JP5343514B2 - Paste type lead acid battery - Google Patents

Paste type lead acid battery Download PDF

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JP5343514B2
JP5343514B2 JP2008285129A JP2008285129A JP5343514B2 JP 5343514 B2 JP5343514 B2 JP 5343514B2 JP 2008285129 A JP2008285129 A JP 2008285129A JP 2008285129 A JP2008285129 A JP 2008285129A JP 5343514 B2 JP5343514 B2 JP 5343514B2
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lattice
bone
paste
type lead
acid battery
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JP2010113933A (en
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晃平 佐野
道男 榑松
剛 風間
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Panasonic Corp
Panasonic Holdings Corp
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Matsushita Electric Industrial Co 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
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    • Y02E60/10—Energy storage using batteries

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Description

本発明はエキスパンド格子を用いたペースト式鉛蓄電池に関するものである。   The present invention relates to a paste type lead-acid battery using an expanded lattice.

ペースト式鉛蓄電池は、鉛−カルシウム系合金等からなる格子に酸化鉛、硫酸、精製水を含むペーストを充填した正極と、鉛−カルシウム系合金等からなる格子に酸化鉛、硫酸、精製水を含むペーストを充填した負極を、ポリオレフィンを代表とする樹脂からなるセパレータを介して対峙させて複数個の極板群を構成し、これらの極板群を複数のセル室からなる電槽に各々挿入して直列に接続し、希硫酸からなる電解液を注入して蓋を電槽に装着して構成される。   Paste-type lead-acid batteries have a positive electrode filled with a paste containing lead oxide, sulfuric acid, and purified water in a lattice made of lead-calcium alloy, etc., and lead oxide, sulfuric acid, and purified water in a lattice made of lead-calcium alloy, etc. A plurality of electrode plate groups are configured by facing a negative electrode filled with a paste through a separator made of a resin typified by polyolefin, and each of these electrode plate groups is inserted into a battery case consisting of a plurality of cell chambers. Then, they are connected in series, and an electrolytic solution made of dilute sulfuric acid is injected and a lid is attached to the battery case.

正極用のエキスパンド格子は、鉛−カルシウム系合金をスラブ状に鋳造し、圧延することでシートを製作し、その後レシプロ方式の切断刃で千鳥状に切れ目を入れながら伸展させ、所望の寸法に切断することで、切り目に応じたパターンの格子骨を有する形状を持って作製できる。このエキスパンド格子は、正極端子やストラップなどの集電部材と接続するための耳部を最上部に有し、ペーストを充填するための網目部（格子骨と空隙とからなる）を下部に有する。なお網目部の最下部には、原材料である平板状の反物の長尺方向に沿った下枠骨が当接している。   The expanded grid for the positive electrode is made by casting a lead-calcium alloy into a slab shape and rolling it, and then extending it while cutting it in a zigzag pattern with a reciprocating cutting blade and cutting it to the desired dimensions. By doing so, it can be produced with a shape having a lattice bone of a pattern corresponding to the cut line. This expanded lattice has an ear portion for connecting to a current collecting member such as a positive electrode terminal and a strap at the uppermost portion, and a mesh portion (consisting of lattice bone and voids) for filling the paste at the lower portion. In addition, the lower frame bone | frame along the elongate direction of the flat fabric thing which is a raw material is contact | abutting to the lowest part of a mesh part.

しかし、アンチモンを含まない鉛−カルシウム系合金は、格子と活物質の密着性やサイクル使用中の格子の伸びに問題があるため、メンテナンスフリー性を保ちつつ、高温雰囲気中でのサイクル寿命特性の向上を図る目的で格子表面にアンチモンを含む層を付与する技術が提案された（例えば、特許文献１）。   However, lead-calcium alloys that do not contain antimony have problems with the adhesion between the lattice and the active material and the elongation of the lattice during cycle use. For the purpose of improving, a technique for providing a layer containing antimony on the lattice surface has been proposed (for example, Patent Document 1).

また、格子の網目部の高さ方向において格子耳部に近い網目部に付与された活物質量に対するアンチモン量を、耳部から離れた網目部に付与された活物質量に対するアンチモン量よりも相対的に多くすることにより、深い放電でのサイクル寿命の向上を図る技術が提案された（例えば、特許文献２）。
特開昭６３−１４８５５７号公報 特開平０３−０４６７６２号公報 In addition, the amount of antimony with respect to the amount of active material applied to the mesh portion near the lattice ear in the height direction of the mesh portion of the lattice is more relative to the amount of antimony with respect to the amount of active material applied to the mesh portion away from the ear portion. As a result, a technique for improving cycle life in deep discharge has been proposed (for example, Patent Document 2).
Japanese Unexamined Patent Publication No. 63-148557 Japanese Patent Laid-Open No. 03-046762

エキスパンド格子は通常、極板強度を強くする目的で、下枠骨をこれに接続する格子骨に比べて太くなるように設計する。しかしこのような設計の下、上述した方法でエキスパンド格子を作製する際、エキスパンド加工時に、下枠骨の変形が少ないため、これに接続する格子骨に応力が集中してしまい、その結果として格子骨の切断が発生するという不具合が発生していた。   The expanded lattice is usually designed to be thicker than the lattice bone connected to the lower frame bone for the purpose of increasing the electrode plate strength. However, under such a design, when the expanded lattice is manufactured by the above-described method, the deformation of the lower frame bone is small during the expansion process, so that stress is concentrated on the lattice bone connected thereto, and as a result, the lattice There was a problem that bone was cut.

また、上述した格子骨の切断が発生しやすい部分に特許文献１および２の技術におけるアンチモンを含む層が存在することで、より格子骨切断が発生しやすくなるという課題を本発明者らは初めて見出した。   Further, the present inventors have for the first time the problem that lattice bone cutting is more likely to occur due to the presence of the antimony-containing layer in the techniques of Patent Documents 1 and 2 in the portion where the lattice bone cutting is likely to occur. I found it.

本発明は上述した課題を解決するものであって、活物質との密着性を確保しつつ、エキスパンド加工時において格子骨の切断が生じにくいエキスパンド格子を有するペースト式鉛蓄電池を提供することを目的とする。   The present invention solves the above-described problems, and an object of the present invention is to provide a paste-type lead storage battery having an expanded lattice that is less likely to cause lattice bone cutting during expansion processing while ensuring adhesion with an active material. And

上述した課題を解決するために、本発明のペースト式鉛蓄電池は、鉛−カルシウム系合金からなり、格子骨からなる略菱目状の網目部の下部に下枠骨を設けたエキスパンド格子を正極に用い、下枠骨に当接する略菱目の下部２辺を除いて、格子骨の表面の少なくとも１面にアンチモン、スズ、銀の少なくとも一つの元素を含ませたことを特徴とする。   In order to solve the above-described problems, a paste-type lead storage battery according to the present invention is made of a lead-calcium alloy, and an expanded lattice having a lower frame bone provided at a lower portion of a substantially rhombic mesh portion made of a lattice bone is a positive electrode. And at least one element of antimony, tin, and silver is included in at least one surface of the lattice bone except for the lower two sides of the substantially rhombus that abuts the lower frame bone.

格子骨のほとんどの箇所の表面に、活物質との密着性が高い金属（アンチモン、スズ、銀の少なくとも一つ）を含ませるとともに、エキスパンド加工時の応力が集中しやすい箇所の格子骨の表面には上記金属を含ませないことで、活物質との密着性を確保しつつ、エキスパンド加工時の格子骨の切断を回避できる。なおエキスパンド加工時の格子骨の切断を回避することで、格子骨が有する集電機能が確保できるので、鉛蓄電池の出力特性や寿命特性が著しく改善すると推測できる。   The surface of most of the lattice bone contains a metal (at least one of antimony, tin, and silver) with high adhesion to the active material, and the surface of the lattice bone where stress during expansion is likely to concentrate By not containing the above metal, it is possible to avoid the cutting of the lattice bone at the time of the expanding process while ensuring the adhesion with the active material. In addition, since the current collecting function of the lattice bone can be ensured by avoiding the cutting of the lattice bone during the expanding process, it can be estimated that the output characteristics and the life characteristics of the lead storage battery are remarkably improved.

本発明によれば、活物質との密着性を確保しつつ、エキスパンド加工時において格子骨の切断が生じにくいエキスパンド格子を有するペースト式鉛蓄電池を提供できる。   ADVANTAGE OF THE INVENTION According to this invention, the paste-type lead acid battery which has an expanded lattice which cannot produce the cutting | disconnection of a lattice bone easily at the time of an expand process can be provided, ensuring the adhesiveness with an active material.

以下に、本発明を実施するための最良の形態について、図を用いて説明する。   The best mode for carrying out the present invention will be described below with reference to the drawings.

本発明のペースト式鉛蓄電池は、鉛−カルシウム系合金からなり、格子骨からなる略菱目状の網目部の下部に下枠骨を設けたエキスパンド格子を正極に用い、下枠骨に当接する略菱目の下部２辺を除いて、格子骨の表面の少なくとも１面にアンチモン、スズ、銀の少なくとも一つの元素を含ませたことを特徴とする。   The paste-type lead-acid battery of the present invention is made of a lead-calcium alloy, and uses an expanded lattice in which a lower frame bone is provided at a lower portion of a substantially rhombic mesh portion made of a lattice bone as a positive electrode, and comes into contact with the lower frame bone. At least one element of antimony, tin, or silver is included in at least one surface of the lattice bone except for the lower two sides of the substantially rhombus.

図１は本発明のペースト式鉛蓄電池におけるエキスパンド格子の概略を示す図であり、図２はその細部を示す図である。正極に用いるエキスパンド格子１は、正極端子やストラップなどの集電部材と接続するための耳部２を最上部に有し、ペーストを充填するための略菱目状の格子ます目８ａ、８ｂおよび８ｃからなる網目部４を下部に有する。なお網目部４の最上部には上枠骨３が当接しており、最下部には下枠骨５ｃが当接している。格子骨５ａは下枠骨５ｃに当接しておらず、略菱目の下部２辺を構成する格子骨５ｂは下枠骨５ｃに当接している。なお上枠骨３を一辺とする最上部の格子ます目８ａおよび下枠骨５ｃを一辺とする最下部の格子ます目８ｂは、略菱目形状を有していない例を示している。   FIG. 1 is a diagram showing an outline of an expanded lattice in a paste type lead-acid battery of the present invention, and FIG. 2 is a diagram showing the details thereof. The expanded grid 1 used for the positive electrode has an ear part 2 for connecting to a current collecting member such as a positive electrode terminal or a strap at the uppermost part, and has substantially rhombic grid grids 8a and 8b for filling the paste. A mesh part 4 made of 8c is provided at the lower part. The upper frame bone 3 is in contact with the uppermost part of the mesh part 4, and the lower frame bone 5c is in contact with the lowermost part. The lattice bone 5a is not in contact with the lower frame bone 5c, and the lattice bone 5b constituting the lower two sides of the approximately rhombus is in contact with the lower frame bone 5c. In addition, the uppermost lattice mesh 8a having the upper frame bone 3 as one side and the lowermost lattice mesh 8b having the lower frame bone 5c as one side show an example having substantially no rhombus shape.

本発明では、格子骨５ａの表面には図２のように少なくとも１面にアンチモン、スズ、銀の少なくとも一つの元素を含ませて表面層７を形成させ、下枠骨５ｃに当接する最下部の略菱目状の格子ます目８ｃの下部２辺を構成する格子骨５ｂおよび下枠骨５ｃの表面にはこの表面層７を設けないようにしたことを特徴とする。   In the present invention, at least one element of antimony, tin, and silver is formed on the surface of the lattice bone 5a as shown in FIG. 2 to form the surface layer 7, and the lowermost portion in contact with the lower frame bone 5c. The surface layer 7 is not provided on the surfaces of the lattice bone 5b and the lower frame bone 5c constituting the lower two sides of the substantially rhombic lattice mesh 8c.

本発明者らは、格子骨５ｂの表面の一部にアンチモン、スズ、銀の少なくとも１元素以上を含む表面層７が付与されていると、これらの金属が付与されていない場合と比べて、格子骨５ｂの強度が低下して切断されやすくなるという課題を見出した。そこで格子骨５ａの表面に、活物質との密着性が高い金属（アンチモン、スズ、銀の少なくとも一つ）を含ませるとともに、下枠骨５ｃとエキスパンド加工時の応力が集中しやすい格子骨５ｂの表面には上記金属を含ませないことで、活物質との密着性を確保しつつ、エキスパンド加工時の格子骨５ｂの切断を回避できるようにした。   When the surface layer 7 containing at least one element of antimony, tin, and silver is applied to a part of the surface of the lattice bone 5b, the present inventors, compared with the case where these metals are not applied, The subject that the intensity | strength of the lattice bone 5b fell and it became easy to cut | disconnect was discovered. Therefore, the surface of the lattice bone 5a includes a metal (at least one of antimony, tin, and silver) that has high adhesion to the active material, and the lower frame bone 5c and the lattice bone 5b that easily concentrates stress during the expansion process. By not including the above metal on the surface, it was possible to avoid the cutting of the lattice bone 5b at the time of the expanding process while ensuring the adhesion with the active material.

本発明の構成によれば、格子の切断が回避できるため、ペースト充填時にエキスパンド格子１がペースト充填ホッパーの中で詰まってラインが停止することを防止できる。またエキスパンド加工時の格子骨５ｂの切断を回避することで、格子骨５ｂが有する集電機能
が確保できるので、鉛蓄電池の出力特性や寿命特性が著しく改善すると推測される。さらには切断された格子骨５ｂが折れ曲がって先端がセパレータを破損させることがないので、電池の短絡を抑制できるものと推測される。 According to the configuration of the present invention, cutting of the grid can be avoided, so that it is possible to prevent the expanded grid 1 from being clogged in the paste filling hopper and stopping the line during paste filling. Moreover, since the current collection function which the lattice bone 5b has can be ensured by avoiding the cutting | disconnection of the lattice bone 5b at the time of an expand process, it is estimated that the output characteristic and lifetime characteristic of a lead storage battery improve remarkably. Furthermore, since the cut lattice bone 5b is not bent and the tip does not damage the separator, it is estimated that the short circuit of the battery can be suppressed.

なお本発明において、格子骨５ｂとそれに接続する格子骨５ａとで構成される接続部６は５ｂに含まれるものとする。また表面層７の幅は特に制限されないが、特性向上を目的に付与しているため、格子骨５ｂにかからないことを前提に広くするのが好ましい。さらに表面層７の厚みは、基板となる鉛シートの厚みの０．５％以上とすることで、表面層７の剥離を顕著に抑制できる。   In the present invention, it is assumed that the connecting portion 6 composed of the lattice bone 5b and the lattice bone 5a connected thereto is included in 5b. The width of the surface layer 7 is not particularly limited, but it is preferably widened on the assumption that it does not cover the lattice bone 5b because it is given for the purpose of improving characteristics. Furthermore, peeling of the surface layer 7 can be remarkably suppressed by setting the thickness of the surface layer 7 to 0.5% or more of the thickness of the lead sheet serving as the substrate.

表面層７の成分は、求める性能に応じて適宜選択できるが、例としてアンチモン濃度が０．２〜５．０質量％である鉛合金等が挙げられる。この表面層７は、箔圧延、溶射、溶湯浸漬等の手法によって、格子骨５ａの表面に設けることができる。   Although the component of the surface layer 7 can be suitably selected according to the performance to request | require, the lead alloy etc. whose antimony density | concentration is 0.2-5.0 mass% are mentioned as an example. The surface layer 7 can be provided on the surface of the lattice bone 5a by a technique such as foil rolling, thermal spraying, or molten metal immersion.

このエキスパンド格子１にペースト練合機で作製した正極ペーストを充填して正極とし、極板群を構成後、電槽に収納し、この電槽に蓋を装着する等、公知の構成によって本発明のペースト式鉛蓄電池を組み立てることができる。   The expanded grid 1 is filled with a positive electrode paste produced by a paste kneading machine to form a positive electrode. After the electrode plate group is configured, it is housed in a battery case and a lid is attached to the battery case. Paste type lead acid battery can be assembled.

以下、本発明の実施例について図面を参照しながら説明する。   Embodiments of the present invention will be described below with reference to the drawings.

（実施例１）
鉛−カルシウム系合金をスラブ状に鋳造し、圧延することでシートを製作し、その後レシプロ方式の切断刃で千鳥状に切れ目を入れながら伸展させた。なお圧延の際に箔圧延にて格子骨５ａのみアンチモン、スズ、銀を含む表面層７を付与し、エキスパンド格子１の連続体を作製した。 Example 1
A lead-calcium alloy was cast into a slab shape and rolled to produce a sheet, and then stretched with a reciprocating type cutting blade while making staggered cuts. In addition, the surface layer 7 containing antimony, tin, and silver was applied only to the lattice bone 5a by foil rolling at the time of rolling, and the continuous body of the expanded lattice 1 was produced.

（比較例１）
圧延の際に箔圧延にて網目部４全体（格子骨５ａおよび５ｂ）に表面層７を付与したこと以外は、実施例１と同様にしてエキスパンド格子１の連続体を作製した。 (Comparative Example 1)
A continuous body of the expanded lattice 1 was produced in the same manner as in Example 1 except that the surface layer 7 was applied to the entire mesh portion 4 (lattice bones 5a and 5b) by foil rolling during rolling.

（比較例２）
圧延の際に箔圧延にて格子骨５ａおよび５ｂの上半分（下枠骨５ｃに当接しない側）に表面層７を付与したこと以外は、実施例１と同様にしてエキスパンド格子１の連続体を作製した。 (Comparative Example 2)
In the same manner as in Example 1 except that the surface layer 7 was applied to the upper halves of the lattice bones 5a and 5b (the side not in contact with the lower frame bone 5c) by foil rolling during rolling, the expanded lattice 1 was continuous. The body was made.

以上のようにして作製したエキスパンド格子の連続体について、格子切断箇所数測定を行なった。１０ｍ当たりの切断箇所数としての結果を（表１）に示す。   With respect to the expanded lattice continuum produced as described above, the number of lattice cuts was measured. The results as the number of cut points per 10 m are shown in (Table 1).

Figure 0005343514
Figure 0005343514

（表１）に示すように、網目部４全体に表面層７を付与した比較例１のみならず、格子骨５ｂの上半分に表面層７を付与した比較例２も、多数の切断が発生した。これは、元々応力が集中しやすい格子骨５ｂに部分的にでも表面層７を付与することにより強度が顕著に低下したためと推測される。これらと比較して、格子骨５ａのみに表面層７を付与した実施例１は切断が発生しなかった。これは、応力が集中しやすい格子骨５ｂに表面層７を付与しないことにより、強度低下を防ぐことができたためと推測される。   As shown in (Table 1), not only Comparative Example 1 in which the surface layer 7 is applied to the entire mesh portion 4, but also Comparative Example 2 in which the surface layer 7 is applied to the upper half of the lattice bone 5b causes a large number of cuts. did. This is presumably because the strength was remarkably lowered by applying the surface layer 7 even partially to the lattice bone 5b where stress tends to concentrate. Compared with these, cutting did not occur in Example 1 in which the surface layer 7 was applied only to the lattice bone 5a. This is presumed to be because strength reduction could be prevented by not providing the surface layer 7 on the lattice bone 5b where stress tends to concentrate.

本発明の構成によれば、エキスパンド格子の切断による不具合を防止できるため、始動用鉛蓄電池をはじめとする、様々な用途のペースト式鉛蓄電池において極めて有用である。   According to the configuration of the present invention, it is possible to prevent problems due to the cutting of the expanded lattice, and thus it is extremely useful in paste-type lead storage batteries for various applications including lead batteries for starting.

本発明のペースト式鉛蓄電池におけるエキスパンド格子の概略を示す図The figure which shows the outline of the expanded lattice in the paste type lead acid battery of this invention 本発明のペースト式鉛蓄電池におけるエキスパンド格子の細部を示す図The figure which shows the detail of the expanded lattice in the paste type lead acid battery of this invention

符号の説明Explanation of symbols

１ エキスパンド格子
２ 耳部
３ 上枠骨
４ 網目部
５ａ 格子骨
５ｂ 格子骨
５ｃ 下枠骨
６ 接続部
７ 表面層
８ａ 格子ます目
８ｂ 格子ます目
８ｃ 格子ます目 DESCRIPTION OF SYMBOLS 1 Expand lattice 2 Ear part 3 Upper frame bone 4 Mesh part 5a Lattice bone 5b Lattice bone 5c Lower frame bone 6 Connection part 7 Surface layer 8a Lattice mesh 8b Lattice mesh 8c Lattice mesh

Claims (1)

鉛−カルシウム系合金からなり、格子骨からなる略菱目状の網目部の下部に下枠骨を設けたエキスパンド格子を、正極に用いたペースト式鉛蓄電池であって、
前記下枠骨に当接する略菱目の下部２辺を除いて、前記格子骨の表面の少なくとも１面にアンチモン、スズ、銀の少なくとも一つの元素を含ませたことを特徴とするペースト式鉛蓄電池。 A paste type lead-acid battery using an expanded lattice made of a lead-calcium alloy and having a lower frame bone at the lower part of a substantially rhombic mesh portion made of a lattice bone,
A paste-type lead-acid battery characterized in that at least one element of antimony, tin, and silver is included in at least one surface of the lattice bone except for the lower two lower sides of the substantially rhombus contacting the lower frame bone .
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JPWO2012153464A1 (en) * 2011-05-12 2014-07-31 パナソニック株式会社 Negative electrode for lead acid battery and lead acid battery
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JPH01183068A (en) * 1988-01-06 1989-07-20 Matsushita Electric Ind Co Ltd Lead-acid battery
JPH02121262A (en) * 1988-10-28 1990-05-09 Matsushita Electric Ind Co Ltd Grid body for lead storage battery
JP2982178B2 (en) * 1989-06-20 1999-11-22 松下電器産業株式会社 Manufacturing method of electrode plate for lead-acid battery
JPH0574464A (en) * 1991-09-12 1993-03-26 Matsushita Electric Ind Co Ltd Sealed lead-acid storage battery
JP4026259B2 (en) * 1998-12-24 2007-12-26 松下電器産業株式会社 Sealed lead acid battery
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