JP2009135061A - Lead acid battery and manufacturing method of lead acid battery - Google Patents

Lead acid battery and manufacturing method of lead acid battery Download PDF

Info

Publication number
JP2009135061A
JP2009135061A JP2007312115A JP2007312115A JP2009135061A JP 2009135061 A JP2009135061 A JP 2009135061A JP 2007312115 A JP2007312115 A JP 2007312115A JP 2007312115 A JP2007312115 A JP 2007312115A JP 2009135061 A JP2009135061 A JP 2009135061A
Authority
JP
Japan
Prior art keywords
powder
lead
current collector
electrode plate
sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2007312115A
Other languages
Japanese (ja)
Inventor
Masanori Sakai
政則 酒井
Satoshi Minoura
敏 箕浦
Yoshiaki Machiyama
美昭 町山
Imakichi Hirasawa
今吉 平沢
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Shin Kobe Electric Machinery Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shin Kobe Electric Machinery Co Ltd filed Critical Shin Kobe Electric Machinery Co Ltd
Priority to JP2007312115A priority Critical patent/JP2009135061A/en
Publication of JP2009135061A publication Critical patent/JP2009135061A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lead acid battery capable of securing a lifetime for a long period. <P>SOLUTION: The lead acid battery has an electrode plate group housed in a battery case. The electrode plate group has a positive electrode plate and a negative electrode plate laminated through a separator. A powder rolled sheet 27 in which powder of lead alloy containing tin 1.5 wt.% is rolled out and formed in sheet form is used as a current collector 28 respectively for the positive electrode plate and the negative electrode plate. The powder rolled sheet 27 is laminated doubly by being folded up into two. The laminated powder rolled sheet 27 is made in one body by a punching work or an expanding work. A positive electrode active material paste and a negative electrode active material paste are respectively coated on the current collector 28. Thereby, deformation due to corrosion of the powder rolled sheet 27 is suppressed, and the thickness of the current collector 28 is increased. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は鉛電池および鉛電池の製造方法に係り、特に、集電体に活物質が保持された極板を備えた鉛電池および該鉛電池の製造方法に関する。   The present invention relates to a lead battery and a method of manufacturing the lead battery, and more particularly to a lead battery including an electrode plate in which an active material is held on a current collector and a method of manufacturing the lead battery.

リチウム二次電池、ニッケル水素電池等の二次電池のなかでも鉛電池は、特に低温特性に優れ、電池特性とコスト面とでバランスのとれた二次電池である。このため、自動車用をはじめとして、ポータブル機器用の電源やコンピュータのバックアップ用にも広く普及している。最近では、電気自動車用の主力電源としてだけでなく、ハイブリッド電気自動車や簡易ハイブリッド自動車等の起動電源や回生電流の回収用としても新たな機能が見直されている。これらの用途では、高出力性能、高入力性能が要求されている。   Among secondary batteries such as lithium secondary batteries and nickel metal hydride batteries, lead batteries are secondary batteries that are particularly excellent in low-temperature characteristics and balanced in battery characteristics and cost. For this reason, it is widely used for power supplies for portable devices and for computer backups as well as for automobiles. Recently, new functions have been reviewed not only as a main power source for electric vehicles but also as a start-up power source and a collection of regenerative current for hybrid electric vehicles and simple hybrid vehicles. In these applications, high output performance and high input performance are required.

一方、鉛電池は、単位体積あたりの重量がリチウム二次電池等に比べて重いため、エネルギー密度の点で遜色する。この原因は、リチウム等と比較して比重の大きい鉛電極を使用すること、および、比重の大きい硫酸を電解液に使用することにある。鉛電極を極力薄くして単位重量あたりの電極面積を広くすれば、鉛電池の軽量化、高エネルギー密度化を図ることが期待できる。ところが、鉛電池では、集電体が電池使用環境で腐食して腐食伸びを生じるため、電気的なショートや電槽の貫通等のトラブルを引き起こし、最終的には電池機能停止に到る。集電体を薄膜化するほど腐食伸びが早期に生じるため、寿命低下を早め信頼性を低下させることとなる。   On the other hand, a lead battery is heavier than a lithium secondary battery or the like because of its heavier weight per unit volume, and is therefore inferior in terms of energy density. This is because a lead electrode having a larger specific gravity than lithium or the like is used and sulfuric acid having a higher specific gravity is used for the electrolyte. If the lead electrode is made as thin as possible to increase the electrode area per unit weight, it can be expected that the lead battery will be reduced in weight and energy density. However, in a lead battery, the current collector corrodes in the battery usage environment and causes corrosion elongation, causing troubles such as an electrical short and penetration of the battery case, and finally the battery function is stopped. As the current collector becomes thinner, the corrosion elongation occurs earlier, so the life is shortened and the reliability is lowered.

また、鉛電池は、自動車用以外にも産業用として広く使用されている。産業用電池では、例えば、１５年相当を越える耐用年数（寿命）が要求されており、高出力性能、高入力性能に加えて、長寿命化を図ることが課題となっている。このため、上述した集電体の腐食伸びを解決することができれば、自動車用電池に限らず、産業用電池においても、一層の高機能化を図ることが期待される。   Lead batteries are widely used not only for automobiles but also for industrial purposes. In industrial batteries, for example, a service life (life) exceeding 15 years is required, and in addition to high output performance and high input performance, there is a problem of extending the life. For this reason, if the corrosion elongation of the current collector described above can be solved, it is expected that not only automobile batteries but also industrial batteries will be further enhanced in functionality.

鉛電池の入出力性能、特に高率での入力性能を向上させる技術としては、例えば、負極の組成を特定の組み合わせとする技術が開示されている（特許文献１参照）。また、鉛電池を軽量化、高出力化するためには、集電体を薄膜化し、同一重量の鉛または鉛合金でできるだけ大面積の集電体を作製し電池を構成する必要がある。集電体の耐食性を向上させ集電体を薄膜化する技術として、本出願人は、鉛粉末または鉛合金粉末を主体とする粉末を圧延してシート状に形成した粉末圧延シートの技術を開示している（例えば、特許文献２参照）。   As a technique for improving the input / output performance of the lead battery, particularly the input performance at a high rate, for example, a technique in which the composition of the negative electrode is a specific combination is disclosed (see Patent Document 1). In addition, in order to reduce the weight and increase the output of a lead battery, it is necessary to make the current collector into a thin film, and to make a current collector with as large an area as possible with the same weight of lead or lead alloy to constitute the battery. As a technology for improving the corrosion resistance of a current collector and reducing the thickness of the current collector, the present applicant discloses a technology of a powder rolling sheet formed by rolling a powder mainly composed of lead powder or lead alloy powder into a sheet shape. (For example, refer to Patent Document 2).

特開２００４−１２７６３６号公報JP 2004-127636 A 特開２００６−６６１７３号公報JP 2006-66173 A

しかしながら、上述したように、産業用電池では、高出力化、高入力化に加えて、長寿命化が要求されている。この点、特許文献１、特許文献２の技術では、これらの要求を満たすには十分とはいえない。換言すれば、特許文献１の技術では、高出力化、高入力化を図ることができるものの、集電体の腐食伸びが生じるため、長寿命化の点では１５年相当の耐用年数を達成することが難しい。また、特許文献２の技術では、集電体の耐食性を向上させ集電体を薄膜化することで高出力化を図ることができるものの、薄膜化した集電体では長期間にわたって強度を維持することが難しくなる。粉末圧延シートの厚さを大きくすることで強度の確保が期待できるが、出力低下を招くこととなる。また、粉末圧延シートでは粉末を略均等に圧着させることで耐食性を向上させるため、厚さを大きくすると粉末粒子間の密着性が低下し、耐食性が不十分となるおそれもある。   However, as described above, industrial batteries are required to have a longer life in addition to higher output and higher input. In this regard, the techniques of Patent Document 1 and Patent Document 2 are not sufficient to satisfy these requirements. In other words, although the technology of Patent Document 1 can achieve high output and high input, the corrosion elongation of the current collector occurs, so that the service life equivalent to 15 years is achieved in terms of extending the life. It is difficult. Further, in the technique of Patent Document 2, although it is possible to achieve high output by improving the corrosion resistance of the current collector and reducing the current collector thickness, the thin current collector maintains strength over a long period of time. It becomes difficult. Ensuring strength can be expected by increasing the thickness of the powder-rolled sheet, but the output will be reduced. In addition, since the powder rolling sheet improves the corrosion resistance by pressing the powder substantially uniformly, if the thickness is increased, the adhesion between the powder particles may be lowered, and the corrosion resistance may be insufficient.

本発明は上記事案に鑑み、長期にわたって寿命を確保することができる鉛電池および該鉛電池の製造方法を提供することを課題とする。   In view of the above-described case, an object of the present invention is to provide a lead battery and a method for manufacturing the lead battery that can ensure a long life.

上記課題を解決するために、本発明の第１の態様は、集電体に活物質が保持された極板を備えた鉛電池において、前記集電体は、鉛粉末または鉛合金粉末を主体とする粉末を圧延してシート状に形成した粉末圧延シートが積層されたものであり、前記積層された粉末圧延シートが穴あけ加工またはエキスパンド加工により一体化されていることを特徴とする。   In order to solve the above-described problems, a first aspect of the present invention is a lead battery including an electrode plate in which an active material is held on a current collector, wherein the current collector is mainly composed of lead powder or lead alloy powder. The powder rolling sheet formed by rolling the powder to form a sheet is laminated, and the laminated powder rolling sheet is integrated by drilling or expanding.

第１の態様では、集電体が粉末圧延シートが積層されているため、粉末圧延シートでは粉末同士が略均等な分散状態で圧着されていることから腐食による変形が抑制され、薄膜状でも積層により厚さが増し強度を確保できると共に、積層された粉末圧延シートが穴あけ加工またはエキスパンド加工により一体化されているため、シート間の剥離が抑制され活物質が確実に保持されるので、鉛電池の寿命を長期にわたって確保することができる。   In the first aspect, since the current collector is formed by laminating a powder rolling sheet, the powder rolling sheet is pressure-bonded in a substantially uniform dispersed state, so that deformation due to corrosion is suppressed, and even a thin film is laminated. As the thickness is increased and the strength is ensured, and the laminated powder rolled sheets are integrated by drilling or expanding, the separation between the sheets is suppressed and the active material is securely held, so the lead battery Can be ensured over a long period of time.

第１の態様において、集電体を粉末圧延シートが折りたたまれることにより積層されたものとしてもよい。粉末圧延シートが、アスペクト比３〜１３の特定方向に配向した結晶粒を有し、結晶粒界、結晶粒内に酸化鉛および過酸化鉛の少なくとも一方を含むことが好ましい。このとき、集電体が、スズ−鉛合金、スズ−カルシウム系鉛合金、スズ−アンチモン系鉛合金、スズ−ストロンチウム系鉛合金およびスズ−バリウム系鉛合金から選択される一種以上の粉末を圧延してシート状に形成したものとしてもよい。   In the first aspect, the current collector may be laminated by folding a powder rolling sheet. It is preferable that the powder-rolled sheet has crystal grains oriented in a specific direction with an aspect ratio of 3 to 13, and includes at least one of lead oxide and lead peroxide in the crystal grain boundaries and crystal grains. At this time, the current collector rolls one or more powders selected from a tin-lead alloy, a tin-calcium lead alloy, a tin-antimony lead alloy, a tin-strontium lead alloy, and a tin-barium lead alloy. And it is good also as what was formed in the sheet form.

また、本発明の第２の態様は、集電体に活物質が保持された極板を備えた鉛電池の製造方法であって、鉛粉末または鉛合金粉末を主体とする粉末を圧延してシート状に形成した粉末圧延シートを積層する積層ステップと、前記積層ステップで積層した粉末圧延シートに穴あけ加工またはエキスパンド加工を施し一体化した集電体を形成する集電体形成ステップと、前記集電体形成ステップで形成した集電体に前記活物質を塗着する塗着ステップと、を含むことを特徴とする。   According to a second aspect of the present invention, there is provided a method of manufacturing a lead battery comprising an electrode plate in which an active material is held on a current collector, wherein the powder mainly composed of lead powder or lead alloy powder is rolled. A laminating step of laminating the rolled powder sheet formed into a sheet, a current collector forming step of forming an integrated current collector by drilling or expanding the rolled powder sheet laminated in the laminating step, and the collector And an applying step of applying the active material to the current collector formed in the electric body forming step.

本発明によれば、集電体が粉末圧延シートが積層されているため、粉末圧延シートでは粉末同士が略均等な分散状態で圧着されていることから腐食による変形が抑制され、薄膜状でも積層により厚さが増し強度を確保できると共に、積層された粉末圧延シートが穴あけ加工またはエキスパンド加工により一体化されているため、シート間の剥離が抑制され活物質が確実に保持されるので、鉛電池の寿命を長期にわたって確保することができる、という効果を得ることができる。   According to the present invention, since the current collector is laminated with a powder rolling sheet, the powder rolling sheet suppresses deformation due to corrosion because the powders are pressure-bonded in a substantially uniform dispersion state, and even in a thin film form As the thickness is increased and the strength is ensured, and the laminated powder rolled sheets are integrated by drilling or expanding, the separation between the sheets is suppressed and the active material is securely held, so the lead battery It is possible to obtain an effect that the lifetime of the can be ensured over a long period of time.

以下、図面を参照して、本発明を適用した鉛電池の実施の形態について説明する。   Hereinafter, embodiments of a lead battery to which the present invention is applied will be described with reference to the drawings.

（構成）
図１に示すように、本実施形態の鉛電池２０は、電池容器となる直方体状の電槽７を有している。電槽７には、１８個の極板群（セル）４が９個×２列となるように収容されている。電槽７の材質には、成形性、絶縁性および耐久性等の点で優れる、例えば、ポリエチレン、ポリプロピレン、アクリルブタジエンスチレン等の高分子樹脂を選択することができる。電槽７の上部はポリエチレン等の高分子樹脂製で水平断面が長方形状の上蓋１０に接着ないし溶着されている。上蓋１０には、一側短辺の両端部に外部へ電力を供給するための正極端子８および負極端子９が立設されている。なお、上蓋１０には図示を省略した排気弁（制御弁）が設けられており、鉛電池１は制御弁式鉛電池である。 (Constitution)
As shown in FIG. 1, the lead battery 20 of this embodiment has a rectangular parallelepiped battery case 7 that serves as a battery container. The battery case 7 accommodates 18 electrode plate groups (cells) 4 in 9 × 2 rows. As the material of the battery case 7, it is possible to select a polymer resin such as polyethylene, polypropylene, and acrylic butadiene styrene that is excellent in terms of moldability, insulation, durability, and the like. The upper part of the battery case 7 is made of a polymer resin such as polyethylene and is adhered or welded to the upper lid 10 whose horizontal cross section is rectangular. The upper lid 10 is provided with a positive electrode terminal 8 and a negative electrode terminal 9 for supplying electric power to both ends of one short side. The upper lid 10 is provided with an exhaust valve (control valve) (not shown), and the lead battery 1 is a control valve type lead battery.

極板群４は、矩形状の正極板１の５枚と負極板２の６枚とがガラス繊維製等のセパレータ３を介して積層されている。セパレータ３の厚さは、１０〜６００μｍに設定することが好ましく、本例では、約２００μｍに設定されている。極板群４では、電槽７内で正極板１および負極板２のそれぞれ上部に位置する一辺から集電タブが上蓋１０側に突出している。集電タブは、極板群４の上部で一側に正極、他側に負極がそれぞれ配列するように設けられている。正極板１の各集電タブおよび負極板２の各集電タブの各突出端部には、それぞれ正極ストラップ５、負極ストラップ６が設けられている。１８個の極板群４は、図示を省略した接続部材で直列接続されている。１８個の極板群４のうち、電槽７内で一側短辺の一側に位置する極板群４の正極ストラップ５が正極端子８に接続されており、他側に位置する極板群４の負極ストラップ６が負極端子９に接続されている。   In the electrode plate group 4, five rectangular positive electrode plates 1 and six negative electrode plates 2 are laminated via a separator 3 made of glass fiber or the like. The thickness of the separator 3 is preferably set to 10 to 600 μm, and is set to about 200 μm in this example. In the electrode plate group 4, a current collecting tab protrudes toward the upper lid 10 from one side located above each of the positive electrode plate 1 and the negative electrode plate 2 in the battery case 7. The current collecting tab is provided so that a positive electrode is arranged on one side and a negative electrode is arranged on the other side above the electrode plate group 4. A positive electrode strap 5 and a negative electrode strap 6 are provided at each protruding end of each current collecting tab of the positive electrode plate 1 and each current collecting tab of the negative electrode plate 2. The 18 electrode plate groups 4 are connected in series by connection members (not shown). Among the 18 electrode plate groups 4, the positive electrode strap 5 of the electrode plate group 4 located on one side of one short side in the battery case 7 is connected to the positive electrode terminal 8, and the electrode plate located on the other side The negative strap 6 of the group 4 is connected to the negative terminal 9.

正極板１、負極板２は、それぞれ、鉛粉末または鉛合金粉末を主体とする粉末を圧延してシート状に形成した粉末圧延シートが積層された集電体を有している。積層された粉末圧延シートは、穴あけ加工またはエキスパンド加工により一体化されている。粉末圧延シートは、本例では、錫（Ｓｎ）を１．５重量％含む鉛合金（Ｐｂ−Ｓｎ系合金）の粉末が圧延されてシート状に形成されている。集電体には、正極活物質ペースト、負極活物質ペーストがそれぞれ塗布されている。穴あけ加工またはエキスパンド加工で格子状に形成された集電体では、両面と格子骨格の間に形成された空隙とに、それぞれ正極活物質ペースト、負極活物質ペーストが保持されている。   Each of the positive electrode plate 1 and the negative electrode plate 2 has a current collector on which a powder rolling sheet formed by rolling a powder mainly composed of lead powder or lead alloy powder is formed. The laminated powder rolled sheets are integrated by drilling or expanding. In this example, the powder rolled sheet is formed into a sheet shape by rolling a powder of a lead alloy (Pb—Sn alloy) containing 1.5% by weight of tin (Sn). A positive electrode active material paste and a negative electrode active material paste are respectively applied to the current collector. In a current collector formed in a lattice shape by drilling or expanding, a positive electrode active material paste and a negative electrode active material paste are respectively held in the voids formed between both surfaces and the lattice skeleton.

（製造）
鉛電池２０は、粉末圧延シートで形成した集電体を用いて正極板１、負極板２を作製し、得られた正極板１、負極板２を配置して組み立てることで製造される。すなわち、粉末圧延シートを形成する圧延工程（積層ステップの一部）、粉末圧延シートを積層する積層工程（積層ステップの一部）、積層した粉末圧延シートに穴あけ加工またはエキスパンド加工を施し一体化した集電体を形成する集電体形成工程（集電体形成ステップ）、集電体に活物質を塗着する塗着工程（塗着ステップ）および正極板、負極板を配設し化成する組立工程を経て鉛電池が製造される。以下、工程順に説明する。 (Manufacturing)
The lead battery 20 is manufactured by producing a positive electrode plate 1 and a negative electrode plate 2 using a current collector formed of a powder rolled sheet, and arranging and assembling the obtained positive electrode plate 1 and negative electrode plate 2. That is, a rolling process for forming a powder-rolled sheet (part of the lamination step), a lamination process for laminating the powder-rolled sheet (part of the lamination step), and punching or expanding the laminated powder-rolled sheet for integration. Current collector forming step for forming a current collector (current collector forming step), coating step for applying an active material to the current collector (coating step), and assembly in which a positive electrode plate and a negative electrode plate are disposed and formed A lead battery is manufactured through the process. Hereinafter, it demonstrates in order of a process.

圧延工程では、正極板１、負極板２の集電体に用いる粉末圧延シートを形成する。粉末圧延シートの形成では、粉末圧延装置が使用される。粉末圧延装置は、図２（Ａ）に示すように、断面略三角状で上部に開口が形成され下部にスリット状の排出口を有するホッパ２２、互いに押圧しあう一対の圧延ローラ２４および図示しない巻取ローラを備えている。圧延ローラ２４は、ホッパ２２の下部（の排出口）に近接して配置されている。   In the rolling process, a powder rolling sheet used for the current collector of the positive electrode plate 1 and the negative electrode plate 2 is formed. In the formation of the powder rolling sheet, a powder rolling apparatus is used. As shown in FIG. 2A, the powder rolling apparatus includes a hopper 22 having a substantially triangular cross section and an opening in the upper part and a slit-like discharge port in the lower part, a pair of rolling rollers 24 that press against each other, and not shown. A winding roller is provided. The rolling roller 24 is disposed in the vicinity of the lower part (the discharge port) of the hopper 22.

原料の粉末、すなわち、主成分の鉛粉末または鉛合金粉末と、必要に応じてアンチモン、ビスマス等の粉末や酸化鉛、酸化アルミニウム等の粉末とを略均一に混合する。原料の各粉末は、空気中や水中に溶融金属を噴霧することによって急冷凝固粉末を生成するガスアトマイズ法や水アトマイズ法で形成する（以下、アトマイズ法で形成された粉末をアトマイズ粉末と呼称する。）。原料粉末として、本例では、錫を１．５重量％含む鉛合金（Ｐｂ−Ｓｎ系合金）で形成した粒径０．０５〜１００μｍ程度のアトマイズ粉末を使用する。アトマイズ粉末をコンベア等で搬送しホッパ２２内に上部の開口から供給する。ホッパ２２内のアトマイズ粉末を下部の排出口から排出し、圧延ローラ２４間に連続的に供給する。ホッパ２２の排出口の寸法は、本例では、スリット幅１．０ｍｍ、長さ約１５０ｍｍに設定する。ホッパ２２から排出されたアトマイズ粉末を圧延ローラ２４間で略均等に押圧し、下方に引き出すことで、厚さ約０．０１〜１．０ｍｍ、幅約１５０ｍｍの帯状の粉末圧延シート２７を形成する。本例では、粉末圧延シート２７の厚さが約２００μｍとなるように圧延ローラ２４の押圧力を設定する。粉末圧延シート２７を巻取ローラでロール状に巻き取る。   The raw material powder, that is, the main component lead powder or lead alloy powder, and the powder of antimony, bismuth, etc., and the powder of lead oxide, aluminum oxide, etc. are mixed almost uniformly as required. Each powder of the raw material is formed by a gas atomizing method or a water atomizing method in which a rapidly solidified powder is produced by spraying molten metal in the air or water (hereinafter, the powder formed by the atomizing method is referred to as an atomized powder). ). In this example, an atomized powder having a particle diameter of about 0.05 to 100 μm formed of a lead alloy (Pb—Sn alloy) containing 1.5 wt% tin is used as the raw material powder. Atomized powder is conveyed by a conveyor or the like and supplied into the hopper 22 from the upper opening. The atomized powder in the hopper 22 is discharged from the lower discharge port and continuously supplied between the rolling rollers 24. In this example, the dimension of the discharge port of the hopper 22 is set to a slit width of 1.0 mm and a length of about 150 mm. The atomized powder discharged from the hopper 22 is pressed almost uniformly between the rolling rollers 24 and drawn downward to form a strip-shaped powder rolled sheet 27 having a thickness of about 0.01 to 1.0 mm and a width of about 150 mm. . In this example, the pressing force of the rolling roller 24 is set so that the thickness of the powder rolling sheet 27 is about 200 μm. The powder rolling sheet 27 is wound up into a roll shape by a winding roller.

粉末圧延シート２７では、Ｐｂ−Ｓｎ系合金のアトマイズ粉末が密度の偏りなく微粒子の状態で略均一に分散している。アトマイズ粉末同士が圧着され、アトマイズ粉末粒子間に金属結合部分が形成されることにより三次元ネットワーク構造を形成している。この粉末圧延シート２７は、アスペクト比が３〜１３の特定方向に配向した結晶粒を有している。また、結晶粒界、結晶粒内には、酸化鉛（ＰｂＯ）または過酸化鉛（ＰｂＯ２）の少なくとも一方が含まれている。 In the powder-rolled sheet 27, the atomized powder of the Pb—Sn alloy is dispersed substantially uniformly in the form of fine particles with no uneven density. Atomized powders are pressure-bonded to each other, and metal bond portions are formed between the atomized powder particles to form a three-dimensional network structure. This powder-rolled sheet 27 has crystal grains oriented in a specific direction with an aspect ratio of 3 to 13. Further, at least one of lead oxide (PbO) and lead peroxide (PbO 2 ) is contained in the crystal grain boundaries and crystal grains.

積層工程では、粉末圧延シート２７を積層する。本例では、粉末圧延シート２７を二つ折りにすることで二重に積層する。圧延工程で巻き取った粉末圧延シート２７を引き出し、正極板１、負極板２の長さの２倍となるようにそれぞれ裁断する。裁断した粉末圧延シート２７を、図２（Ｂ）に示すように、両端部が重なる方向（矢印Ａ方向）に中央部で折りたたむ。粉末圧延シート２７を二つに折りたたむことで二重に積層した集電体２８は、図２（Ｃ）に示すように、粉末圧延シート２７の２倍の厚さを有している。   In the laminating step, the powder rolling sheet 27 is laminated. In this example, the powder-rolled sheet 27 is doubled by folding it in half. The powder rolled sheet 27 wound up in the rolling process is pulled out and cut so as to be twice the length of the positive electrode plate 1 and the negative electrode plate 2. As shown in FIG. 2B, the cut powder rolled sheet 27 is folded at the center in the direction in which both ends overlap (arrow A direction). The current collector 28 that is double-stacked by folding the powder-rolled sheet 27 in two has a thickness twice that of the powder-rolled sheet 27 as shown in FIG.

集電体形成工程では、集電体２８に穴あけ加工またはエキスパンド加工を施し一体化させる。穴あけ加工では、穿孔用工具を使用し、矩形状の集電体２８に、例えば、直径が５ｍｍの穿孔を形成する。また、エキスパンド加工では、カッタ等の刃物を使用し、矩形状の集電体２８に、例えば、５ｍｍの長さで１ｍｍの間隔をあけて切開部を形成した後、両端を略均等に引っ張る。穴あけ加工またはエキスパンド加工を施すことで、集電体２８は、格子状を呈し打ち抜き格子またはエキスパンド格子を形成する。穿孔や切開部を形成するときに、積層した粉末圧延シート２７間が接合するため、格子状に形成された集電体２８では、積層した粉末圧延シート２７が穿孔や切開部の周囲で一体化している。   In the current collector forming step, the current collector 28 is subjected to drilling or expanding and integrated. In the drilling process, a drilling tool is used to form a hole having a diameter of, for example, 5 mm in the rectangular current collector 28. Further, in the expanding process, a cutting tool such as a cutter is used, and an incision portion is formed in a rectangular current collector 28 with a length of 5 mm, for example, with an interval of 1 mm, and then both ends are pulled substantially evenly. By performing drilling or expanding, the current collector 28 has a lattice shape and forms a punched lattice or an expanded lattice. Since the stacked powder rolled sheets 27 are joined when the perforations or incisions are formed, in the current collector 28 formed in a lattice shape, the stacked powder rolled sheets 27 are integrated around the perforations or incisions. ing.

塗着工程では、集電体２８に正極活物質ペースト、負極活物質ペーストをそれぞれ塗着し正極板１、負極板２を形成する。正極活物質ペーストは、本例では、リグニンの０．３重量％、硫酸バリウムまたは硫酸ストロンチウムの０．２重量％、カーボン粉末の０．１重量％、残部鉛粉を混練機で混練した混合物に水を１２重量％加えて混練し、さらに、この混練した鉛粉に希硫酸（２０℃での比重１．２６）の１３重量％を加えて混練することで調製する。集電体２８に正極活物質ペーストを塗着（格子骨格間に形成された空隙に充填）してから、温度５０℃、湿度９５％中に１８時間放置して熟成した後に、温度１１０℃で２時間放置して乾燥させ未化成の正極板１を作製する。未化成の正極板１は、本例では、厚さが１．０ｍｍとなるように成型する。   In the coating process, the positive electrode active material paste and the negative electrode active material paste are respectively applied to the current collector 28 to form the positive electrode plate 1 and the negative electrode plate 2. In this example, the positive electrode active material paste is a mixture obtained by kneading 0.3% by weight of lignin, 0.2% by weight of barium sulfate or strontium sulfate, 0.1% by weight of carbon powder, and the remaining lead powder with a kneader. It is prepared by adding 12% by weight of water and kneading, and further adding 13% by weight of dilute sulfuric acid (specific gravity 1.26 at 20 ° C.) to the kneaded lead powder and kneading. After the positive electrode active material paste was applied to the current collector 28 (filled in the voids formed between the lattice skeletons), it was left to mature for 18 hours in a temperature of 50 ° C. and a humidity of 95%, and then at a temperature of 110 ° C. It is allowed to stand for 2 hours and dried to produce an unformed positive electrode plate 1. In this example, the unformed positive electrode plate 1 is molded so as to have a thickness of 1.0 mm.

一方、負極活物質ペーストは、本例では、リグニンの０．３重量％、硫酸バリウムまたは硫酸ストロンチウムの０．２重量％、カーボン粉末の０．１重量％、残部鉛粉を混練機で混練した混合物に水を１２重量％加えて混練し、さらに、この混練した鉛粉に希硫酸（２０℃での比重１．２６）の１３重量％を加えて混練することで調製する。集電体２８に負極活物質ペーストを塗着（格子骨格間に形成された空隙に充填）してから、温度５０℃、湿度９５％中に１８時間放置して熟成した後に、温度１１０℃で２時間放置して乾燥させ未化成の負極板２を作製する。未化成の負極板２は、本例では、厚さが１．０ｍｍとなるように成型する。   On the other hand, in this example, the negative electrode active material paste was kneaded with 0.3% by weight of lignin, 0.2% by weight of barium sulfate or strontium sulfate, 0.1% by weight of carbon powder, and the remaining lead powder with a kneader. 12% by weight of water is added to the mixture and kneaded. Further, 13% by weight of dilute sulfuric acid (specific gravity of 1.26 at 20 ° C.) is added to the kneaded lead powder and kneaded. After the negative electrode active material paste was applied to the current collector 28 (filled in the voids formed between the lattice skeletons), it was left to mature for 18 hours at a temperature of 50 ° C. and a humidity of 95%, and then at a temperature of 110 ° C. It is allowed to stand for 2 hours and dried to produce an unformed negative electrode plate 2. In this example, the unformed negative electrode plate 2 is molded so as to have a thickness of 1.0 mm.

（電池組立）
組立工程では、極板群４を電槽７に収容した後、化成することで鉛電池１を完成させる。未化成の正極板１の５枚と負極板２の６枚とをセパレータ３を介して積層し、同極性の極板同士を正極ストラップ５、負極ストラップ６でそれぞれ連結して極板群４を作製する。極板群４の１８個を電槽７内に収容し１８直列に接続してから、電槽７内に比重１．０５（２０℃）の希硫酸電解液を注液して未化成電池を作製する。この未化成電池を９Ａで４２時間化成した後に電解液を排出し、再び比重１．２８（２０℃）の希硫酸電解液を注液する。正極端子８および負極端子９をそれぞれ溶接し、上蓋１０で密閉して鉛電池１を完成させた。各極板群４の電圧（セル電圧）は２．０Ｖに設定されており、極板群４を１８直列に接続した鉛電池２０では平均放電電圧が３６Ｖ、容量が１８Ａｈである。 (Battery assembly)
In the assembly process, after the electrode plate group 4 is accommodated in the battery case 7, the lead battery 1 is completed by chemical conversion. 5 sheets of the unformed positive electrode plate 1 and 6 sheets of the negative electrode plate 2 are laminated via the separator 3, and the electrode plates 4 having the same polarity are connected to each other by the positive electrode strap 5 and the negative electrode strap 6. Make it. After 18 pieces of the electrode plate group 4 are accommodated in the battery case 7 and connected in series 18, a dilute sulfuric acid electrolyte solution having a specific gravity of 1.05 (20 ° C.) is injected into the battery case 7 to prepare an unformed battery. Make it. After this unformed battery is formed at 9A for 42 hours, the electrolytic solution is discharged, and a diluted sulfuric acid electrolytic solution having a specific gravity of 1.28 (20 ° C.) is injected again. The positive electrode terminal 8 and the negative electrode terminal 9 were each welded and sealed with the upper lid 10 to complete the lead battery 1. The voltage (cell voltage) of each electrode plate group 4 is set to 2.0 V, and the average discharge voltage is 36 V and the capacity is 18 Ah in the lead battery 20 in which the electrode plate groups 4 are connected in 18 series.

（作用等）
次に、本実施形態の鉛電池１の作用等について、集電体２８の作用を中心に説明する。 (Action etc.)
Next, the operation and the like of the lead battery 1 of the present embodiment will be described focusing on the operation of the current collector 28.

本実施形態では、正極板１、負極板２をそれぞれ構成する集電体２８が粉末圧延シート２７を積層し一体化することで形成されている。従来のように集電体として焼結等の熱処理でシート状に形成された金属シートを用いる場合、鉛等の融点の低い金属では結晶粒が粗大化し、粒子同士が結合して大粒子になりやすいため、得られる金属シート中では粒子の分散状態が変化する。このため、集電体に用いたときに、腐食伸びや腐食減肉が生じやすく、セパレータや電槽を破損して出力や寿命を低下させることがある。これに対して、粉末圧延シート２７では、Ｐｂ−Ｓｎ系合金のアトマイズ粉末が直接圧延されてシート状に形成されるため、アトマイズ粉末が密度の偏りなく微粒子の状態で略均一に分散している。アトマイズ粉末同士は圧着されており、アトマイズ粉末粒子間に金属結合部分が形成されることにより三次元ネットワーク構造が形成されている。このため、粉末圧延シート２７の耐食性が向上し、腐食伸び等の変形を抑制することができる。   In the present embodiment, the current collectors 28 constituting the positive electrode plate 1 and the negative electrode plate 2 are formed by laminating and integrating powder rolling sheets 27. When using a metal sheet formed into a sheet by heat treatment such as sintering as a current collector as in the past, crystals with a low melting point, such as lead, become coarse and the particles combine to become large particles. Since it is easy, the dispersion state of particles changes in the obtained metal sheet. For this reason, when it uses for a collector, corrosion elongation and corrosion thinning are easy to occur, and a separator and a battery case may be damaged and output and life may be reduced. On the other hand, in the powder rolling sheet 27, the atomized powder of the Pb—Sn alloy is directly rolled and formed into a sheet shape, so that the atomized powder is dispersed almost uniformly in a fine particle state with no uneven density. . The atomized powders are pressure-bonded to each other, and a three-dimensional network structure is formed by forming metal bonding portions between the atomized powder particles. For this reason, the corrosion resistance of the powder rolling sheet 27 is improved, and deformation such as corrosion elongation can be suppressed.

また、アトマイズ粉末を圧延してシート状に形成した粉末圧延シート２７では、厚さを大きくすることが難しく薄膜状に形成される。厚さを大きくすると、アトマイズ粉末間が密着せず、耐食性が不十分となる。また、薄膜状の粉末圧延シート２７をそのまま集電体とすると、腐食伸びを抑制することはできるが、例えば、長期間（１５年相当）にわたり使用される産業用途の鉛電池では集電体の強度が不足することとなる。本実施形態では、粉末圧延シート２７が積層され集電体２８が形成されるため、集電体２８では厚さが増大するので、強度を確保することができる。また、粉末圧延シート２７が従来の金属シートと比較してより薄く高強度のため、粉末圧延シート２７を積層した集電体２８では厚さが大きくなるものの、金属シートの集電体より薄膜化することができる。このため、薄膜化した高強度の集電体では、鉛電池２８全体として原料の鉛資源の使用量が減少するので、鉛資源の有効利用を図ることができる。   Moreover, in the powder rolling sheet | seat 27 which rolled the atomized powder and formed in the sheet form, it is difficult to enlarge thickness and it forms in a thin film form. When the thickness is increased, the atomized powders do not adhere to each other, and the corrosion resistance becomes insufficient. Further, if the thin-film powder-rolled sheet 27 is used as a current collector as it is, the corrosion elongation can be suppressed. For example, in a lead battery for industrial use used for a long period (equivalent to 15 years), The strength will be insufficient. In this embodiment, since the powder rolling sheet 27 is laminated | stacked and the electrical power collector 28 is formed, since thickness increases in the electrical power collector 28, intensity | strength can be ensured. In addition, since the powder rolled sheet 27 is thinner and stronger than the conventional metal sheet, the current collector 28 on which the powder rolled sheet 27 is laminated has a larger thickness, but it is thinner than the metal sheet current collector. can do. For this reason, since the amount of lead resources used as a raw material for the lead battery 28 as a whole is reduced in the thin-film high-strength current collector, the lead resources can be effectively used.

更に、本実施形態では、集電体２８が、積層された粉末圧延シート２７が穴あけ加工またはエキスパンド加工により一体化されている。このため、粉末圧延シート２７間の剥離を抑制し、正極活物質、負極活物質を確実に保持することができ、格子骨格間に形成された空隙に充填される分で活物質保持量を増やすことができる。これにより、集電体２８を用いた鉛電池１の出力性能を確保することができる。従って、鉛電池１では、集電体２８の寿命低下が抑制され、出力性能が確保されるので、電力の安定供給および鉛電池の高信頼化を図ることができる。このような鉛電池１は、入出力性能を確保することに加えて、長寿命化を要求される産業用途に好適に使用することができる。   Further, in the present embodiment, the current collector 28 and the laminated powder rolled sheet 27 are integrated by drilling or expanding. For this reason, peeling between the powder-rolled sheets 27 can be suppressed, the positive electrode active material and the negative electrode active material can be reliably held, and the amount of active material retained is increased by the amount filled in the gap formed between the lattice skeletons. be able to. Thereby, the output performance of the lead battery 1 using the current collector 28 can be ensured. Therefore, in the lead battery 1, since the lifetime reduction of the collector 28 is suppressed and output performance is ensured, stable supply of electric power and high reliability of the lead battery can be achieved. Such a lead battery 1 can be suitably used for industrial applications that require long life in addition to ensuring input / output performance.

また更に、従来の金属シートでは、結晶粒界が外部の腐食因子の影響を受けると粒界腐食が進行しやすくなり、特に、金属偏析物等が存在すると、偏析元素、偏析化合物接触部を起点として腐食反応が進行しやすくなる。これに対して、粉末圧延シート２７では、粒子径が数十μｍのアトマイズ粉末が直接圧延されるため、アスペクト比３〜１３の特定方向に配向した結晶粒を有している。このため、粉末圧延シート２７のアトマイズ粉末粒子間に金属結合部分が形成され、アトマイズ粉末粒子同士の境界には偏析元素が極端に少ない境界層が形成される。これにより、粉末圧延シート２７の腐食が抑制されるので、腐食伸びを抑えることができる。   Furthermore, in conventional metal sheets, when the grain boundaries are affected by external corrosion factors, intergranular corrosion is likely to proceed. In particular, if there are metal segregated materials, segregation elements and segregation compound contact points are the origin. As a result, the corrosion reaction is likely to proceed. In contrast, the powder-rolled sheet 27 has crystal grains oriented in a specific direction with an aspect ratio of 3 to 13 because the atomized powder having a particle size of several tens of μm is directly rolled. For this reason, a metal bond part is formed between the atomized powder particles of the powder rolling sheet 27, and a boundary layer with extremely few segregating elements is formed at the boundary between the atomized powder particles. Thereby, since the corrosion of the powder rolling sheet | seat 27 is suppressed, corrosion elongation can be suppressed.

更にまた、鉛集電体が腐食すると、自らの腐食生成物の一つである鉛酸化物を生成するが、生成した鉛酸化物のうち酸化鉛（ＰｂＯ）を経て形成される過酸化鉛（ＰｂＯ２）が反応活物質のため、結晶粒界に鉛酸化物が存在すると、偏析元素のように腐食が進行する。粉末圧延シート２７では、結晶粒界、結晶粒内に酸化鉛または過酸化鉛の少なくとも一方が含まれている。このため、鉛酸化物が鉛や鉛合金に分散されるので、粒界での腐食が抑えられ、かつ、再結晶が抑制されて新たな粒界成長が抑制されることから、粒界腐食を最小限に抑え、腐食伸びを抑えることができる。 Furthermore, when the lead current collector corrodes, lead oxide, which is one of its own corrosion products, is produced. Among the produced lead oxides, lead peroxide (PbO) formed through lead oxide (PbO) Since PbO 2 ) is a reactive material, if lead oxide is present at the grain boundaries, corrosion proceeds like a segregated element. In the powder rolling sheet 27, at least one of lead oxide or lead peroxide is contained in the crystal grain boundaries and crystal grains. For this reason, since lead oxide is dispersed in lead and lead alloy, corrosion at grain boundaries is suppressed, and recrystallization is suppressed and new grain boundary growth is suppressed. Minimizes corrosion elongation.

なお、本実施形態では、平均放電電圧が３６Ｖ（充電電圧が４２Ｖ）の鉛電池１を例示したが、本発明は、電圧域に制限されるものではない。直列接続する極板群４の数を変えることで、例えば、平均放電電圧が１２Ｖ（充電電圧が１４Ｖ）の鉛電池も作製可能であり、本発明の種々の特性は電圧域で変るものではない。また、鉛電池１の容量を１８Ａｈとする例を示したが、本発明はこれに限定されるものではない。例えば、３００Ａｈ程度の容量を有する産業用鉛電池に適用した場合でも、上述した効果を得ることができる。   In the present embodiment, the lead battery 1 having an average discharge voltage of 36 V (charge voltage is 42 V) is exemplified, but the present invention is not limited to the voltage range. By changing the number of electrode groups 4 connected in series, for example, a lead battery having an average discharge voltage of 12 V (charge voltage: 14 V) can be produced, and various characteristics of the present invention do not change in the voltage range. . Moreover, although the example which sets the capacity | capacitance of the lead battery 1 to 18 Ah was shown, this invention is not limited to this. For example, even when applied to an industrial lead battery having a capacity of about 300 Ah, the above-described effects can be obtained.

また、本実施形態では、集電体２８を形成する粉末圧延シート２７の原料としてＰｂ−Ｓｎ系合金のアトマイズ粉末を用いる例を示したが、本発明はこれに限定されるものではない。Ｐｂ−Ｓｎ系合金以外に、スズ−カルシウム系鉛合金（Ｐｂ−Ｓｎ−Ｃａ系合金）、スズ−アンチモン系鉛合金（Ｐｂ−Ｓｎ−Ｓｂ系合金）、スズ−ストロンチウム系鉛合金（Ｐｂ−Ｓｎ−Ｓｒ系合金）およびスズ−バリウム系鉛合金（Ｐｂ−Ｓｎ−Ｂａ系合金）の粉末を用いることができる。また、粉末圧延シート２７の形成時に、鉛または鉛合金のアトマイズ粉末に加えて、酸化鉛や酸化アルミニウム等の粉末を混合するようにしてもよい。このようにすれば、結晶粒の粗大化が抑制されるため、粉末圧延シート２７の耐食性を向上させることができる。   In this embodiment, an example in which atomized powder of a Pb—Sn alloy is used as a raw material of the powder rolling sheet 27 forming the current collector 28 is shown, but the present invention is not limited to this. Besides Pb-Sn alloy, tin-calcium lead alloy (Pb-Sn-Ca alloy), tin-antimony lead alloy (Pb-Sn-Sb alloy), tin-strontium lead alloy (Pb-Sn) -Sr alloy) and tin-barium lead alloy (Pb-Sn-Ba alloy) powders can be used. Moreover, when forming the powder rolling sheet 27, in addition to the atomized powder of lead or lead alloy, powders such as lead oxide and aluminum oxide may be mixed. In this way, since the coarsening of crystal grains is suppressed, the corrosion resistance of the powder rolled sheet 27 can be improved.

更に、本実施形態では、積層した粉末圧延シート２７を一体化するために穴あけ加工またはエキスパンド加工を施す例を示したが、本発明はこれに限定されるものではなく、積層した粉末圧延シート２７間が剥離しないように一体化されていればよい。本実施形態で例示したように、二つに折りたたむことで剥離を抑制することはできるが、穴あけ加工またはエキスパンド加工を施すことで確実に一体化することができる。   Furthermore, in this embodiment, an example in which drilling or expanding is performed to integrate the laminated powder rolled sheet 27 is shown, but the present invention is not limited to this, and the laminated powder rolled sheet 27 is not limited thereto. What is necessary is just to integrate so that a space | interval may not peel. As illustrated in this embodiment, peeling can be suppressed by folding in two, but it can be reliably integrated by performing drilling or expanding.

また更に、本実施形態では、集電体２８として粉末圧延シート２７を二つ折りにして二重に積層した例を示したが、本発明はこれに限定されるものではない。例えば、三つ折りや四つ折りとしてもよく、矩形状等に裁断した粉末圧延シートの複数枚を積層するようにしてもよい。また、二重に積層する以外に三重以上に積層してもよい。   Furthermore, in the present embodiment, an example is shown in which the powder rolled sheet 27 is folded in half as the current collector 28 and laminated twice, but the present invention is not limited to this. For example, it may be tri-folded or quadruple-folded, and a plurality of powder-rolled sheets cut into a rectangular shape or the like may be laminated. Moreover, you may laminate | stack in more than triple besides laminating | stacking twice.

本発明は長期にわたって寿命を確保することができる鉛電池および該鉛電池の製造方法を提供するため、鉛電池の製造、販売に寄与するので、産業上の利用可能性を有する。   The present invention contributes to the manufacture and sales of lead batteries in order to provide a lead battery and a method for manufacturing the lead battery that can ensure a long-term life, and thus has industrial applicability.

本発明を適用した実施形態の鉛電池を一部破断して示す斜視図である。1 is a perspective view showing a partially broken lead battery according to an embodiment to which the present invention is applied. 実施形態の鉛電池を構成する集電体の製造過程での状態を示す断面図であり、（Ａ）は粉末圧延装置でアトマイズ粉末を圧延することにより粉末圧延シートを形成したときの状態、（Ｂ）は粉末圧延シートを二つに折りたたむときの状態、（Ｃ）は粉末圧延シートが二つに折り折りたたまれることで二重に積層された状態をそれぞれ示す。It is sectional drawing which shows the state in the manufacture process of the electrical power collector which comprises the lead battery of embodiment, (A) is a state when forming a powder rolling sheet | seat by rolling atomized powder with a powder rolling apparatus, ( B) shows a state when the powder-rolled sheet is folded in two, and (C) shows a state where the powder-rolled sheet is folded in two so as to be double-layered.

符号の説明Explanation of symbols

１ 正極板
２ 負極板
２０ 鉛電池
２７ 粉末圧延シート
２８ 集電体 DESCRIPTION OF SYMBOLS 1 Positive electrode plate 2 Negative electrode plate 20 Lead battery 27 Powder rolling sheet 28 Current collector

Claims (5)

集電体に活物質が保持された極板を備えた鉛電池において、前記集電体は、鉛粉末または鉛合金粉末を主体とする粉末を圧延してシート状に形成した粉末圧延シートが積層されたものであり、前記積層された粉末圧延シートが穴あけ加工またはエキスパンド加工により一体化されていることを特徴とする鉛電池。   In a lead battery having an electrode plate in which an active material is held on a current collector, the current collector is formed by laminating a powder rolling sheet formed by rolling a powder mainly composed of lead powder or lead alloy powder. A lead battery characterized in that the laminated powder rolled sheets are integrated by drilling or expanding. 前記集電体は、前記粉末圧延シートが折りたたまれることにより積層されたものであることを特徴とする請求項１に記載の鉛電池。   The lead battery according to claim 1, wherein the current collector is laminated by folding the powder rolling sheet. 前記粉末圧延シートは、アスペクト比３〜１３の特定方向に配向した結晶粒を有し、結晶粒界、結晶粒内に酸化鉛または過酸化鉛の少なくとも一方を含むことを特徴とする請求項１に記載の鉛電池。   The powder-rolled sheet has crystal grains oriented in a specific direction with an aspect ratio of 3 to 13, and includes at least one of lead oxide or lead peroxide in the crystal grain boundaries and crystal grains. Lead battery described in 1. 前記粉末圧延シートは、スズ鉛合金、スズ−カルシウム系鉛合金、スズ−アンチモン系鉛合金、スズ−ストロンチウム系鉛合金およびスズ−バリウム系鉛合金から選択される一種以上の粉末を圧延してシート状に形成したものであることを特徴とする請求項３に記載の鉛電池。   The powder rolled sheet is a sheet obtained by rolling at least one powder selected from a tin lead alloy, a tin-calcium lead alloy, a tin-antimony lead alloy, a tin-strontium lead alloy, and a tin-barium lead alloy. The lead battery according to claim 3, wherein the lead battery is formed in a shape. 集電体に活物質が保持された極板を備えた鉛電池の製造方法であって、
鉛粉末または鉛合金粉末を主体とする粉末を圧延してシート状に形成した粉末圧延シートを積層する積層ステップと、
前記積層ステップで積層した粉末圧延シートに穴あけ加工またはエキスパンド加工を施し一体化した集電体を形成する集電体形成ステップと、
前記集電体形成ステップで形成した集電体に前記活物質を塗着する塗着ステップと、
を含むことを特徴とする製造方法。 A method of manufacturing a lead battery including an electrode plate in which an active material is held on a current collector,
Lamination step of laminating a powder rolling sheet formed by rolling a powder mainly composed of lead powder or lead alloy powder,
A current collector forming step for forming a current collector integrated by performing drilling or expanding on the powder rolled sheet laminated in the laminating step;
A coating step of coating the active material on the current collector formed in the current collector forming step;
The manufacturing method characterized by including.
JP2007312115A 2007-12-03 2007-12-03 Lead acid battery and manufacturing method of lead acid battery Pending JP2009135061A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007312115A JP2009135061A (en) 2007-12-03 2007-12-03 Lead acid battery and manufacturing method of lead acid battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2007312115A JP2009135061A (en) 2007-12-03 2007-12-03 Lead acid battery and manufacturing method of lead acid battery

Publications (1)

Publication Number Publication Date
JP2009135061A true JP2009135061A (en) 2009-06-18

Family

ID=40866737

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2007312115A Pending JP2009135061A (en) 2007-12-03 2007-12-03 Lead acid battery and manufacturing method of lead acid battery

Country Status (1)

Country Link
JP (1) JP2009135061A (en)

Similar Documents

Publication Publication Date Title
EP2822076B1 (en) Electrode assembly, and battery cell and device comprising same
EP2471129B1 (en) Electrical storage device and electrode thereof
US20160336593A1 (en) Electrical device
JP2015506563A (en) Electrode assembly comprising electrode units having the same overall width and different overall lengths, battery cell including the same, and device
JPH10270013A (en) Electrode for nonaqueous electrolyte secondary battery and its manufacture
US11799069B2 (en) Intermittently coated dry electrode for energy storage device and method of manufacturing the same
JP7261995B2 (en) All-solid-state battery and manufacturing method thereof
CN110192300A (en) Laminated secondary cell and its manufacturing method and apparatus
US6371997B1 (en) Method for manufacturing lithium polymer secondary battery and lithium polymer secondary battery made by the method
EP3098890B1 (en) Electrical device
JP5050564B2 (en) Current collector for positive electrode or negative electrode of lead acid battery and method for producing the same, lead acid battery and method for producing the same
EP0994522A2 (en) Lithium polymer battery
JP5600940B2 (en) Lead battery
JP2009135061A (en) Lead acid battery and manufacturing method of lead acid battery
JP2003338310A (en) Lead storage battery
JP2002075433A (en) Cell
JP5088666B2 (en) Lead-acid battery, lead-acid battery current collector and method for producing the same
KR100445416B1 (en) Battery collector capable of preventing short circuit and separation of active materials, and manufacturing method thereof
JP2009193835A (en) Lead-acid battery, and manufacturing method thereof
JPH04167373A (en) Lithium cell
JP2009158244A (en) Lead-acid storage battery
JP2009295317A (en) Cylindrical alkaline storage battery and method of manufacturing the same
JPH05290834A (en) Electrode plate for lead-acid battery and manufacture thereof