JP3648780B2 - Method for manufacturing current collector for sealed lead-acid battery - Google Patents

Method for manufacturing current collector for sealed lead-acid battery Download PDF

Info

Publication number
JP3648780B2
JP3648780B2 JP02653595A JP2653595A JP3648780B2 JP 3648780 B2 JP3648780 B2 JP 3648780B2 JP 02653595 A JP02653595 A JP 02653595A JP 2653595 A JP2653595 A JP 2653595A JP 3648780 B2 JP3648780 B2 JP 3648780B2
Authority
JP
Japan
Prior art keywords
current collector
protrusions
lead
acid battery
molten
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.)
Expired - Fee Related
Application number
JP02653595A
Other languages
Japanese (ja)
Other versions
JPH08222230A (en
Inventor
有彦 武政
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.)
Shin Kobe Electric Machinery Co Ltd
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 JP02653595A priority Critical patent/JP3648780B2/en
Publication of JPH08222230A publication Critical patent/JPH08222230A/en
Application granted granted Critical
Publication of JP3648780B2 publication Critical patent/JP3648780B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related 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

Landscapes

  • Cell Electrode Carriers And Collectors (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Description

【０００１】
【産業上の利用分野】
本発明は、密閉形鉛蓄電池用集電体の製造方法に関するものである。
【０００２】
【従来の技術】
従来の密閉形鉛蓄電池用集電体は、鋳型に鉛又は鉛合金を流し込んで形成した厚さ１〜６mm程度の鋳造格子体からなるもの、厚さ１〜２mm程度の鉛又は鉛合金シート若しくはフィルムの所々に切れ目を入れ、これら切れ目を延ばすことにより格子状にしたエキスパンド格子体からなるものであった。
【０００３】
しかしながら、エキスパンド格子体は鋳造格子体に比べると、構造材としての強度が小さく、延び（ｇｒｏｗｔｈ）が問題になるので、一般的に正極板に用いられることは少ない。
【０００４】
以上のような格子状の集電体に、主に一酸化鉛からなるペースト状物質を充填し、その後に熟成，化成工程を経ることによって発電に必要な活物質とした極板を得ることができる。この場合、集電体は、集電機能の他に、活物質保持機能が要求される。
【０００５】
一方、密閉形鉛蓄電池の小形、軽量化を図るには極板の薄型化が必要であるが、鋳造により厚さ１mm以下の格子の製造は非常に困難で、且つ製造工程上扱い難い。
【０００６】
そこで、格子状の集電体の代わりに、図６に示すように、薄いシート状若しくはフィルム状の集電体１ａ，１ｂを用い、この集電体１ａの表面を覆うように正極活物質２ａを配置して正極板３ａを構成し、また集電体１ｂの表面を覆うように負極活物質２ｂを配置して負極板３ｂを構成し、これら正極板３ａと負極板３ｂとをその正極活物質２ａと負極活物質２ｂとが向かい合うようにしてガラス繊維不織布からなる隔離体４を介して対向配置することにより極板群５を構成し、該極板群５をフィルム状若しくはシート状の樹脂からなる電槽６内に収容して密閉形鉛蓄電池を構成することが提案されている（特開平２−６００６８号公報）。
【０００７】
このようにシート状若しくはフィルム状の集電体１ａ，１ｂを用いると、密閉形鉛蓄電池の小形、軽量化を図る上で有利である。
【０００８】
【発明が解決しようとする課題】
しかしながら、このようにシート状若しくはフィルム状の集電体１ａ，１ｂを用いた場合、格子状の集電体を用いた場合に比べ、充放電中に集電体１ａ，１ｂから活物質２ａ，２ｂが剥離し易く、密閉形鉛蓄電池の寿命が短いという問題点がある。これは活物質２ａ，２ｂが充放電中に膨脹，収縮するので、シート状若しくはフィルム状のような平板状の集電体１ａ，１ｂでは、活物質２ａ，２ｂの膨脹，収縮時の動きを抑える作用がないためである。
【０００９】
本発明の目的は、シート状若しくはフィルム状をしていても活物質の剥離を防止できる密閉形鉛蓄電池用集電体の製造方法を提供することにある。
【００１０】
【課題を解決するための手段】
請求項１に記載の密閉形鉛蓄電池用集電体の製造方法は、上部に複数個の小孔を有する容器の中に溶融した鉛又は鉛合金を入れ、前記各小孔から前記溶融した鉛又は鉛合金を押し出して突起をそれぞれ形成し、これら突起の上にシート状若しくはフィルム状の集電体本体を接触させ、かかる状態で前記集電体本体を引き上げることにより前記集電体本体に前記各突起が一体化された集電体を形成することを特徴とする。
請求項２に記載の密閉形鉛蓄電池用集電体の製造方法は、シート状若しくはフィルム状の集電体本体の突起を設ける予定箇所以外の表面に予め酸化被膜を形成し、上部に複数個の小孔を有する容器の中に溶融した鉛又は鉛合金を入れ、前記各小孔から前記溶融した鉛又は鉛合金を押し出して突起をそれぞれ形成し、これら突起の上に前記集電体本体をその各突起を設ける予定箇所を対応させて接触させ、かかる状態で前記集電体本体を引き上げることにより前記集電体本体に前記各突起が一体化された集電体を形成することを特徴とする。
請求項３に記載の密閉形鉛蓄電池用集電体の製造方法は、シート状若しくはフィルム状の集電体本体の突起を設ける予定箇所にゴム状板の各突起を当ててマスクしてこれら突起を設ける予定箇所以外の表面に予め酸化被膜を形成し、上部に複数個の小孔を有する容器の中に溶融した鉛又は鉛合金を入れ、前記各小孔から前記溶融した鉛又は鉛合金を押し出して突起をそれぞれ形成し、これら突起の上に前記集電体本体をその各突起を設ける予定箇所を対応させて接触させ、かかる状態で前記集電体本体を引き上げることにより前記集電体本体に前記各突起が一体化された集電体を形成することを特徴とする。
請求項４に記載の密閉形鉛蓄電池用集電体の製造方法は、請求項１，２，３のいずれか１つにおいて、前記集電体本体を前記各突起に接触させる際に前記集電体本体の他の面を冷却手段で冷却することを特徴とする。
【００１１】
【作用】
請求項１に記載の密閉形鉛蓄電池用集電体の製造方法は、上部に複数個の小孔を有する容器の中に溶融した鉛又は鉛合金を入れ、各小孔から溶融した鉛又は鉛合金を押し出して突起をそれぞれ形成し、これら突起の上にシート状若しくはフィルム状の集電体本体を接触させ、かかる状態で集電体本体を引き上げることにより該集電体本体に各突起が一体化された集電体を形成する方法をとるので、各小孔から溶融した鉛又は鉛合金を押し出すことにより、溶融した鉛又は鉛合金は表面張力により球状の形をとり、このため球状の各突 起が付いた集電体の形成を容易に行うことができる。
請求項２に記載の密閉形鉛蓄電池用集電体の製造方法は、シート状若しくはフィルム状の集電体本体の突起を設ける予定箇所以外の表面に予め酸化被膜を形成し、上部に複数個の小孔を有する容器の中に溶融した鉛又は鉛合金を入れ、各小孔から溶融した鉛又は鉛合金を押し出して突起をそれぞれ形成し、これら突起の上に集電体本体をその各突起を設ける予定箇所を対応させて接触させ、かかる状態で集電体本体を引き上げることにより該集電体本体に各突起が一体化された集電体を形成する方法をとるので、集電体本体に酸化被膜を設けたところでは溶融した鉛又は鉛合金の濡れ性が悪くなり、このため表面張力で球状をなしている溶融状態の各突起を集電体本体に接触させて一体化するときに、これら溶融状態の各突起が平面状に広がってしまうのを防止しつつ、球状の各突起が付いた集電体の形成を容易に行うことができる。
請求項３に記載の密閉形鉛蓄電池用集電体の製造方法は、シート状若しくはフィルム状の集電体本体の突起を設ける予定箇所にゴム状板の各突起を当ててマスクしてこれら突起を設ける予定箇所以外の表面に予め酸化被膜を形成し、上部に複数個の小孔を有する容器の中に溶融した鉛又は鉛合金を入れ、各小孔から溶融した鉛又は鉛合金を押し出して突起をそれぞれ形成し、これら突起の上に集電体本体をその各突起を設ける予定箇所を対応させて接触させ、かかる状態で集電体本体を引き上げることにより該集電体本体に各突起が一体化された集電体を形成する方法をとるので、集電体本体の突起を設ける各予定箇所にゴム状板の各突起を当てつつ該集電体本体の他の表面に酸化被膜を形成ことにより、突起を設ける各予定箇所に酸化被膜が形成されるのを防止でき、このため表面張力で球状をなしている溶融状態の各突起を集電体本体に接触させて一体化するときに、これら溶融状態の各突起が平面状に広がってしまうのを防止しつつ、突起を設ける各予定箇所に確実に球状の各突起を一体化させて、球状の突起が付いた集電体の形成を容易に行うことができる。
請求項４に記載の密閉形鉛蓄電池用集電体の製造方法では、集電体本体を各突起に接触させる際に該集電体本体の他の面を冷却手段で冷却する方法をとるので、各突起の冷却速度が速くなり、球状の各突起を球状のまま確実に集電体本体と一体化させることができる。
【００１２】
【実施例】
図１は、本発明に係る密閉形鉛蓄電池用集電体７の一実施例を示したものである。
【００１３】
本実施例の密閉形鉛蓄電池用集電体７は、鉛又は鉛合金よりなるシート状若しくはフィルム状の集電体本体８の片側表面の複数箇所に鉛又は鉛合金よりなる突起９が一体に設けられた構造になっている。この場合、各突起９は、図示のようにおおむね球状をしていることが好ましい。
【００１４】
このような密閉形鉛蓄電池用集電体７は、集電体本体８の表面に複数の突起９が設けられているので、これら突起９側で該集電体本体８に配置される活物質の剥離をこれら突起９で抑制することができ、サイクル寿命性能の優れた電池を得ることができる。また、これら突起９は、集電能力の向上にも寄与するので、この面でも電池性能を向上させることができる。
【００１５】
図２は、本発明に係る密閉形鉛蓄電池用極板１０の一実施例を示したものである。
【００１６】
本実施例の密閉形鉛蓄電池用極板１０は、鉛又は鉛合金よりなるシート状若しくはフィルム状の集電体本体８の片側表面の複数箇所に鉛又は鉛合金よりなる突起９が一体に設けられている集電体７に、各突起９が埋没するように活物質１１が配置された構造になっている。この場合も、各突起９は、図示のようにおおむね球状をしていることが好ましい。
【００１７】
このような密閉形鉛蓄電池用極板１０は、集電体本体８の表面に各突起９が一体に設けられている集電体７に、これら突起９が埋没するように活物質１１が配置された構造になっているので、これら突起９で活物質１１の剥離を抑制することができ、サイクル寿命性能の優れた電池を得ることができる。また、これら突起９は、集電能力の向上にも寄与するので、この面でも電池性能を向上させることができる。
【００１８】
図３は、本発明に係る密閉形鉛蓄電池の一実施例を示したものである。
【００１９】
本実施例の密閉形鉛蓄電池は、鉛又は鉛合金よりなるシート状若しくはフィルム状の集電体本体８ａ，８ｂの片側表面の複数箇所に鉛又は鉛合金よりなる突起９ａ，９ｂが一体に設けられている集電体７ａ，７ｂを用い、この集電体７ａに各突起９ａが埋没するように正極活物質１１ａが配置されて正極板１０ａが構成され、また集電体７ｂに各突起９ｂが埋没するように負極活物質１１ｂが配置されて負極板１０ｂが構成され、これら正極板１０ａと負極板１０ｂとがその正極活物質１１ａと負極活物質１１ｂとが向かい合うようにしてガラス繊維不織布からなる隔離体４を介して対向配置されることによりして極板群５が構成され、該極板群５がフィルム状若しくはシート状の樹脂からなる電槽６内に収容された構造になっている。
【００２０】
このような密閉形鉛蓄電池は、集電体本体８ａ，８ｂの表面の複数箇所に突起９ａ，９ｂが一体に設けられている集電体７ａ，７ｂに、これら突起９ａ，９ｂが埋没するように活物質１１ａ，１１ｂが配置された構造になっている極板１０ａ，１０ｂを用いて形成されているので、これら突起９ａ，９ｂで活物質１１ａ，１１ｂの剥離を抑制することができ、サイクル寿命性能の優れた電池を得ることができる。また、これら突起９ａ，９ｂは、集電能力の向上にも寄与するので、この面でも電池性能を向上させることができる。
【００２１】
次に、本発明に係る密閉形鉛蓄電池の構造の一例を図３を参照してより具体的に説明する。
【００２２】
集電体本体８ａ，８ｂは、Ｐｂ−Ｓｎ合金からなる厚さ 200μｍ、縦 140mm，横66mmのシート状のもので、その表面にＰｂ−Ｓｎ合金からなる直径約１mmの球状の突起９ａ，９ｂを一定間隔で32個設けて集電体７ａ，７ｂを構成している。集電体７ａには各突起９ａが埋め込まれるように正極活物質１１ａが充填されて正極板１０ａが構成されている。また、集電体７ｂには各突起９ｂが埋め込まれるように負極活物質１１ｂが充填されて負極板１０ｂが構成されている。これら正極板１０ａと負極板１０ｂとは、ガラス繊維不織布からなる隔離体４を介して正極活物質１１ａと負極活物質１１ｂとが向かい合うように配置されて極板群５が構成され、該極板群５がフィルム状若しくはシート状の樹脂からなる電槽６内に収容されて２Ｖ，３Ａｈの密閉形鉛蓄電池が構成されている。この密閉形鉛蓄電池を本発明品と称する。
【００２３】
この本発明品と、図６に示すような表面に突起を設けてない従来の集電体１ａ，１ｂを用いた密閉形鉛蓄電池（これを従来品と称する。）とのサイクル寿命試験を行った。
【００２４】
図４は、そのサイクル寿命試験結果を示したものである。試験条件は、１ＣＡの定電流で、1.6 Ｖ／セルまで放置し、その後制限電流0.6 ＣＡ，2.5 Ｖ／セルの定電圧で3.5 ｈ充電を行うパターンを１サイクルとした。該図に示したとおり、本発明品のサイクル寿命性能が従来品に比べ良くなっているのがわかる。従来品が寿命になった時点で本発明品と共に解体し、正極板断面を観察してみると、本発明品の場合は集電体から活物質の剥離が従来品に対し10％以下に抑えられていた。
【００２５】
図５は、本発明に係る密閉形鉛蓄電池用集電体の製造方法を示したものである。まず、溶融したＰｂ−Ｓｎ合金１２を容器１３に入れる。該容器１３は一方側の平坦な上面板１４に、集電体本体８に設ける突起９の数と同じだけの数の小孔１５を設ける。この容器１０の他方には、絞り部１６を介して上向きの筒状の加圧部１７を設ける。この筒状の加圧部１７の上向き開口部にはピストンよりなる加圧手段１８を設ける。
【００２６】
かかる構造で、加圧手段１８により溶融したＰｂ−Ｓｎ合金１２に圧力をかけ、各小孔１５から溶融したＰｂ−Ｓｎ合金１２を上面板１４の表面に押し出すと、溶融したＰｂ−Ｓｎ合金１２は表面張力によりそれぞれおおむね球状の突起９となる。
【００２７】
次に、これら突起９の上に集電体本体８を接触させ、加圧手段１８で容器１３内の溶融したＰｂ−Ｓｎ合金１２に圧力をかけながら集電体本体８を上方に引き上げることにより集電体本体８上に突起９を一体に形成する。
【００２８】
しかし、ただ単に溶融したＰｂ−Ｓｎ合金１２の突起９を集電体本体８に接触した場合、溶融状態のＰｂ−Ｓｎ合金１２の突起９が集電体本体８の表面に濡れ広がって球状とはならない。
【００２９】
そこで、次のような手段をとることにより、集電体本体８の表面に球状の突起９を形成させる。まず、集電体本体８の突起９が設けられる各予定箇所の表面をマスクして、例えば突起を有するゴム状板を集電体本体８に当て、その後高温，高湿度雰囲気に集電体本体８を放置する。これにより集電体本体８の突起９を設ける予定箇所以外の表面に酸化被膜が形成されて、突起９を設ける際の溶融したＰｂ−Ｓｎ合金１２の濡れ性が悪くなり、突起９を設ける予定箇所のみは濡れ性が良いため、その部分に球状の突起９を確実に設けることができる。
【００３０】
また、集電体本体８の突起９を設けない方の面に冷却板よりなる冷却手段１９を当てることにより冷却速度を速め、球状のまま突起９を凝固させる。
【００３１】
【発明の効果】
本発明に係る密閉形鉛蓄電池用集電体の製造方法によれば、下記のような優れた効果を得ることができる。
【００３２】
請求項１に記載の密閉形鉛蓄電池用集電体の製造方法は、上部に複数個の小孔を有する容器の中に溶融した鉛又は鉛合金を入れ、各小孔から溶融した鉛又は鉛合金を押し出して突起をそれぞれ形成し、これら突起の上にシート状若しくはフィルム状の集電体本体を接触させ、かかる状態で集電体本体を引き上げることにより該集電体本体に各突起が一体化された集電体を形成する方法をとるので、各小孔から溶融した鉛又は鉛合金を押し出すことにより、溶融した鉛又は鉛合金は表面張力により球状の形をとり、このため球状の各突起が付いた集電体の形成を容易に行うことができる。
請求項２に記載の密閉形鉛蓄電池用集電体の製造方法は、シート状若しくはフィルム状の集電体本体の突起を設ける予定箇所以外の表面に予め酸化被膜を形成し、上部に複数個の小孔を有する容器の中に溶融した鉛又は鉛合金を入れ、各小孔から溶融した鉛又は鉛合金を押し出して突起をそれぞれ形成し、これら突起の上に集電体本体をその各突起を設ける予定箇所を対応させて接触させ、かかる状態で集電体本体を引き上げることにより該集電体本体に各突起が一体化された集電体を形成する方法をとるので、集電体本体に酸化被膜を設けたところでは溶融した鉛又は鉛合金の濡れ性が悪くなり、このため表面張力で球状をなしている溶融状態の各突起を集電体本体に接触させて一体化するときに、これら溶融状態の各突起が平面状に広がってしまうのを防止しつつ、球状の各突起が付いた集電体の形成を容易に行うことができる。
請求項３に記載の密閉形鉛蓄電池用集電体の製造方法は、シート状若しくはフィルム状 の集電体本体の突起を設ける予定箇所にゴム状板の各突起を当ててマスクしてこれら突起を設ける予定箇所以外の表面に予め酸化被膜を形成し、上部に複数個の小孔を有する容器の中に溶融した鉛又は鉛合金を入れ、各小孔から溶融した鉛又は鉛合金を押し出して突起をそれぞれ形成し、これら突起の上に集電体本体をその各突起を設ける予定箇所を対応させて接触させ、かかる状態で集電体本体を引き上げることにより該集電体本体に各突起が一体化された集電体を形成する方法をとるので、集電体本体の突起を設ける各予定箇所にゴム状板の各突起を当てつつ該集電体本体の他の表面に酸化被膜を形成ことにより、突起を設ける各予定箇所に酸化被膜が形成されるのを防止でき、このため表面張力で球状をなしている溶融状態の各突起を集電体本体に接触させて一体化するときに、これら溶融状態の各突起が平面状に広がってしまうのを防止しつつ、突起を設ける各予定箇所に確実に球状の各突起を一体化させて、球状の突起が付いた集電体の形成を容易に行うことができる。
請求項４に記載の密閉形鉛蓄電池用集電体の製造方法では、集電体本体を各突起に接触させる際に該集電体本体の他の面を冷却手段で冷却する方法をとるので、各突起の冷却速度が速くなり、球状の各突起を球状のまま確実に集電体本体と一体化させることができる。
【図面の簡単な説明】
【図１】 本発明に係る密閉形鉛蓄電池用集電体の一実施例を示した横断面図である。
【図２】 本発明に係る密閉形鉛蓄電池用極板の一実施例を示した横断面図である。
【図３】 本発明に係る密閉形鉛蓄電池の一実施例を示した横断面図である。
【図４】 本発明に係る密閉形鉛蓄電池と従来の密閉形鉛蓄電池とのサイクル寿命特性の比較図である。
【図５】 本発明に係る密閉形鉛蓄電池用集電体の製造方法を示した横断面図である。
【図６】 従来の密閉形鉛蓄電池の横断面図である。
【符号の説明】
１ａ，１ｂ 集電体
２ａ 正極活物質
２ｂ 負極活物質
３ａ 正極板
３ｂ 負極板
４ 隔離体
５ 極板群
６ 電槽
７，７ａ，７ｂ 集電体
８，８ａ，８ｂ 集電体本体
９，９ａ，９ｂ 突起
１０ 密閉形鉛蓄電池用極板
１１ 活物質
１１ａ 正極活物質
１１ｂ 負極活物質
１２ Ｐｂ−Ｓｎ合金
１３ 容器
１４ 上面板
１５ 小孔
１６ 絞り部
１７ 加圧部
１８ 加圧手段
１９ 冷却手段[0001]
[Industrial application fields]
The present invention relates to a method for producing a current collector for a sealed lead-acid battery.
[0002]
[Prior art]
Conventional current collectors for sealed lead-acid batteries are composed of a cast grid having a thickness of about 1 to 6 mm formed by pouring lead or a lead alloy into a mold, a lead or lead alloy sheet having a thickness of about 1 to 2 mm, or The film was made of an expanded lattice that was cut into portions of the film and formed into a lattice by extending these cuts.
[0003]
However, the expanded lattice body is less used as a positive electrode plate because the strength as a structural material is small and the growth becomes a problem as compared with the cast lattice body.
[0004]
It is possible to obtain an electrode plate as an active material necessary for power generation by filling a grid-like current collector as described above with a paste-like substance mainly composed of lead monoxide and then performing an aging and chemical conversion process. it can. In this case, the current collector is required to have an active material holding function in addition to the current collecting function.
[0005]
On the other hand, in order to reduce the size and weight of the sealed lead-acid battery, it is necessary to make the electrode plate thin. However, it is very difficult to manufacture a grid having a thickness of 1 mm or less by casting, and it is difficult to handle in the manufacturing process.
[0006]
Therefore, instead of the grid-shaped current collector, as shown in FIG. 6, thin sheet or film-shaped current collectors 1a and 1b are used, and the positive electrode active material 2a is covered so as to cover the surface of the current collector 1a. Is arranged to form the positive electrode plate 3a, and the negative electrode active material 2b is arranged so as to cover the surface of the current collector 1b to form the negative electrode plate 3b, and the positive electrode plate 3a and the negative electrode plate 3b are connected to the positive electrode active material. An electrode plate group 5 is formed by disposing the material 2a and the negative electrode active material 2b so as to face each other through a separator 4 made of a glass fiber nonwoven fabric, and the electrode plate group 5 is formed into a film-like or sheet-like resin. It has been proposed that a sealed lead-acid battery is configured by being housed in a battery case 6 made of (Japanese Patent Laid-Open No. 2-60068).
[0007]
Using the sheet-like or film-like current collectors 1a and 1b as described above is advantageous in reducing the size and weight of the sealed lead-acid battery.
[0008]
[Problems to be solved by the invention]
However, when the sheet-like or film-like current collectors 1a and 1b are used in this way, the current collectors 1a and 1b are changed from the current collectors 1a and 1b during charging and discharging, compared to the case where the grid-like current collector is used. There is a problem that 2b is easy to peel off and the life of the sealed lead-acid battery is short. This is because the active materials 2a and 2b expand and contract during charging / discharging, and the plate-like current collectors 1a and 1b, such as sheet or film, cause the movement of the active materials 2a and 2b during expansion and contraction. This is because there is no action to suppress.
[0009]
The objective of this invention is providing the manufacturing method of the electrical power collector for sealed lead acid batteries which can prevent peeling of an active material, even if it is a sheet form or a film form .
[0010]
[Means for Solving the Problems]
The method of manufacturing a current collector for a sealed lead-acid battery according to claim 1, wherein molten lead or a lead alloy is placed in a container having a plurality of small holes in the upper portion, and the molten lead is introduced from each of the small holes. Alternatively, a lead alloy is extruded to form protrusions, a sheet-like or film-like current collector body is brought into contact with the protrusions, and the current collector body is pulled up in this state to bring the current collector body into the current collector body. A current collector is formed by integrating the protrusions.
The method for manufacturing a current collector for a sealed lead-acid battery according to claim 2 is characterized in that an oxide film is formed in advance on the surface of the sheet-shaped or film-shaped current collector main body other than where the projections are to be provided, The molten lead or lead alloy is put into a container having small holes, and the molten lead or lead alloy is extruded from the small holes to form protrusions, and the current collector body is formed on the protrusions. It is characterized by forming a current collector in which the protrusions are integrated with the current collector body by bringing the current collector body in this state by bringing the current protrusions into contact with each other where the respective protrusions are to be provided. To do.
The method for producing a current collector for a sealed lead-acid battery according to claim 3 masks the protrusions of the rubber-like plate by applying the protrusions on the rubber-like plate to the positions where the protrusions of the sheet-like or film-like current collector body are to be provided. An oxide film is formed in advance on the surface other than the planned location, and molten lead or a lead alloy is put in a container having a plurality of small holes in the upper portion, and the molten lead or lead alloy is introduced from each of the small holes. Protrusions are formed by extrusion, and the current collector main body is brought into contact with the current collector main body corresponding to the locations where the respective protrusions are to be provided, and the current collector main body is pulled up in such a state. A current collector in which the protrusions are integrated is formed.
The method for producing a current collector for a sealed lead-acid battery according to claim 4 is characterized in that, in any one of claims 1, 2, and 3, the current collector is brought into contact with each of the protrusions when the current collector body is brought into contact with the protrusions. The other surface of the body body is cooled by a cooling means.
[0011]
[Action]
The method for manufacturing a current collector for a sealed lead-acid battery according to claim 1, wherein molten lead or a lead alloy is placed in a container having a plurality of small holes in the upper portion, and the molten lead or lead is obtained from each small hole. Protrusions are formed by extruding the alloy, and a sheet-like or film-like current collector main body is brought into contact with the protrusions. In this state, the current collector main body is pulled up so that each protrusion is integrated with the current collector main body. Therefore, by extruding the molten lead or lead alloy from each small hole, the molten lead or lead alloy takes a spherical shape due to the surface tension. the collision caused is marked with formation of the current collector can be easily performed.
The method for manufacturing a current collector for a sealed lead-acid battery according to claim 2 is characterized in that an oxide film is formed in advance on the surface of the sheet-shaped or film-shaped current collector main body other than where the projections are to be provided, The molten lead or lead alloy is put into a container having a small hole, and the molten lead or lead alloy is extruded from each small hole to form protrusions, and the current collector body is placed on each of the protrusions. The current collector body has a method of forming a current collector in which the protrusions are integrated with the current collector body by pulling up the current collector body in such a state. When the oxide film is provided on the surface, the wettability of the molten lead or lead alloy deteriorates. For this reason, when the molten projections having a spherical shape due to the surface tension are brought into contact with the current collector body to be integrated. These projections in the molten state are spread in a planar shape. While preventing it would of, it is possible to easily form the current collectors with the protrusions spherical.
The method for producing a current collector for a sealed lead-acid battery according to claim 3 masks the protrusions of the rubber-like plate by applying the protrusions on the rubber-like plate to the positions where the protrusions of the sheet-like or film-like current collector body are to be provided. An oxide film is formed in advance on the surface other than the planned location, and molten lead or lead alloy is put in a container having a plurality of small holes in the upper part, and the molten lead or lead alloy is extruded from each small hole. Protrusions are formed, and the current collector main body is brought into contact with the protrusions in correspondence with the locations where the respective protrusions are to be provided. In this state, the current collector main body is pulled up so that the protrusions are formed on the current collector main body. Since the method of forming an integrated current collector is adopted, an oxide film is formed on the other surface of the current collector body while applying each protrusion of the rubber-like plate to each predetermined position where the protrusion of the current collector body is provided. Oxide film at each planned location to provide protrusions Therefore, when the molten projections having a spherical shape due to the surface tension are brought into contact with the current collector body and integrated, the molten projections spread in a plane. It is possible to easily form the current collector with the spherical protrusions by securely integrating the spherical protrusions at each predetermined place where the protrusions are provided.
In the method for producing a current collector for a sealed lead-acid battery according to claim 4, when the current collector body is brought into contact with each protrusion, the other surface of the current collector body is cooled by a cooling means. The cooling rate of each protrusion is increased, and each spherical protrusion can be reliably integrated with the current collector main body while maintaining the spherical shape.
[0012]
【Example】
FIG. 1 shows an embodiment of a current collector 7 for a sealed lead-acid battery according to the present invention.
[0013]
In the sealed lead-acid battery current collector 7 of this embodiment, protrusions 9 made of lead or lead alloy are integrally formed at a plurality of locations on one side surface of a sheet-like or film-like current collector body 8 made of lead or lead alloy. It has a provided structure. In this case, it is preferable that each protrusion 9 has a substantially spherical shape as illustrated.
[0014]
In such a sealed lead-acid battery current collector 7, a plurality of protrusions 9 are provided on the surface of the current collector body 8, so that the active material disposed on the current collector body 8 on the protrusion 9 side. Can be suppressed by these protrusions 9, and a battery having excellent cycle life performance can be obtained. Moreover, since these protrusions 9 contribute to the improvement of the current collecting ability, the battery performance can be improved also in this aspect.
[0015]
FIG. 2 shows an embodiment of an electrode plate 10 for a sealed lead-acid battery according to the present invention.
[0016]
The electrode plate 10 for a sealed lead-acid battery of the present embodiment is integrally provided with protrusions 9 made of lead or lead alloy at a plurality of locations on one side surface of a sheet-like or film-like current collector body 8 made of lead or lead alloy. The active material 11 is arranged in the current collector 7 so that each protrusion 9 is buried. Also in this case, it is preferable that each protrusion 9 has a substantially spherical shape as shown in the drawing.
[0017]
In such a sealed lead-acid battery electrode plate 10, the active material 11 is arranged so that the protrusions 9 are buried in the current collector 7 in which the protrusions 9 are integrally provided on the surface of the current collector body 8. Because of the above structure, it is possible to suppress the peeling of the active material 11 with these protrusions 9 and to obtain a battery with excellent cycle life performance. Moreover, since these protrusions 9 contribute to the improvement of the current collecting ability, the battery performance can be improved also in this aspect.
[0018]
FIG. 3 shows an embodiment of a sealed lead-acid battery according to the present invention.
[0019]
In the sealed lead-acid battery of this embodiment, protrusions 9a and 9b made of lead or lead alloy are integrally provided at a plurality of positions on one side surface of the current collector main body 8a or 8b made of lead or lead alloy. The positive electrode active material 11a is arranged so that the protrusions 9a are buried in the current collector 7a using the current collectors 7a and 7b, and the positive electrode plate 10a is formed. The current collector 7b has the protrusions 9b. The negative electrode active material 11b is arranged so as to be buried to constitute the negative electrode plate 10b, and the positive electrode plate 10a and the negative electrode plate 10b are made of glass fiber nonwoven fabric so that the positive electrode active material 11a and the negative electrode active material 11b face each other. The electrode plate group 5 is configured by being opposed to each other via the separator 4 and the electrode plate group 5 is housed in a battery case 6 made of a film-like or sheet-like resin. Yes.
[0020]
In such a sealed lead-acid battery, the projections 9a and 9b are embedded in the current collectors 7a and 7b in which the projections 9a and 9b are integrally provided at a plurality of locations on the surface of the current collector main bodies 8a and 8b. Are formed using the electrode plates 10a and 10b having a structure in which the active materials 11a and 11b are arranged on the surface, so that the protrusions 9a and 9b can prevent the active materials 11a and 11b from being peeled off. A battery having excellent life performance can be obtained. Moreover, since these protrusions 9a and 9b contribute to the improvement of the current collecting ability, the battery performance can be improved also in this aspect.
[0021]
Next, an example of the structure of the sealed lead-acid battery according to the present invention will be described more specifically with reference to FIG.
[0022]
The current collector main bodies 8a and 8b are in the form of a sheet made of Pb—Sn alloy having a thickness of 200 μm, length of 140 mm and width of 66 mm, and spherical protrusions 9a and 9b made of Pb—Sn alloy having a diameter of about 1 mm. The current collectors 7a and 7b are configured by providing 32 at regular intervals. The current collector 7a is filled with a positive electrode active material 11a so that each protrusion 9a is embedded, thereby forming a positive electrode plate 10a. The current collector 7b is filled with the negative electrode active material 11b so that the protrusions 9b are embedded in the negative electrode plate 10b. The positive electrode plate 10a and the negative electrode plate 10b are arranged so that the positive electrode active material 11a and the negative electrode active material 11b face each other with the separator 4 made of a glass fiber nonwoven fabric, and the electrode plate group 5 is configured. The group 5 is housed in a battery case 6 made of a film-like or sheet-like resin to constitute a 2V, 3 Ah sealed lead-acid battery. This sealed lead-acid battery is referred to as a product of the present invention.
[0023]
A cycle life test was performed between the product of the present invention and a sealed lead-acid battery (referred to as a conventional product) using conventional current collectors 1a and 1b having no protrusions on the surface as shown in FIG. It was.
[0024]
FIG. 4 shows the results of the cycle life test. The test condition was a constant current of 1 CA, which was allowed to stand up to 1.6 V / cell, and then a pattern in which charging was performed for 3.5 h at a constant current of 0.6 CA and a constant voltage of 2.5 V / cell was defined as one cycle. As shown in the figure, it can be seen that the cycle life performance of the product of the present invention is better than that of the conventional product. When the conventional product reaches the end of its life, it is disassembled together with the product of the present invention, and the cross section of the positive electrode plate is observed. In the case of the product of the present invention, the separation of the active material from the current collector is suppressed to 10% or less of the conventional product. It was done.
[0025]
FIG. 5 shows a method for manufacturing a current collector for a sealed lead-acid battery according to the present invention. First, the molten Pb—Sn alloy 12 is put in the container 13. The container 13 is provided with as many small holes 15 as the number of projections 9 provided on the current collector body 8 on a flat top plate 14 on one side. On the other side of the container 10, an upward cylindrical pressurizing part 17 is provided via a throttle part 16. A pressurizing means 18 made of a piston is provided in the upward opening of the cylindrical pressurizing portion 17.
[0026]
With such a structure, when a pressure is applied to the molten Pb—Sn alloy 12 by the pressurizing means 18 and the molten Pb—Sn alloy 12 is pushed out from the small holes 15 onto the surface of the upper surface plate 14, the molten Pb—Sn alloy 12 Become substantially spherical projections 9 due to surface tension.
[0027]
Next, the current collector main body 8 is brought into contact with the protrusions 9, and the current collector main body 8 is pulled upward while applying pressure to the molten Pb—Sn alloy 12 in the container 13 by the pressurizing means 18. A protrusion 9 is integrally formed on the current collector body 8.
[0028]
However, when the molten Pb—Sn alloy 12 protrusion 9 is in contact with the current collector body 8, the molten Pb—Sn alloy 12 protrusion 9 wets and spreads on the surface of the current collector body 8 to form a spherical shape. Must not.
[0029]
Therefore, spherical protrusions 9 are formed on the surface of the current collector body 8 by taking the following means. First, the surface of each predetermined place where the protrusion 9 of the current collector body 8 is provided is masked, and a rubber-like plate having protrusions, for example, is applied to the current collector body 8, and then the current collector body is exposed to a high temperature and high humidity atmosphere. Leave 8 As a result, an oxide film is formed on the surface of the current collector body 8 other than where the projections 9 are to be provided, and the wettability of the molten Pb—Sn alloy 12 when the projections 9 are provided is deteriorated, and the projections 9 are provided. Since only the portion has good wettability, the spherical protrusion 9 can be reliably provided in that portion.
[0030]
Further, the cooling means 19 made of a cooling plate is applied to the surface of the current collector body 8 where the protrusions 9 are not provided to increase the cooling rate, and the protrusions 9 are solidified while being spherical.
[0031]
【The invention's effect】
According to the method for producing a current collector for a sealed lead-acid battery according to the present invention, the following excellent effects can be obtained.
[0032]
The method for manufacturing a current collector for a sealed lead-acid battery according to claim 1, wherein molten lead or a lead alloy is placed in a container having a plurality of small holes in the upper portion, and the molten lead or lead is obtained from each small hole. Protrusions are formed by extruding the alloy, and a sheet-like or film-like current collector main body is brought into contact with the protrusions. In this state, the current collector main body is pulled up so that each protrusion is integrated with the current collector main body. Therefore, by extruding the molten lead or lead alloy from each small hole, the molten lead or lead alloy takes a spherical shape due to the surface tension. The current collector with the protrusion can be easily formed.
The method for manufacturing a current collector for a sealed lead-acid battery according to claim 2 is characterized in that an oxide film is formed in advance on the surface of the sheet-shaped or film-shaped current collector main body other than where the projections are to be provided, The molten lead or lead alloy is put into a container having a small hole, and the molten lead or lead alloy is extruded from each small hole to form protrusions, and the current collector body is placed on each of the protrusions. The current collector body has a method of forming a current collector in which the protrusions are integrated with the current collector body by pulling up the current collector body in such a state. When the oxide film is provided on the surface, the wettability of the molten lead or lead alloy deteriorates. For this reason, when the molten projections having a spherical shape due to the surface tension are brought into contact with the current collector body to be integrated. These projections in the molten state are spread in a planar shape. While preventing it would of, it is possible to easily form the current collectors with the protrusions spherical.
The method for producing a current collector for a sealed lead-acid battery according to claim 3 masks the protrusions of the rubber-like plate by applying the protrusions on the rubber-like plate to the positions where the protrusions of the sheet-like or film-like current collector body are to be provided. An oxide film is formed in advance on the surface other than the planned location, and molten lead or lead alloy is put in a container having a plurality of small holes in the upper part, and the molten lead or lead alloy is extruded from each small hole. Protrusions are formed, and the current collector main body is brought into contact with the protrusions in correspondence with the locations where the respective protrusions are to be provided. In this state, the current collector main body is pulled up so that the protrusions are formed on the current collector main body. Since the method of forming an integrated current collector is adopted, an oxide film is formed on the other surface of the current collector body while applying each protrusion of the rubber-like plate to each predetermined position where the protrusion of the current collector body is provided. Oxide film at each planned location to provide protrusions Therefore, when the molten projections having a spherical shape due to the surface tension are brought into contact with the current collector body and integrated, the molten projections spread in a plane. It is possible to easily form the current collector with the spherical protrusions by securely integrating the spherical protrusions at each predetermined place where the protrusions are provided.
In the method for producing a current collector for a sealed lead-acid battery according to claim 4, when the current collector body is brought into contact with each protrusion, the other surface of the current collector body is cooled by a cooling means. The cooling rate of each protrusion is increased, and each spherical protrusion can be reliably integrated with the current collector main body while maintaining the spherical shape.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing one embodiment of a sealed lead-acid battery current collector according to the present invention.
FIG. 2 is a cross-sectional view showing an embodiment of an electrode plate for a sealed lead-acid battery according to the present invention.
FIG. 3 is a cross-sectional view showing an embodiment of a sealed lead-acid battery according to the present invention.
FIG. 4 is a comparison diagram of cycle life characteristics between a sealed lead-acid battery according to the present invention and a conventional sealed lead-acid battery.
FIG. 5 is a cross-sectional view showing a method for manufacturing a current collector for a sealed lead-acid battery according to the present invention.
FIG. 6 is a cross-sectional view of a conventional sealed lead-acid battery.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1a, 1b Current collector 2a Positive electrode active material 2b Negative electrode active material 3a Positive electrode plate 3b Negative electrode plate 4 Separator 5 Electrode plate group 6 Battery case 7, 7a, 7b Current collector 8, 8a, 8b Current collector body 9, 9a , 9b Projection 10 Electrode plate for sealed lead-acid battery 11 Active material 11a Positive electrode active material 11b Negative electrode active material 12 Pb-Sn alloy 13 Container 14 Upper surface plate 15 Small hole 16 Restriction part 17 Pressure part 17 Pressure part 18 Cooling part

Claims (4)

上部に複数個の小孔を有する容器の中に溶融した鉛又は鉛合金を入れ、前記各小孔から前記溶融した鉛又は鉛合金を押し出して突起をそれぞれ形成し、これら突起の上にシート状若しくはフィルム状の集電体本体を接触させ、かかる状態で前記集電体本体を引き上げることにより前記集電体本体に前記各突起が一体化された集電体を形成することを特徴とする密閉形鉛蓄電池用集電体の製造方法。A molten lead or lead alloy is put into a container having a plurality of small holes in the upper part, and the molten lead or lead alloy is extruded from each of the small holes to form protrusions, and a sheet-like shape is formed on these protrusions. Alternatively, the film-shaped current collector body is brought into contact, and in such a state, the current collector body is pulled up to form a current collector in which the protrusions are integrated with the current collector body. Of producing a current collector for a lead-acid battery. シート状若しくはフィルム状の集電体本体の突起を設ける予定箇所以外の表面に予め酸化被膜を形成し、上部に複数個の小孔を有する容器の中に溶融した鉛又は鉛合金を入れ、前記各小孔から前記溶融した鉛又は鉛合金を押し出して突起をそれぞれ形成し、これら突起の上に前記集電体本体をその各突起を設ける予定箇所を対応させて接触させ、かかる状態で前記集電体本体を引き上げることにより前記集電体本体に前記各突起が一体化された集電体を形成することを特徴とする密閉形鉛蓄電池用集電体の製造方法。Forming an oxide film in advance on the surface of the sheet-like or film-like current collector body other than the planned location for providing the protrusions, putting molten lead or a lead alloy in a container having a plurality of small holes in the upper part, The molten lead or lead alloy is extruded from each small hole to form protrusions, and the current collector main body is brought into contact with these protrusions in correspondence with the locations where the respective protrusions are to be provided. A method of manufacturing a current collector for a sealed lead-acid battery, wherein the current collector is formed by pulling up the current body to form a current collector in which the protrusions are integrated with the current collector body. シート状若しくはフィルム状の集電体本体の突起を設ける予定箇所にゴム状板の各突起を当ててマスクしてこれら突起を設ける予定箇所以外の表面に予め酸化被膜を形成し、上部に複数個の小孔を有する容器の中に溶融した鉛又は鉛合金を入れ、前記各小孔から前記溶融した鉛又は鉛合金を押し出して突起をそれぞれ形成し、これら突起の上に前記集電体本体をその各突起を設ける予定箇所を対応させて接触させ、かかる状態で前記集電体本体を引き上げることにより前記集電体本体に前記各突起が一体化された集電体を形成することを特徴とする密閉形鉛蓄電池用集電体の製造方法。 A sheet-like or film-like current collector main body is to be provided with projections on the rubber plate to mask the projections, and an oxide film is formed in advance on the surface other than the locations where the projections are to be provided. The molten lead or lead alloy is put into a container having small holes, and the molten lead or lead alloy is extruded from the small holes to form protrusions, and the current collector body is formed on the protrusions. It is characterized by forming a current collector in which the protrusions are integrated with the current collector body by bringing the current collector body in this state by bringing the current protrusions into contact with each other where the respective protrusions are to be provided. To manufacture a current collector for a sealed lead-acid battery. 前記集電体本体を前記各突起に接触させる際に前記集電体本体の他の面を冷却手段で冷却することを特徴とする請求項１，２，３のいずれか１つに記載の密閉形鉛蓄電池用集電体の製造方法。 The hermetic seal according to any one of claims 1, 2, and 3, wherein when the current collector main body is brought into contact with the protrusions, the other surface of the current collector main body is cooled by a cooling means. Of producing a current collector for a lead-acid battery.
JP02653595A 1995-02-15 1995-02-15 Method for manufacturing current collector for sealed lead-acid battery Expired - Fee Related JP3648780B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP02653595A JP3648780B2 (en) 1995-02-15 1995-02-15 Method for manufacturing current collector for sealed lead-acid battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP02653595A JP3648780B2 (en) 1995-02-15 1995-02-15 Method for manufacturing current collector for sealed lead-acid battery

Publications (2)

Publication Number Publication Date
JPH08222230A JPH08222230A (en) 1996-08-30
JP3648780B2 true JP3648780B2 (en) 2005-05-18

Family

ID=12196194

Family Applications (1)

Application Number Title Priority Date Filing Date
JP02653595A Expired - Fee Related JP3648780B2 (en) 1995-02-15 1995-02-15 Method for manufacturing current collector for sealed lead-acid battery

Country Status (1)

Country Link
JP (1) JP3648780B2 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4518625B2 (en) * 2000-05-30 2010-08-04 京セラ株式会社 Electric double layer capacitor
TWI485905B (en) * 2014-07-18 2015-05-21 Iner Aec Executive Yuan Thin film battery structure and manufacturing method thereof

Also Published As

Publication number Publication date
JPH08222230A (en) 1996-08-30

Similar Documents

Publication Publication Date Title
TWI715576B (en) Longitudinal constraints for energy storage devices
KR101389609B1 (en) Lithium secondary battery and use thereof
KR20220009492A (en) Separators for three-dimensional batteries
US5344727A (en) Bipolar battery electrode
JPH10188938A (en) Battery device
KR100646508B1 (en) Separator and Secondary Battery with the same
US6232017B1 (en) Grid for lead acid battery
JPS59207558A (en) Manufacture of closed lead-acid battery
US6371997B1 (en) Method for manufacturing lithium polymer secondary battery and lithium polymer secondary battery made by the method
JP3648780B2 (en) Method for manufacturing current collector for sealed lead-acid battery
JPS62229772A (en) Lead-acid battery
JPH0524628B2 (en)
JP3814074B2 (en) Non-aqueous electrochemical element
US4194060A (en) Electric accumulator and storage cell
JPH0883617A (en) Electrode plate for lead-acid battery
KR20240005703A (en) Battery assembly with protective layer and method of manufacturing same
KR100250381B1 (en) The method to support active material of plate for lead acid battery and its applied battery
CN114447262A (en) Pole piece, coating device, battery cell, battery pack and manufacturing method of battery cell
JPS58154171A (en) Lead-acid battery
JPH0514464Y2 (en)
JP3094396B2 (en) Manufacturing method of sealed lead-acid battery
JP3624583B2 (en) Manufacturing method of electrode plate for sealed lead-acid battery
JP2737227B2 (en) Sealed lead-acid battery
JPH055646Y2 (en)
JP2001273918A (en) Manufacturing method of cylindrical sealed lead-acid battery

Legal Events

Date Code Title Description
A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20040825

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20041020

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20050125

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20050207

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20080225

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20090225

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20090225

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20100225

Year of fee payment: 5

LAPS Cancellation because of no payment of annual fees