JP4501330B2 - Lead acid battery - Google Patents
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- JP4501330B2 JP4501330B2 JP2002150321A JP2002150321A JP4501330B2 JP 4501330 B2 JP4501330 B2 JP 4501330B2 JP 2002150321 A JP2002150321 A JP 2002150321A JP 2002150321 A JP2002150321 A JP 2002150321A JP 4501330 B2 JP4501330 B2 JP 4501330B2
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- 239000002253 acid Substances 0.000 title claims description 9
- 210000000988 bone and bone Anatomy 0.000 claims description 14
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 11
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 229910001245 Sb alloy Inorganic materials 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 210000005069 ears Anatomy 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 229910000882 Ca alloy Inorganic materials 0.000 description 2
- 229910014474 Ca-Sn Inorganic materials 0.000 description 2
- 102100023170 Nuclear receptor subfamily 1 group D member 1 Human genes 0.000 description 2
- 229910020220 Pb—Sn Inorganic materials 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000009784 over-discharge test Methods 0.000 description 1
- 238000009783 overcharge test Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Connection Of Batteries Or Terminals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、特に正極を構成する部材にはアンチモン（Ｓｂ）を含まない鉛蓄電池に関するものである。
【０００２】
【従来の技術】
従来の鉛蓄電池の正極格子体にはＰｂ−Ｓｂ合金が用いられていたが、減液が多く保存特性に優れないなどの問題があった。この理由として、鉛蓄電池を充放電すると、徐々に正極格子体に含まれているＳｂが溶出して負極に析出し、析出したＳｂによって負極における水素過電圧が低下して水素ガスが発生しやすくなることが原因である。さらに電池の充放電を継続して行うと、すると負極上のＳｂ析出量が増加し、さらに減液が進行する。減液が進行しても補水を怠った場合には、負極棚および負極耳部が電解液から露出する。一旦これらの負極部材が電解液から露出すると急激に腐食が進行し、短寿命に至る問題があった。
【０００３】
【発明が解決しようとする課題】
近年、このような腐食とこれによる短寿命を抑制するために、正極格子体には実質上Ｓｂを含まないＰｂ−Ｃａ−Ｓｎ合金を用いた、優れたメンテナンスフリー性を持つ電池が一般化している。しかし、正極板を集合溶接する正極棚や棚から導出した正極柱もしくは正極接続体にはＳｂを含むＰｂ−Ｓｂ合金を用いることが一般的に行われてきた。
【０００４】
正極格子体にＳｂを含まないＰｂ合金を用いた蓄電池はＰｂ−Ｓｂ合金を用いた蓄電池に比較して大幅に減液量は低下するものの、蓄電池の寿命末期において正極の棚、極柱および接続体に含まれるＳｂが負極耳部を中心とする部分に偏析する傾向があることがわかってきた。このようなＳｂが偏析した負極耳部が電解液から露出した場合、負極耳部の表面で腐食が進行して厚みが薄くなることによって、耳部の強度が低下してしまうという課題があった。
【０００５】
前記した課題を解決するために、本発明の請求項１の発明は格子耳部と格子骨部からなる負極格子を備えた負極板と格子耳部と格子骨部からなる正極格子を備えた正極板を有し、同極性の極板耳部を集合溶接する棚およびこの棚より導出された極柱もしくは接続体を備えた鉛蓄電池において、正極格子と正極棚と正極極柱および正極接続体で構成される正極部材は実質上Ｓｂを含有しない鉛もしくは鉛合金からなり、負極格子と負極棚と負極極柱および負極接続体で構成される負極部材のうち負極格子骨部を除く部位は実質上Ｓｂを含有しない鉛もしくは鉛合金からなり、負極格子骨部はＳｂを含み、前記Ｓｂの負極活物質量に対する含有量が０．００１〜０．１質量％であるとともに、正極格子の正極活物質と接する表面の少なくとも一部に、Ｓｎを２％以上含有する鉛合金層を備えることを特徴とする鉛蓄電池を示すものである。
【０００７】
【発明の実施の形態】
本発明の実施の形態による鉛蓄電池を図面を用いて説明する。
【０００８】
図１は本発明の鉛蓄電池を構成する極板群１を示す破載図である。正極板（図示せず）は正極耳部１と正極格子骨（図示せず）とで構成される正極格子体に活物質が充填された構成を有している。この正極板と負極板２がセパレータ３を介して互いに対向している。
【０００９】
負極板２は負極耳部５と負極格子骨４とで構成される負極格子体６を有している。同極性の耳部同士を集合溶接してそれぞれ正極棚８および負極棚７が形成され、それぞれの棚に極柱もしくは接続体が形成される。図１に示した例では正極、負極ともにそれぞれ棚に正極接続体８および負極接続体９を設けた例を示している。
【００１０】
本発明において正極耳部１、正極格子骨、正極棚８、正極接続体８および正極極柱（これらを総称して正極部材）は実質上Ｓｂを含まないＰｂもしくはＰｂ合金で構成する。ただし、数ｐｐｍ程度の不純物として含まれるＳｂは除く。正極においては酸化腐食が進行するため、Ｐｂ−Ｓｎ合金を用いることが好ましい。
【００１１】
一方、負極に関しては負極耳部５、負極棚７、負極接続体９および負極極柱を正極部材と同様、実質上Ｓｂを含まないＰｂもしくはＰｂ合金で構成する。ただし、負極格子骨４にＳｂを含むよう構成する。負極格子骨にＳｂを含有させる場合、特にメンテナンスフリー電池において負極格子体６をＰｂ−Ｃａ合金で構成する場合にはＰｂ−Ｃａ合金表面にＳｂを含む層、具体的にはＰｂ−Ｓｂ合金層を配置する。
【００１２】
本発明においては負極格子骨４に添加するＳｂ量を負極活物質量に対して０．００１質量％〜０．１質量％の範囲に限定する。このような極板群を用い、定法に従って組み立てることにより本発明の鉛蓄電池を得ることができる。
【００１３】
さらに、正極格子体の正極活物質と接触する表面の少なくとも一部に２質量％以上のＳｎを含むＰｂ−Ｓｎ合金層を配置する。
【００１４】
この本発明の構成による電池は、上述した課題である寿命サイクル時の減液の増加を抑制して、かつ負極における腐食を解消し、優れた寿命性能を寄与するものである。
【００１５】
【実施例】
本発明例および従来例による電池を作成し、過充電試験および過放電試験を行うことによって減液量、負極耳部の腐食の有無および充電受け入れ性の評価を行った。
【００１６】
本発明の鉛蓄電池の正極格子体にはＰｂ−Ｃａ−Ｓｎ合金を用い、合金組成はＰｂ−０．０７質量％Ｃａ−１．３質量％Ｓｎである。この合金（シート１）を段階的に圧延した後にエキスパンド加工を行って格子体を形成し、活物質ペーストを充填して正極板（Ｐ１）を作製した。また、シート１に厚さ約０．２ｍｍのＰｂ−７質量％Ｓｎ合金（シート２）を重ね合わせて段階的に圧延し、以後同様の過程を経て正極板（Ｐ２）を作製した。一方、負極板はＰｂ−０．０７質量％Ｃａ−０．２５質量％Ｓｎ合金（シート３）を、正極と同様に圧延した後エキスパンド加工を経て格子体を作成した。その後、活物質量に対してＳｂを０．０１０質量％添加した活物質ペーストを格子体に充填して負極板（Ｎ１）を得た。また、シート４に厚さ約０．２ｍｍのＰｂ−２質量％Ｓｂ合金（シート４）を重ね合わせて段階的に圧延し、以後同様の過程を経て負極板（Ｎ２）を作製した。セパレータには、厚さ約０．３ｍｍの微孔性ポリエチレン製シートを用いて、正極板を包み込む形の袋状セパレータを作製した。
【００１７】
上記の２種類の正極板と２種類の負極板を用いて、１セル当たり正極板５枚と負極板６枚から成る極板群を用いて５５Ｄ２３形の自動車用鉛蓄電池（１２Ｖ４８Ａｈ）を作製した。また、極板群を形成する際、正極における極板を接続する棚及びセル間を接合する接続体にはＳｂを含有しない合金を用いて正極全体にＳｂを含有しない構成とした。
【００１８】
また、比較のために（従来の製造法による）、シート１に厚さ約０．２ｍｍのＰｂ−７質量％Ｓｂ合金（シート５）を重ね合わせて段階的に圧延し、以後同様の過程を経て正極板を作製した（Ｐ０）。負極板はシート３を段階的に圧延して同様の過程を経て作製した（Ｎ０）。この格子体を用いた構成の電池を従来例の電池とした。詳細な電池構成の条件を表１に示す。
【００１９】
【表１】
≪試験１≫
各々異なる構成の電池について、課題である減液特性と負極における腐食を評価するために次のようなパターンの寿命試験を実施した。この寿命試験は過充電傾向の使われ方を想定した試験パターンであり、７５℃雰囲気中で１３．８Ｖ定電圧充電を連続で１２０時間行うサイクルを繰り返した。また、減液が進行して極板上部が電解液から露出した状態を想定するために、電解液を下限水準に減らした状態で試験を行った。その後、負極耳表面に生成した腐食生成物を除去、負極耳厚みの測定を行い、初期状態の耳厚みに対する試験終了後の耳厚みの比率を百分率で求めた。
【００２１】
この試験結果を表１に示す。表内の寿命試験評価は、従来の構成からなる電池Ａの減液量及び腐食度を１００として各々の構成からなる電池を比較した。従来例の電池Ａは、正極において図１に示すような箇所の接続体、棚、格子体表面にＳｂを含有し、負極にはＳｂを含まない構成である。これに対してＢ１〜Ｃ２は各電池とも正極にＳｂを含まず、負極にＳｂを含有する構成の電池である。従来例の電池Ａに対してＢ１〜Ｃ２は減液量が約７〜８割程度と少ない結果であった。特に従来例Ａは、初期における減液は少なかったものの、サイクルが進行すると徐々に減液が増大する傾向が見られた。これは、サイクルが進行するに従って正極に含有しているＳｂが溶出して負極に析出し、水素過電圧が低下して水素ガスが発生することに起因していると考えられる。初期は正極から負極へのＳｂ析出量も少ないが、サイクル進行に伴い徐々にＳｂ析出量も増加して減液が増大したと考えられる。これに対してＢ１〜Ｃ２は、正極のＳｂを排除してあらかじめ負極に微量なＳｂを付与することで、サイクル進行に伴う減液の増大を解消し適度な減液量に抑制している結果と想定できる。また、Ｂ１とＢ２においてはややＢ１の減液量が多かった。この理由は明確ではないが、Ｂ１は負極活物質上にＳｂが存在しているために、Ｓｂ上での反応表面積がＢ２より広範囲であることが考えられる。
【００２２】
また、従来例Ａは負極棚部及び耳部において腐食の進行が見られたが、Ｂ１〜Ｃ２においては全く腐食が見られず初期と同じ状態であった。この理由としては、従来例Ａの正極に含有されているＳｂが起因していると推察できる。前述したように正極のＳｂは、サイクル進行に伴って溶出して負極に析出するが、極板内でも反応利用度が高いと考えられる上部に多く析出する。特に活物質で覆われていない棚部や極板耳部及び上枠骨にＳｂが偏析すると推定される（図２に負極板の耳部及び上枠骨を示す）。サイクル進行に従って、Ｓｂが偏析した箇所は露出して、表面は薄い液膜に覆われてｐＨが増大すると考えられる。その後、ｐＨ増大によってＰｂの溶解が起こりやすくなり、Ｓｂ上では水素ガスが発生し、Ｐｂ上ではＰｂが溶解して硫酸鉛が生成する局部電池を形成して、腐食が進行していると推察される。これに対して、Ｂ１〜Ｃ２は正極にＳｂを含んでいないために、電解液へ溶出して負極上部に析出することもなく、電解液が減少して負極上部が露出しても局部電池を形成しないために腐食が進行しなかったと考えられ、腐食を防止しているといえる。また、Ｂ１〜Ｃ２において腐食に差異は見られなかった。このことからも腐食は正極のＳｂが溶出して負極上部へ析出していることが原因であることが言え、正極にＳｂが含有されてない電池では差が見られなかったと考えられる。
【００２３】
≪試験２≫
次に、前記した過充電傾向を想定した寿命試験とは別に過放電放置を想定した試験を行った。この試験条件は、９．６Ａで５時間定電流放電を実施した後に、４０℃雰囲気中で１０Ｗの負荷を接続して１４日間放電し、負荷を取り外して開路状態にして引き続き４０℃雰囲気中で１４日間放置した。その後、１５．０Ｖで４時間回復充電を実施した後、５時間率放電によって容量を評価した。この試験結果を（表１）に示す。表内の試験評価は、従来の構成からなる従来例Ａの回復容量を１００として各々の構成からなる電池を比較した。従来例Ａと比較して、Ｂ１とＢ２は著しく容量が低下していた。ところで、従来例Ａの正極格子表面のＳｂ層は、先に述べてきた充電受け入れ性を向上させる効果と共に、過放電放置後に格子体と活物質との界面に生成する不導態膜の影響を緩和する効果が知られている。よって、Ｂ１とＢ２は過放電放置によって生成した界面の不導体膜の影響を受け、充電しても回復できずに容量が低下したと考えられる。これに対して、Ｃ１と本発明例Ｃ２は従来例Ａと同等の容量が得られた。これは、Ｃ１と本発明例Ｃ２における正極格子体表面のＳｎ層が従来例ＡのＳｂ層と同様の効果が考えられ、生成した界面の不導体膜の影響を緩和していることが推定できる
【００２４】
以上のように、本発明の鉛蓄電池は、課題である負極棚部および負極耳部の腐食を抑制することができる。また、過放電放置の場合も想定して、正極格子体表面の少なくとも一部に、Ｓｎを２質量％以上含有する鉛合金層を形成する正極板を用いることにより、過放電放置後の充電受入れ性を改善できる。
【００２５】
以上、本発明の鉛蓄電池は、負極棚部および負極耳部の腐食が抑制できる。さらに、正極格子体表面の少なくとも一部に、Ｓｎを２質量％以上含有する鉛合金層を形成する正極板を用いるため、本発明の鉛蓄電池は過放電した場合も容量低下を防ぎ安定した特性を得ることができる。
【図面の簡単な説明】
【図１】極板群構成を示す一部破載図
【符号の説明】
１ 極板群
２ 正極耳部
３ セパレータ
４ 負極格子骨
５ 負極耳部
６ 負極格子体
７ 負極棚
８ 正極接続体
９ 負極接続体[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a lead-acid battery that does not contain antimony (Sb) in the member constituting the positive electrode.
[0002]
[Prior art]
A Pb—Sb alloy was used for the positive electrode grid of a conventional lead storage battery, but there were problems such as a large amount of liquid reduction and poor storage characteristics. The reason for this is that when the lead-acid battery is charged and discharged, Sb contained in the positive electrode grid gradually elutes and precipitates on the negative electrode, and the hydrogen overvoltage at the negative electrode is lowered by the deposited Sb, and hydrogen gas is easily generated. Is the cause. If the battery is continuously charged and discharged, the amount of Sb deposited on the negative electrode increases, and the liquid reduction proceeds. If water replenishment is neglected even if the liquid reduction proceeds, the negative electrode shelf and the negative electrode ear are exposed from the electrolyte. Once these negative electrode members are exposed from the electrolyte, there is a problem that the corrosion rapidly proceeds and the life is shortened.
[0003]
[Problems to be solved by the invention]
In recent years, in order to suppress such corrosion and the short life due thereto, a battery having an excellent maintenance-free property using a Pb—Ca—Sn alloy containing substantially no Sb in the positive electrode grid has been generalized. Yes. However, it has been generally performed to use a Pb—Sb alloy containing Sb for the positive electrode shelf for collective welding of the positive electrode plates, the positive electrode column derived from the shelf, or the positive electrode connector.
[0004]
The storage battery using a Pb alloy that does not contain Sb in the positive electrode lattice body has a significantly reduced liquid reduction compared to the storage battery using the Pb-Sb alloy, but at the end of the storage battery life, the positive electrode shelf, the pole column, and the connection It has been found that Sb contained in the body tends to segregate in a portion centering on the negative electrode ear. When the negative electrode ear portion where such Sb is segregated is exposed from the electrolytic solution, there is a problem that the strength of the ear portion is reduced due to the progress of corrosion on the surface of the negative electrode ear portion to reduce the thickness. .
[0005]
In order to solve the above-described problems, the invention of claim 1 of the present invention is a positive electrode including a negative electrode plate including a negative electrode lattice including a lattice ear portion and a lattice bone portion, and a positive electrode lattice including a lattice ear portion and a lattice bone portion. In a lead-acid battery having a plate and a shelf for collective welding of electrode plate ears of the same polarity and a pole column or connection body derived from this shelf, a positive grid, a positive shelf, a positive pole column, and a positive electrode connection body The constructed positive electrode member is made of lead or a lead alloy substantially containing no Sb, and the negative electrode member composed of the negative electrode lattice, the negative electrode shelf, the negative electrode pole column, and the negative electrode connecting body is substantially free from the portion of the negative electrode lattice. It is made of lead or lead alloy not containing Sb, the negative electrode lattice bone part contains Sb, the content of the Sb with respect to the negative electrode active material amount is 0.001 to 0.1% by mass, and the positive electrode active material of the positive electrode lattice At least part of the surface in contact with Shows the lead-acid battery, characterized in that it comprises a lead alloy
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The lead acid battery by embodiment of this invention is demonstrated using drawing.
[0008]
FIG. 1 is a broken view showing an electrode plate group 1 constituting the lead storage battery of the present invention. The positive electrode plate (not shown) has a configuration in which an active material is filled in a positive electrode lattice body composed of a positive electrode ear 1 and a positive electrode lattice bone (not shown). The positive electrode plate and the
[0009]
The
[0010]
In the present invention, the positive electrode ear 1, the positive electrode lattice bone, the
[0011]
On the other hand, with respect to the negative electrode, the
[0012]
In the present invention, the amount of Sb added to the
[0013]
Furthermore, a Pb—Sn alloy layer containing 2% by mass or more of Sn is disposed on at least a part of the surface of the positive electrode lattice body that contacts the positive electrode active material .
[0014]
The battery according to the configuration of the present invention suppresses the increase in liquid reduction during the life cycle, which is the problem described above, and eliminates corrosion in the negative electrode, thereby contributing to excellent life performance.
[0015]
【Example】
The batteries according to the examples of the present invention and the conventional examples were prepared, and the amount of liquid reduction, the presence or absence of corrosion of the negative electrode ears, and the charge acceptance were evaluated by performing an overcharge test and an overdischarge test.
[0016]
A Pb—Ca—Sn alloy is used for the positive electrode lattice of the lead storage battery of the present invention, and the alloy composition is Pb—0.07 mass% Ca—1.3 mass% Sn. This alloy (sheet 1) was rolled in stages and then expanded to form a lattice, and filled with an active material paste to produce a positive electrode plate (P1). Further, a Pb-7 mass% Sn alloy (sheet 2) having a thickness of about 0.2 mm was superposed on the sheet 1 and rolled in a stepwise manner, and thereafter, a positive electrode plate (P2) was produced through the same process. On the other hand, the negative electrode plate was rolled with a Pb-0.07 mass% Ca-0.25 mass% Sn alloy (sheet 3) in the same manner as the positive electrode and then expanded to form a lattice. Thereafter, an active material paste to which 0.010% by mass of Sb was added with respect to the amount of the active material was filled in the lattice body to obtain a negative electrode plate (N1). Further, a Pb-2 mass% Sb alloy (sheet 4) having a thickness of about 0.2 mm was superposed on the
[0017]
Using the above-mentioned two types of positive electrode plates and two types of negative electrode plates, a 55D23 type automotive lead acid battery (12V48Ah) was prepared using an electrode plate group consisting of 5 positive plates and 6 negative plates per cell. . Further, when forming the electrode plate group, the whole positive electrode was made to contain no Sb by using an alloy containing no Sb for the connecting body that connects the cells and the shelves connecting the electrode plates in the positive electrode.
[0018]
For comparison (according to a conventional manufacturing method), a Pb-7 mass% Sb alloy (sheet 5) having a thickness of about 0.2 mm is superimposed on the sheet 1 and rolled stepwise, and the same process is performed thereafter. After that, a positive electrode plate was produced (P0). The negative electrode plate was produced through a similar process by rolling the
[0019]
[Table 1]
≪Test 1≫
Each battery having a different configuration was subjected to a life test with the following pattern in order to evaluate the liquid reduction characteristics and the corrosion of the negative electrode, which are problems. This life test is a test pattern that assumes how the overcharge tendency is used, and a cycle in which 13.8 V constant voltage charge is continuously performed for 120 hours in a 75 ° C. atmosphere was repeated. Moreover, in order to assume the state where the liquid reduction progressed and the upper part of the electrode plate was exposed from the electrolytic solution, the test was performed with the electrolytic solution reduced to the lower limit level. Then, the corrosion product produced | generated on the negative electrode ear surface was removed, the negative electrode ear thickness was measured, and the ratio of the ear thickness after completion | finish of a test with respect to the ear thickness of an initial state was calculated | required in percentage.
[0021]
The test results are shown in Table 1. The life test evaluation in the table was made by comparing the batteries having the respective configurations with the liquid reduction amount and the corrosion degree of the battery A having the conventional configuration being 100. The battery A of the conventional example has a configuration in which Sb is contained on the surface of the connecting body, the shelf, and the lattice body in the positive electrode as shown in FIG. 1, and the negative electrode does not contain Sb. On the other hand , B1 to C2 are batteries each having a configuration in which Sb is not included in the positive electrode and Sb is included in the negative electrode. Compared to the battery A of the conventional example, B1 to C2 had a small liquid reduction amount of about 70 to 80%. In particular, in the conventional example A, although the liquid reduction at the initial stage was small, there was a tendency that the liquid reduction gradually increased as the cycle progressed. This is considered to be caused by the fact that Sb contained in the positive electrode is eluted and deposited on the negative electrode as the cycle progresses, and the hydrogen overvoltage is reduced to generate hydrogen gas. Initially, the amount of Sb deposited from the positive electrode to the negative electrode is small, but it is considered that the amount of Sb deposited gradually increased as the cycle progressed, and the liquid reduction increased. On the other hand , B1 to C2 eliminates the positive electrode Sb and gives a small amount of Sb to the negative electrode in advance, thereby eliminating the increase in liquid reduction accompanying the progress of the cycle and suppressing it to an appropriate liquid reduction amount. Can be assumed. Moreover, in B1 and B2, the amount of liquid reduction of B1 was somewhat large. The reason for this is not clear, but since Bb has Sb on the negative electrode active material, it is considered that the reaction surface area on Sb is wider than that of B2.
[0022]
Further, in the conventional example A, the progress of corrosion was observed in the negative electrode shelf portion and the ear portion, but in B1 to C2 , no corrosion was observed and the state was the same as the initial state. As this reason, it can be inferred that Sb contained in the positive electrode of Conventional Example A is caused. As described above, Sb of the positive electrode elutes with the progress of the cycle and deposits on the negative electrode. However, a large amount of Sb is deposited on the upper portion of the electrode plate, which is considered to have high reaction utilization. In particular, it is estimated that Sb segregates on the shelf portion, the electrode plate ear portion, and the upper frame bone that are not covered with the active material (the ear portion and the upper frame bone of the negative electrode plate are shown in FIG. 2). As the cycle progresses, the portion where Sb segregates is exposed, and the surface is covered with a thin liquid film, which is thought to increase the pH. Thereafter, Pb is easily dissolved by pH increase, and hydrogen gas is generated on Sb, and Pb dissolves on Pb to form a local battery in which lead sulfate is generated. Is done. On the other hand, since B1 to C2 do not contain Sb in the positive electrode, it does not elute into the electrolyte and deposit on the upper part of the negative electrode. It is considered that the corrosion did not proceed because it was not formed, and it can be said that the corrosion was prevented. Further , no difference was observed in corrosion between B1 and C2 . From this, it can be said that the corrosion is caused by the elution of Sb of the positive electrode and precipitating on the upper part of the negative electrode, and it is considered that no difference was observed in the batteries in which the positive electrode did not contain Sb.
[0023]
Next, in addition to the above-described life test assuming an overcharge tendency, a test assuming overdischarge was performed. The test conditions were as follows: after conducting a constant current discharge at 9.6 A for 5 hours, a 10 W load was connected in a 40 ° C. atmosphere and discharged for 14 days; Left for 14 days. Then, after carrying out recovery charging at 15.0 V for 4 hours, the capacity was evaluated by 5-hour rate discharge. The test results are shown in (Table 1). In the test evaluation in the table, the recovery capacity of the conventional example A having the conventional configuration was set to 100, and the batteries having the respective configurations were compared. Compared to Conventional Example A, the capacities of B1 and B2 were significantly reduced. By the way, the Sb layer on the surface of the positive electrode lattice in Conventional Example A has the effect of improving the charge acceptability described above and the influence of the non-conductive film generated at the interface between the lattice body and the active material after being left overdischarged. The mitigating effect is known. Therefore, it is considered that B1 and B2 are affected by the non-conductive film at the interface generated by being left overdischarged, and cannot be recovered even after charging, and the capacity is reduced. On the other hand, C1 and Example C2 of the present invention have the same capacity as Conventional Example A. This is because the Sn layer on the surface of the positive electrode grid in C1 and Invention Example C2 is considered to have the same effect as the Sb layer in Conventional Example A, and it can be estimated that the influence of the generated non-conductive film on the interface is mitigated. [0024]
As described above, the lead storage battery of the present invention can suppress the corrosion of the negative electrode shelf and the negative electrode ear , which are problems . In addition, assuming the case of overdischarge leaving, by using a positive electrode plate that forms a lead alloy layer containing 2 mass% or more of Sn on at least a part of the surface of the positive electrode grid body, accepting charge after being left overdischarged. Can improve sex.
[0025]
As mentioned above, the lead acid battery of this invention can suppress corrosion of a negative electrode shelf part and a negative electrode ear | edge part. Furthermore, since the positive electrode plate which forms the lead alloy layer containing 2% by mass or more of Sn on at least a part of the surface of the positive electrode lattice body is used, the lead storage battery of the present invention has stable characteristics that prevent a decrease in capacity even when overdischarged. Can be obtained.
[Brief description of the drawings]
FIG. 1 is a partially broken view showing the configuration of an electrode plate group.
DESCRIPTION OF SYMBOLS 1
Claims (1)
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| JP2002150321A JP4501330B2 (en) | 2002-05-24 | 2002-05-24 | Lead acid battery |
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| JP2002150321A JP4501330B2 (en) | 2002-05-24 | 2002-05-24 | Lead acid battery |
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Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006114417A (en) * | 2004-10-18 | 2006-04-27 | Matsushita Electric Ind Co Ltd | Lead-acid storage battery |
| JP4892827B2 (en) * | 2004-11-12 | 2012-03-07 | パナソニック株式会社 | Lead acid battery |
| JP4896392B2 (en) * | 2004-11-12 | 2012-03-14 | パナソニック株式会社 | Lead acid battery |
| JP2005302302A (en) * | 2004-04-06 | 2005-10-27 | Matsushita Electric Ind Co Ltd | Lead storage battery |
| JP4904686B2 (en) * | 2004-11-25 | 2012-03-28 | パナソニック株式会社 | Lead acid battery |
| JP2006114416A (en) * | 2004-10-18 | 2006-04-27 | Matsushita Electric Ind Co Ltd | Lead-acid battery |
| TWI251365B (en) * | 2004-04-02 | 2006-03-11 | Matsushita Electric Ind Co Ltd | Lead-acid battery |
| JP4904674B2 (en) * | 2004-08-27 | 2012-03-28 | パナソニック株式会社 | Lead acid battery |
| EP1737062B1 (en) | 2004-04-08 | 2008-09-17 | Matsushita Electric Industrial Co., Ltd. | Lead storage battery |
| JP5044888B2 (en) * | 2004-12-03 | 2012-10-10 | パナソニック株式会社 | Liquid lead-acid battery |
| JP2006164598A (en) * | 2004-12-03 | 2006-06-22 | Matsushita Electric Ind Co Ltd | Lead acid battery |
| DE602005023126D1 (en) * | 2004-04-28 | 2010-10-07 | Panasonic Corp | lead-acid battery |
| TWI333290B (en) * | 2004-06-16 | 2010-11-11 | Panasonic Corp | Lead-acid battery |
| CN108630900B (en) * | 2010-05-10 | 2021-11-09 | 新神户电机株式会社 | Lead-acid battery |
| DE112013000779T5 (en) * | 2012-01-31 | 2014-10-30 | Panasonic Corporation | Lead-acid battery |
| JP6197426B2 (en) * | 2013-07-16 | 2017-09-20 | 株式会社Ｇｓユアサ | Lead acid battery |
| CN114284583A (en) * | 2021-12-27 | 2022-04-05 | 河南超威正效电源有限公司 | Method for reducing EFB power-on and power-off pool water loss |
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| JPH01189859A (en) * | 1988-01-22 | 1989-07-31 | Japan Storage Battery Co Ltd | Lead-acid battery |
| JPH0574464A (en) * | 1991-09-12 | 1993-03-26 | Matsushita Electric Ind Co Ltd | Sealed lead-acid storage battery |
| JPH07211306A (en) * | 1994-01-20 | 1995-08-11 | Matsushita Electric Ind Co Ltd | Sealed lead-acid battery |
| JPH09283137A (en) * | 1996-04-11 | 1997-10-31 | Japan Storage Battery Co Ltd | Lead-acid battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS646374A (en) * | 1987-06-29 | 1989-01-10 | Matsushita Electric Ind Co Ltd | Lead storage battery |
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|---|---|---|---|---|
| JPH01189859A (en) * | 1988-01-22 | 1989-07-31 | Japan Storage Battery Co Ltd | Lead-acid battery |
| JPH0574464A (en) * | 1991-09-12 | 1993-03-26 | Matsushita Electric Ind Co Ltd | Sealed lead-acid storage battery |
| JPH07211306A (en) * | 1994-01-20 | 1995-08-11 | Matsushita Electric Ind Co Ltd | Sealed lead-acid battery |
| JPH09283137A (en) * | 1996-04-11 | 1997-10-31 | Japan Storage Battery Co Ltd | Lead-acid battery |
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