JP2005302395A - Lead storage battery - Google Patents
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- JP2005302395A JP2005302395A JP2004113827A JP2004113827A JP2005302395A JP 2005302395 A JP2005302395 A JP 2005302395A JP 2004113827 A JP2004113827 A JP 2004113827A JP 2004113827 A JP2004113827 A JP 2004113827A JP 2005302395 A JP2005302395 A JP 2005302395A
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
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.
車両のエンジン始動用やバックアップ電源用といった様々な用途に鉛蓄電池が用いられている。その中でも始動用の鉛蓄電池は、エンジン始動用セルモータへの電力供給とともに、車両に搭載された各種電気・電子機器へ電力を供給する。エンジン始動後、鉛蓄電池はオルタネータによって充電される。ここで、鉛蓄電池の充電と放電とがバランスし、鉛蓄電池のＳＯＣ（充電状態）が９０〜１００％に維持されるよう、オルタネータの出力電圧および出力電流が設定されている。 Lead-acid batteries are used for various purposes such as vehicle engine starting and backup power supply. Among them, the lead acid battery for starting supplies power to various electric / electronic devices mounted on the vehicle as well as supplying power to the cell motor for starting the engine. After the engine is started, the lead storage battery is charged by an alternator. Here, the output voltage and output current of the alternator are set so that charging and discharging of the lead storage battery are balanced and the SOC (charged state) of the lead storage battery is maintained at 90 to 100%.
近年、環境保全の観点から、車両の燃費向上が検討されている。例えば、車両の一時的な停車中にエンジンを停止するアイドルストップ車や、車両の減速を車両の運動エネルギーを電気エネルギーに変換し、この電気エネルギーを蓄電することによって行う回生ブレーキシステムが実用化されている。 In recent years, improvement in fuel efficiency of vehicles has been studied from the viewpoint of environmental conservation. For example, idle-stop cars that stop the engine while the vehicle is temporarily stopped, and regenerative braking systems that convert the vehicle's kinetic energy into electrical energy and store this electrical energy are put into practical use. ing.
前記したような、アイドルストップ車ではエンジン停止中、鉛蓄電池は充電されない一方で、搭載機器へは電力供給をし続ける必要があるため、必然的に放電深度は深くなる。また、回生ブレーキシステムを搭載した車両では、回生時の電気エネルギーを蓄電するために、鉛蓄電池のＳＯＣを従来より低く、５０〜９０％程度に制御する必要がある。 In the idling stop vehicle as described above, the lead storage battery is not charged while the engine is stopped. On the other hand, it is necessary to continue to supply power to the on-board equipment, which inevitably increases the depth of discharge. In addition, in a vehicle equipped with a regenerative braking system, it is necessary to control the SOC of the lead storage battery to about 50 to 90%, which is lower than before, in order to store electric energy during regeneration.
従って、これらのシステムを搭載した車両において、鉛蓄電池はより深い放電深度、低いＳＯＣで使用されることになり、このような車両に適用するために、鉛蓄電池は深い放電が行われた時の寿命特性が要求される。このような深放電寿命における鉛蓄電池の劣化要因は深放電による正極における活物質の劣化と活物質−格子界面の高抵抗層の形成によるインピーダンスの増加および負極活物質の充電受入性低下とこれによる正極活物質の充電不足による劣化が主要因であった。 Therefore, in a vehicle equipped with these systems, the lead storage battery is used at a deeper discharge depth and lower SOC, and for application to such a vehicle, the lead storage battery is used when a deep discharge is performed. Life characteristics are required. The deterioration factors of lead-acid batteries in such a deep discharge life are due to the deterioration of the active material in the positive electrode due to deep discharge, the increase in impedance due to the formation of a high resistance layer at the active material-lattice interface, and the decrease in charge acceptance of the negative electrode active material. The main factor was deterioration due to insufficient charging of the positive electrode active material.
鉛蓄電池の深放電による正極の劣化を抑制するために、例えば特許文献１には鉛−カルシウム−スズ合金の正極格子表面にスズおよびアンチモンを含有する鉛合金層を形成することが示されている。正極格子表面に存在するスズおよびアンチモンは活物質の劣化および活物質−格子界面での高抵抗層の形成を抑制する効果がある。
In order to suppress the deterioration of the positive electrode due to the deep discharge of the lead storage battery, for example,
また、特許文献１の鉛蓄電池のような正極格子表面に配置したアンチモンは、蓄電池の充放電を繰り返すうちに負極活物質表面に電析し、負極の充電電位を貴に移行させる。これにより、蓄電池の充電電圧は低下する。その結果、自動車用をはじめ、鉛蓄電池で一般に用いられている定電圧充電を行った場合、充電電圧の低下に伴い、充電電流は増加する。従って、正極での充電電気量が増加するため、正極活物質の劣化が抑制されるという効果もあった。
しかしながら、正極格子表面に存在するアンチモンは負極活物質のみならず、負極格子耳部にも析出する。従来の車両にように、鉛蓄電池のＳＯＣが高頻度で９０％以上である場合には、負極格子耳部に移行したアンチモンは鉛蓄電池に殆ど悪影響を及ぼすことがなく、問題とはならなかった。しかしながら、アイドルストップ車や回生ブレーキシステム
を搭載したような車両は前記したようにＳＯＣが９０％未満〜８０％の低ＳＯＣ領域で用いられる頻度が高く、負極格子耳部に析出したアンチモンが、負極格子耳部の腐食に影響することがわかってきた。この負極格子耳部の腐食により、負極格子の集電性が低下し、最終的には断線することによって、蓄電池容量が急激に低下する可能性があった。
However, antimony present on the surface of the positive electrode lattice is deposited not only on the negative electrode active material but also on the negative electrode lattice ears. When the SOC of the lead storage battery is 90% or more as in the conventional vehicle, the antimony that has migrated to the negative electrode grid ears has almost no adverse effect on the lead storage battery and did not cause a problem. . However, as described above, an idling stop vehicle or a vehicle equipped with a regenerative braking system is frequently used in a low SOC region where the SOC is less than 90% to 80%. It has been found to affect the lattice ear corrosion. Due to the corrosion of the negative electrode grid ears, the current collecting property of the negative electrode grid is lowered, and eventually the storage battery capacity may be rapidly reduced by disconnection.
一方、Ｓｂの負極格子耳部への析出を抑制するため、正極格子表面に含Ｓｂ層を設けない場合、負極活物質へのＳｂの移行がないので、充電電圧は低下せず、その結果、充電電流が低下し、正極が充電不足となり、短寿命となっていた。 On the other hand, when the Sb-containing layer is not provided on the surface of the positive electrode lattice in order to suppress the precipitation of Sb on the negative electrode lattice edges, there is no transition of Sb to the negative electrode active material, so the charging voltage does not decrease. The charging current decreased, the positive electrode became insufficiently charged, and the life was short.
本発明は、前記したような、アイドルストップ車や回生ブレーキシステム搭載車等に用いられるような低ＳＯＣ領域で用いられる頻度が高い自動車用鉛蓄電池における、負極格子耳の腐食を抑制し、長寿命で信頼性の高い鉛蓄電池を提供することを目的とする。 The present invention suppresses the corrosion of the negative electrode grid ear in the automobile lead-acid battery that is frequently used in the low SOC region such as used in an idle stop vehicle or a vehicle equipped with a regenerative brake system, and has a long service life. The purpose is to provide a highly reliable lead-acid battery.
上記目的を達成するために本発明の鉛蓄電池は、Ｓｂを含まない正極格子からなる正極板と、Ｓｂを含まない負極格子で構成され負極活物質と接する表面の少なくとも一部にＳｂを含む負極表面層を形成する負極板と、前記正極・負極板間に介挿されたセパレータとからなることを特徴とするものである。 In order to achieve the above object, a lead storage battery according to the present invention includes a positive electrode plate made of a positive electrode lattice not containing Sb, and a negative electrode containing Sb on at least a part of a surface in contact with the negative electrode active material, the negative electrode lattice not containing Sb. It consists of the negative electrode plate which forms a surface layer, and the separator inserted between the said positive electrode and negative electrode plates.
これにより、アイドルストップ車や回生ブレーキシステム搭載車等に用いられるような低ＳＯＣ領域で用いられる頻度が高い自動車用鉛蓄電池における、負極格子耳の腐食を抑制し、長寿命で信頼性の高い鉛蓄電池を提供することができる。 As a result, the lead grid battery for automobiles, which is frequently used in low-SOC areas, such as those used in idle stop cars and regenerative braking systems, suppresses corrosion of the negative electrode grid ears and has a long life and high reliability. A storage battery can be provided.
また、負極表面層に含むＳｂ量を４０〜５００ｐｐｍとすることで、更に好適な鉛蓄電池を提供することができる。 Moreover, the more suitable lead acid battery can be provided because the amount of Sb contained in a negative electrode surface layer shall be 40-500 ppm.
また、負極表面層にＳｎを１．０〜１０．０質量％含むことで、更に好適な鉛蓄電池を提供することができる。 Moreover, a more suitable lead acid battery can be provided by including 1.0-10.0 mass% of Sn in a negative electrode surface layer.
また、負極表面層を負極格子の下部に設けることで、更に好適な鉛蓄電池を提供することができる。 Moreover, a more suitable lead storage battery can be provided by providing a negative electrode surface layer below the negative electrode grid.
さらに、Ｐｂ−Ｃａ−Ｓｎ合金からなる正極格子で構成され、正極活物質と接する表面の少なくとも一部に前記正極格子より高濃度のＳｎを含む正極表面層を形成すると、更に好適な鉛蓄電池を提供することができる。 Furthermore, when a positive electrode surface layer comprising a positive electrode lattice made of a Pb—Ca—Sn alloy and containing Sn at a higher concentration than the positive electrode lattice is formed on at least a part of the surface in contact with the positive electrode active material, a more suitable lead-acid battery is obtained. Can be provided.
本発明の鉛蓄電池によれば、アイドルストップ車や回生ブレーキシステム搭載車等に用いられるような低ＳＯＣ領域で用いられる頻度が高い自動車用鉛蓄電池において、負極格子耳の腐食を抑制し、長寿命で信頼性の高い鉛蓄電池を提供することができることから、工業上、極めて有用である。 According to the lead acid battery of the present invention, in a lead acid battery for automobiles frequently used in a low SOC region such as used in an idle stop car or a car equipped with a regenerative brake system, corrosion of the negative electrode grid ear is suppressed, and a long life is achieved. In addition, it is possible to provide a highly reliable lead storage battery, which is extremely useful industrially.
以下、本発明を実施するための最良の形態について、図面を参照しながら説明する。本発明の鉛蓄電池に用いる正極格子の母材は実質上Ｓｂを含まない鉛合金により作成される。Ｓｂを含まない鉛合金としては、強度および耐腐食性の面でＰｂ−Ｃａ−Ｓｎ合金を用いる。正極格子中のＣａの量としては格子強度の観点から、０．０３〜０．１０質量％、Ｓｎの量としては格子強度および耐腐食性の観点より、０．６０〜１．８０質量％が適切であり、１．２０〜１．８０質量％であれば更に良い。なお、本発明において、正極格子中に、実質上Ｓｂを含まないとは、０．００２質量％以下を意味する。この程度の含有量
のＳｂが正極格子に含まれたとしても、負極にには移行せず、結果として負極における自己放電量や、電解液の減液といった鉛蓄電池のメンテナンスフリー性能に影響を与えることはない。
The best mode for carrying out the present invention will be described below with reference to the drawings. The base material of the positive electrode lattice used in the lead storage battery of the present invention is made of a lead alloy substantially free of Sb. As a lead alloy not containing Sb, a Pb—Ca—Sn alloy is used in terms of strength and corrosion resistance. The amount of Ca in the positive electrode lattice is 0.03 to 0.10% by mass from the viewpoint of lattice strength, and the amount of Sn is 0.60 to 1.80% by mass from the viewpoint of lattice strength and corrosion resistance. It is appropriate, and it is better if it is 1.20 to 1.80% by mass. In the present invention, the fact that the positive electrode lattice does not substantially contain Sb means 0.002 mass% or less. Even if this amount of Sb is contained in the positive electrode grid, it does not shift to the negative electrode, and as a result, it affects the self-discharge amount in the negative electrode and the maintenance-free performance of the lead-acid battery such as the reduction of the electrolyte. There is nothing.
また、格子の作成方法としては、従来から知られている鋳造格子、連続鋳造格子あるいは、上記鉛合金の圧延体にパンチング加工やエキスパンド加工を施した格子体を用いることができる。 In addition, as a method of creating a lattice, a conventionally known cast lattice, continuous cast lattice, or a lattice body obtained by subjecting a rolled body of the lead alloy to punching or expanding can be used.
上記の正極格子に正極活物質ペーストを充填後、熟成乾燥することにより、未化成状態の正極板を得る。なお、正極活物質ペーストとしては、従来から知られているように、鉛酸化物および金属鉛を成分とする鉛粉を水と希硫酸で練合して得ることができる。 After filling the positive electrode grid with the positive electrode active material paste, the positive electrode plate in an unformed state is obtained by aging and drying. As known in the art, the positive electrode active material paste can be obtained by kneading lead powder containing lead oxide and metal lead as components with water and dilute sulfuric acid.
次に、負極格子は母材合金として実質上Ｓｂを含まない鉛合金により作成される。負極格子に連設される集電耳部におけるＳｂの存在は腐食の要因となるので、Ｓｂは０．００１質量％以下とする。また、この母材合金として、正極格子と同様のＰｂ−Ｃａ−Ｓｎ合金やＰｂ−Ｃａ合金を用いることができる。なお、Ｐｂ−Ｃａ−Ｓｎ合金において、Ｓｎは前述のように、格子強度を向上したり、鋳造格子作成時の溶融鉛の湯流れ性を向上するので、０．２質量％〜０．６質量％程度添加してもよい。なお、負極格子中のＣａ量は正極と同様、格子強度を確保することを主目的として０．０３〜０．１０質量％添加する。 Next, the negative electrode lattice is made of a lead alloy substantially free of Sb as a base material alloy. Since the presence of Sb in the current collecting ear portion connected to the negative electrode grid causes corrosion, Sb is set to 0.001% by mass or less. Moreover, as this base material alloy, the same Pb-Ca-Sn alloy and Pb-Ca alloy as a positive electrode grid can be used. Note that, in the Pb—Ca—Sn alloy, Sn improves the lattice strength and improves the molten metal flowability of molten lead at the time of forming the cast lattice, as described above. About% may be added. The amount of Ca in the negative electrode lattice is 0.03 to 0.10% by mass for the main purpose of securing the lattice strength, as in the positive electrode.
本発明では、負極格子の負極活物質と接する表面の少なくとも一部にＳｂを含む表面層を形成する。なお、この表面層の形成方法として、負極格子の中骨表面にＰｂ−Ｓｂ合金を溶射することができる。また、負極格子の母材合金スラブにＰｂ−Ｓｂ合金箔を重ね合わせ、圧延一体化したシートをパンチング加工あるいはエキスパンド加工により、格子体を作成すればよい。 In the present invention, a surface layer containing Sb is formed on at least a part of the surface of the negative electrode grid contacting the negative electrode active material. As a method for forming this surface layer, a Pb—Sb alloy can be sprayed onto the inner surface of the negative electrode lattice. In addition, a Pb—Sb alloy foil is superposed on the base metal alloy slab of the negative electrode lattice, and a rolled and integrated sheet may be formed by punching or expanding.
また、本発明において、好ましくはこの表面層中のＳｂ濃度を４０〜５００ｐｐｍとする。また、Ｐｂ−Ｓｂ合金箔を負極格子表面上に圧延時に貼り合わせる場合には、Ｐｂ−Ｓｂ合金箔中に１〜１０質量％のＳｎを含むＰｂ−Ｓｎ−Ｓｂ合金とすることが好ましい。Ｓｎの添加により、合金箔の機械的強度が向上するため、製造工程において合金箔が切断してしまうといった問題を回避できる。また、合金箔の機械的強度向上に伴い、合金箔と負極格子合金母材スラブとを圧延一体化する際、合金箔の張力をより高く設定できるため、合金箔の母材スラブ上での蛇行を抑制し、寸法精度を確保して両者を一体化できる。 In the present invention, the Sb concentration in the surface layer is preferably 40 to 500 ppm. Moreover, when bonding Pb-Sb alloy foil on the negative electrode lattice surface at the time of rolling, it is preferable to set it as the Pb-Sn-Sb alloy which contains 1-10 mass% Sn in Pb-Sb alloy foil. Since the mechanical strength of the alloy foil is improved by adding Sn, the problem that the alloy foil is cut in the manufacturing process can be avoided. In addition, as the mechanical strength of the alloy foil is improved, when the alloy foil and the negative electrode grid alloy base material slab are rolled and integrated, the tension of the alloy foil can be set higher, so that the meandering of the alloy foil on the base material slab Can be suppressed, and dimensional accuracy can be secured and both can be integrated.
また、合金箔の厚みは０．１〜０．２ｍｍ程度が取扱い上、好ましい。このような厚みの合金箔を１０．０ｍｍ厚の母材合金スラブと重ね合わせ、最終厚みを０．８ｍｍまで圧延した場合、０．８ｍｍの圧延シート上に５．０〜１０．０μｍ程度の厚みでＰｂ−Ｓｂ層が形成される。 The thickness of the alloy foil is preferably about 0.1 to 0.2 mm for handling. When the alloy foil having such a thickness is overlapped with a base metal alloy slab having a thickness of 10.0 mm and rolled to a final thickness of 0.8 mm, the thickness is about 5.0 to 10.0 μm on a 0.8 mm rolled sheet. Thus, a Pb—Sb layer is formed.
上述により得た負極格子に負極活物質ペーストを充填し、熟成乾燥して未化成状態の負極板を作成する。負極活物質ペーストとして、従来から知られているような鉛粉を水、希硫酸で練合して得ることができる。また、負極活物質中に通常添加する、リグニン、硫酸バリウム、カーボン等の添加剤の添加ももちろん差し支えない。また、リグニンにかえて、ビスフェノールスルホン酸系化合物（例えば、日本製紙株式会社製ビスパース（商品名））を用いることができる。 The negative electrode grid obtained as described above is filled with a negative electrode active material paste and aged and dried to prepare an unformed negative electrode plate. As a negative electrode active material paste, a conventionally known lead powder can be obtained by kneading with water or dilute sulfuric acid. Of course, additives such as lignin, barium sulfate and carbon which are usually added to the negative electrode active material may be added. Further, in place of lignin, a bisphenolsulfonic acid compound (for example, Nippon Paper Industries Co., Ltd. Bispers (trade name)) can be used.
この負極板および上述の正極板とガラス繊維やポリプロピレン樹脂繊維等の耐酸性繊維で構成したマットセパレータもしくはポリエチレンセパレータとを組み合わせて極板群を構成する。この極板群を用いて鉛蓄電池を構成することにより、本発明の鉛蓄電池を得ることができる。 The negative electrode plate and the positive electrode plate described above are combined with a mat separator or polyethylene separator made of acid-resistant fibers such as glass fibers and polypropylene resin fibers to constitute an electrode plate group. The lead storage battery of this invention can be obtained by comprising a lead storage battery using this electrode group.
通常の公称電圧１２Ｖの自動車用鉛蓄電池とする場合、上述の極板群の６個を電槽に収納し、極板群間を直列に接続した後、電槽開口部を蓋で覆うとともに、直列接続において両端に位置する極板群から導出した極柱を蓋にインサート成形された端子ブッシングに挿通し、端子ブッシングと極柱先端を溶接すれば良い。その後、蓋に設けた注液口より希硫酸電解液を注液して、化成充電を行うことにより、完成した蓄電池を得る。 When it is set as a lead acid battery for automobiles having a normal nominal voltage of 12 V, six of the electrode plate groups described above are housed in a battery case, and the electrode plate groups are connected in series, and then the battery case opening is covered with a lid, What is necessary is just to insert the pole pillar derived | led-out from the electrode group located in both ends in series connection in the terminal bushing insert-molded by the lid | cover, and to weld a terminal bushing and a pole pillar front-end | tip. Then, the completed storage battery is obtained by injecting dilute sulfuric acid electrolyte from the injection port provided in the lid, and performing chemical charging.
なお、Ｓｂを含む表面層は負極格子耳部には形成せず、負極活物質と接する表面の少なくとも一部とする。好ましくは、Ｓｂを含む表面層を形成する位置は蓄電池を構成したときに、負極格子の重力方向の下部とする。これは、以下に述べる理由による。 Note that the surface layer containing Sb is not formed on the negative electrode lattice tab but is at least part of the surface in contact with the negative electrode active material. Preferably, the position where the surface layer containing Sb is formed is the lower part in the gravitational direction of the negative electrode lattice when the storage battery is configured. This is for the reason described below.
深い充放電の繰返しにより、電解液中の硫酸濃度は重力方向下部が高く、重力方向上部が低くなる、成層化現象が発生する。硫酸濃度が高い部分では正・負極ともに硫酸鉛が蓄積しやすくなる。これは負極において特に顕著である。下部にＳｂを集中して配置すれば、下部での水素ガス発生が顕著になるので、水素ガス発生による液攪拌が行われ、成層化現象が解消しやすくなり、電池寿命に良い影響を与えるためである。 Due to repeated deep charge and discharge, the sulfuric acid concentration in the electrolytic solution causes a stratification phenomenon in which the lower part in the gravitational direction is higher and the upper part in the gravitational direction is lower. In areas where the sulfuric acid concentration is high, lead sulfate tends to accumulate in both positive and negative electrodes. This is particularly noticeable in the negative electrode. If Sb is concentrated in the lower part, hydrogen gas generation in the lower part becomes remarkable, so liquid agitation is performed by hydrogen gas generation, and the stratification phenomenon is easily eliminated, which has a positive effect on battery life. It is.
図１に正極箔、負極箔、箔貼付位置をパラメータとして鉛蓄電池を作成した時のサイクル寿命特性、耳腐食量、減液量を示す。 FIG. 1 shows the cycle life characteristics, the amount of ear corrosion, and the amount of liquid reduction when a lead-acid battery was prepared with the positive electrode foil, the negative electrode foil, and the foil attachment position as parameters.
電池形式はＪＩＳ Ｄ５３０１「始動用鉛蓄電池」に規定する３４Ｂ１９形鉛蓄電池（１２Ｖ２７Ａｈ）とした。 The battery type was a 34B19 type lead acid battery (12V27Ah) defined in JIS D5301 “lead acid battery for starting”.
サイクル寿命特性試験はＪＩＳ Ｄ５３０１「始動用鉛蓄電池」に規定する軽負荷寿命試験を行った。 The cycle life characteristic test was a light load life test defined in JIS D5301 “Lead-Starting Storage Battery”.
耳腐食量（％）は、２５Ａ放電６０秒と１５Ｖ定電圧充電６０秒とを１５０サイクル繰り返した後に、１４．５Ｖの定電圧充電を１時間行い、６週間保存して、試験前後の耳部断面積の減少割合を比較している。さらに減液量は、４０℃環境下において２７Ａ放電６０秒と１４．５Ｖ充電（最大電流２７Ａ）９０秒とを５００サイクル繰り返した後の電解液体積減量（％）を比較している。 The ear corrosion amount (%) was obtained by repeating 25 cycles of 60 seconds of 25A discharge and 60 seconds of 15V constant voltage charge, followed by 14.5 V constant voltage charge for 1 hour and storing for 6 weeks. The rate of decrease in cross-sectional area is compared. Furthermore, the amount of liquid reduction compares the volume reduction (%) of the electrolyte after 500 cycles of 27 A discharge 60 seconds and 14.5 V charge (maximum current 27 A) 90 seconds in a 40 ° C. environment.
同図の電池Ａ、Ｂから、負極の表面層にＳｂを有していないと、サイクル寿命特性もしくは耳腐食量の点で特性が悪く、アイドルストップ車や回生ブレーキシステム搭載車等に用いられるような低ＳＯＣ領域で用いられる頻度が高い自動車用鉛蓄電池において用いるには適していないことがわかる。 From the batteries A and B in the figure, if the surface layer of the negative electrode does not have Sb, the cycle life characteristic or the ear corrosion amount is poor, so that it can be used for an idle stop vehicle or a vehicle equipped with a regenerative brake system. It can be seen that it is not suitable for use in an automotive lead-acid battery that is frequently used in a low SOC region.
同図の電池Ｃ−１からＣ−５を見ると、負極表面層のＳｂ量が増えるほどサイクル寿命特性が向上することがわかる。しかしながら、負極表面層のＳｂ量が６００ｐｐｍまで増えると耳腐食量及び減液量の面で若干劣る。従って、負極表面層のＳｂ量は４０ｐｐｍ〜５００ｐｐｍであることが特に好ましいことがわかる。 From the batteries C-1 to C-5 in the figure, it can be seen that the cycle life characteristics improve as the Sb amount of the negative electrode surface layer increases. However, when the amount of Sb in the negative electrode surface layer increases to 600 ppm, the ear corrosion amount and the liquid reduction amount are slightly inferior. Therefore, it can be seen that the Sb content of the negative electrode surface layer is particularly preferably 40 ppm to 500 ppm.
また、同図の電池Ｃ−６、Ｃ−７を比較すると、正極格子より高濃度のＳｎを含む正極表面層を形成することで、サイクル寿命特性が向上することがわかる。なお、耳腐食量及び減液量の点では変化はない。 In addition, when the batteries C-6 and C-7 in the figure are compared, it can be seen that the cycle life characteristics are improved by forming a positive electrode surface layer containing Sn at a higher concentration than the positive electrode lattice. There is no change in the amount of ear corrosion and liquid reduction.
図２に負極格子に負極表面層を設ける位置のイメージ図を示す。電池Ｃ−３とＣ−３−１〜Ｃ−３−３とを比較すると、その負極表面層を設ける位置により、特性に変化が出ることがわかる。負極格子の下部１／３に負極表面層を設けた場合、負極表面層を全面に設
けたものと遜色のないサイクル寿命特性を得ることができる。これは、下部にＳｂを集中して配置すれば、下部での水素ガス発生が顕著になるので、水素ガス発生による液攪拌が行われ、成層化現象が解消しやすくなり、電池寿命に良い影響を与えるためである。また、負極表面層を設ける位置を下部１／３のみとすれば、材料費を削減でき、電池製造コストを低減できる。
FIG. 2 shows an image diagram of a position where the negative electrode surface layer is provided on the negative electrode lattice. Comparing batteries C-3 and C-3-1 to C-3-3 shows that the characteristics change depending on the position where the negative electrode surface layer is provided. When the negative electrode surface layer is provided on the lower third of the negative electrode lattice, cycle life characteristics comparable to those provided on the entire surface of the negative electrode surface layer can be obtained. This is because, if Sb is concentrated in the lower part, hydrogen gas generation at the lower part becomes remarkable, so liquid agitation is performed by hydrogen gas generation, and the stratification phenomenon is easily eliminated, which has a positive effect on the battery life. Is to give. Further, if the position where the negative electrode surface layer is provided is only the lower third, the material cost can be reduced and the battery manufacturing cost can be reduced.
さらに、電池ＤからＦを比較すると、負極表面層に含むＳｎ量を１〜１０質量％にしておくと、サイクル寿命特性の点で特に好ましいことがわかる。Ｓｎ量は１０質量％を越えてもサイクル寿命特性の点で不都合はないが、製造コストの面で１０％以下にすることが好ましい。 Further, when batteries D to F are compared, it is found that it is particularly preferable in terms of cycle life characteristics when the amount of Sn contained in the negative electrode surface layer is 1 to 10% by mass. Even if the Sn amount exceeds 10% by mass, there is no inconvenience in terms of cycle life characteristics, but it is preferably 10% or less in terms of production cost.
本発明によれば、負極格子耳の腐食を抑制し、長寿命で信頼性の高い鉛蓄電池を提供することができることから、アイドルストップ車や回生ブレーキシステム搭載車等に用いられるような低ＳＯＣ領域で用いられる頻度が高い自動車用鉛蓄電池において有用である。 According to the present invention, it is possible to provide a lead-acid battery having a long life and high reliability by suppressing the corrosion of the negative electrode grid ear, and therefore, a low SOC region used in an idle stop vehicle, a vehicle equipped with a regenerative brake system, and the like. This is useful in lead-acid batteries for automobiles that are frequently used in
Claims (5)
A positive electrode surface layer comprising a positive electrode lattice made of a Pb-Ca-Sn alloy and having a higher concentration of Sn than the positive electrode lattice is formed on at least a part of a surface in contact with the positive electrode active material. 4. Lead acid battery in any one of 4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004113827A JP2005302395A (en) | 2004-04-08 | 2004-04-08 | Lead storage battery |
| KR1020067017135A KR101128586B1 (en) | 2004-04-08 | 2005-04-07 | Lead storage battery |
| EP05728390A EP1737062B1 (en) | 2004-04-08 | 2005-04-07 | Lead storage battery |
| CNB2005800104279A CN100446330C (en) | 2004-04-08 | 2005-04-07 | Lead storage battery |
| TW094110987A TWI254478B (en) | 2004-04-08 | 2005-04-07 | Lead-acid battery |
| US10/587,186 US8071239B2 (en) | 2004-04-08 | 2005-04-07 | Long life and low corrosion lead storage battery |
| DE602005009814T DE602005009814D1 (en) | 2004-04-08 | 2005-04-07 | lead-acid battery |
| PCT/JP2005/006869 WO2005099020A1 (en) | 2004-04-08 | 2005-04-07 | Lead storage battery |
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| JP2004113827A JP2005302395A (en) | 2004-04-08 | 2004-04-08 | Lead storage battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012153464A1 (en) * | 2011-05-12 | 2012-11-15 | パナソニック株式会社 | Lead-acid battery anode and lead-acid battery |
| JP2013140678A (en) * | 2011-12-28 | 2013-07-18 | Gs Yuasa Corp | Liquid lead-acid battery, battery system using the same and usage of liquid lead-acid battery |
| JP2014203678A (en) * | 2013-04-05 | 2014-10-27 | パナソニック株式会社 | Lead storage battery |
| JP2015022796A (en) * | 2013-07-16 | 2015-02-02 | パナソニック株式会社 | Lead storage battery |
| US10096862B2 (en) | 2013-11-29 | 2018-10-09 | Gs Yuasa International Ltd. | Lead-acid battery |
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| WO2011077621A1 (en) * | 2009-12-27 | 2011-06-30 | テルモ株式会社 | Electronic thermometer |
| WO2013031263A1 (en) * | 2011-09-01 | 2013-03-07 | 新神戸電機株式会社 | Lead storage cell |
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| JP3358508B2 (en) * | 1997-09-09 | 2002-12-24 | 松下電器産業株式会社 | Expanded grid for lead-acid battery |
| JP4686808B2 (en) * | 2000-04-05 | 2011-05-25 | パナソニック株式会社 | Lead acid battery |
| JP4815665B2 (en) * | 2000-11-27 | 2011-11-16 | パナソニック株式会社 | Lead acid battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012153464A1 (en) * | 2011-05-12 | 2012-11-15 | パナソニック株式会社 | Lead-acid battery anode and lead-acid battery |
| JP2013140678A (en) * | 2011-12-28 | 2013-07-18 | Gs Yuasa Corp | Liquid lead-acid battery, battery system using the same and usage of liquid lead-acid battery |
| JP2014203678A (en) * | 2013-04-05 | 2014-10-27 | パナソニック株式会社 | Lead storage battery |
| JP2015022796A (en) * | 2013-07-16 | 2015-02-02 | パナソニック株式会社 | Lead storage battery |
| US10096862B2 (en) | 2013-11-29 | 2018-10-09 | Gs Yuasa International Ltd. | Lead-acid battery |
| CN112542654A (en) * | 2014-01-02 | 2021-03-23 | 达拉米克有限责任公司 | Multilayer separator and methods of making and using |
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| CN100446330C (en) | 2008-12-24 |
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