JP5000799B2

JP5000799B2 - Lead acid battery

Info

Publication number: JP5000799B2
Application number: JP2000303078A
Authority: JP
Inventors: 英俊阿部; 智樹小浦方; 利通高田; 靖之根兵; 徹萬ヶ原; 修平竹島
Original assignee: Furukawa Battery Co Ltd
Current assignee: Furukawa Battery Co Ltd
Priority date: 1999-12-24
Filing date: 2000-10-03
Publication date: 2012-08-15
Anticipated expiration: 2020-10-03
Also published as: JP2001243940A

Description

【０００１】
【発明の属する技術分野】
本発明は、鉛蓄電池に関する。
【０００２】
【従来の技術】
従来の密閉鉛蓄電池では、極板群の負極ストラップ及び負極耳は気相中に露出しているため、過充電時に正極で発生した酸素ガスの大部分は、負極板で吸収されるが、その一部は、負極ストラップや負極耳の表面に接触し、酸化鉛を生成し、腐食が進行し、負極ストラップや耳の内部まで腐食する。一方、気相中の希硫酸電解液の蒸気は、負極ストラップや耳に付着し、生成した酸化鉛と反応し、水を生成し、希硫酸電解液が希釈、消費され電池寿命を短縮する。また、フロート充電などの充電中に正極から酸素が発生していると、負極ストラップの上面を酸化し貴へ分極して負極板の電位と負極ストラップ上面の電位の電位差が大きくなり、還元電位を超えるため、カソーディックな保護がされなくなり、腐食を促進する。
耳の酸素ガスとの接触による酸化腐食を防止するための発明が、特開平４−２４９０６４号公報に開示されている。即ちこの公報では、極板群が電解液中に浸漬された液式の鉛蓄電池において厳しい状況下で使用され、電解液面が適正レベル以下に下がった場合に、負極ストラップと負極板の耳が気相に曝され、負極板の耳が酸素ガスと反応し、酸化腐食することを生ずることを防止するためには、実施例１に記載のように、耐酸性の多孔性マット状体の多数個を用意し、その夫々の多孔性マット状体を極板群の負極ストラップに接続する負極板の耳列の各相隣る耳間に形成される夫々の空間に１個ずつ夫々差し込み、耳の表面に密着させて酸素ガスと接触しないようにした蓄電池用組立体を具備した鉛蓄電池とするか、或いは、負極ストラップ周辺をも酸化腐食から防止するためには、実施例２に記載のように、極板群を電槽内に収容後、極板群と電槽との隙間をホットメルトで目張りし、次にフェノール発泡樹脂の原料液を負極板の耳と耳の間及び負極ストラップ周辺に注入し、注入後十数分で発泡及び硬化を完了した後、負極板耳と耳との間にほぼ隙間なく存在し、耳とよく密着した連続気泡を有するフェノール樹脂を生成せしめた蓄電池用組立体を具備した鉛蓄電池とするかの発明を開示している。
また、特開平８−１６２１４９号公報に開示の発明は、上記に引用した公報に開示の発明では、リテーナーとは物理的に別体のマット状体を挿入している関係上、本来的に別部材であるマット状体とリテーナーとの間に腐食隙間が不可避的に発生するので、その境界隙間を経て酸素ガスが侵入し耳部に到達するため、耳部における異常腐食を防止するには充分でないとの見地から、該リテーナー本体と該リテーナー本体と一体的に形成され該負極ストラップの下面に接触するまでに延ばされ、且つ各相隣る耳の対向面を被覆することにより、前記の境界隙間をなくして、負極耳部における異常腐食を一層抑制できる密閉鉛蓄電池に係る発明を開示している。
【０００３】
【発明が解決しようとする課題】
しかし乍ら、上記の特開平４−２４９０６４号公報に開示の発明では、実施例１の鉛蓄電池用組立体を構成するには、該多孔性のマット状体を極板群の耳列の各相隣る耳間の空間に１つずつ差し込まなければならず、作業が非能率であるばかりでなく、該組立体は、各耳の側面はマット状体で保護されていないので、酸化腐食を生ずる不都合をもたらす。また、耳と耳との間及び負極ストラップ周辺を発泡体で包む必要がある場合の実施例２の鉛蓄電池用組立体を構成するには、上記のように、極板群を電槽内に収容後、発泡性樹脂原液を電槽内に注入する前に、先ず、極板群と電槽との間隔をホットメルトで目張りする必要がある。次いで、その目張りをした後、発泡性樹脂原液が全ての耳間の空間及びストラップの情報までの極板群の上方の空間を満たすに足る多量に注入する面倒且つ非能率な作業を要し、製造コストの増大する鉛蓄電池をもたらす。更には、注入した多量の原液が硬化するまで待たねばならない実施例では十数分という相当の時間を要する。更には、原液が耳間の空間から流出し空間内を満たす保証もない。而も、極板群と電槽との間隔が広過ぎてホットメルトによる目張りができない鉛蓄電池には適用できない不都合をもたらす。
また、上記の特開平８−１６２１４９号公報に開示の発明は、負極耳の側面及び負極ストラップの表面全面の腐食を防止することができない不都合を有する。
そこで、かかる従来の技術の課題を解決し、簡単な作業で且つ迅速に負極耳及び負極ストラップを酸化腐食から防止し得られる鉛蓄電池の開発が望まれる。
更に、上記に開示の従来の鉛蓄電池では、下記の不都合が回避できない。即ち、鉛蓄電池の負極ストラップが、気相に露出している状態において、特に、長期のフロート充電に入ると、負極ストラップへの硫酸供給は、特開平４−２４９０６４号公報及び特開平８−１６２１４９号公報では、ガラス繊維又は発泡樹脂から成る多孔性のマット状体及びマット状体と耳間の間隙から毛細管現象により滲み上がり供給されるが、その滲み上がり供給の途上で、負極ストラップに達する前に硫酸は多くは極板の耳群の金属鉛や酸化鉛と接触し、反応して硫酸鉛となり消費され、その結果、負極ストラップへの硫酸供給量が減少し、負極ストラップ表面を保護する硫酸鉛の生成量が減少する嫌いがある。
また、上記従来のマットの有無に拘わらず、特に大型の縦長の密閉鉛蓄電池では長期の保証が求められるが、電解液中の硫酸が比重が大きいために、極板群の下部へ沈降するいわゆる成層化現象を起こし易い。このような状態になると極板群の上部の硫酸濃度が低くなるため、極板群の上部の硫酸分をマットを介して毛細管現象により負極ストラップ上部へ供給する構造にしても保護膜生成効果は小さくなった。
このような見地より、上記従来の技術のかかる問題を解決し、長期使用における硫酸により負極ストラップの鉛が溶解することを保持し、長期間に亘り負極ストラップを良好に保護すると共に電解液の成層化現象を防止し得る長期に亘り高信頼性を有する鉛蓄電池の開発が望まれる。
【０００４】
【課題を解決するための手段】
本発明は、上記従来の課題を解消した鉛蓄電池を提供するもので、鉛蓄電池用の負極板と正極板とをリテーナーを介して積層した積層体の上面の両側において突出し且つ一列に並ぶ負極耳列及び正極耳列を夫々負極ストラップ及び正極ストラップで接続して成る極板群とは別個に、吸液性肉厚板状マットの一端に開口した耳挿入用スリットを存し配設した複数個の吸液性歯状突起とこれら吸液性歯状突起を共通に連接し且つ負極耳列の少なくとも中間の耳の側面に当接密着せしめる長手の連接用吸液性成形マット板部とを一体成形して成る肉厚板状のくし形吸液性成形マットを用意し、該くし形吸液性成形マットを、その耳挿入用スリットに該極板群の負極耳列の中間の耳へ密嵌挿入せしめると共に、その夫々の吸液性歯状突起を負極ストラップの下面と各相隣る耳の対向面で囲繞された夫々の対応する空間内に差し込み、その夫々の吸液性歯状突起の四周面を該負極ストラップの下面、相隣る耳の対向面、リテーナーの上端面に密着せしめると共に、該長手の連接用吸液性成形マット板部を負極耳列の少なくとも中間の耳の側面に当接密着せしめるように該極板群に装着せしめたことを特徴とする鉛蓄電池用組立体を具備して成る。
更に本発明に係る鉛蓄電池は、上記本発明に係るくし形吸液性成形マットの該長手の連接用吸液性成形マット板部の上面を延長して該負極ストラップの側面に当接密着せしめる長手の吸液性マット板部を一体成形して成るＬ字状吸液性成形マットを用意し、そのくし形吸液性成形マットを請求項１に記載の要領で該極板群に装着せしめたことを特徴とする鉛蓄電池用組立体を具備して成る。
更に本発明に係る鉛蓄電池は、上記本発明に係るＬ字状吸液性成形マットの該負極ストラップの側面に当接密着せしめる長手の吸液性マット板部の上縁から水平に延長して該負極ストラップの上面に密着せしめる長手の吸液性マット板部を一体成形すると共に、その下面と歯状突起列の上面との間に負極ストラップを密嵌収容スペースを存してコ字状凹溝を形成して成るコ字状吸液性成形マットを用意し、そのくし形吸液性成形マットを前記の要領で該極板群に装着したことを特徴とする蓄電池用組立体を具備して成る。
更に本発明に係る鉛蓄電池は、上記の本発明に係る所望の形状の吸液性成形マットにこれから下方に延長して、リテーナーの上部側面又は側縁に接触せしめる吸液性下垂部を設けて成る吸液性成形マットを用意し、そのくし形吸液性成形マットを前記の要領で該極板群に装着したことを特徴とする蓄電池用組立体を具備して成る。
更に本発明に係る鉛蓄電池は、上記の負極ストラップの酸化防止に加え、硫酸イオンを積極的に供給して負極ストラップの硫酸に対する溶解を防止し、長期に亘り良好な電池性能の良い鉛蓄電池を提供するもので、請求項１乃至４のいずれか１つに記載の鉛蓄電池において、くし形吸液性成形マットは、硫酸カルシウム製であることを特徴とする。
更に本発明に係る鉛蓄電池は、上記の硫酸カルシウム製くし形吸液性成形マットを容易に作製し提供するもので、硫酸カルシウム製くし形吸液性成形マットは、無水硫酸カルシウムの粉末又は／及び硫酸カルシウム０．５水塩の粉末を水又は希硫酸で混練して成るペーストを所定の型に入れ反応硬化、脱型して成るものである。
【０００５】
【発明の実施の形態】
次に本発明の実施例を添付図面に基づいて説明する。
本発明は、電解液を極板群に含浸せしめた密閉式鉛蓄電池及び極板群を電解液に浸漬した液式の鉛蓄電池のいずれにも適用できるが、図示の実施例は、密閉式鉛蓄電池に適用した場合で説明する。
図１乃至図４は、本発明の実施の１例を示す。同図において１は極板群を示す。該極板群１は、常法に従い５枚の負極板２，２，…と４枚の正極板３，３，…を電解液を吸収保持し且つ正，負極板より縦，横寸法の大きい耐酸性の有機又は無機繊維の不織布などから成るリテーナー４，４，…を介し交互に積層し且つ負極板の耳２ａ，２ａ，…と正極板３の耳（図示しない）が左右に交互に配置された状態で積層し、その積層対の上面の上方に突出してその１側に負極耳列が突出し、その他側に正極耳列（図示しない）が形成されるようにし、その一列に並んだ負極耳２ａ，２ａ，…の上部に接続する負極ストラップ５をキャストオンストラップ方式などで形成し、その一列に並んだ正極耳の上部に接続する正極ストラップ（図示しない）を形成して極板群を形成した。
【０００６】
本発明は、このように構成した該極板群１に、図１に示すように、その負極ストラップ５の下面と一列に並ぶ負極耳列２ａ，２ａ，…の各相隣る耳２ａ，２ａの対向面とで囲繞形成された夫々の空間７，７，…内に、該極板群１とは別個に本発明の特徴とする下記構成の肉厚板状のくし形吸液性成形マット６を予め作製しておき、これをこれに形成した耳挿入用スリット６ａ，６ａ，…に、該極板群１の負極耳列２ａ，２ａ，…を密嵌挿入すると共に、各耳挿入用スリット６ａを介して配設されている夫々の吸液性歯状突起６ｂ，６ｂ，…を該極板群１の負極ストラップ５の下面と負極耳列の各相隣る耳２ａ，２ａの対向面とで囲繞形成される夫々の空間７，７，…内に一挙に差し込んで各該吸液性歯状突起６ｂの四周面が図２乃至図４に示すように、夫々対応する負極ストラップ５の下面、相隣る耳２ａ，２ａの対向内面、リテーナー４の上端面及び負極耳列の各耳２ａの側面に接触するようにした状態に該極板群１に装着して成る鉛蓄電池用組立体Ａを構成し、これを１個のセル室から成る角形電槽又は複数個のセル室から成るモノブロック式角形電槽に収容し、常法により鉛蓄電池を製造する。図示の例では、上記本発明の鉛蓄電池用組立体Ａをモノブロック式電槽８の内部の仕切壁８ａで複数個のセル室８ｂ，８ｂに仕切られた各セル室８ｂに収容し、常法により図示しないが、その仕切壁８ａの貫通孔を各正，負極ストラップから立ち上がるセル間接続耳を介し直列接続して本発明の鉛蓄電池を構成する。更に、この電槽８の上面に蓋を密閉し、両端のセル室の端子用負極ストラップと端子用正極ストラップの上面の正，負極柱を夫々植設し、その正，負極柱の上端部を蓋の外部に突出させた正，負極端子とし、各セル室８ｂ内に極板群及び吸液性成形マットに浸み込む量の希硫酸電解液を注入含浸させて密閉式鉛蓄電池とする。
【０００７】
本発明の上記の肉厚板状の該くし形吸液性成形マット６を該極板群１への装着は、該極板群を該電槽８の各セル室８ｂ内に収容する前でも後でも良い。図２乃至図４は、電槽８の一端の負極端子用セル室８ｂ内に収容された本発明の鉛蓄電池用組立体Ａの負極ストラップ５側を示し、その上面に負極端子用極柱（図示しない）を植設される。
【０００８】
該くし形吸液性成形マット６、例えば、耐酸性のパルプ、植物繊維、無機繊維、合成繊維などの電気絶縁性材料に耐酸性の無機又は合成樹脂製の結着剤を少量添加混合したものを成形用鋳型に入れ、加熱加圧して製造される。そのくし形吸液性成形マット６は、剛性でも柔軟弾性を有するものでも差支えない。また、本発明の該くし形吸液性成形マット６は次のように作製しても良い。即ち、鋳型により前記の空間内に密嵌挿入するに足る長矩形で肉厚板の吸液性成形マットを作製した後、その一端に開口し、極板群１の耳列２ａ，２ａ，…の少なくとも中間の耳を密嵌挿入するに適した幅と長さの耳挿入用スリット６ａをコ字状に切り欠き形成することにより、その耳挿入用スリット６ａを存して極板群１の負極ストラップ５の下面と各相隣る耳２ａ，２ａの対向内面に差し込んだとき、これらの面とリテーナー４の上端面に摺接密着するに適した太さをもつ断面角形の吸液性歯状突起６ｂ，６ｂと、該吸液性成形マットの他端側で、これら吸液性歯状突起６ｂ，６ｂ，…を共通に連接する共通の長手の連接用吸液性成形マット板部６ｃとが形成されるようにして本発明の該くし形吸液性成形マット６を製造するようにしても良い。
尚、図面で６ｂ１は、各吸液性歯状突起６ｂの先端の四周縁に設けたテーパー状の傾斜面を示し、これにより、各吸液性歯状突起６ｂを該空間７内への差し込みを円滑に行うようにし、その装着が完了したときは、図示のように負極ストラップ５より前方へ突出し、該負極ストラップ５の下面全面は、該吸液性歯状突起６ｂの平坦な上面に密着するようにした。
【０００９】
かくして、本発明の肉厚板状の該くし形吸液性成形マット６は、図１に示すように負極耳挿入用スリット６ａ，６ａ，…を存して配設された吸液性歯状突起６ｂ，６ｂ，…を長手の連接用吸液性成形マット板部６ｃで連接した構成であるので、その夫々の吸液性歯状突起６ｂ，６ｂ，…を該極板群１の前記の空間７，７，…に一度に一挙に差し込み装着することができるので、極板群１への該くし形吸液性成形マット６の装着作業が容易迅速に得られるばかりでなく、その装着により構成された該鉛蓄電池用組立体Ａは、これを電槽８内の各セル室８ｂ内に収容することにより、図２乃至図４に明示するように、該極板群１の各空間７に装填されたその各吸液性歯状突起６ｂは、その断面角形の四周面において、その対応する負極ストラップ５の内面、その相隣る耳の対向内面及びそのリテーナーの上端面に密接するので蓄電池のフロート充電時などにおいて発生する酸素ガスとの接触による酸化反応を防止し、更に、同時に、その吸液性によって、電解液を保持し、負極ストラップ５の下面、耳の対向内面に常に電解液による湿潤状態に保持するので、更に酸化反応を防止し、負極ストラップをカソーディックに保護するなどの作用効果をもたらす。これに加え、更に本発明のその鉛蓄電池用組立体Ａは、その長手の連接用吸液性成形マット板部６ｃを有するので、これが負極耳列の耳の側面に当接密着し、耳の側面の酸化腐食を防止する。また、常に硫酸電解液が接触する耳及びストラップの面は、薄い緻密な硫酸鉛の保護膜が生成するなどの効果をもたらす。
【００１０】
図５乃至図７は、本発明の他の実施例を示し、その吸液性成形マットは、図５に示すように、前記のくし形吸液性成形マット６の歯状突起６ｂ，６ｂ，…を連接した共通一枚の長手の連接用吸液性成形マット板部６ｃを上方に延長して負極ストラップ５の側面に当接密着せしめるための長手の吸液性マット板部６ｄを一体に成形して成るＬ字状吸液性成形マット６Ａに構成したものである。この場合、図示のように、該共通一枚の長手の連接用吸液性成形マット板部６ｃは、その長さ方向の両端を延長し、その延長板部６ｃ１，６ｃ１を有するものに一体成形により形成し、これら延長板部６ｃ１，６ｃ１で負極耳列の両端の耳２ａ，２ａの側面に当接密着せしめるようにし、この延長板部６ｃ１，６ｃ１をもつ長手の連接用吸液性成形マット板部６ｃの上面にこれに対応して延長された延長板部６ｃ１，６ｃ１をもつ長手の吸液性マット板部６ｄを一体成形により形成し、該負極ストラップ５の側面を全長に亘り当接密着するようにすることが好ましく、一般である。
【００１１】
図６及び図７は、図５示のＬ字状吸液性成形マット６Ａを、そのくし形吸液性成形マット６で図１に示す鉛蓄電池用極板群１に、先の実施例と同じ要領で装着して本発明の鉛蓄電池用組立体Ｂを構成し、これを電槽８内に具備せしめたものである。
かくして、該極板群１は、該Ｌ字状吸液性成形マット６Ａにより、その負極ストラップ５の下面全面ばかりでなく、その側面全面に亘り酸素ガスとの接触から保護されると同時に、電解液の供給により湿潤され、腐食防止が先の実施例より一層良好に得られ、また同時に、その負極耳列２ａ，２ａ，…の全ての耳２ａをその対向内面ばかりでなく、その側面の腐食防止が得られる。
【００１２】
図８乃至図１０は、本発明の更に他の実施例を示す。図８は、吸液性成形マットの更に変形例を示し、図５に示す好ましいＬ字状吸液性成形マット６Ａの負極ストラップ５の側面に接触せしめる長手の吸液性マット板部６ｄの上縁から一体に水平に延び該負極ストラップ５の上面全面に接触せしめる長手の吸液性マット板部６ｅを一体に延長成形すると共にその下面の吸液性歯状突起列６ｂ，６ｂ，…の上面との間に負極ストラップ５を密嵌収容する高さスペースＳを存してコ字状凹溝９を形成して成るコ字状吸液性成形マット６Ｂを作製し、これを、図９及び図１０に示すように、そのくし形吸液性成形マット６を該極板群１に先の実施例と同じ要領で装着して本発明の鉛蓄電池用組立体Ｃを構成し、これを電槽８内に具備せしめたものである。
尚、図面で６ｅ１は、該負極ストラップ５の上面に被着すべき吸液性マット板部６ｅの先端の下縁に形成した先端に至るに従い上向きに開拡する傾斜面を示し、これにより、該コ字状凹溝９内に該負極ストラップ５を差し込み収容するその作業が円滑に行われるようにし、装着後は、該負極ストラップ５の前方に突出し、該負極ストラップ５の上面全面に該吸液性マット板部６ｅの平坦な下面が密着するようにした。
かくして、該極板群１は、該コ字状吸液性成形マット６Ｂにより、負極ストラップ５の下面全面及び側面全面ばかりでなくその上面全面に亘り酸素ガスとの接触から保護されると同時に、電解液の供給により湿潤され、特に、該負極ストラップ５の上層部を電位的にカソーディックに保護され、その表面が被覆保護されない場合に比し、一層長期に亘り、負極板と電位差が殆どない良好な状態を確保することができる。尚、負極耳列の各耳の両面及び側面は、その該Ｌ字状の吸液性成形マット６Ａにより保護されることは前記の実施例と変わりがない。
【００１３】
鉛蓄電池の充放電を繰り返して長期に亘り使用している過程で、正極板３，３，…の伸びにより該吸液性成形マット６，６Ａ，６Ｂは上方へ持ち上げられて、その下面で接触していたリテーナー４，４，…の上端面から離隔され、リテーナー４，４，…からの電解液の供給が絶たれてしまい、やがて吸液性成形マット６，６Ａ，６Ｂは乾いて腐食防止の目的が達成できなくなる惧れがある。
このような正極板３，３，…の伸びにより、該吸液性成形マット６，６Ａ，６Ｂの下面がリテーナー４，４，…から離れても、上記のような不都合を生じないようにするため、本発明は、前記の各種形状の吸液性成形マット６，６Ａ，６Ｂに、これから下方に延びる吸液性下垂部を設け、これをその極板群へ装着したとき、その吸液性下垂部がリテーナー４，４，…の上部の側面又は側縁に接触せしめておくことにより、上記の問題を解消するようにした。
【００１４】
その実施例を図１１乃至図１４に示す。
図１１は、前記のコ字状吸液性成形マット６Ｂの下面、更に詳細には、その夫々の吸液性歯状突起６ｂ，６ｂ，…の下面の幅方向の中央から該長手の連接用吸液性成形マット板部６ｃの下面にかけて、これから一体に下方に且つその吸液性歯状突起６ｂの長さ方向に延びる断面角形の吸液性下垂部材６ｆ，６ｆ，…を一体成形により突設して成る吸液性成形マット６Ｂ′を作製し、これを図１２に示すように、極板群１に装着して鉛蓄電池用組立体Ｃ′を構成したとき、その各吸液性歯状突起６ｂの下面は、２枚のリテーナー４，４の上端面に接触されると共にその中央の吸液性下垂部材６ｆは、正，負極板の上端面より上方に突出する２枚のリテーナー４，４の間の空間部に挿入され、その両リテーナー４，４の突出した上部の対向側面４ａがその吸液性下垂部材６ｆの両側面に接触した状態となるので、正極板３の伸びで、該吸液性歯状突起６ｂの下面が該リテーナー４，４の上端面から離れても、依然、吸液性下垂部材６ｆはその両側面でリテーナー４，４の上部対向面で接触を維持しているので、リテーナー４，４からの電解液の該吸液性成形マット６Ｂへの供給は絶たれることなく維持される。
【００１５】
図１３は、図１１の吸液性成形マット６Ｂ′の変形例を示し、コ字状吸液性成形マット６Ｂは変わらないが、その吸液性下垂部材６ｆをその長手の連接用吸液性成形マット板部６ｃの下縁からその全長に亘り一体に下垂せしめた肉薄で柔軟性の矩形板状の吸液性下垂部材６ｆを一体成形により設けて成る吸液性成形マット６Ｂ″に構成したもので、これを、図１４に示すように、極板群１に装着して鉛蓄電池用組立体Ｃ″を構成したとき、その矩形板状の吸液性下垂部材６ｆは、各リテーナー４，４の上端面からその一側の隅角部から上部の１側縁に沿って接触した状態になるので、正極板３が伸び、該吸液性成形マット６Ｂ″の下面を押し上げられ、リテーナー４，４の上端面から離れても、その吸液性下垂部材６ｆの下端部において、リテーナー４との接触は維持されるので、リテーナー４，４，…を電解液の該マット６Ｂ″への供給は維持される。
【００１６】
更に、本発明の鉛蓄電池に用いるくし形吸液性成形マットとして、硫酸カルシウムから成るくし形吸液性成形マットを用いるようにすることにより、上記実施例のくし形吸液性成形マットと同様に、上記の負極ストラップ又は／及び耳列２ａ，２ａ，…を酸素ガスとの接触から保護すると共に電解液を供給することにより、その酸化を防止し電位差を減少せしめることに加え、硫酸電解液に自己の硫酸イオンを供給して、負極ストラップ又は／及び耳列２ａ，２ａ，…の鉛が硫酸に溶解することを防止し、電解液の成層化現象を防止し長期に亘り信頼性の高い鉛蓄電池をもたらす特有の効果をもたらす。
硫酸カルシウム製のくし形吸液性成形マットは、必要に応じ、先の実施の態様に例示した図１、図５、図８、図１１及び図１３に示すと同じ各種形状のくし形吸液性成形マット６，６Ａ，６Ｂ，６Ｂ′，６Ｂ″の夫々の形状に成形したものを使用できることは言うまでもない。
【００１７】
硫酸カルシウム製のくし形吸液性成形マットの製造は、無水硫酸カルシウム（ＣａＳＯ₄）の粉末又は硫酸カルシウム０．５水塩（ＣａＳＯ₄・０．５Ｈ₂Ｏ）の粉末の単独又はその両者の混合粉末を主体とし、これに水又は希硫酸を適量添加し、混練し、そのペーストを、上記の各種の成形マットの形状に対応した型に入れて反応硬化させた後、脱型することにより硫酸カルシウム２水塩（ＣａＳＯ₄・２Ｈ₂Ｏ）、いわゆるセッコウから成る簡単且つ安価なくし形吸液性成形マットを製造することができる。
また、吸液性、負極ストラップや耳への密着性を増大せしめるために、上記の成形原料である、無水硫酸カルシウムの粉末又は／及び硫酸カルシウム０．５水塩の粉末に、耐酸性の天然又は合成の有機質の短繊維、ガラス、シリカなどの無機の短繊維や粉末、耐酸性のパルプ、ゴム又は合成樹脂粉末、バーミキュライトなどの多孔質粉末などの充填剤を適量添加し、水又は希硫酸と混練して成るペーストを上記のように反応、硬化成形することにより、微多孔性と柔軟弾性を付与された硫酸カルシウム主体のくし形吸液性成形マットとしたものを使用することができる。
【００１８】
上記の硫酸カルシウム製の形状の異なるくし形吸液性成形マット６，６Ａ，…６Ｂ″を夫々図１〜図４、図６〜図７、図９〜図１０、図１２、図１４示のように、極板群の負極ストラップ５又は／及び耳列２ａ，２ａ，…に装着して使用するときは、上記の負極ストラップ５の酸化防止効果をもたらし、その上、下記の作用効果をもたらす。
即ち、密閉鉛蓄電池の夫々の鉛蓄電池用組立体Ａ，Ｂ，Ｃ，Ｃ′，Ｃ″を具備した鉛蓄電池１の夫々は、その負極ストラップ５に装着した多孔質の硫酸カルシウム製のくし形吸液性成形マットは、注液時に吸収した電解液とリテーナーに含有する電解液を吸収するために、長期に亘って電解液を負極ストラップ５の表面に供給できる。更に電解液の硫酸イオン濃度が硫酸鉛の溶解を大きくするまでの低濃度になったときは、負極ストラップ５や耳２ａの鉛の溶解に優先して硫酸カルシウムは電離して硫酸イオンを供給するので、負極ストラップ表面に生成している保護膜である硫酸鉛層の溶解を抑える。これは硫酸カルシウムの溶解度積Ｋｓｐは６×１０^-5と硫酸鉛の溶解度積Ｋｓｐは２×１０^-8に比較して大きいので、負極ストラップ５腐食の原因となる硫酸鉛からのＰｂ²⁺イオンの電離が始まる前に、優先して解離してＣａ²⁺とＳＯ₄ ^2-を供給させるために、ＳＯ₄ ^2-の共通イオン効果により、硫酸鉛の電離を抑制するので保護膜である硫酸鉛層を長期に亘り保護することが可能になると推定され、電池の長期のバックアップ電源用フロート充電などの長期使用において有効である。
また、同時に負極ストラップ５へのイオンの移動が容易になるために、負極板２と負極ストラップ５上面の電位差が小さくなり、腐食発生点の負極ストラップ５上面の電位が、より安定な卑側へシフトするために電位的にも腐食を抑制できる。
【００１９】
次に比較試験につき詳述する。
実施例１
絶縁材料として耐酸性パルプを用い、これに対しアクリル系接着剤を３重量％添加、混合したものを３種の鋳型に充填し、加熱加圧して図１に示す肉厚板状のくし形吸液性成形マットを成形し、これを負極板５枚と正極板４枚とをこれら正，負極板より寸法の大きいガラス繊維から成るリテーナーを介して積層し、積層体の上面に左右に突出して並ぶ負極板耳列及び正極板耳列をキャストオンストラップ法により負極ストラップ及び正極ストラップを接続して作製した極板群に装着して鉛蓄電池用組立体Ａを構成した。
実施例２
実施例１と同じ混合物を用い、同様にして図５に示すＬ字状吸液性成形マットを成形し、これを実施例１と同じ極板群に装着して鉛蓄電池用組立体Ｂを構成した。
実施例３
実施例１と同じ混合物を用い、同様にして図８に示すコ字状吸液性成形マットを成形し、これを実施例１と同じ極板群に装着して鉛蓄電池用組立体Ｃを構成した。
実施例４
実施例１で使用した耐酸性パルプを主体としたくし形吸液性成形マットに代え、硫酸カルシウム０．５水塩の粉末を適量の水で混練したペーストを型に入れ反応硬化、脱型して成る図１に示す肉厚板状の硫酸カルシウム２水塩製のくし形吸液性成形マットを用い、これを実施例１と同じ極板群に装着して鉛蓄電池用組立体Ｄを構成した。
比較例１
特開平４−２４９０６４号公報に開示のマット状体に対応する吸液性成形マットを、実施例１に用いた混合物を材料として成形したものを４個用意し、これを実施例１に用いた極板群の耳間に夫々差し込み、その各吸液性マットの四周面を負極ストラップの下面、相隣る耳間の対向内面及びリテーナーの上端面に密着させた鉛蓄電池用組立体を構成した。
比較例２
特開平８−１６２１４９号公報に開示に倣い、予め、実施例１で用いたリテーナーの上端と一体に、実施例１で用いた混合物を用いて吸液性成形マットを成形しておき、この吸液性成形マット付きリテーナーを介して５枚の負極板と４枚の正極板を該リテーナーを介して積層し、正，負極耳列に夫々正，負極ストラップを接続して極板群を構成したとき、その各リテーナーの上部に一体の吸液性成形マットはその負極ストラップの下面、相隣る耳間の対向内面に密着した状態の鉛蓄電池用組立体を構成した。
比較例３
実公平２−１８９２３号公報に開示に倣い、実施例１で用いた極板群の正，負極耳列にその上方のストラップの非吸液性で且つポリエステル製のくし状絶縁板の各間隙を各耳に差し込み、耳間の空間内に歯状突起を挿入して密着して成る鉛蓄電池用組立体を構成した。
【００２０】
次に、上記のこれら鉛蓄電池組立体の夫々を、常法に従い１つのセル室から成る角形電槽に収容し、比重１．３０の希硫酸電解液３Ｋｇを注入して、施蓋密閉してＭＳＥ２００の密閉鉛蓄電池Ａ，Ｂ，Ｃ，Ｄ，Ｅ，Ｆ，Ｇを夫々作製した。この場合、該極板群には、水銀／硫酸第一水銀参照電極を設置し、負極電位とストラップ電位を測定できるようにした。次に、夫々の密閉蓄電池に２サイクルの充放電を行い、容量がほゞ同等であることを確認した後、２．２３Ｖ／セルの定電圧充電を行い、充電電流が垂下して安定してから上記各部の電位を測定した。その結果を下記表１に示す。
【００２１】
【表１】

【００２２】
上記表１から、実施例１，２，３，４の電池Ａ，Ｂ，Ｃ，Ｄは負極板と負極ストラップ上面の電位の電位差は、比較例１〜３の電池Ｅ，Ｆ，Ｇに比し小さくなり、腐食防止効果が大きいことが判る。
また、Ｐｂ／Ｐｂ²⁺平衡電位は、−９５０ｍＶ付近であることから、実施例１，２，３，４の電池Ａ，Ｂ，Ｃ，Ｄの負極ストラップの上面の還元域であるから腐食域を脱しているに対し、比較例１〜３は酸化腐食域であり、腐食が回避できないことが判る。
更に、これら密閉電池を５０℃雰囲気で２．２３Ｖのフロート充電試験を３ヶ月行って変化を観察したところ、実施例１，２，３，４の電池Ａ，Ｂ，Ｃ，Ｄは、負極ストラップの腐食が認められなかった。比較例１及び２の電池Ｅ，Ｆは負極ストラップ上面及び側面及び耳の側面に腐食が認められた。比較例３の電池Ｇはストラップの上面及び側面及び耳の対向面及び側面に腐食の生成が認められた。実施例１〜３が示すように、一般に、吸液性成形マットにより密着被覆される面積が大きく、酸素ガスとの遮断された状態で電解液の供給により常にその負極ストラップ及び耳の表面が湿潤しているほど電位差が小さく且つ腐食防止効果が大きいことが判る。
【００２３】
上記の実施例では、本発明の該吸液性成形マットを密閉式鉛蓄電池に適用した場合で説明したが、極板群を浸漬した液式の鉛蓄電池において、その液面が規正レベル以下に下がったときにも有効である。
【００２４】
【発明の効果】
このように本発明によるときは、極板群とは別個に、肉厚板状の一端に開口して形成した耳挿入用スリットを介し配設された極板群の負極ストラップの下面と負極耳列の相隣る耳の対向面とリテーナーなどのセパレータの上端面とに密着せしめる吸液性歯状突起を長手の連接用吸液性成形マット板部で連接した肉厚板状のくし形吸液性成形マットを用意したので、その各吸液性歯状突起を該極板群の各相隣る耳の空間に差し込むと共に、その長手の連接用吸液性成形マット板部を耳列の各耳の側面に当接せしめることにより、夫々の吸液性歯状突起四周面を負極ストラップの内面及び負極耳列の各相隣る耳の対向面に密着せしめることと、長手の連接用吸液性成形マット板部を各耳の側面に密着せしめることが一挙に得られ、従来に比し極板群へのその装着作業を容易迅速に行うことができ、簡単且つ迅速に鉛蓄電池用組立体を構成でき、これを具備した鉛蓄電池は、そのくし形吸液性成形マットによりこれに接触するリテーナーからの電解液により、極板耳部の表面を湿潤させ良好に酸化腐食を防止できる。
また、本発明は、該くし形吸液性成形マットに一体に具備したＬ字状吸液性成形マット或いはコ字状吸液性成形マットを用意したので、そのくし形吸液性成形マットを極板群への装着作業と同時に、負極ストラップの側面、或いはその上面を吸液性マット板部で夫々密着被覆された更に酸化腐食防止の保証された夫々の鉛蓄電池用組立体が簡単且つ迅速に得られる。而も、酸素ガスと遮断した状態で常に電解液がリテーナーからその表面に供給されるので、これらの鉛蓄電池用組立体を具備した鉛蓄電池は、負極耳の対向面及び側面及び負極ストラップの下面、更には、側面及び上面を酸素ガスとの接触を遮断し、同時にリテーナーからの電解液がこれらの表面に常に供給されるので、負極耳及び負極ストラップの酸化腐食を防止でき、また、負極ストラップの電位と負極板の電位との電位差を減少せしめ或いは殆ど零とすると共に、還元電位を維持し、長期に亘り腐食を防止できる。
更に、これら吸液性成形マットに吸液性垂下部を設けるときは、これら吸液性成形マットのくし形吸液性成形マットを極板群への装着と同時に、その下端部をリテーナーと接触せしめられるので、正極板が伸びても吸液性垂下部を介しリテーナーからの電解液の供給が維持できる効果をもたらす。
更に、本発明のこれらの形状の異なる夫々のくし形吸液性成形マットを硫酸カルシウム製とするときは、上記の負極ストラップ又は／及び耳に対し、酸化防止効果と電解液の硫酸供給をもたらす上に、長期使用で電解液濃度が低下した時、硫酸カルシウムの硫酸イオンを供給し、負極ストラップ及び耳の電解液による溶解を防止すると共に、電解液の成層化現象を抑止し、長期に亘り高信頼性の鉛蓄電池をもたらす。
【図面の簡単な説明】
【図１】本発明実施の１例の鉛蓄電池用組立体の分解斜面図。
【図２】図１の鉛蓄電池用組立体を具備した鉛蓄電池の要部の上面図。
【図３】図２のＩＩＩ−ＩＩＩ線裁断面図。
【図４】図２のＩＶ−ＩＶ線裁断面図。
【図５】本発明の他の実施例の吸液性成形マットの斜面図。
【図６】図５に示す吸液性成形マットを極板群に装着して成る鉛蓄電池用組立体を具備した鉛蓄電池の図４と同様の裁断面図。
【図７】図６のＶＩＩ−ＶＩＩ線裁断面図。
【図８】本発明の更に他の実施例の吸液性成形マットの斜面図。
【図９】図８に示す吸液性成形マットを極板群に装着して成る鉛蓄電池用組立体を具備した鉛蓄電池の図４と同様の裁断面図。
【図１０】図９のＸ−Ｘ線裁断面図。
【図１１】本発明の変形例の吸液性成形マットの斜面図。
【図１２】図１１に示す吸液性成形マットを極板群に装着して成る鉛蓄電池用組立体を具備した鉛蓄電池の図４と同様の裁断面図。
【図１３】本発明の更に変形例の吸液性成形マットの斜面図。
【図１４】図１３に示す吸液性成形マットを極板群に装着して成る鉛蓄電池用組立体を具備した鉛蓄電池の図３と同様の裁断面図。
【符号の説明】
１極板群
６くし形吸液性成形マット
６ＡＬ字状吸液性成形マット
６Ｂコ字状吸液性成形マット
６Ｂ′，６Ｂ″ 下垂部を備えた吸液性成形マット
６ａ耳挿入用スリット
６ｂ吸液性歯状突起
６ｃ長手の連接用吸液性成形マット板部
６ｄストラップ側面当接用長手の吸液性マット板部
６ｅ負極ストラップ上面密着用長手の吸液性マット板部
６ｆ垂下部
Ａ，Ｂ，Ｃ，Ｃ′，Ｃ″ 鉛蓄電池用組立体
２負極板
２ａ負極耳
３正極板
４リテーナー
４ａリテーナーの側面
４ｂリテーナーの側縁
５負極ストラップ
７空間
８電槽
Ｓスペース
９コ字状凹溝[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a lead-acid battery.
[0002]
[Prior art]
  In the conventional sealed lead-acid battery, the negative electrode strap and the negative electrode ear of the electrode plate group are exposed in the gas phase, so most of the oxygen gas generated at the positive electrode during overcharge is absorbed by the negative electrode plate. A part contacts the surface of the negative electrode strap or the negative electrode ear to generate lead oxide, and the corrosion progresses to corrode the negative electrode strap or the inside of the ear. On the other hand, the vapor of the dilute sulfuric acid electrolyte in the gas phase adheres to the negative electrode strap and the ear and reacts with the produced lead oxide to produce water, diluting and consuming the dilute sulfuric acid electrolyte to shorten the battery life. In addition, if oxygen is generated from the positive electrode during charging such as float charging, the upper surface of the negative electrode strap is oxidized and polarized to noble, and the potential difference between the potential of the negative electrode plate and the upper surface of the negative electrode strap increases, and the reduction potential is increased. Therefore, cathodic protection is not provided and corrosion is accelerated.
  An invention for preventing oxidative corrosion due to contact with the oxygen gas in the ear is disclosed in Japanese Patent Application Laid-Open No. 4-249064. That is, in this publication, when the electrode plate group is used in a severe condition in a liquid type lead-acid battery immersed in an electrolyte, and the electrolyte surface falls below an appropriate level, the ears of the negative electrode strap and the negative electrode plate are In order to prevent the negative electrode plate from reacting with the oxygen gas and causing oxidative corrosion due to exposure to the gas phase, as described in Example 1, a large number of acid-resistant porous mats are used. Prepare one piece and insert each of the porous mat-like bodies one by one into each space formed between adjacent ears of the ear row of the negative electrode plate connected to the negative electrode strap of the electrode plate group. In order to provide a lead-acid battery having an accumulator assembly that is in close contact with the surface of the battery so that it does not come into contact with oxygen gas, or to prevent the periphery of the negative electrode strap from oxidative corrosion, as described in Example 2 In addition, after accommodating the electrode plate group in the battery case, the electrode plate group and the battery case After filling the gap with hot melt, and then injecting the phenol foam resin raw material liquid between the ears and the ears of the negative electrode plate and around the negative electrode strap, foaming and curing are completed ten minutes after the injection, and then the negative electrode plate ear The present invention discloses a lead-acid battery comprising an assembly for a storage battery in which a phenolic resin having open cells that are in close contact with the ears is present with almost no gap between them and the ears.
  Further, the invention disclosed in Japanese Patent Application Laid-Open No. 8-162149 is essentially different from the invention disclosed in the above-cited publication because a mat-like body that is physically separate from the retainer is inserted. Corrosion gaps inevitably occur between the mat-like body that is a member and the retainer, so oxygen gas enters through the boundary gaps and reaches the ears, which is sufficient to prevent abnormal corrosion in the ears The retainer body and the retainer body are formed integrally with the retainer body and are extended to contact the lower surface of the negative electrode strap, and by covering the opposing surfaces of the adjacent ears, An invention relating to a sealed lead-acid battery capable of further suppressing abnormal corrosion at the negative electrode ear by eliminating the boundary gap is disclosed.
[0003]
[Problems to be solved by the invention]
  However, in the invention disclosed in the above-mentioned Japanese Patent Laid-Open No. 4-249064, in order to construct the lead-acid battery assembly of Example 1, the porous mat-like body is placed on each of the ear rows of the electrode plate group. Not only is the work inefficient, it must be inserted one by one into the space between adjacent ears, but the assembly is not subject to oxidative corrosion because the sides of each ear are not protected by mats. Cause inconveniences. Moreover, in order to comprise the assembly for lead acid batteries of Example 2 when it is necessary to wrap between the ears and between the ear straps and the periphery of the negative electrode strap, the electrode plate group is placed in the battery case as described above. After the containment, before the foamable resin stock solution is injected into the battery case, it is first necessary to stretch the gap between the electrode plate group and the battery case with hot melt. Then, after the cover, it takes a cumbersome and inefficient work of injecting a large amount of foaming resin stock solution to fill the space between all the ears and the space above the electrode plate group to the information of the strap, This results in a lead acid battery with increased manufacturing costs. Furthermore, in an embodiment that must wait until a large amount of the injected stock solution is cured, it takes a considerable time of ten minutes. Furthermore, there is no guarantee that the stock solution will flow out of the space between the ears and fill the space. In addition, the distance between the electrode plate group and the battery case is so wide that it causes inconveniences that cannot be applied to lead storage batteries that cannot be hot-melted.
  Further, the invention disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 8-162149 has a disadvantage that the corrosion of the side surface of the negative electrode ear and the entire surface of the negative electrode strap cannot be prevented.
  Therefore, it is desired to develop a lead-acid battery that solves the problems of the conventional technology and can quickly prevent the negative electrode ear and the negative electrode strap from oxidative corrosion with simple work.
  Furthermore, the conventional lead storage battery disclosed above cannot avoid the following disadvantages. That is, in the state where the negative electrode strap of the lead storage battery is exposed to the gas phase, particularly when long-term float charging is started, the sulfuric acid supply to the negative electrode strap is disclosed in JP-A-4-24964 and JP-A-8-162149. In the Gazette, a porous mat-like body made of glass fiber or foamed resin and a bleed-up supply by capillarity from the gap between the mat-like body and the ear, but before reaching the negative strap in the course of the bleed-up supply In most cases, sulfuric acid comes into contact with metallic lead or lead oxide in the ear group of the electrode plate and reacts to be consumed as lead sulfate. As a result, the amount of sulfuric acid supplied to the negative electrode strap decreases, and the sulfuric acid that protects the negative electrode strap surface. I hate reducing the amount of lead produced.
  Regardless of the presence or absence of the conventional mat, a long vertical sealed lead-acid battery requires a long-term guarantee, but the sulfuric acid in the electrolyte has a large specific gravity, so that it settles to the lower part of the electrode plate group. Prone to stratification. In such a state, since the sulfuric acid concentration at the upper part of the electrode plate group is lowered, the protective film generating effect is also achieved by supplying the sulfuric acid content at the upper part of the electrode plate group to the upper part of the negative electrode strap by capillary action through the mat It has become smaller.
  From this point of view, the above-mentioned problems of the conventional technique are solved, the lead of the negative electrode strap is dissolved by sulfuric acid in a long-term use, and the negative electrode strap is well protected for a long period of time and the electrolyte is stratified. Development of a lead-acid battery having high reliability over a long period of time capable of preventing the crystallization phenomenon is desired.
[0004]
[Means for Solving the Problems]
  The present invention provides a lead-acid battery in which the above-described conventional problems are eliminated, and the negative-electrode ears projecting on both sides of the upper surface of a laminate in which a negative-electrode plate for a lead-acid battery and a positive-electrode plate are laminated via a retainer and arranged in a row. Separately from the electrode plate group formed by connecting the row and the positive electrode ear row with the negative electrode strap and the positive electrode strap, respectively, a plurality of ear insertion slits opened at one end of the liquid-absorbing thick plate-like mat The liquid-absorbing tooth-like protrusions and the liquid-absorbing tooth-like protrusions are connected in common and are in contact with and in close contact with at least the middle ear side surface of the negative electrode ear row.For connectionLiquid absorptionMoldingA thick plate-like comb-shaped liquid-absorbing molding mat formed by integrally molding the mat plate portion is prepared, and the comb-shaped liquid-absorbing molding mat is inserted into the ear insertion slit of the negative electrode ear row of the electrode plate group And insert each liquid-absorbing tooth-like protrusion into the corresponding space surrounded by the lower surface of the negative electrode strap and the opposing surface of each adjacent ear, The four circumferential surfaces of the water-absorbing tooth-like projections are brought into close contact with the lower surface of the negative electrode strap, the adjacent surface of the adjacent ear, and the upper end surface of the retainer, andFor connectionLiquid absorptionMoldingA lead-acid battery assembly is provided, wherein the mat plate portion is attached to the electrode plate group so that the mat plate portion is in contact with and in close contact with the side surface of at least the middle ear of the negative electrode ear row.
  Furthermore, the lead-acid battery according to the present invention is a liquid absorbing property for the longitudinal connection of the comb-shaped liquid absorbing molding mat according to the present invention.MoldingAn L-shaped liquid-absorbing molded mat is prepared by integrally forming a long liquid-absorbing mat plate portion that extends the upper surface of the mat plate portion and comes into close contact with the side surface of the negative electrode strap. A lead-acid battery assembly is provided, in which an adhesive molding mat is attached to the electrode plate group in the manner described in claim 1.
  Furthermore, the lead storage battery according to the present invention extends horizontally from the upper edge of the longitudinal liquid-absorbent mat plate portion that abuts and adheres to the side surface of the negative electrode strap of the L-shaped liquid-absorbent molded mat according to the present invention. A longitudinal liquid-absorbing mat plate portion that is brought into close contact with the upper surface of the negative electrode strap is integrally formed, and the negative strap is tightly fitted between the lower surface and the upper surface of the tooth-shaped projection row so as to have a U-shaped recess. A U-shaped liquid-absorbing molding mat having a groove is prepared, and the comb-shaped liquid-absorbing molding mat is mounted on the electrode plate group in the manner described above. It consists of
  Furthermore, the lead-acid battery according to the present invention is provided with a liquid-absorbing drooping portion that extends downward from the liquid-absorbing molding mat having a desired shape according to the present invention so as to contact the upper side surface or side edge of the retainer. A liquid-absorbing molding mat is prepared, and the comb-shaped liquid-absorbing molding mat is mounted on the electrode plate group as described above, and the storage battery assembly is provided.
  Furthermore, the lead storage battery according to the present invention provides a lead storage battery having good battery performance over a long period of time by actively supplying sulfate ions to prevent dissolution of the negative strap in sulfuric acid, in addition to the above-described prevention of oxidation of the negative strap. The lead-acid battery according to any one of claims 1 to 4, wherein the comb-shaped liquid-absorbing molded mat is made of calcium sulfate.
  Further, a lead storage battery according to the present invention is to easily produce and provide the calcium sulfate comb-shaped absorbent mat as described above, and the calcium sulfate comb-shaped liquid absorbent molded mat comprises anhydrous calcium sulfate powder or / And a paste made by kneading calcium sulfate 0.5 hydrate powder with water or dilute sulfuric acid is put in a predetermined mold and reactedCure, Demolded.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
  Next, embodiments of the present invention will be described with reference to the accompanying drawings.
  The present invention can be applied to either a sealed lead-acid battery in which an electrode plate group is impregnated with an electrode plate group or a liquid-type lead acid battery in which an electrode plate group is immersed in an electrolyte solution. This will be described in the case of application to a storage battery.
  1 to 4 show an example of implementation of the present invention. In the figure, 1 indicates an electrode plate group. The electrode plate group 1 has five

negative electrode plates

2, 2,... And four

positive electrode plates

3, 3,. Are alternately stacked via

retainers

4, 4,... Made of acid-resistant organic or inorganic fiber non-woven fabric, and the

negative electrode tabs

2a, 2a,. In this state, the negative electrode array is formed so that a negative electrode ear row (not shown) is formed on one side and a positive electrode ear row (not shown) is formed on the other side. The negative electrode strap 5 connected to the upper part of the

ears

2a, 2a,... Is formed by a cast-on strap method or the like, and the positive electrode strap (not shown) connected to the upper part of the positive electrode ears arranged in a row is formed. Formed.
[0006]
As shown in FIG. 1, the present invention provides the electrode plate group 1 thus configured with

adjacent ears

2a, 2a of the negative

electrode ear rows

2a, 2a,. In each space 7, 7,... Surrounded by the opposite surface of the plate, a thick plate-like comb-shaped liquid-absorbing molding mat having the following structure, which is a feature of the present invention, separately from the electrode plate group 1 6 are prepared in advance, and the negative

electrode ear rows

2a, 2a,... Of the electrode plate group 1 are tightly inserted into the

ear insertion slits

6a, 6a,. Respectively disposed through the slit 6aLiquid absorptionThe tooth-

like protrusions

6b, 6b,... Are surrounded by the lower surface of the negative electrode strap 5 of the electrode plate group 1 and the opposing surfaces of the

adjacent ears

2a, 2a of the negative electrode ear row. Plug it in at onceLiquid absorptionAs shown in FIGS. 2 to 4, the four circumferential surfaces of the tooth-like protrusions 6 b are the lower surfaces of the corresponding negative electrode straps 5, the opposing inner surfaces of

adjacent ears

2 a and 2 a, the upper end surface of the retainer 4, and the respective ears of the negative electrode ear row. The lead-acid battery assembly A is configured to be attached to the electrode plate group 1 so as to be in contact with the side surface of 2a, and this is constituted by a rectangular battery case comprising one cell chamber or a plurality of cell chambers. The lead-acid battery is manufactured by a conventional method. In the illustrated example, the lead-acid battery assembly A according to the present invention is accommodated in each cell chamber 8b divided into a plurality of

cell chambers

8b and 8b by a partition wall 8a inside the monoblock type battery case 8, Although not shown by the method, the lead-acid battery of the present invention is configured by connecting the through holes of the partition wall 8a in series via inter-cell connection ears rising from the positive and negative straps. Further, the lid is sealed on the upper surface of the battery case 8, and the positive and negative pole columns are implanted on the upper surfaces of the terminal negative straps and the terminal positive straps of the cell chambers at both ends. Positive and negative terminals protruding outside the lid are used, and each cell chamber 8b is infused and impregnated with an amount of dilute sulfuric acid electrolyte soaked into the electrode plate group and the liquid-absorbent molding mat to form a sealed lead-acid battery.
[0007]
The comb-shaped liquid-absorbing molding mat 6 having a thick plate shape according to the present invention is attached to the electrode plate group 1 even before the electrode plate group is accommodated in each cell chamber 8b of the battery case 8. Later. 2 to 4 show the negative electrode strap 5 side of the lead-acid battery assembly A of the present invention housed in the negative electrode terminal cell chamber 8b at one end of the battery case 8, and the negative electrode terminal pole ( (Not shown) is planted.
[0008]
The comb-shaped liquid-absorbing molding mat 6, for example, an acid-insulating material such as acid-resistant pulp, vegetable fiber, inorganic fiber, or synthetic fiber, with a small amount of acid-resistant inorganic or synthetic resin binder added and mixed Is put into a molding mold and heated and pressed. The comb-shaped liquid-absorbing molding mat 6 can be either rigid or flexible. The comb-shaped liquid-absorbing molding mat of the present invention6May be produced as follows. That is, a long rectangular and thick plate liquid-absorbing molding mat that is sufficient to be tightly inserted into the space by a mold is prepared, and then opened at one end thereof, and the

ear rows

2a, 2a,. An ear insertion slit 6a having a width and length suitable for tightly inserting at least the middle ear of the electrode is cut into a U-shape so that the ear insertion slit 6a exists and When inserted into the lower surface of the negative electrode strap 5 and the opposing inner surfaces of the

adjacent ears

2a, 2a, the square cross section has a thickness suitable for sliding contact with the upper surface of the retainer 4 and these surfaces.Liquid absorptionAt the other end side of the tooth-

like protrusions

6b and 6b and the liquid-absorbing molding mat,Liquid absorptionThe combs of the present invention are formed so as to form a common longitudinally connecting liquid-absorbing molded mat plate portion 6c for connecting the tooth-

like protrusions

6b, 6b,.SuckingThe liquid molding mat 6 may be manufactured.
In the drawing, 6b1 represents eachLiquid absorptionThe taper-shaped inclined surface provided in the four peripheral edges of the tip of the tooth-like protrusion 6b is shown.Liquid absorptionThe tooth-like protrusion 6b is smoothly inserted into the space 7, and when the mounting is completed, it protrudes forward from the negative strap 5 as shown, and the entire lower surface of the negative strap 5Liquid absorptionIt was made to adhere to the flat upper surface of the tooth-like projection 6b.
[0009]
Thus, the thick plate-like comb-shaped liquid-absorbing molding mat 6 of the present invention has a liquid-absorbing tooth-like shape provided with

slits

6a, 6a,. Since the

projections

6b, 6b,... Are connected to each other by a longitudinal connecting liquid-absorbing molded mat plate portion 6c, each of the

protrusions

6b, 6b,.Liquid absorptionSince the tooth-

like protrusions

6b, 6b,... Can be inserted into the spaces 7, 7,.CombNot only can the mounting operation of the liquid-absorbing molding mat 6 be obtained easily and quickly, but the lead storage battery assembly A configured by the mounting should be accommodated in each cell chamber 8b in the battery case 8. As shown in FIGS. 2 to 4, each of the liquid-absorbent tooth-like projections 6b loaded in each space 7 of the electrode plate group 1 has its corresponding negative electrode strap on the quadrangular surface of the square cross section. 5 is in close contact with the inner surface of the adjacent ear, the opposite inner surface of the adjacent ear, and the upper end surface of the retainer, so that an oxidation reaction due to contact with oxygen gas generated at the time of float charging of the storage battery is prevented. Depending on the nature, the electrolyte solution is held, and the lower surface of the negative electrode strap 5 and the inner surface facing the ear are always kept in a wet state by the electrolytic solution, so that the oxidation reaction is further prevented and the negative electrode strap is protected cathodically. Bring. In addition to this, the lead-acid battery assembly A of the present invention has the longitudinal connecting liquid-absorbing molded mat plate portion 6c, which is in close contact with the side surface of the ear of the negative electrode ear row, and Prevent side oxidative corrosion. In addition, the surface of the ear and the strap that are always in contact with the sulfuric acid electrolyte solution has an effect that a thin dense lead sulfate protective film is formed.
[0010]
FIGS. 5 to 7 show another embodiment of the present invention. As shown in FIG. 5, the liquid-absorbing molding mat has tooth-

like protrusions

6b, 6b, 6b of the comb-shaped liquid-absorbing molding mat 6, as shown in FIG. ... Are joined together with a long liquid-absorbing mat plate portion 6d for extending the upper portion of the liquid-absorbing molded mat plate portion 6c. This is formed into an L-shaped liquid-absorbing molding mat 6A formed by molding. In this case, as shown in the drawing, the common one-piece longitudinal connecting liquid-absorbing molded mat plate portion 6c is integrally formed to extend both ends in the length direction and have the extension plate portions 6c1 and 6c1. The extension plate portions 6c1 and 6c1 are in contact with and in close contact with the side surfaces of the

ears

2a and 2a at both ends of the negative electrode ear row, and have the extension plate portions 6c1 and 6c1.LongitudinalA longitudinal liquid-absorbing mat plate portion 6d having extension plate portions 6c1 and 6c1 extended correspondingly on the upper surface of the connecting liquid-absorbing molded mat plate portion 6c is formed by integral molding. It is preferable that the side surfaces are in close contact with each other over the entire length.
[0011]
6 and FIG. 7 show the L-shaped liquid-absorbing molding mat 6A shown in FIG. 5 in the lead-acid battery electrode group 1 shown in FIG. The lead-acid battery assembly B according to the present invention is mounted in the same manner, and is provided in the battery case 8.
Thus, the electrode plate group 1 is protected from contact with oxygen gas not only on the entire lower surface of the negative electrode strap 5 but also on the entire side surface thereof by the L-shaped liquid absorbent molding mat 6A. It is moistened by the supply of liquid, and corrosion prevention is obtained better than in the previous embodiment. At the same time, all the ears 2a of the negative

electrode ear rows

2a, 2a,. Prevention is obtained.
[0012]
8 to 10 show still another embodiment of the present invention. FIG. 8 shows a further modification of the liquid-absorbing molding mat, and is provided on the longitudinal liquid-absorbing mat plate portion 6d that is brought into contact with the side surface of the negative electrode strap 5 of the preferred L-shaped liquid-absorbing molding mat 6A shown in FIG. An elongated liquid-absorbent mat plate portion 6e extending horizontally from the edge and contacting the entire upper surface of the negative electrode strap 5 is integrally extended and formed on the lower surface thereof.Liquid absorptionA U-shaped liquid-absorbing molding mat formed by forming a U-shaped groove 9 with a height space S for tightly fitting and accommodating the negative strap 5 between the upper surfaces of the tooth-

like projection rows

6b, 6b,. 9B and FIG. 9 and FIG. 10, the comb-shaped liquid-absorbing molded mat 6 is attached to the electrode plate group 1 in the same manner as in the previous embodiment, as shown in FIGS. Assembly C is constructed and provided in the battery case 8.
  In addition, 6e1 in drawing shows the inclined surface which spreads upwards as it reaches the front-end | tip formed in the lower edge of the front-end | tip of the liquid-absorbing mat board part 6e which should be adhere | attached on the upper surface of this negative electrode strap 5, The operation of inserting and accommodating the negative strap 5 into the U-shaped concave groove 9 is performed smoothly, and after mounting, the negative strap 5 protrudes forward of the negative strap 5 and is absorbed on the entire upper surface of the negative strap 5. The flat bottom surface of the liquid mat plate portion 6e was in close contact.
  Thus, the electrode plate group 1 is protected from contact with oxygen gas over the entire upper surface as well as the entire lower surface and side surfaces of the negative electrode strap 5 by the U-shaped liquid-absorbing molding mat 6B. It is wetted by the supply of the electrolytic solution, and in particular, the upper layer portion of the negative electrode strap 5 is protected cathodically in terms of potential, and there is almost no potential difference with the negative electrode plate over a longer period than when the surface is not covered and protected. A good state can be secured. It should be noted that both sides and side surfaces of each ear of the negative electrode ear row are protected by the L-shaped liquid-absorbent molding mat 6A, which is the same as in the above embodiment.
[0013]
  In the process of repeatedly charging and discharging the lead storage battery for a long time, the liquid-absorbing molded

mats

6, 6A, 6B are lifted upward by the extension of the

positive plates

3, 3,. Is separated from the upper end surface of the

retainers

4, 4, etc., and the supply of the electrolyte from the

retainers

4, 4, etc. is cut off, and the liquid

absorbent molding mats

6, 6 A, 6 B are eventually dried to prevent corrosion. There is a possibility that the purpose of this will not be achieved.
Due to the elongation of the

positive electrode plates

3, 3,..., Even if the lower surfaces of the liquid

absorbent molding mats

6, 6A, 6B are separated from the

retainers

4, 4,. Therefore, according to the present invention, when the liquid-absorbing

molding mats

6, 6 A, 6 B having various shapes are provided with a liquid-absorbing drooping portion that extends downward from the mats, The above-mentioned problem is solved by allowing the drooping portion to contact the upper side surface or side edge of the

retainers

4, 4,.
[0014]
Examples thereof are shown in FIGS.
FIG. 11 shows the lower surface of the U-shaped liquid-absorbing molding mat 6B, more specifically,Liquid absorptionFrom the center in the width direction of the lower surface of the tooth-

like protrusions

6b, 6b,.ReamCommon useLiquid-absorbing moldingFrom the bottom surface of the mat plate portion 6c, it is lowered downward andLiquid absorptionA liquid-absorbing molding mat 6B 'formed by integrally projecting liquid-absorbing

drooping members

6f, 6f,... Having a square cross section extending in the length direction of the tooth-like protrusions 6b, as shown in FIG. In addition, when the lead storage battery assembly C ′ is constructed by being mounted on the electrode plate group 1,Liquid absorptionThe lower surface of the tooth-like protrusion 6b is in contact with the upper end surfaces of the two

retainers

4 and 4, and the liquid-absorbing drooping member 6f at the center thereof is two retainers that protrude upward from the upper end surfaces of the positive and negative electrode plates. 4 is inserted into the space between the four

retainers

4 and 4, and the upper opposing side surfaces 4a of the

retainers

4 and 4 project from each other are in contact with both side surfaces of the liquid-absorbing drooping member 6f. And theLiquid absorptionEven if the lower surface of the tooth-like protrusion 6b is separated from the upper end surface of the

retainers

4 and 4, the liquid-absorbing drooping member 6f still maintains contact with the upper facing surfaces of the

retainers

4 and 4 on both sides thereof. The supply of the electrolytic solution from the

retainers

4 and 4 to the liquid absorbent molding mat 6B is maintained without being cut off.
[0015]
FIG. 13 shows a modified example of the liquid-absorbing molding mat 6B ′ shown in FIG.ReamCommon useLiquid-absorbing moldingA liquid-absorbing molded mat 6B ″ comprising a thin and flexible rectangular plate-shaped liquid-absorbing drooping member 6f that is integrally suspended over the entire length from the lower edge of the mat plate portion 6c. Then, as shown in FIG. 14, when the lead storage battery assembly C ″ is configured by being attached to the electrode plate group 1, the rectangular plate-like liquid-absorbing drooping member 6 f is provided by the

retainers

4, 4. Since the positive electrode plate 3 extends and the lower surface of the liquid-absorbing molding mat 6B ″ is pushed up, the

retainer

4, 4, since the contact with the retainer 4 is maintained at the lower end of the liquid-absorbing drooping member 6 f even if it is separated from the upper end surface of the liquid 4, the

retainers

4, 4. Maintained.
[0016]
Furthermore, by using a comb-shaped liquid-absorbing molding mat made of calcium sulfate as the comb-shaped liquid-absorbing molding mat used in the lead storage battery of the present invention, it is the same as the comb-shaped liquid-absorbing molding mat of the above embodiment. In addition to protecting the negative electrode strap and / or the

ear rows

2a, 2a,... From contact with oxygen gas and supplying the electrolyte, the oxidation is prevented and the potential difference is reduced. ... by supplying its own sulfate ions to the lead strap and / or the

lead

2a, 2a, ... to prevent the lead from dissolving in the sulfuric acid, to prevent the stratification phenomenon of the electrolyte and to be highly reliable for a long time Produces unique effects that lead to lead-acid batteries.
The comb-shaped liquid-absorbing molding mat made of calcium sulfate has various shapes as shown in FIGS. 1, 5, 8, 11, and 13 illustrated in the previous embodiment, if necessary.CombNeedless to say, the liquid-absorbing molded

mats

6, 6A, 6B, 6B 'and 6B "can be used.
[0017]
  Comb-shaped absorbent mats made of calcium sulfate are manufactured using anhydrous calcium sulfate (CaSO_Four) Powder or calcium sulfate 0.5 hydrate (CaSO_Four・ 0.5H₂O) The powder is mainly composed of a single powder or a mixture of both, and an appropriate amount of water or dilute sulfuric acid is added to the mixture, kneaded, and the paste is placed in a mold corresponding to the shape of the above various molding mats. After curing, the mold is demolded to obtain calcium sulfate dihydrate (CaSO_Four・ 2H₂O) A simple and inexpensive comb-shaped liquid-absorbing molding mat made of so-called gypsum can be produced.
  In addition, in order to increase the liquid absorption, adhesion to the negative electrode strap and the ear, the anhydrous calcium sulfate powder and / or calcium sulfate 0.5 hydrate powder, which is the above molding raw material, is acid-resistant natural. Or add appropriate amount of filler such as synthetic organic short fiber, inorganic short fiber and powder such as glass and silica, acid resistant pulp, rubber or synthetic resin powder, porous powder such as vermiculite, water or dilute sulfuric acid A paste formed by kneading and reacting and curing as described above can be used as a calcium sulfate-based comb-shaped liquid-absorbing molding mat imparted with microporosity and soft elasticity.
[0018]
  The comb-shaped liquid-absorbing

molding mats

6, 6 A,... 6 B ″ having different shapes made of calcium sulfate are respectively shown in FIGS. 1 to 4, 6 to 7, 9 to 10, 12, and 14. As described above, when attached to the negative electrode strap 5 of the electrode plate group and / or the

ear rows

2a, 2a,... .
  That is, each of the lead storage batteries 1 including the respective lead storage battery assemblies A, B, C, C ′, and C ″ of the sealed lead storage battery is formed of a porous calcium sulfate comb attached to the negative electrode strap 5. In order to absorb the electrolytic solution absorbed at the time of injection and the electrolytic solution contained in the retainer, the absorbent absorbent mat can supply the electrolytic solution to the surface of the negative electrode strap 5 over a long period of time. When the concentration is low enough to increase the dissolution of lead sulfate, calcium sulfate ionizes and supplies sulfate ions in preference to the dissolution of lead in the negative electrode strap 5 and the ear 2a. The dissolution of the lead sulfate layer, which is a protective film, is suppressed because the solubility product Ksp of calcium sulfate is 6 × 10^-FiveAnd the solubility product Ksp of lead sulfate is 2 × 10^-8Pb from lead sulfate causing negative electrode strap 5 corrosion²⁺Before ionization begins, the ions dissociate preferentially and Ca²⁺And SO_Four ^2-SO to supply_Four ^2-It is estimated that the lead sulfate layer, which is a protective film, can be protected over a long period of time due to the suppression of ionization of lead sulfate due to the common ion effect, and is effective for long-term use such as float charging for long-term backup power sources of batteries It is.
  At the same time, the movement of ions to the negative electrode strap 5 is facilitated, so that the potential difference between the negative electrode plate 2 and the upper surface of the negative electrode strap 5 is reduced, and the electric potential of the upper surface of the negative electrode strap 5 at the point of corrosion becomes more stable. Because of the shift, corrosion can be suppressed also in terms of potential.
[0019]
  Next, the comparative test will be described in detail.
  Example 1
  Acid-resistant pulp is used as the insulating material, and 3% by weight of acrylic adhesive is added and mixed into the three molds. A liquid molding mat is molded, and five negative plates and four positive plates are laminated through a retainer made of glass fibers having dimensions larger than those of the positive and negative plates, and protrude left and right on the upper surface of the laminate. The assembled negative electrode plate ear row and positive electrode plate ear row were attached to an electrode plate group produced by connecting the negative electrode strap and the positive electrode strap by a cast-on strap method to constitute an assembly A for a lead storage battery.
  Example 2
  Using the same mixture as in Example 1, the L-shaped liquid-absorbing molding mat shown in FIG. 5 is formed in the same manner, and this is mounted on the same electrode plate group as in Example 1 to constitute the lead-acid battery assembly B. did.
  Example 3
  Using the same mixture as in Example 1, a U-shaped liquid-absorbing molding mat shown in FIG. 8 was formed in the same manner, and this was mounted on the same electrode plate group as in Example 1 to constitute a lead-acid battery assembly C. did.
  Example 4
  Instead of the comb-shaped liquid-absorbing molding mat mainly composed of acid-resistant pulp used in Example 1, a paste obtained by kneading calcium sulfate 0.5 hydrate powder with an appropriate amount of water was put into a mold, and reaction-cured and demolded. 1 is used to construct a lead-acid battery assembly D by using the thick plate-like calcium sulfate dihydrate comb-shaped absorbent absorbent mat shown in FIG. did.
  Comparative Example 1
  Four liquid-absorbing molding mats corresponding to the mat-like body disclosed in JP-A-4-249064 were prepared using the mixture used in Example 1 as a material, and these were used in Example 1. An assembly for a lead storage battery was constructed in which each of the absorbent mats was inserted between the ears of the electrode plate group, and the four circumferential surfaces of the respective liquid-absorbent mats were brought into close contact with the lower surface of the negative electrode strap, the opposing inner surface between adjacent ears, and the upper end surface of the retainer. .
  Comparative Example 2
  Following the disclosure in Japanese Patent Application Laid-Open No. 8-162149, a liquid-absorbing molding mat is molded in advance using the mixture used in Example 1 integrally with the upper end of the retainer used in Example 1. 5 negative plates and 4 positive plates were laminated through the retainer with a liquid molding mat, and the positive and negative electrode straps were respectively connected to the positive and negative electrode rows to form a plate group. At that time, the liquid absorbent molding mat integral with the upper part of each retainer constituted a lead-acid battery assembly in a state of being in close contact with the lower surface of the negative electrode strap and the inner surface facing each other between adjacent ears.
  Comparative Example 3
  Following the disclosure in Japanese Utility Model Publication No. 2-18923, the gaps of the non-liquid-absorbing and comb-shaped insulating plates made of polyester are provided in the positive and negative electrode ear rows of the electrode plate group used in Example 1 above the straps. A lead-acid battery assembly was constructed that was inserted into each ear and inserted into close contact with a space between the ears.
[0020]
  Next, each of the above lead storage battery assemblies is housed in a rectangular battery case composed of one cell chamber according to a conventional method, and 3 kg of dilute sulfuric acid electrolyte solution with a specific gravity of 1.30 is injected, and the lid is sealed. MSE200 sealed lead-acid batteries A, B, C, D, E, F, and G were produced. In this case, a mercury / mercuric sulfate reference electrode was installed in the electrode plate group so that the negative electrode potential and the strap potential could be measured. Next, after charging / discharging each sealed storage battery for 2 cycles and confirming that the capacities are almost equal, charging is performed at a constant voltage of 2.23 V / cell, and the charging current drops and stabilizes. From the above, the potential of each part was measured. The results are shown in Table 1 below.
[0021]
[Table 1]

[0022]
  From Table 1 above, the batteries A, B, C, and D of Examples 1, 2, 3, and 4 are different from the batteries E, F, and G of Comparative Examples 1 to 3 in the potential difference between the negative electrode plate and the upper surface of the negative strap. It can be seen that the corrosion prevention effect is large.
  Pb / Pb²⁺Since the equilibrium potential is around -950 mV, the corrosion area is removed because it is the reduction area on the upper surface of the negative electrode strap of batteries A, B, C, and D of Examples 1, 2, 3, and 4, It can be seen that Comparative Examples 1 to 3 are oxidative corrosion areas and corrosion cannot be avoided.
  Furthermore, when these sealed batteries were subjected to a float charge test at 2.23 V in a 50 ° C. atmosphere for 3 months and observed changes, the batteries A, B, C, and D of Examples 1, 2, 3, and 4 were negative straps. No corrosion was observed. In the batteries E and F of Comparative Examples 1 and 2, corrosion was observed on the upper surface and side surfaces of the negative electrode strap and the side surfaces of the ears. In the battery G of Comparative Example 3, generation of corrosion was observed on the upper and side surfaces of the strap and the opposite and side surfaces of the ear. As shown in Examples 1 to 3, in general, the area covered tightly by the liquid-absorbing molding mat is large, and the negative electrode strap and the ear surface are always wet by supplying the electrolytic solution in a state of being blocked from oxygen gas. It can be seen that the lower the potential difference, the smaller the potential difference and the greater the corrosion prevention effect.
[0023]
  In the above embodiment, the liquid-absorbing molded mat of the present invention has been described as applied to a sealed lead-acid battery. However, in a liquid-type lead-acid battery in which an electrode plate group is immersed, the liquid level is below a regulation level. It is also effective when lowered.
[0024]
【The invention's effect】
  As described above, according to the present invention, the lower surface of the negative electrode strap and the negative electrode ear of the electrode plate group disposed through the ear insertion slit formed to open at one end of the thick plate shape separately from the electrode plate group. The liquid-absorbing tooth-like projections that are in close contact with the opposite surface of the adjacent ears of the row and the upper end surface of a separator such as a retainerFor connectionLiquid absorptionMoldingWe have prepared a thick plate-shaped comb-shaped liquid-absorbing molding mat connected to the mat plate.Liquid absorptionInsert the dents into the adjacent ear spaces of the plate group andFor connectionLiquid absorptionMoldingBy bringing the mat plate part into contact with the side of each ear of the ear row,Liquid absorptionClose contact of the four circumferential surfaces of the tooth-like protrusions to the inner surface of the negative electrode strap and the adjacent surface of each adjacent ear of the negative electrode ear row;Longitudinal connectionLiquid absorptionMoldingThe mat plate part can be brought into close contact with the side of each ear at once, and the mounting operation to the electrode plate group can be easily and quickly performed compared to the conventional structure, and the assembly for the lead storage battery is configured easily and quickly. In addition, the lead-acid battery having this can wet the surface of the electrode plate ears with the electrolytic solution from the retainer in contact with the comb-shaped liquid-absorbing molding mat, and can prevent oxidative corrosion well.
  In the present invention, an L-shaped liquid-absorbing molding mat or a U-shaped liquid-absorbing molding mat provided integrally with the comb-shaped liquid-absorbing molding mat is prepared. At the same time as attaching to the electrode plate group, each lead-acid battery assembly with the side surface of the negative strap or the upper surface thereof closely coated with the liquid-absorbent mat plate portion and further guaranteed to prevent oxidative corrosion is simple and quick. Is obtained. However, since the electrolyte is always supplied from the retainer to the surface of the lead storage battery in a state where it is cut off from oxygen gas, the lead storage battery including these lead storage battery assemblies has the opposite surface and side surface of the negative electrode ear and the lower surface of the negative electrode strap. In addition, the side surface and the upper surface are blocked from contact with oxygen gas, and at the same time, the electrolytic solution from the retainer is always supplied to these surfaces, so that the oxidative corrosion of the negative electrode ear and the negative electrode strap can be prevented. The potential difference between the potential of the negative electrode and the potential of the negative electrode plate can be reduced or made almost zero, and the reduction potential can be maintained to prevent corrosion over a long period of time.
  Furthermore, when these liquid-absorbing molding mats are provided with liquid-absorbing drooping parts, the lower-end part of the liquid-absorbing molding mat is brought into contact with the retainer at the same time that the comb-shaped liquid-absorbing molding mat is mounted on the electrode plate group. Therefore, even if the positive electrode plate extends, an effect of maintaining the supply of the electrolytic solution from the retainer through the liquid-absorbing hanging portion is brought about.
  Further, when each of the comb-shaped liquid-absorbing molding mats having different shapes according to the present invention is made of calcium sulfate, the above-described negative electrode strap or / and the ear are provided with an antioxidant effect and supply of sulfuric acid to the electrolytic solution. On top of that, when the electrolyte concentration decreases with long-term use, sulfate ions of calcium sulfate are supplied to prevent dissolution by the electrolyte solution of the negative electrode strap and the ear, and also suppress the stratification phenomenon of the electrolyte, Provides a highly reliable lead acid battery.
[Brief description of the drawings]
FIG. 1 is an exploded perspective view of an example lead-acid battery assembly according to an embodiment of the present invention.
2 is a top view of the main part of a lead storage battery including the lead storage battery assembly of FIG. 1. FIG.
3 is a sectional view taken along line III-III in FIG.
4 is a sectional view taken along line IV-IV in FIG. 2;
FIG. 5 is a perspective view of a liquid absorbent molding mat according to another embodiment of the present invention.
6 is a cross-sectional view similar to FIG. 4 of a lead storage battery including a lead storage battery assembly in which the liquid-absorbing molded mat shown in FIG. 5 is mounted on an electrode plate group.
7 is a sectional view taken along line VII-VII in FIG.
FIG. 8 is a perspective view of a liquid absorbent molding mat according to still another embodiment of the present invention.
9 is a cross-sectional view similar to FIG. 4 of a lead storage battery including a lead storage battery assembly in which the liquid-absorbing molded mat shown in FIG. 8 is mounted on an electrode plate group.
10 is a sectional view taken along line XX in FIG. 9;
FIG. 11 is a perspective view of a liquid absorbent molding mat according to a modification of the present invention.
12 is a cross-sectional view similar to FIG. 4 of a lead storage battery including a lead storage battery assembly in which the liquid-absorbing molded mat shown in FIG. 11 is mounted on an electrode plate group.
FIG. 13 is a perspective view of a liquid-absorbing molding mat according to a further modification of the present invention.
14 is a cross-sectional view similar to FIG. 3 of a lead storage battery including a lead storage battery assembly in which the liquid-absorbing molded mat shown in FIG. 13 is mounted on an electrode plate group.
[Explanation of symbols]
  1 plate group
  6 Comb-shaped absorbent mat
  6A L-shaped liquid absorbent molding mat
  6B U-shaped liquid absorbent molding mat
  6B ', 6B "Liquid-absorbing molding mat with hanging parts
  6a Slit for ear insertion
  6b Absorbent dentate protrusion
  6c LongitudinalFor connectionLiquid absorptionMoldingMatt board
  6dstrapLong liquid-absorbing mat plate for side contact
  6e For adhesion of negative electrode strap upper surfaceLongitudinalAbsorbent mat board
  6f hanging part
  A, B, C, C ', C "assembly for lead acid battery
  2 Negative electrode plate
  2a Negative electrode ear
  3 Positive plate
  4 Retainer
  4a Side of retainer
  4b Side edge of retainer
  5 Negative strap
  7 space
  8 battery case
  S space
  9 U-shaped groove

Claims

A negative electrode plate and a positive electrode ear row which are projected on both sides of the upper surface of the laminate obtained by laminating a negative electrode plate and a positive electrode plate for a lead storage battery via a retainer and are connected in a row with a negative electrode strap and a positive electrode strap, respectively. Separately from the group, a plurality of liquid-absorbing tooth-like projections arranged in the presence of an ear insertion slit opened at one end of the liquid-absorbing thick plate-like mat and these liquid-absorbing tooth-like protrusions are connected in common. In addition, a thick plate-like comb-shaped liquid-absorbing molding mat is prepared by integrally molding a long- joint liquid-absorbing molding mat plate portion that is in contact with and in close contact with at least the middle ear side surface of the negative electrode ear row. The comb-shaped liquid-absorbing molding mat is inserted into the ear-inserting slit in close contact with the middle ear of the negative-electrode ear row of the electrode plate group, and the respective liquid-absorbing tooth-like projections are formed on the lower surface of the negative electrode strap. And the corresponding space surrounded by the opposite surface of each adjacent ear The insertion, the lower surface of the negative electrode strap four circumferential surfaces of the respective liquid-absorbent teeth, opposing surfaces of Aitonaru ear, with allowed to contact the upper end surface of the retainer, connecting a liquid-absorbent molding mat board hand the long A lead-acid battery comprising a lead-acid battery assembly, wherein the electrode plate group is attached so that the portion is in contact with and in close contact with at least a middle ear side surface of the negative electrode ear row.

The longitudinal liquid-absorbing mat plate of the comb-shaped liquid-absorbing molded mat according to claim 1, wherein the upper surface of the longitudinal connection liquid-absorbing molded mat plate portion is extended and brought into contact with and in close contact with the side surface of the negative electrode strap. A lead having an L-shaped liquid-absorbing molding mat formed by integrally molding a portion, and the comb-shaped liquid-absorbing molding mat is attached to the electrode plate group as described in claim 1. A lead storage battery comprising an assembly for a storage battery.

The L-shaped liquid-absorbent molding mat according to claim 2 is horizontally extended from the upper edge of the long liquid-absorbent mat plate portion that is in contact with and in close contact with the side surface of the negative electrode strap and is in close contact with the upper surface of the negative electrode strap. A U-shape formed by integrally forming a longitudinal liquid-absorbent mat plate portion and forming a U-shaped concave groove with a space for tightly fitting a negative strap between the lower surface and the upper surface of the row of teeth. A lead-acid battery comprising a storage battery assembly, characterized in that a liquid-like liquid-absorbing molding mat is prepared, and the comb-shaped liquid-absorbing molding mat is attached to the electrode plate group as described in claim 1. .

4. A liquid-absorbing mold comprising the liquid-absorbing molding mat of any one of claims 1 to 3 provided with a liquid-absorbing drooping portion extending downward from the mat and contacting the upper side surface or side edge of the retainer. A lead storage battery comprising an assembly for a storage battery, characterized in that a molding mat is prepared, and the comb-shaped liquid-absorbing molding mat is attached to the electrode plate group as described in claim 1.

The lead acid battery according to any one of claims 1 to 4, wherein the liquid-absorbing molded mat is made of calcium sulfate.

Calcium sulfate comb-shaped absorbent mats are prepared by adding a paste prepared by kneading anhydrous calcium sulfate powder and / or calcium sulfate 0.5 hydrate powder with water or dilute sulfuric acid into a predetermined mold, and performing reaction hardening and removal. The lead acid battery according to claim 5, which is formed by molding.