JP5088679B2 - Lead acid battery - Google Patents
Lead acid battery Download PDFInfo
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- JP5088679B2 JP5088679B2 JP2007228671A JP2007228671A JP5088679B2 JP 5088679 B2 JP5088679 B2 JP 5088679B2 JP 2007228671 A JP2007228671 A JP 2007228671A JP 2007228671 A JP2007228671 A JP 2007228671A JP 5088679 B2 JP5088679 B2 JP 5088679B2
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- lead alloy
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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
Description
本発明は、鉛蓄電池に関するものである。 The present invention relates to a lead-acid battery.
鉛蓄電池は、安価で信頼性が高いという特徴を有するために、自動車用のバッテリ、ゴルフカート等の電動車両の動力源、更には無停電電源装置等の産業機器用の蓄電池として広く使用をされている。 Lead storage batteries are inexpensive and highly reliable, and are widely used as storage batteries for automobile batteries, power sources for electric vehicles such as golf carts, and industrial equipment such as uninterruptible power supplies. ing.
鉛蓄電池の格子には、生産性の向上やメンテナンスフリー性の向上を目的として従来の鉛−アンチモン系合金からなる鋳造格子に代わってアンチモンを含有しない鉛−カルシウム−スズ合金シートをエキスパンド加工したエキスパンド格子が普及している。このエキスパンド格子は格子の水素過電圧を低下させるアンチモンを含有しないので電池の充電中におけるガス発生と、これによる電解液量の減少を抑制すると共に自己放電を抑制することができる利点がある。しかしながら、正極にこのようなアンチモンを含まない格子を用いた場合には、電池の深い充放電サイクルにおいて早期に容量が低下するという問題がある。 Expanded lead-calcium-tin alloy sheets that do not contain antimony instead of conventional lead-antimony alloy casting grids for the purpose of improving productivity and improving maintenance-free properties for lead-acid battery grids The lattice is widespread. Since this expanded lattice does not contain antimony which lowers the hydrogen overvoltage of the lattice, there is an advantage that self-discharge can be suppressed while suppressing gas generation during the charging of the battery and a decrease in the amount of electrolyte due to this. However, when such a lattice not containing antimony is used for the positive electrode, there is a problem that the capacity is quickly reduced in a deep charge / discharge cycle of the battery.
このような問題点を解決するために、特許文献１には格子表面にアンチモンを多量に含んだ層を形成させたエキスパンド格子が示されている。格子表面層に存在するアンチモンは充放電の繰り返しによる格子と活物質との密着性の低下を抑制し、それにより格子−活物質界面の硫酸鉛化を防ぐことができ、早期容量低下を抑制する。 In order to solve such problems, Patent Document 1 discloses an expanded lattice in which a layer containing a large amount of antimony is formed on the lattice surface. Antimony present in the lattice surface layer suppresses the decrease in adhesion between the lattice and the active material due to repeated charge and discharge, thereby preventing lead sulfate formation at the lattice-active material interface, thereby suppressing the early decrease in capacity. .
しかしながら、特許文献１ではアンチモンを含有した格子のため、ガス発生による電解液の減少と自己放電が増大する可能性がありメンテナスフリー性に問題があるように思われる。 However, in Patent Document 1, since it is a lattice containing antimony, there is a possibility that there is a possibility of a decrease in electrolyte due to gas generation and an increase in self-discharge, and there is a problem in maintainability.
本発明では、アンチモンを含まない鉛合金圧延シートをエキスパンド加工して得られた正極格子を用いた鉛蓄電池において、前記鉛合金圧延シートの表面に、酸素を含んでいる鉛合金粉末を圧延して作製された圧延層を有しており、前記鉛合金粉末の酸化度が８０％以下であることを特徴とする。さらに好ましくは、酸化度４０〜８０％の鉛合金粉末と酸化度０．０５％以下の鉛合金粉末を混合して作製された圧延層を有していることを特徴とする。さらに、酸化度４０〜８０％の鉛合金粉末と酸化度０．０５％以下の鉛合金粉末の配合比率が５：９５〜９５：５であることを特徴とする。 In the present invention, in a lead storage battery using a positive electrode grid obtained by expanding a lead alloy rolled sheet not containing antimony, a lead alloy powder containing oxygen is rolled on the surface of the lead alloy rolled sheet. have fabricated rolled layer, the degree of oxidation of the lead alloy powder is characterized in der Rukoto 80% or less. More preferably, it has a rolled layer produced by mixing a lead alloy powder having an oxidation degree of 40 to 80% and a lead alloy powder having an oxidation degree of 0.05% or less. Furthermore, the mixing ratio of the lead alloy powder having an oxidation degree of 40 to 80% and the lead alloy powder having an oxidation degree of 0.05% or less is 5:95 to 95: 5.
酸素を含んでいる鉛合金粉末を用いて作製された圧延シートは、表面が酸化され、その内部には金属部を有する構造になっている。これを圧延すると鉛合金粉末の表面酸化層が破壊されることで金属部が露出し、お互いの金属部同士が接触し、圧延シートとなる。表面酸化層は酸化鉛であり、鉛蓄電池の電解液である硫酸水溶液に触れると硫酸鉛に変化し、充電により二酸化鉛へと変化するため、酸素を含んでいる鉛合金粉末から作製された圧延シートは耐食性が低下する傾向がある。一方、活物質と集電体の密着性を考えた場合、熟成時の密着性が向上することにより、活物質の重負荷特性が向上することになる。したがって、著しく耐食性が低下してしまう場合は集電体としては使用できないが、集電体表面での活物質との密着性を向上するために使用することができる。 The rolled sheet produced using the lead alloy powder containing oxygen has a structure in which the surface is oxidized and a metal part is provided inside thereof. When this is rolled, the surface oxide layer of the lead alloy powder is destroyed, so that the metal part is exposed, and the metal parts come into contact with each other to form a rolled sheet. The surface oxide layer is lead oxide, and it changes to lead sulfate when it comes into contact with the sulfuric acid aqueous solution that is the electrolyte of lead-acid batteries, and changes to lead dioxide by charging, so the rolling made from lead alloy powder containing oxygen Sheets tend to have reduced corrosion resistance. On the other hand, when considering the adhesion between the active material and the current collector, the heavy load property of the active material is improved by improving the adhesion at the time of aging. Accordingly, when the corrosion resistance is remarkably lowered, it cannot be used as a current collector, but can be used for improving the adhesion with the active material on the surface of the current collector.
鉛合金粉末の酸化度が４０％以上になると密着性が安定する傾向がある。８０％以上になると圧延時の金属部同士の接触が不足し、圧延シートの作製が困難になる。そのため、金属同士の接触を確保するために、酸化度０．０５％以下の鉛合金粉末を少なくとも２０
％以上混ぜ合わせることにより、圧延シートの作製が可能となる。
When the oxidation degree of the lead alloy powder is 40% or more, the adhesion tends to be stabilized. If it is 80% or more, contact between metal parts at the time of rolling becomes insufficient, and it becomes difficult to produce a rolled sheet. Therefore, in order to ensure the contact between metals, at least 20 lead alloy powder having an oxidation degree of 0.05% or less is required.
By mixing at least%, a rolled sheet can be produced.
本発明により、アンチモンを含有しない鉛−カルシウム合金の格子における深い充放電サイクルによっておこる早期容量低下を抑制した鉛蓄電池を提供する。 According to the present invention, there is provided a lead storage battery in which an early capacity decrease caused by a deep charge / discharge cycle in a lattice of a lead-calcium alloy containing no antimony is suppressed.
以下具体例をあげ、本発明を更に詳しく説明するが、発明の主旨を越えない限り、本発明は実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples unless it exceeds the gist of the invention.
アンチモンを含有しない鉛−カルシウム合金からなる連続シートをエキスパンド加工して格子を得た。この格子に酸化鉛を主成分とする鉛粉と、鉛丹、カットファイバ、硫酸、水を混合したペーストを充填した。このようにして充填したものを熟成、乾燥して、未化成の正極板を作製した。次にこの未化成の正極板７枚と未化成の負極板８枚とをセパレーターを介して交互に配置し、希硫酸中で化成し２Ｖ単電池とした。 A continuous sheet made of a lead-calcium alloy containing no antimony was expanded to obtain a lattice. This lattice was filled with a paste in which lead powder containing lead oxide as a main component, red lead, cut fiber, sulfuric acid, and water were mixed. The product filled in this manner was aged and dried to produce an unformed positive electrode plate. Next, the seven unformed positive electrode plates and the eight unformed negative electrode plates were alternately arranged via separators, and formed in dilute sulfuric acid to obtain a 2V single cell.
次にガスアトマイズ製法により平均粒径が２０〜２５μｍの鉛合金粉末を作製した。鉛合金粉末は、酸化度（酸化鉛質量が粉末質量に占める百分率）により鉛合金粉末Ａと鉛合金粉末Ｂを作製し、配合比率を変えて混合する。この混合粉をロール間に投入して冷間圧延し、厚さ０．５ｍｍの圧延シートを作製する。ここで、鉛−カルシウム合金からなる連続シートを作製する際に、前記圧延シートを同時に圧延することで、集電体表面に鉛合金粉末から作製したを圧延層を存在するようにした。表面に存在する圧延シートに使用した鉛合金粉末の酸化度と配合比率の組み合わせを表１に示す。 Next, a lead alloy powder having an average particle size of 20 to 25 μm was prepared by a gas atomizing method. The lead alloy powder is prepared by preparing a lead alloy powder A and a lead alloy powder B according to the degree of oxidation (percentage of the lead oxide mass in the powder mass) and changing the blending ratio. This mixed powder is put between rolls and cold-rolled to produce a rolled sheet having a thickness of 0.5 mm. Here, when producing a continuous sheet made of a lead-calcium alloy, the rolled sheet was rolled at the same time, so that a rolled layer was formed on the current collector surface from the lead alloy powder. Table 1 shows combinations of oxidation degree and blending ratio of the lead alloy powder used for the rolled sheet existing on the surface.
続いて前述の製法と同様に正極板を作製し、２Ｖ単電池を作製した。
これらの電池を重負荷特性の評価として、５時間率サイクル試験（放電電流：７．２Ａ、温度２５℃、放電終止電圧：１．７５Ｖ、充電終止：放電量の１３０％）に供した結果も表１に示した。
Then, the positive electrode plate was produced similarly to the above-mentioned manufacturing method, and the 2V single battery was produced.
As a result of subjecting these batteries to a heavy load characteristic evaluation, they were subjected to a 5-hour rate cycle test (discharge current: 7.2 A, temperature 25 ° C., discharge end voltage: 1.75 V, charge end: 130% of the discharge amount). It is shown in Table 1.
この結果、鉛合金粉末から作製した圧延シートが集電体表面に存在することにより、重負荷特性が向上することがわかった。酸化度が４０％以上の鉛合金粉末を用いると圧延シートの作製が困難となり、歩留まりが悪化し、９０％以上では全く作製できなかった（表１中の仕様１〜１１）。そこで、酸化度８０％の鉛合金粉末と酸化度０．０５％の鉛合金粉末を５：９５〜９５：５の範囲で混ぜ合わせることにより、圧延シートの作製も可能となり、重負荷特性も良好な結果を得ることができた（表１中仕様１３〜１９）。 As a result, it was found that the heavy load characteristics were improved by the presence of the rolled sheet produced from the lead alloy powder on the surface of the current collector. When a lead alloy powder having an oxidation degree of 40% or more is used, it becomes difficult to produce a rolled sheet, the yield deteriorates, and when it is 90% or more, it cannot be produced at all (specifications 1 to 11 in Table 1). Therefore, by mixing lead alloy powder with an oxidation degree of 80% and lead alloy powder with an oxidation degree of 0.05% in the range of 5:95 to 95: 5, it becomes possible to produce a rolled sheet and good heavy load characteristics. Results were obtained (specifications 13 to 19 in Table 1).
以上のように本発明は、アンチモンを含有しない鉛−カルシウム合金の格子を用いた正極板において深い充放電サイクルによっておこる早期容量低下を抑制することが可能であり、工業的価値が極めて大きい。 As described above, the present invention can suppress an early capacity decrease caused by a deep charge / discharge cycle in a positive electrode plate using a lead-calcium alloy lattice that does not contain antimony, and has a great industrial value.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007228671A JP5088679B2 (en) | 2007-09-04 | 2007-09-04 | Lead acid battery |
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|---|---|---|---|
| JP2007228671A JP5088679B2 (en) | 2007-09-04 | 2007-09-04 | Lead acid battery |
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| JP2009064563A JP2009064563A (en) | 2009-03-26 |
| JP5088679B2 true JP5088679B2 (en) | 2012-12-05 |
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| JP6392601B2 (en) * | 2014-09-16 | 2018-09-19 | Ｄｏｗａホールディングス株式会社 | Nonferrous metal electrowinning method and anode manufacturing method used therefor |
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| JPH0896811A (en) * | 1994-09-27 | 1996-04-12 | Shin Kobe Electric Mach Co Ltd | Current collector for lead-acid battery and manufacture thereof |
| JP2002319409A (en) * | 2001-04-20 | 2002-10-31 | Japan Storage Battery Co Ltd | Lead acid storage battery anode current collector and lead acid storage battery using the same |
| JP4613550B2 (en) * | 2004-08-26 | 2011-01-19 | 新神戸電機株式会社 | Lead-acid battery current collector and lead-acid battery |
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