 V, and the charge / discharge was repeated as one cycle.

（放電容量評価試験）
前記参考例３〜６および比較例１、比較例２に係る電池であって、化成済みの蓄電池をそれぞれ１０個用意し、周囲温度２０℃において充電電流０．１ＩｔＡで１６時間充電後、１時間放置した後、放電電流０．２ＩｔＡにおいて放電カット電圧１．０Ｖにて放電し、放電容量を求めた。 (Discharge capacity evaluation test)
The batteries according to Reference Examples 3 to 6, Comparative Example 1 and Comparative Example 2, each of which was prepared with 10 formed storage batteries, charged for 16 hours at a charging current of 0.1 ItA at an ambient temperature of 20 ° C., and 1 hour After being left standing, the battery was discharged at a discharge cut voltage of 1.0 V at a discharge current of 0.2 ItA, and the discharge capacity was determined.

（充放電サイクル試験）
前記参考例３〜６および比較例１、比較例２に係る電池であって、化成済みの蓄電池をそれぞれ１０個用意し、該蓄電池を周囲温度２０℃において充電電流１ＩｔＡで１．０５時間充電（１０５％充電）し、１時間放置した後、放電電流１ＩｔＡにおいて放電カット電圧１．０Ｖにて放電した。該充放電を１サイクルとしてサイクルを繰り返し行った。放電容量が該サイクルの１サイクル目の放電容量の６０％に低下したサイクル数をもって当該蓄電池のサイクル寿命とした。 (Charge / discharge cycle test)
The batteries according to Reference Examples 3 to 6, Comparative Example 1 and Comparative Example 2, each of which was prepared 10 storage batteries, and the storage batteries were charged at an ambient temperature of 20 ° C. with a charging current of 1 ItA for 1.05 hours ( 105%) and left for 1 hour, and then discharged at a discharge cut voltage of 1.0 V at a discharge current of 1 ItA. The charge / discharge cycle was repeated for one cycle. The cycle number of the storage battery was defined as the number of cycles in which the discharge capacity was reduced to 60% of the discharge capacity in the first cycle of the cycle.

表１に、放電容量評価試験、充放電サイクル試験の結果を示す（１０個の平均値）を示す。また、図６に充放電サイクル数と放電容量の関係を示す。   Table 1 shows the results of the discharge capacity evaluation test and the charge / discharge cycle test (10 average values). FIG. 6 shows the relationship between the number of charge / discharge cycles and the discharge capacity.

表１の放電容量に示したように、参考例３〜６および比較例１、比較例２に係る電池を０．２ＩｔＡで充電および放電を行ったときには、これらの電池の間に放電容量に大きな差が認められない。しかし、表１および図６に示したように、参考例３〜６のサイクル特性に比べて比較例１、比較例２のサイクル特性は劣っている。比較例１、比較例２ともにＮ／Ｐが１．３０であり参考例３〜６と等しいが、負極板の基板を偏心させてない比較例１においては負極板の最外周の外側の合剤層に含まれる活物質が殆ど起電反応に寄与しないために充電リザーブ量が少なく、サイクル性能が劣るものと考えられる。また、薄い合剤層の厚さ／厚い合剤層の厚さの比を０：１０とした比較例２は、充電および放電を１ＩｔＡで行ったときに、充電受け入れ性能が劣るためか、あるいは、合剤層と基板との密着性でサイクルとともに合剤層と基板との接触界面の電気抵抗が増大するためか、参考例３〜６に比べてサイクル性能が劣るものと考えられる。 As shown in the discharge capacity of Table 1, when the batteries according to Reference Examples 3 to 6 and Comparative Examples 1 and 2 were charged and discharged at 0.2 ItA, the discharge capacity was large between these batteries. There is no difference. However, as shown in Table 1 and FIG. 6, the cycle characteristics of Comparative Examples 1 and 2 are inferior to those of Reference Examples 3 to 6 . In Comparative Example 1 and Comparative Example 2, N / P is 1.30, which is equal to Reference Examples 3 to 6 , but in Comparative Example 1 in which the substrate of the negative electrode plate is not decentered, the mixture on the outermost periphery of the negative electrode plate Since the active material contained in the layer hardly contributes to the electromotive reaction, it is considered that the amount of charge reserve is small and the cycle performance is inferior. Further, in Comparative Example 2 in which the ratio of the thickness of the thin mixture layer / the thickness of the thick mixture layer is 0:10, the charge acceptance performance is inferior when charging and discharging are performed at 1 ItA, or It is considered that the cycle performance is inferior to that of Reference Examples 3 to 6 because the electrical resistance at the contact interface between the mixture layer and the substrate increases with the cycle due to the adhesion between the mixture layer and the substrate.

また、参考例３〜６のなかでは参考例３〜５が特に優れたサイクル特性を有しているところから、基板を偏心させた部分の基板を境にした負極板の合剤層の厚さの比を１：９〜４：６に設定するのが好ましく、１：９〜３：７に設定するのがさらに好ましい。 Further, among Reference Examples 3 to 6 , since Reference Examples 3 to 5 have particularly excellent cycle characteristics, the thickness of the mixture layer of the negative electrode plate with the substrate at the part where the substrate is eccentric is the boundary. Is preferably set to 1: 9 to 4: 6, and more preferably set to 1: 9 to 3: 7.

（実施例５）
前記参考例３において、図５に示したように負極板の全領域において基板を偏心させた。基板を境にして片側の合剤層の厚さを０．０３ｍｍ、他方の側の合剤層の厚さを０．２７ｍｍ（厚さの小さい合剤層の厚さ：厚さの大きい合剤層の厚さ＝１：９）とした。極群の巻き終わり周（極群の最外周）において負極板が外側、正極板が内側になるように、また、基板を偏心させることによって、基板を境にして厚さを０．２７ｍｍと大きくした合剤層を内側に配置し、厚さを０．０３ｍｍと小さく合剤層を外側に配置した。それ以外は参考例３と同じ構成とした。該例を実施例５とする。 (Example 5)
In Reference Example 3 , as shown in FIG. 5, the substrate was eccentric in the entire area of the negative electrode plate. The thickness of the mixture layer on one side is 0.03 mm from the substrate, and the thickness of the mixture layer on the other side is 0.27 mm (thickness of the mixture layer having a small thickness: the mixture having a large thickness) Layer thickness = 1: 9). By decentering the substrate so that the negative electrode plate is on the outer side and the positive electrode plate is on the inner side at the end of winding of the pole group (the outermost circumference of the pole group), the thickness is increased to 0.27 mm with the substrate as a boundary. The mixture layer was arranged on the inside, and the mixture layer was arranged on the outside with a small thickness of 0.03 mm. Otherwise, the configuration was the same as in Reference Example 3 . This example is referred to as Example 5.

（実施例６）
前記実施例５において、基板を境にして片側の合剤層の厚さを０．０９ｍｍ、他方の側の合剤層の厚さを０．２１ｍｍ（厚さの小さい合剤層の厚さ：厚さの大きい合剤層の厚さ＝３：７）とした。それ以外は実施例５と同じ構成とした。該例を実施例６とする。 (Example 6)
In Example 5, the thickness of the mixture layer on one side was 0.09 mm, and the thickness of the mixture layer on the other side was 0.21 mm (thickness of the mixture layer having a small thickness: The thickness of the mixture layer having a large thickness was set to 3: 7). Otherwise, the configuration was the same as in Example 5. This example is referred to as Example 6.

表２に比較例１と合わせて実施例５、実施例６の放電容量評価試験、充放電サイクル試験の結果を示す（１０個の平均値）を示す。また、図７に充放電サイクル数と放電容量の関係を示す。   Table 2 shows the results of the discharge capacity evaluation test and charge / discharge cycle test of Example 5 and Example 6 together with Comparative Example 1 (10 average values). FIG. 7 shows the relationship between the number of charge / discharge cycles and the discharge capacity.

実施例５および実施例６に係る電池は、前記参考例３、参考例５に比べるとサイクル特性が劣るが、負極板の基板を極板の全領域において偏心させたにも拘わらず、表２のサイクル寿命および図７に示したように、比較例１に比べて優れたサイクル特性を有している。負極板の基板に高い開口率（開口率４５％）を有する穿孔金属基板を用いたことと、最外周部分の正極板に対向しない部分の負極活物質量を減らしたことによって比較例１に比べて大きい充電リザーブ量を確保することができ、比較例１を上回るサイクル特性が得られたものと考えられる。 The batteries according to Example 5 and Example 6 are inferior in cycle characteristics as compared with Reference Example 3 and Reference Example 5 , but despite the fact that the negative electrode substrate is decentered in the entire region of the electrode plate, Table 2 As shown in FIG. 7 and the cycle life of FIG. Compared to Comparative Example 1 by using a perforated metal substrate having a high aperture ratio (aperture ratio 45%) for the substrate of the negative electrode plate and reducing the amount of the negative electrode active material in the portion not facing the positive electrode plate in the outermost peripheral portion. Thus, it is considered that a large charge reserve amount can be ensured, and the cycle characteristics exceeding Comparative Example 1 are obtained.

（参考例７）
前記参考例３において、負極板の厚さ方向に対する基板の位置が変化する部分（図１のＸ）に幅３ｍｍに亘り、穿孔を設けなかった。それ以外は参考例３と同じとした。該例を参考例７とする。 ( Reference Example 7)
In Reference Example 3 , no perforation was provided over a width of 3 mm in a portion where the position of the substrate relative to the thickness direction of the negative electrode plate changed (X in FIG. 1). Otherwise, it was the same as Reference Example 3 . This example is referred to as Reference Example 7 .

（参考例８）
前記参考例５において、負極板の厚さ方向に対する基板の位置が変化する部分（図１のＸ）に幅３ｍｍに亘り、穿孔を設けなかった。それ以外は参考例５と同じとした。該例を参考例８とする。 ( Reference Example 8)
In Reference Example 5 , no perforation was provided over a width of 3 mm in the portion where the position of the substrate relative to the thickness direction of the negative electrode plate changed (X in FIG. 1). Otherwise, it was the same as Reference Example 5 . This example is referred to as Reference Example 8 .

（極板群量産試作）
前記参考例３、参考例５、参考例７、参考例８、比較例１、比較例２に係る極板板群を量産用製造ラインを適用して各５千個づつ作製し、極板群を解体して不良（負極板の基板切れ、負極板の活物質の脱落）の有無を調べた。また、参考例７、参考例８の極板群を１０個抽出し、前記同様に円筒形のニッケル水素電池を作製して放電容量試験、充放電サイクル試験に供した。 (Pole group mass production trial production)
The electrode plate groups according to Reference Example 3 , Reference Example 5 , Reference Example 7 , Reference Example 8 , Comparative Example 1, and Comparative Example 2 were manufactured by applying a production line for mass production to 5,000 pieces each, and the electrode plate group Was disassembled and examined for the presence of defects (cutting of the negative electrode plate, dropping of the active material of the negative electrode plate). In addition, ten electrode plate groups of Reference Example 7 and Reference Example 8 were extracted, and a cylindrical nickel-metal hydride battery was produced in the same manner as described above and subjected to a discharge capacity test and a charge / discharge cycle test.

該量産試作結果（不良率および放電容量試験、充放電サイクル試験）を表３に示す。また、図８に充放電サイクル数と放電容量の関係を示す。   Table 3 shows the results of the mass production trial production (defective rate and discharge capacity test, charge / discharge cycle test). FIG. 8 shows the relationship between the number of charge / discharge cycles and the discharge capacity.

参考例７、参考例８においては、前記負極板の位置Ｘに基板に帯状に穿孔を設けない部分を設けたために該部分の基板の機械的強度が大きく、極板厚さを調整するためのプレス加工時あるいは極板群の捲回時において極板切れの発生を抑制することができ、表３の製造不良率に示したように、基板を同じように偏芯させた参考例３、参考例５に比べて製造不良率を低減することができた。一方、負極板の基板を境にして、厚さの小さい合剤層／厚さの大きい合剤層の比を０：１０とした比較例２の場合は、極板厚さを調整するためのプレス加工時あるいは極板群の捲回時において活物質の脱落が発生し、製造不良率が高い結果となった。また、表３のサイクル寿命、図８に示したように、負極板の基板に穿孔を設けない部分を設けた参考例７および参考例８は、基板の全領域に穿孔を設けた参考例３、参考例５に比べて同等以上のサイクル性能を示した。 In Reference Example 7 and Reference Example 8 , since the portion where the perforations are not provided in the strip shape is provided at the position X of the negative electrode plate, the mechanical strength of the substrate in the portion is large, and the thickness of the electrode plate is adjusted. it is possible to suppress the occurrence of the electrode plate breakage during winding of press working or when the electrode plate group times, as shown in the production fraction defective in Table 3, example 3 in which the same manner by eccentric substrate, reference Compared to Example 5 , the manufacturing defect rate could be reduced. On the other hand, in the case of Comparative Example 2 in which the ratio of the mixture layer having a small thickness / the mixture layer having a large thickness was set to 0:10 with the substrate of the negative electrode plate as a boundary, the electrode plate thickness was adjusted. The active material fell off during press working or winding of the electrode plate group, resulting in a high production defect rate. In addition, as shown in FIG. 8 in the cycle life of Table 3, Reference Example 7 and Reference Example 8 in which the substrate of the negative electrode plate was provided with no perforations were provided in Reference Example 3 in which perforations were provided in the entire region of the substrate. Compared to Reference Example 5 , the cycle performance was equivalent or better.

本発明は、捲回式極群を備えるニッケル水素蓄電池などの円筒形蓄電池において、生産性を低下させることなく、充放電サイクル特性に優れたアルカリ蓄電池を提供するもので産業上の利用価値の高いものである。   The present invention provides an alkaline storage battery excellent in charge / discharge cycle characteristics without reducing productivity in a cylindrical storage battery such as a nickel metal hydride storage battery having a wound electrode group, and has high industrial utility value. Is.

参考例の第１の実施形態に係るアルカリ二次電池用負極板を長辺に平行な面で切断した断面構造を模式的に示した図である。It is the figure which showed typically the cross-sectional structure which cut | disconnected the negative electrode plate for alkaline secondary batteries which concerns on 1st Embodiment of a reference example by the surface parallel to a long side. 参考例の第１の実施形態に係る捲回式極群を捲回端面に平行な面で切断して捲回式極群の構造を模式的に示した図である。It is the figure which showed typically the structure of the winding type pole group by cut | disconnecting the winding type pole group which concerns on 1st Embodiment of a reference example by the surface parallel to the winding end surface. 従来のアルカリ二次電池用負極板を長辺に平行な面で切断した断面構造を模式的に示した図である。It is the figure which showed typically the cross-sectional structure which cut | disconnected the conventional negative electrode plate for alkaline secondary batteries by the surface parallel to a long side. 本発明の実施形態に係るアルカリ二次電池用負極板の基板の平面構造を模式的に示す図である。It is a figure which shows typically the planar structure of the board | substrate of the negative electrode plate for alkaline secondary batteries which concerns on embodiment of this invention. 本発明の第２の実施形態に係るアルカリ二次電池用負極板を長辺に平行な面で切断した断面構造を模式的に示した図である。It is the figure which showed typically the cross-sectional structure which cut | disconnected the negative electrode plate for alkaline secondary batteries which concerns on the 2nd Embodiment of this invention by the surface parallel to a long side. 参考例電池及び比較例電池の充放電サイクル数と放電容量の関係を示すグラフである。It is a graph which shows the relationship between the number of charging / discharging cycles of a reference example battery and a comparative example battery, and discharge capacity. 実施例電池及び比較例電池の充放電サイクル数と放電容量の関係を示すグラフである。It is a graph which shows the relationship between the number of charging / discharging cycles of an example battery and a comparative example battery, and discharge capacity. 参考例電池及び比較例電池の充放電サイクル数と放電容量の関係を示すグラフである。It is a graph which shows the relationship between the number of charging / discharging cycles of a reference example battery and a comparative example battery, and discharge capacity. 従来提案の捲回式極板群の断面構造を模式的に示す図である。It is a figure which shows typically the cross-sectional structure of the winding type | formula electrode group of a proposal conventionally.

符号の説明Explanation of symbols

１ 負極板
２ 基板
３ 合剤層
Ｘ 負極板の厚さ方向に対して基板の位置が変化する部分
４ 捲回式極群
７ 穿孔



DESCRIPTION OF SYMBOLS 1 Negative electrode plate 2 Substrate 3 Mixture layer X The part in which the position of a board | substrate changes with respect to the thickness direction of a negative electrode plate 4 Winding type pole group 7 Perforation



Claims (2)

矩形状の正極板、セパレータおよび負極板を積層した捲回式極板群を備え、該捲回式極板群の最外周において負極板が正極板の外側に位置するように配置したアルカリ二次電池であって、前記負極板は、穿孔を有する金属板からなる基板の両面に活物質粉末を主構成物質とする合剤層を有し、厚さが一様であり、前記捲回式極板群の最外周側に位置する部分の基板を極板の厚さ方向の中心に対して片側に偏心させ、前記基板を偏心させることにより基板を境として厚さを大きくした負極板の合剤層を正極板に対向させたものであり、
負極板は、全体に亘って基板を偏心させたものであることを特徴とするアルカリ二次電池。 An alkaline secondary provided with a wound-type electrode plate group in which a rectangular positive electrode plate, a separator and a negative electrode plate are laminated, and arranged so that the negative electrode plate is located outside the positive electrode plate at the outermost periphery of the wound-type electrode plate group In the battery, the negative electrode plate has a mixture layer containing active material powder as a main constituent material on both surfaces of a substrate made of a metal plate having perforations, and has a uniform thickness. A negative electrode plate mixture in which the portion of the substrate located on the outermost peripheral side of the plate group is decentered to one side with respect to the center in the thickness direction of the electrode plate, and the substrate is decentered to increase the thickness from the substrate as a boundary. all SANYO made to face a layer on the positive electrode plate,
2. An alkaline secondary battery, wherein the negative electrode plate is an eccentric substrate. 前記基板を前記極板の厚さ方向の中心に対して片側に偏心させた部分の基板を境とした表裏２面の合剤層の厚さの比が１：９〜４：６であることを特徴とする請求項１に記載のアルカリ二次電池。The ratio of the thicknesses of the mixture layers on the front and back surfaces of the substrate that is decentered to one side with respect to the center in the thickness direction of the electrode plate is 1: 9 to 4: 6. The alkaline secondary battery according to claim 1.
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