JP2003142085A - Lead-acid battery - Google Patents
Lead-acid batteryInfo
- Publication number
- JP2003142085A JP2003142085A JP2001337351A JP2001337351A JP2003142085A JP 2003142085 A JP2003142085 A JP 2003142085A JP 2001337351 A JP2001337351 A JP 2001337351A JP 2001337351 A JP2001337351 A JP 2001337351A JP 2003142085 A JP2003142085 A JP 2003142085A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- lead
- active material
- acid battery
- electrode active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は鉛蓄電池に関する。FIELD OF THE INVENTION The present invention relates to a lead storage battery.
【０００２】[0002]
【従来の技術】近年、自動車の高性能化が進むにつれ、
エンジンルーム内により多くの機器が搭載されるように
なり、蓄電池の周囲の冷却空間が減少している。また、
エンジン自体の高性能化により、エンジンに発熱量も増
加している。そのためにエンジンルーム内の蓄電池の温
度はますます高くなる傾向にある。特に夏場では、蓄電
池温度が９０℃以上になる場合もある。自動車に搭載さ
れる蓄電池としては鉛蓄電池が主流であるが、高温下に
おいては、常温下における場合よりも性能の低下が早
い。この原因としては、主に負極板の劣化が考えられ
る。すなわち、鉛蓄電池の負極板には、高温寿命性能を
改善するため、従来からパルプ廃液を原料とする有機添
加剤リグニンが添加されているが、蓄電池温度上昇とと
もに、負極板に添加したリグニンの電解液への溶解度が
増して溶出したり分解したりすることにより、負極活物
質中に残存するリグニン量が少なくなってしまうためで
ある。なお、リグニンには、負極活物質の表面積を大き
くして放電容量を多くするという作用効果がある。かか
る問題を解決するために、負極活物質に添加剤を加える
ことにより負極でのリグニンの分解を抑え、鉛蓄電池の
高温での寿命性能を向上させることが提案されている。
例えば、特開平８−３２９９４８号には、かかる目的か
ら、負極活物質中に鉛よりも水素過電圧の低い金属やそ
の酸化物を添加することが開示されている。具体的に
は、通常、負極板に添加されるリグニン、バリウム、カ
ーボン以外に、Ｓb、Ｎi、Ｃo、Ｍo、Ｂｉ、Ｐt、Ａｕ
等を添加するというものである。2. Description of the Related Art In recent years, as the performance of automobiles has advanced,
More equipment has been installed in the engine room, and the cooling space around the storage battery has decreased. Also,
Due to the high performance of the engine itself, the amount of heat generated by the engine is also increasing. Therefore, the temperature of the storage battery in the engine room tends to become higher and higher. Especially in summer, the storage battery temperature may reach 90 ° C. or higher. Lead-acid batteries are the mainstream of storage batteries installed in automobiles, but their performance deteriorates faster at high temperatures than at room temperature. The main cause is considered to be deterioration of the negative electrode plate. That is, in order to improve the high temperature life performance, the negative electrode plate of the lead acid battery has conventionally been added with an organic additive lignin made from pulp waste liquid, but as the temperature of the battery increases, electrolysis of the lignin added to the negative electrode plate is performed. This is because the amount of lignin remaining in the negative electrode active material decreases due to the increased solubility in the liquid and the elution or decomposition. The lignin has the effect of increasing the surface area of the negative electrode active material and increasing the discharge capacity. In order to solve such a problem, it has been proposed to suppress the decomposition of lignin in the negative electrode by adding an additive to the negative electrode active material to improve the life performance of the lead storage battery at high temperature.
For example, Japanese Patent Application Laid-Open No. 8-329948 discloses adding a metal having a hydrogen overvoltage lower than that of lead or an oxide thereof to the negative electrode active material for this purpose. Specifically, in addition to lignin, barium, and carbon which are usually added to the negative electrode plate, Sb, Ni, Co, Mo, Bi, Pt, Au
Etc. are to be added.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記提
案でも今だ耐高温性能は十分ではなく、さらなる改善が
求められている。However, even with the above proposal, the high temperature resistance is still insufficient, and further improvement is required.
【０００４】本発明はかかる課題を解決するためになさ
れたものであり、その目的は耐高温性能やハイレート特
性に優れた鉛蓄電池を提供することである。The present invention has been made to solve the above problems, and an object thereof is to provide a lead storage battery excellent in high temperature resistance and high rate characteristics.
【０００５】[0005]
【課題を解決するための手段】前記課題を解決するため
の第１の発明は、非Ｓb系負極格子と、Ｂａを０．１〜
３重量％、グラファイトもしくはカーボンを０．１〜
２．５重量％含む負極活物質とを有する負極板を備え、
前記負極活物質がＳb、Ｓｎ、Ｂｉ、Ｚｎ、Ｓｅ、Ｍ
ｎ、Ｃａ、Ｍｇ、Ｓrの群から選ばれた少なくとも1種を
含むことを特徴とする鉛蓄電池である。第２の発明は、
第１の発明において、負極活物質が、Ｓbが０．００５
〜０．５重量％、Ｓnが０．０５〜０．８重量％、Ｂｉ
が０．００８〜０．５重量％、Ｚｎが０．００４〜０．
６重量％、Ｓｅが０．００５〜０．３重量％、Ｍｎが
０．００５〜０．５重量％、Ｃａが０．００６〜０．６
重量％、Ｍｇが０．００５〜０．７重量％、Ｓrが０．
００７〜０．５重量％の群から選ばれた少なくとも1種
を含むことを特徴とする鉛蓄電池である。第３の発明
は、第１又は２の発明において、負極活物質が、Ｓb、
Ｓｎ、Ｂｉ、Ｚｎ、Ｓｅ、Ｍｎ、Ｃａ、Ｍｇ、Ｓrの群
から選ばれた少なくとも1種を含む鉛合金から製作され
たことを特徴とする鉛蓄電池である。第４の発明は、第
１又は２の発明において、負極板が、Ｓb、Ｓｎ、Ｂ
ｉ、Ｚｎ、Ｓｅ、Ｍｎ、Ｃａ、Ｍｇ、Ｓrの群から選ば
れた少なくとも1種を含む電解液中で化成されたことを
特徴とする鉛蓄電池である。第５の発明は、第１又は２
の発明において、負極板が、Ｓb、Ｓｎ、Ｂｉ、Ｚｎ、
Ｓｅ、Ｍｎ、Ｃａ、Ｍｇ、Ｓrの群から選ばれた少なく
とも1種を含む電解液中に浸漬後、熟成されたことを特
徴とする鉛蓄電池である。第６の発明は、第１、２、
３、４又は５の発明において、電槽化成終了時の硫酸電
解液比重（２０℃換算）が１．２６以上、より好ましく
は１．２８〜１．３０であることを特徴とする鉛蓄電池
である。第７の発明は、第１、２、３、４、５又は６の
発明において、負極活物質密度が２．５〜３．８g／ｃ
ｍ3であることを特徴とする鉛蓄電池である。第８の発
明は、第１、２、３、４、５、６又は７の発明におい
て、グラファイトもしくはカーボンの比表面積が２０〜
５００m２／ｇであることを特徴とする鉛蓄電池であ
る。A first invention for solving the above-mentioned problems is to provide a non-Sb system negative electrode grid and Ba in an amount of 0.1 to 0.1%.
3% by weight, 0.1% graphite or carbon
A negative electrode plate having a negative electrode active material containing 2.5% by weight,
The negative electrode active material is Sb, Sn, Bi, Zn, Se, M
A lead-acid battery containing at least one selected from the group consisting of n, Ca, Mg, and Sr. The second invention is
In the first invention, the negative electrode active material has Sb of 0.005.
~ 0.5 wt%, Sn 0.05-0.8 wt%, Bi
Is 0.008 to 0.5% by weight, and Zn is 0.004 to 0.
6 wt%, Se 0.005-0.3 wt%, Mn 0.005-0.5 wt%, Ca 0.006-0.6
Wt%, 0.005 to 0.7 wt% of Mg, and Sr of 0.
A lead storage battery comprising at least one selected from the group of 007 to 0.5% by weight. A third invention is the same as the first or second invention, wherein the negative electrode active material is Sb,
It is a lead acid battery manufactured from a lead alloy containing at least one selected from the group consisting of Sn, Bi, Zn, Se, Mn, Ca, Mg and Sr. 4th invention is the negative electrode plate in 1st or 2nd invention, Comprising: Sb, Sn, B
A lead storage battery characterized by being formed in an electrolytic solution containing at least one selected from the group consisting of i, Zn, Se, Mn, Ca, Mg and Sr. The fifth invention is the first or second invention.
In the invention, the negative electrode plate is Sb, Sn, Bi, Zn,
A lead-acid battery characterized by being aged after being immersed in an electrolytic solution containing at least one selected from the group of Se, Mn, Ca, Mg, and Sr. A sixth invention is the first, second,
In the invention of 3, 4 or 5, a sulfuric acid electrolyte specific gravity (at 20 ° C. conversion) at the end of battery case formation is 1.26 or more, more preferably 1.28 to 1.30. is there. A seventh invention is the first, second, third, fourth, fifth or sixth invention, wherein the negative electrode active material density is 2.5 to 3.8 g / c.
It is a lead acid battery characterized by being m3. An eighth invention is the first, second, third, fourth, fifth, sixth or seventh invention, wherein the specific surface area of graphite or carbon is 20 to
It is a lead-acid battery characterized by having a capacity of 500 m2 / g.
【０００６】[0006]
【発明の実施の形態】第１の発明において、非Ｓb系負
極格子とは、不純物レベルの量を除いてＳbを含まない
負極格子のことであり、Ｐb−Ｓｎ合金、Ｐb−Ｃａ合金
等で形成され、鋳造式、エキスパンド式などがある。活
物質に含まれるＢaには、放電で生成する硫酸鉛の結晶
が成長する核となり、放電容量の低下や活物質の収縮を
防ぎ、ハイレート性能を向上させる効果がある。グラフ
ァイトやカーボンは、水素過電圧をやや小さくし、導電
性を与えて化成を容易にするとともに、充電受け入れ性
を改善する効果がある反面、Ｂａを吸着し、その効果を
低減させるが、負極活物質中にＢａを０．１〜３重量
％、グラファイトもしくはカーボンを０．１〜２重量％
含ませるとともに、Ｓb、Ｓｎ、Ｂｉ、Ｚｎ、Ｓｅ、Ｍ
ｎ、Ｃａ、Ｍｇ、Ｓrの群から選ばれた少なくとも1種を
共存させることによる相乗効果により、耐高温性能を改
善し、ハイレート特性、寿命特性に優れた鉛蓄電池が提
供される。そのメカニズムは必ずしも明らかではない
が、Ｓb、Ｓｎ、Ｂｉ、Ｚｎ、Ｓｅ、Ｍｎ、Ｃａ、Ｍ
ｇ、Ｓrを添加することにより活物質が微細化するので
はないかと推察される。尚、Ｂａ、Ｓb、Ｓｎ、Ｂｉ、
Ｚｎ、Ｓｅ、Ｍｎ、Ｃａ、Ｍｇ、Ｓrは金属や化合物の
形態で負極活物質中の含ませることができ、化合物の場
合の含有量は単体換算の値である。第２の発明によれ
ば、それぞれの含有量の好適値がＳbは０．００５〜
０．５重量％、Ｓnは０．０５〜０．８重量％、Ｂｉは
０．００８〜０．５重量％、Ｚｎは０．００４〜０．６
重量％、Ｓｅは０．００５〜０．３重量％、Ｍｎは０．
００５〜０．５重量％、Ｃａは０．００６〜０．６重量
％、Ｍｇは０．００５〜０．７重量％、Ｓrは０．００
７〜０．５重量％であり、これによって耐高温性能を改
善し、ハイレート特性に優れた鉛蓄電池が提供される。
第３の発明によれば、負極活物質が、Ｓb、Ｓｎ、Ｂ
ｉ、Ｚｎ、Ｓｅ、Ｍｎ、Ｃａ、Ｍｇ、Ｓrの群から選ば
れた少なくとも1種を含む鉛合金から製作されるので、
これら元素が均質に含有され、耐高温性能を改善し、ハ
イレート特性に優れた鉛蓄電池が提供される。尚、鉛合
金や鉛合金から鉛粉を作る方法は公知である。第４の発
明によれば、負極板が、Ｓb、Ｓｎ、Ｂｉ、Ｚｎ、Ｓ
ｅ、Ｍｎ、Ｃａ、Ｍｇ、Ｓrの群から選ばれた少なくと
も1種を含む電解液中で化成されることにより、これら
が負極活物質上析出するので、活物質微細化に効果的で
あり、もって耐高温性能を改善し、ハイレート特性に優
れた鉛蓄電池が提供される。なお、化成については、通
常の化成条件に従って行うことができる。第５の発明に
よれば、負極板が、Ｓb、Ｓｎ、Ｂｉ、Ｚｎ、Ｓｅ、Ｍ
ｎ、Ｃａ、Ｍｇ、Ｓrの群から選ばれた少なくとも1種を
含む電解液中に浸漬後、熟成されるので、熟成中に活物
質の微細化が起こるため、耐高温性能を改善し、ハイレ
ート特性に優れた鉛蓄電池が提供される。尚、電解液中
への浸漬時間については、負極板の大きさや電解液濃度
等を勘案して、適宜、設定することができ、また熟成に
ついては、当業者において周知慣用の条件で実施するこ
とができる。第６の発明によれば、電槽化成終了時の硫
酸電解液比重（２０℃換算）が１．２６以上、より好ま
しくは１．２８〜１．３０であるので、活物質の微細化
が進み、耐高温性能を改善し、ハイレート特性に優れた
鉛蓄電池が提供される。第７の発明によれば、負極活物
質密度が２．５〜３．８g／ｃｍ3であるので、従来のよ
うに３．９g／ｃｍ3以上の高密度なものに比べ、耐高温
性能を改善し、ハイレート特性に優れた鉛蓄電池が提供
される。第８の発明によれば、グラファイトもしくはカ
ーボンの比表面積が２０〜５００m２／ｇであるので、
従来のような比表面積が１５m２／ｇ程度のものに比
べ、耐高温性能を改善し、ハイレート特性に優れた鉛蓄
電池が提供される。BEST MODE FOR CARRYING OUT THE INVENTION In the first invention, the non-Sb-based negative electrode lattice is a negative electrode lattice which does not contain Sb except for the amount of impurity level, and is made of Pb-Sn alloy, Pb-Ca alloy or the like. It is formed, and there are casting type, expanding type and so on. Ba contained in the active material serves as a nucleus for growing crystals of lead sulfate generated by discharge, and has an effect of preventing reduction in discharge capacity and contraction of the active material, and improving high rate performance. Graphite and carbon have an effect of slightly reducing hydrogen overvoltage, giving conductivity and facilitating chemical conversion, and improving charge acceptability. On the other hand, they adsorb Ba and reduce the effect, but the negative electrode active material 0.1 to 3% by weight of Ba and 0.1 to 2% by weight of graphite or carbon
Sb, Sn, Bi, Zn, Se, M
Provided is a lead-acid battery having improved high-temperature resistance performance and excellent high rate characteristics and life characteristics due to the synergistic effect of coexisting at least one selected from the group consisting of n, Ca, Mg, and Sr. Although the mechanism is not always clear, Sb, Sn, Bi, Zn, Se, Mn, Ca, M
It is speculated that the addition of g and Sr may make the active material finer. In addition, Ba, Sb, Sn, Bi,
Zn, Se, Mn, Ca, Mg, and Sr can be contained in the negative electrode active material in the form of a metal or a compound, and the content in the case of a compound is a value calculated as a simple substance. According to the second invention, the preferable value of each content is Sb of 0.005 to 0.005.
0.5 wt%, Sn 0.05-0.8 wt%, Bi 0.008-0.5 wt%, Zn 0.004-0.6
%, Se is 0.005 to 0.3% by weight, and Mn is 0.
005-0.5 wt%, Ca 0.006-0.6 wt%, Mg 0.005-0.7 wt%, Sr 0.00
7 to 0.5 wt%, which provides a lead-acid battery with improved high temperature resistance and excellent high rate characteristics.
According to the third invention, the negative electrode active material is Sb, Sn, B.
Since it is made from a lead alloy containing at least one selected from the group of i, Zn, Se, Mn, Ca, Mg, and Sr,
Provided is a lead storage battery in which these elements are uniformly contained, the high temperature resistance is improved, and the high rate characteristics are excellent. Incidentally, a method of producing lead powder from a lead alloy or a lead alloy is known. According to the fourth invention, the negative electrode plate is Sb, Sn, Bi, Zn, S.
e, Mn, Ca, Mg, and Sr are formed in an electrolytic solution containing at least one selected from the group, and these are deposited on the negative electrode active material, which is effective for making the active material finer. Therefore, a lead storage battery having improved high temperature resistance and excellent high rate characteristics is provided. The chemical conversion can be carried out under normal chemical conversion conditions. According to the fifth invention, the negative electrode plate is Sb, Sn, Bi, Zn, Se, M.
It is soaked in an electrolyte containing at least one selected from the group consisting of n, Ca, Mg, and Sr, and then aged, so that the active material becomes finer during the aging, improving the high temperature resistance performance and increasing the high rate. A lead storage battery having excellent characteristics is provided. Incidentally, the immersion time in the electrolytic solution can be appropriately set in consideration of the size of the negative electrode plate, the electrolytic solution concentration, etc., and the aging should be carried out under the conditions commonly known to those skilled in the art. You can According to the sixth aspect of the invention, the specific gravity of the sulfuric acid electrolyte (converted to 20 ° C.) at the end of battery case formation is 1.26 or more, more preferably 1.28 to 1.30, so that the active material becomes finer. A lead storage battery having improved high temperature resistance and excellent high rate characteristics is provided. According to the seventh invention, since the density of the negative electrode active material is 2.5 to 3.8 g / cm3, the high temperature resistance performance is improved as compared with the conventional one having a high density of 3.9 g / cm3 or more. Provided is a lead storage battery having excellent high rate characteristics. According to the eighth invention, since the specific surface area of graphite or carbon is 20 to 500 m2 / g,
Provided is a lead-acid battery having improved high temperature resistance and excellent high rate characteristics as compared with a conventional one having a specific surface area of about 15 m 2 / g.
【０００７】[0007]
【実施例】まず、各種添加元素が耐高温性能、ハイレー
ト特性に及ぼす影響を調べるため、第１の試験を行っ
た。用いた負極格子は、０．０６％Ｃａ−１％Ｓｎ−Ｐ
bであり、リグニンを０．２重量％含む他は図１の構成
の負極活物質を充填して、１．７ｍｍ厚さの負極板を製
作した。また正極板は負極格子と同組成の格子に通常の
ペーストを充填して製作した。尚、添加物は金属粉末の
状態で鉛粉の混合し、定法に従って負極活物質ペースト
とした。この試験における負極活物質密度は３g／ｃｍ
3、カーボンの比表面積は１００m２／ｇである。EXAMPLES First, a first test was conducted in order to investigate the influence of various additive elements on the high temperature resistance performance and high rate characteristics. The negative electrode grid used is 0.06% Ca-1% Sn-P.
b, and a negative electrode plate having a thickness of 1.7 mm was manufactured by filling the negative electrode active material having the structure of FIG. 1 except that it contained 0.2% by weight of lignin. The positive electrode plate was manufactured by filling a grid having the same composition as the negative electrode grid with a normal paste. The additive was mixed with lead powder in the state of metal powder to prepare a negative electrode active material paste according to a conventional method. The negative electrode active material density in this test is 3 g / cm
3. The specific surface area of carbon is 100 m2 / g.
【０００８】これらの負極板１１枚と２．３ｍｍ厚さの
正極板１０枚および微細ガラス繊維からなるガラスマッ
トセパレータとを用いて蓄電池を組み立てた後、所定の
注液、充電を行って液比重１. ３２（２０℃）、容量約
６３Ａｈ（３ｈＲ）−１２Ｖのリテーナ式密閉鉛蓄電池
を製作した。A storage battery was assembled using 11 of these negative plates, 10 of the positive plates having a thickness of 2.3 mm, and a glass mat separator made of fine glass fibers, and then the specific gravity was applied to the storage battery to charge it to obtain a liquid specific gravity. A retainer-type sealed lead-acid battery of 1.32 (20 ° C) and a capacity of about 63Ah (3hR) -12V was manufactured.
【０００９】これらの蓄電池を、まず３ＣＡでの初期容
量試験に供し、その後、５０℃の水槽中で、放電深さ８
０％、定電流で放電量の１１０％を充電するパターンで
充放電を繰り返し、蓄電池の寿命性能を調べた。初期容
量試験における放電時間はほぼ同等であったが、平均電
圧には添加物の有無により差があった。平均電圧の相対
値と、寿命に達したサイクル数の相対値を図２に示す。
なお、ここで言う寿命とは、３ＣＡ容量が初期の７０％
以下の容量に達したことを指す。また性能を３ＣＡ容量
で評価しているのは、３ＣＡつまり大電流で放電した場
合の性能は負極板の性能で支配されており、評価に適し
ていることによる。この結果から明らかなように、電池
記号０に比べ、添加物を有する電池1〜９は、平均電圧
及びサイクル数において優れている。平均電圧が優れて
いるということは、添加物によりハイレート性能が改善
されたことを意味し、サイクル数が優れていることは、
耐高温性能が改善されたことを意味する。次に、添加物
の量が寿命性能やハイレート性能の及ぼす影響を調べる
ため、第２の試験を行った。負極活物質への添加は図３
に示す通りであり、他は第１の試験と同様の構成とした
（従って、図３における電池１と図１における電池１と
は同じ構成）。そして第１の試験と同様の試験に供し
た。試験結果を、図２の場合と同じく相対値で示す。こ
の結果から明らかなように、カーボン及びＢaを１．５
重量％含む場合、Ｓbは０．００５〜０．５重量％が効
果的である。同様な試験の結果、Ｓnは０．０５〜０．
８重量％、Ｂｉは０．００８〜０．５重量％、Ｚｎは
０．００４〜０．６重量％、Ｓｅは０．００５〜０．３
重量％、Ｍｎは０．００５〜０．５重量％、Ｃａは０．
００６〜０．６重量％、Ｍｇは０．００５〜０．７重量
％、Ｓrは０．００７〜０．５重量％が好適であること
が分かった。次に、カーボン及びＢaの量の好適範囲を
調べるため、第３の試験を行った。図５の構成の以外は
第１の試験と同様である（従って、図５の電池１は図１
及び図３の電池１と同じ構成）。そして第１の試験と同
様の試験に供した。試験結果を、図２、図４の場合と同
じく相対値で図６に示す。この結果から明らかなよう
に、本発明の実施例（＊印）であるＢａが０．１〜３重
量％、カーボンが０．１〜２重量％のものはハイレート
性能、耐高温性能が良好であることが分かる。この試験
ではＳｂが０．２５％であったが、Ｓbが０．００５〜
０．５重量％、Ｓnが０．０５〜０．８重量％、Ｂｉが
０．００８〜０．５重量％、Ｚｎが．００４〜０．６重
量％、Ｓｅが０．００５〜０．３重量％、Ｍｎが０．０
０５〜０．５重量％、Ｃａが０．００６〜０．６重量
％、Ｍｇが０．００５〜０．７重量％、Ｓrが０．００
７〜０．５重量％の範囲においても同様な傾向が見られ
た。本発明の効果は、非Ｓb系負極格子と、Ｂａを０．
１〜３重量％、グラファイトもしくはカーボンを０．１
〜２重量％含む負極活物質とを有する負極板を備え、前
記負極活物質がＳb、Ｓｎ、Ｂｉ、Ｚｎ、Ｓｅ、Ｍｎ、
Ｃａ、Ｍｇ、Ｓrの群から選ばれた少なくとも1種を含む
ことにより奏されるが、その合計量が余り多くなると活
物質量が低下しエネルギー密度が低下するので、３％以
下とするのがよい。これらを負極活物質に含ませる方法
としては、Ｓb、Ｓｎ、Ｂｉ、Ｚｎ、Ｓｅ、Ｍｎ、Ｃ
ａ、Ｍｇ、Ｓrの群から選ばれた少なくとも1種を含む鉛
合金から鉛粉を製作する方法、負極板をＳb、Ｓｎ、Ｂ
ｉ、Ｚｎ、Ｓｅ、Ｍｎ、Ｃａ、Ｍｇ、Ｓrの群から選ば
れた少なくとも1種を含む電解液中で化成する方法等が
あり、その効果をより高める方法としては、負極板をＳ
b、Ｓｎ、Ｂｉ、Ｚｎ、Ｓｅ、Ｍｎ、Ｃａ、Ｍｇ、Ｓrの
群から選ばれた少なくとも1種を含む電解液中に浸漬
後、熟成したり、比重１．２６以上、より好ましくは
１．２８〜１．３０（２０℃換算）の硫酸電解液を用い
て電槽化成したりすることもできる。本発明の効果は、
負極活物質密度を２．５〜３．８g／ｃｍ3、グラファイ
トもしくはカーボンの比表面積が２０〜５００m２／ｇ
とすることにより、一層大である。These storage batteries were first subjected to an initial capacity test at 3 CA, and then, at a discharge depth of 8 in a water tank at 50 ° C.
The charging / discharging was repeated in a pattern of 0% and 110% of the discharge amount at a constant current, and the life performance of the storage battery was examined. The discharge time in the initial capacity test was almost the same, but the average voltage was different depending on the presence or absence of the additive. FIG. 2 shows the relative value of the average voltage and the relative value of the number of cycles that reached the end of life.
In addition, the life referred to here means that the capacity of 3 CA is 70% of the initial value.
Indicates that the following capacity has been reached. The reason why the performance is evaluated by the 3CA capacity is that the performance in the case of discharging at 3CA, that is, a large current is governed by the performance of the negative electrode plate and is suitable for the evaluation. As is clear from this result, the batteries 1 to 9 having the additive are superior in the average voltage and the number of cycles to the battery code 0. An excellent average voltage means that the additive has improved the high rate performance, and an excellent cycle number means that
This means that the high temperature resistance performance is improved. Next, a second test was conducted to investigate the influence of the amount of the additive on the life performance and the high rate performance. Figure 3 shows the addition to the negative electrode active material.
And the other configurations were the same as those of the first test (therefore, the battery 1 in FIG. 3 and the battery 1 in FIG. 1 have the same configuration). And it used for the test similar to a 1st test. The test results are shown by relative values as in the case of FIG. As is clear from this result, carbon and Ba are 1.5
When it is included by weight, 0.005 to 0.5% by weight of Sb is effective. As a result of a similar test, Sn was 0.05 to 0.
8 wt%, Bi 0.008 to 0.5 wt%, Zn 0.004 to 0.6 wt%, Se 0.005 to 0.3
% By weight, Mn is 0.005-0.5% by weight, Ca is 0.1.
It has been found that 006 to 0.6 wt%, Mg to 0.005 to 0.7 wt% and Sr to 0.007 to 0.5 wt% are suitable. Next, a third test was conducted in order to investigate the preferable range of the amounts of carbon and Ba. 5 is the same as the first test except for the configuration of FIG. 5 (therefore, the battery 1 of FIG.
And the same configuration as the battery 1 in FIG. 3). And it used for the test similar to a 1st test. The test results are shown in FIG. 6 as relative values as in the cases of FIGS. As is clear from these results, the examples (*) of the present invention having 0.1 to 3% by weight of Ba and 0.1 to 2% by weight of carbon have good high rate performance and high temperature resistance. I know there is. In this test, Sb was 0.25%, but Sb was 0.005-
0.5 wt%, Sn 0.05 to 0.8 wt%, Bi 0.008 to 0.5 wt%, Zn. 004 to 0.6% by weight, Se 0.005 to 0.3% by weight, Mn 0.0
05-0.5% by weight, Ca 0.006-0.6% by weight, Mg 0.005-0.7% by weight, Sr 0.00
A similar tendency was observed in the range of 7 to 0.5% by weight. The effect of the present invention is that the non-Sb-based negative electrode lattice and Ba are less than 0.
1-3% by weight, graphite or carbon 0.1
A negative electrode plate having a negative electrode active material of about 2% by weight, wherein the negative electrode active material is Sb, Sn, Bi, Zn, Se, Mn,
It is achieved by including at least one selected from the group consisting of Ca, Mg, and Sr. However, if the total amount is too large, the amount of active material decreases and the energy density decreases, so it should be 3% or less. Good. As a method of incorporating these into the negative electrode active material, Sb, Sn, Bi, Zn, Se, Mn, C
a method for producing lead powder from a lead alloy containing at least one selected from the group of Mg, Sr, and Sb, Sn, B for the negative electrode plate
There is a method of chemical formation in an electrolytic solution containing at least one selected from the group consisting of i, Zn, Se, Mn, Ca, Mg and Sr. As a method of further enhancing the effect, the negative electrode plate may be S.
After being immersed in an electrolytic solution containing at least one selected from the group consisting of b, Sn, Bi, Zn, Se, Mn, Ca, Mg, and Sr, it is aged or has a specific gravity of 1.26 or more, more preferably 1. It is also possible to form a battery case by using a sulfuric acid electrolytic solution of 28 to 1.30 (converted at 20 ° C.). The effect of the present invention is
Negative electrode active material density is 2.5 to 3.8 g / cm3, specific surface area of graphite or carbon is 20 to 500 m2 / g
And is even greater.
【００１０】[0010]
【発明の効果】以上述べたように、本発明によれば、耐
高温性能やハイレート特性に優れた鉛蓄電池を提供が可
能となり、今後ますます発展するであろう車社会への貢
献は大である。As described above, according to the present invention, it becomes possible to provide a lead-acid battery excellent in high temperature resistance and high rate characteristics, and it will make a great contribution to the automobile society that will continue to develop in the future. is there.
【図１】 第１の試験の電池構成を示す図である。FIG. 1 is a diagram showing a battery configuration of a first test.
【図２】 第１の試験結果を示す図である。FIG. 2 is a diagram showing a first test result.
【図３】 第２の試験の電池構成を示す図である。FIG. 3 is a diagram showing a battery configuration of a second test.
【図４】 第２の試験結果を示す図である。FIG. 4 is a diagram showing a second test result.
【図５】 第３の試験の電池構成を示す図である。FIG. 5 is a diagram showing a battery configuration of a third test.
【図６】 第３の試験結果を示す図である。FIG. 6 is a diagram showing a third test result.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｍ 4/62 Ｈ０１Ｍ 4/62 Ｂ 4/73 4/73 Ａ 10/06 10/06 Ｚ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) H01M 4/62 H01M 4/62 B 4/73 4/73 A 10/06 10/06 Z
Claims (8)
量％、グラファイトもしくはカーボンを０．１〜２．５
重量％含む負極活物質とを有する負極板を備え、前記負
極活物質がＳb、Ｓｎ、Ｂｉ、Ｚｎ、Ｓｅ、Ｍｎ、Ｃ
ａ、Ｍｇ、Ｓrの群から選ばれた少なくとも1種を含むこ
とを特徴とする鉛蓄電池。1. A non-Sb type negative electrode grid, 0.1 to 3% by weight of Ba, and 0.1 to 2.5 of graphite or carbon.
A negative electrode plate having a negative electrode active material in an amount of 1% by weight, wherein the negative electrode active material is Sb, Sn, Bi, Zn, Se, Mn, C.
A lead acid battery containing at least one selected from the group consisting of a, Mg and Sr.
０．５重量％、Ｓnが０．０５〜０．８重量％、Ｂｉが
０．００８〜０．５重量％、Ｚｎが０．００４〜０．６
重量％、Ｓｅが０．００５〜０．３重量％、Ｍｎが０．
００５〜０．５重量％、Ｃａが０．００６〜０．６重量
％、Ｍｇが０．００５〜０．７重量％、Ｓrが０．００
７〜０．５重量％の群から選ばれた少なくとも1種を含
むことを特徴とする、請求項１記載の鉛蓄電池。2. The negative electrode active material contains Sb of 0.005 to 0.005.
0.5 wt%, Sn 0.05-0.8 wt%, Bi 0.008-0.5 wt%, Zn 0.004-0.6
% By weight, Se 0.005 to 0.3% by weight, Mn 0.
005-0.5 wt%, Ca 0.006-0.6 wt%, Mg 0.005-0.7 wt%, Sr 0.00
The lead-acid battery according to claim 1, comprising at least one selected from the group of 7 to 0.5% by weight.
Ｓｅ、Ｍｎ、Ｃａ、Ｍｇ、Ｓrの群から選ばれた少なく
とも1種を含む鉛合金から製作されたことを特徴とす
る、請求項1又は２記載の鉛蓄電池。3. The negative electrode active material is Sb, Sn, Bi, Zn,
The lead acid battery according to claim 1 or 2, which is manufactured from a lead alloy containing at least one selected from the group of Se, Mn, Ca, Mg, and Sr.
ｅ、Ｍｎ、Ｃａ、Ｍｇ、Ｓrの群から選ばれた少なくと
も1種を含む電解液中で化成されたことを特徴とする、
請求項1又は２記載の鉛蓄電池。4. The negative electrode plate is Sb, Sn, Bi, Zn, S
e, Mn, Ca, Mg, Sr formed in an electrolytic solution containing at least one selected from the group,
The lead-acid battery according to claim 1 or 2.
ｅ、Ｍｎ、Ｃａ、Ｍｇ、Ｓrの群から選ばれた少なくと
も1種を含む電解液中に浸漬後、熟成されたことを特徴
とする、請求項1又は２記載の鉛蓄電池。5. The negative electrode plate is Sb, Sn, Bi, Zn, S
3. The lead storage battery according to claim 1, which is aged after being immersed in an electrolytic solution containing at least one selected from the group consisting of e, Mn, Ca, Mg, and Sr.
換算）が１．２６以上であることを特徴とする、請求項
１、２、３、４又は５記載の鉛蓄電池。6. Specific gravity of sulfuric acid electrolyte (20 ° C. at the end of battery case formation)
The lead acid battery according to claim 1, 2, 3, 4, or 5, characterized in that the conversion) is 1.26 or more.
であることを特徴とする、請求項１、２、３、４、５又
は６記載の鉛蓄電池。7. The negative electrode active material has a density of 2.5 to 3.8 g / cm3.
The lead-acid battery according to claim 1, 2, 3, 4, 5, or 6, characterized in that.
が２０〜５００m２／ｇであることを特徴とする、請求
項１、２、３、４、５、６又は７記載の鉛蓄電池。8. The lead-acid battery according to claim 1, wherein the specific surface area of graphite or carbon is 20 to 500 m 2 / g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001337351A JP2003142085A (en) | 2001-11-02 | 2001-11-02 | Lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001337351A JP2003142085A (en) | 2001-11-02 | 2001-11-02 | Lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003142085A true JP2003142085A (en) | 2003-05-16 |
Family
ID=19152005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001337351A Pending JP2003142085A (en) | 2001-11-02 | 2001-11-02 | Lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003142085A (en) |
Cited By (11)
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|---|---|---|---|---|
| CN102903932A (en) * | 2012-10-18 | 2013-01-30 | 双登集团股份有限公司 | Lead-acid storage battery positive electrode plate for electric automobile |
| JP2015128053A (en) * | 2013-11-29 | 2015-07-09 | 株式会社Ｇｓユアサ | Lead storage battery |
| US20160240857A1 (en) * | 2015-02-18 | 2016-08-18 | Gs Yuasa International Ltd. | Lead-acid battery |
| JP2016173911A (en) * | 2015-03-17 | 2016-09-29 | 株式会社Ｇｓユアサ | Control valve-type lead storage battery |
| US10084208B2 (en) | 2014-12-18 | 2018-09-25 | Gs Yuasa International Ltd. | Lead-acid battery |
| WO2018199053A1 (en) * | 2017-04-28 | 2018-11-01 | 株式会社Ｇｓユアサ | Lead acid battery |
| US10608242B2 (en) | 2015-03-30 | 2020-03-31 | Gs Yuasa International Ltd. | Lead-acid battery |
| US10622634B2 (en) | 2015-05-29 | 2020-04-14 | Gs Yuasa International Ltd. | Lead-acid battery and method for producing lead-acid battery |
| CN112366289A (en) * | 2020-11-09 | 2021-02-12 | 超威电源集团有限公司 | Lead-acid storage battery positive electrode lead paste and preparation method thereof |
| CN112436144A (en) * | 2020-11-06 | 2021-03-02 | 风帆有限责任公司 | Preparation method of positive lead paste and positive plate of lead-acid storage battery |
| JP2021068549A (en) * | 2019-10-21 | 2021-04-30 | 株式会社Ｇｓユアサ | Lead-acid battery |
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| CN112436144A (en) * | 2020-11-06 | 2021-03-02 | 风帆有限责任公司 | Preparation method of positive lead paste and positive plate of lead-acid storage battery |
| CN112366289A (en) * | 2020-11-09 | 2021-02-12 | 超威电源集团有限公司 | Lead-acid storage battery positive electrode lead paste and preparation method thereof |
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