JP5656068B2 - Liquid lead-acid battery - Google Patents
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Description
この発明は液式鉛蓄電池に関し、特にアンチモンが5000質量ppm以下の鉛または鉛合金からなる接続部材を正極及び負極に用いた鉛蓄電池に関する。 The present invention relates to a liquid lead-acid battery, and more particularly to a lead-acid battery using a connecting member made of lead or a lead alloy having antimony of 5000 ppm by mass or less as a positive electrode and a negative electrode.
鉛蓄電池の接続部材は、一般に正極格子及び負極格子とは別の材料で構成され、特に制御弁式でない液式の鉛蓄電池では、2〜5質量%程度のアンチモンを含む鉛−アンチモン系合金で構成されるのが普通である。なお鉛蓄電池の接続部材とは、正極板群を接続する正極ストラップ、負極板群を接続する負極ストラップ、隣り合うセルの正極ストラップと負極ストラップとを隔壁を通して接続するセル間接続導体、及び鉛蓄電池の出力端子に接続された正負の極柱からなる。発明者は、鉛蓄電池でのアンチモン元素の役割に付いて検討し、接続部材でのアンチモン含有量を50〜5000質量ppmとし、正極格子と負極格子の合金をアンチモンを含まない合金とすることを提案した（特許文献１：特開2008−218258）。この鉛蓄電池では、接続部材の機械的強度が高く、電解液の減液速度が低く、充電受入性が高いため、寿命性能に優れた液式鉛蓄電池が得られる。 The lead-acid battery connecting member is generally made of a material different from the positive and negative grids, and in particular for a liquid lead-acid battery that is not a control valve type, it is a lead-antimony alloy containing about 2 to 5% by mass of antimony. Usually composed. The lead-acid battery connection member includes a positive electrode strap that connects the positive electrode plate group, a negative electrode strap that connects the negative electrode plate group, an inter-cell connection conductor that connects the positive electrode strap and the negative electrode strap of adjacent cells through a partition, and a lead acid battery. It consists of positive and negative poles connected to the output terminal. The inventor examined the role of antimony element in the lead-acid battery, determined that the antimony content in the connecting member was 50 to 5000 ppm by mass, and the alloy of the positive and negative grids was an antimony-free alloy. Proposed (Patent Document 1: JP 2008-218258). In this lead storage battery, since the mechanical strength of the connecting member is high, the liquid reduction rate of the electrolytic solution is low, and the charge acceptability is high, a liquid lead storage battery having excellent life performance can be obtained.
自動車用の鉛蓄電池では、燃費の向上のためにアイドリングストップ性能が要求されている。この点に関して、特許文献２：特開2008−243487は、リチウムイオンとアルミニウムイオンとを鉛蓄電池の電解液に添加することを提案している。リチウムイオンは正極利用率を向上させて放電容量を増加させ、アルミニウムイオンは負極のサルフェーションを防止してアイドリングストップ寿命を向上させるとされている。なお特許文献２は液式鉛蓄電池の接続部材の材質に付いて記載していないので、接続部材は2〜5質量%程度のアンチモンを含むものと推定される。 Lead-acid batteries for automobiles are required to have idling stop performance in order to improve fuel efficiency. In this regard, Patent Document 2: Japanese Patent Application Laid-Open No. 2008-243487 proposes to add lithium ions and aluminum ions to the electrolyte of the lead storage battery. Lithium ions improve the positive electrode utilization rate and increase discharge capacity, and aluminum ions prevent sulfation of the negative electrode and improve the idling stop life. Since Patent Document 2 does not describe the material of the connection member of the liquid lead-acid battery, the connection member is estimated to contain about 2 to 5% by mass of antimony.
液式鉛蓄電池のアイドリングストップ性能に関して、電池工業会規格（SBA S 0101）が25℃での寿命性能を問題にしているなど、常温での性能が主に検討されている。しかしながら自動車のエンジンルームは一般に外気温よりも高い温度になり、特に夏期の日中に長時間自動車を運転すると、60℃以上の温度になることがある。また春秋でも、沖縄及び南九州で日中に長時間自動車を運転すると、エンジンルームは60℃程度の温度になることがある。そこで実使用時のアイドリングストップ性能を向上させるためには、高温でのアイドリングストップ寿命性能を向上させる必要がある。 Regarding the idling stop performance of liquid lead-acid batteries, the performance at room temperature has been mainly studied, such as the battery industry association standard (SBA S 0101) has a problem of the life performance at 25 ° C. However, the engine room of an automobile is generally at a temperature higher than the outside air temperature. In particular, when the automobile is operated for a long time during the summer, the temperature may be 60 ° C. or higher. Even in spring and autumn, if the car is driven for a long time in Okinawa and South Kyushu during the day, the engine room may reach a temperature of about 60 ° C. Therefore, in order to improve the idling stop performance in actual use, it is necessary to improve the idling stop life performance at a high temperature.
この発明の基本的課題は、高温でも常温でもアイドリングストップ寿命性能に優れた液式鉛蓄電池を提供することにある。
この発明での追加の課題は、高温でも常温でも減液速度を接続部材が2〜5質量%程度のアンチモンを含む従来の液式鉛蓄電池以下に制限することにある。
A basic object of the present invention is to provide a liquid lead-acid battery that is excellent in idling stop life performance at both high temperature and room temperature.
An additional problem in the present invention is to limit the liquid reduction rate at a high temperature or a normal temperature to less than that of a conventional liquid lead-acid battery in which the connection member contains about 2 to 5% by mass of antimony.
この発明は、鉛−カルシウム−スズ系合金からなる正極格子、鉛−カルシウム−スズ系合金からなる負極格子、正極活物質、負極活物質、電解液、及び接続部材を備えた液式鉛蓄電池であって、
接続部材は鉛を主成分とし、かつアンチモン含有量が5000質量ppm以下で、
負極活物質、正極活物質、及び電解液の少なくともいずれかが、アンチモン、ニッケル、銀、モリブデン、銅、及びテルルからなる群の少なくとも一員の元素を含有し、
負極活物質、正極活物質、及び電解液での、アンチモンの含有量と、ニッケル、銀、モリブデンの含有量の10倍と、銅の含有量の5倍と、テルルの含有量の20倍との和が、負極活物質との質量比で100〜1000質量ppmであり、
電解液はアルミニウムイオンとリチウムイオンとを各0.02〜0.2mol/L含有することを特徴とする。
The present invention relates to a liquid lead-acid battery comprising a positive electrode lattice made of a lead-calcium-tin alloy, a negative electrode lattice made of a lead-calcium-tin alloy, a positive electrode active material, a negative electrode active material, an electrolytic solution, and a connecting member. There,
The connecting member is composed mainly of lead, and the antimony content is 5000 mass ppm or less,
At least one of the negative electrode active material, the positive electrode active material, and the electrolytic solution contains at least one member of the group consisting of antimony, nickel, silver, molybdenum, copper, and tellurium,
Antimony content in negative electrode active material, positive electrode active material, and electrolyte, 10 times the content of nickel, silver, molybdenum, 5 times the content of copper, and 20 times the content of tellurium Is a mass ratio of 100 to 1000 mass ppm with the negative electrode active material,
The electrolyte solution is characterized by containing 0.02 to 0.2 mol / L of aluminum ions and lithium ions.
またこの発明は、鉛−カルシウム−スズ系合金からなる正極格子、鉛−カルシウム−スズ系合金からなる負極格子、正極活物質、負極活物質、電解液、及び接続部材を備えた液式鉛蓄電池であって、
接続部材は鉛を主成分とし、かつアンチモン含有量が5000質量ppm以下で、
負極活物質、正極活物質、及び電解液の少なくともいずれかが、アンチモンを含有し、
負極活物質、正極活物質、及び電解液でのアンチモンの合計含有量が、負極活物質との質量比で100〜1000質量ppmであり、
電解液はアルミニウムイオンとリチウムイオンとを各0.02〜0.2mol/L含有することを特徴とする。
The present invention also provides a liquid lead-acid battery comprising a positive electrode lattice made of a lead-calcium-tin alloy, a negative electrode lattice made of a lead-calcium-tin alloy, a positive electrode active material, a negative electrode active material, an electrolytic solution, and a connecting member. Because
The connecting member is composed mainly of lead, and the antimony content is 5000 mass ppm or less,
At least one of the negative electrode active material, the positive electrode active material, and the electrolytic solution contains antimony,
The total content of antimony in the negative electrode active material, the positive electrode active material, and the electrolyte is 100 to 1000 ppm by mass with respect to the negative electrode active material,
The electrolyte solution is characterized by containing 0.02 to 0.2 mol / L of aluminum ions and lithium ions.
この発明はさらに、鉛−カルシウム−スズ系合金からなる正極格子、鉛−カルシウム−スズ系合金からなる負極格子、正極活物質、負極活物質、電解液、及び接続部材を備えた液式鉛蓄電池であって、
接続部材は鉛を主成分とし、かつアンチモン含有量が5000質量ppm以下で、
負極活物質、正極活物質、及び電解液の少なくともいずれかが、ニッケル、銀、モリブデンからなる群の少なくとも一員の元素を含有し、
負極活物質、正極活物質、及び電解液での、前記少なくとも一員の元素の合計含有量が、負極活物質との質量比で10〜100質量ppmであり、
電解液はアルミニウムイオンとリチウムイオンとを各0.02〜0.2mol/L含有することを特徴とする。なおニッケルのみを加えても、あるいは銀のみを加えても、またモリブデンのみを加えても良い。
The present invention further includes a positive electrode lattice made of a lead-calcium-tin alloy, a negative electrode lattice made of a lead-calcium-tin alloy, a positive electrode active material, a negative electrode active material, an electrolytic solution, and a liquid lead storage battery comprising a connecting member. Because
The connecting member is composed mainly of lead, and the antimony content is 5000 mass ppm or less,
At least one of the negative electrode active material, the positive electrode active material, and the electrolytic solution contains at least one element of the group consisting of nickel, silver, and molybdenum,
In the negative electrode active material, the positive electrode active material, and the electrolytic solution, the total content of the at least one member element is 10 to 100 ppm by mass with respect to the negative electrode active material,
The electrolyte solution is characterized by containing 0.02 to 0.2 mol / L of aluminum ions and lithium ions. Note that only nickel, silver alone, or molybdenum alone may be added.
この発明は、鉛−カルシウム−スズ系合金からなる正極格子、鉛−カルシウム−スズ系合金からなる負極格子、正極活物質、負極活物質、電解液、及び接続部材を備えた液式鉛蓄電池であって、
接続部材は鉛を主成分とし、かつアンチモン含有量が5000質量ppm以下で、
負極活物質、正極活物質、及び電解液の少なくともいずれかが、銅を含有し、
負極活物質、正極活物質、及び電解液での銅の合計含有量が、負極活物質との質量比で20〜200質量ppmであり、
電解液はアルミニウムイオンとリチウムイオンとを各0.02〜0.2mol/L含有することを特徴とする。
The present invention relates to a liquid lead-acid battery comprising a positive electrode lattice made of a lead-calcium-tin alloy, a negative electrode lattice made of a lead-calcium-tin alloy, a positive electrode active material, a negative electrode active material, an electrolytic solution, and a connecting member. There,
The connecting member is composed mainly of lead, and the antimony content is 5000 mass ppm or less,
At least one of the negative electrode active material, the positive electrode active material, and the electrolytic solution contains copper,
The total content of copper in the negative electrode active material, the positive electrode active material, and the electrolytic solution is 20 to 200 ppm by mass with respect to the negative electrode active material,
The electrolyte solution is characterized by containing 0.02 to 0.2 mol / L of aluminum ions and lithium ions.
この発明はまた、鉛−カルシウム−スズ系合金からなる正極格子、鉛−カルシウム−スズ系合金からなる負極格子、正極活物質、負極活物質、電解液、及び接続部材を備えた液式鉛蓄電池であって、
接続部材は鉛を主成分とし、かつアンチモン含有量が5000質量ppm以下で、
負極活物質、正極活物質、及び電解液の少なくともいずれかが、テルルを含有し、
負極活物質、正極活物質、及び電解液でのテルルの合計含有量が、負極活物質との質量比で5〜50質量ppmであり、
電解液はアルミニウムイオンとリチウムイオンとを各0.02〜0.2mol/L含有することを特徴とする。
The present invention also provides a positive lead grid made of a lead-calcium-tin alloy, a negative grid made of a lead-calcium-tin alloy, a positive electrode active material, a negative electrode active material, an electrolytic solution, and a liquid lead storage battery including a connecting member. Because
The connecting member is composed mainly of lead, and the antimony content is 5000 mass ppm or less,
At least one of the negative electrode active material, the positive electrode active material, and the electrolytic solution contains tellurium,
The total content of tellurium in the negative electrode active material, the positive electrode active material, and the electrolyte is 5 to 50 ppm by mass with respect to the negative electrode active material,
The electrolyte solution is characterized by containing 0.02 to 0.2 mol / L of aluminum ions and lithium ions.
この明細書において、接続部材は正負の極柱、セル間接続導体、正負のストラップから成り、接続部材でのアンチモン含有量は0を含み、鉛中の不純物としてのアンチモン濃度が例えば5質量ppmの場合、接続部材でのアンチモン含有量は例えば5〜5000質量ppmとなる。アンチモンの不純物濃度が例えば１質量ppmの場合、接続部材でのアンチモン含有量は例えば1〜5000質量ppmとなる。アンチモン、ニッケル、銀、モリブデン、銅、及びテルルの含有量は金属換算で定め、これらの元素の添加形態は金属でも酸化物等の化合物でも良い。正極格子と負極格子は鉛−カルシウム−スズ系合金からなれば良く、従来から活物質との密着性を改善するために、正極格子の表層に鉛−アンチモン等の合金層を設ける技術があるが、アンチモンが正極格子質量に対して1000質量ppm未満であれば本発明へのこの技術の適用を排除するものではない。 In this specification, the connection member is composed of positive and negative pole columns, inter-cell connection conductors, positive and negative straps, the antimony content in the connection member includes 0, and the concentration of antimony as an impurity in lead is, for example, 5 mass ppm. In this case, the antimony content in the connecting member is, for example, 5 to 5000 ppm by mass. When the impurity concentration of antimony is, for example, 1 mass ppm, the antimony content in the connecting member is, for example, 1 to 5000 mass ppm. The content of antimony, nickel, silver, molybdenum, copper, and tellurium is determined in terms of metal, and the addition form of these elements may be a metal or a compound such as an oxide. The positive electrode lattice and the negative electrode lattice may be made of a lead-calcium-tin alloy, and conventionally there is a technique of providing an alloy layer such as lead-antimony on the surface layer of the positive electrode lattice in order to improve the adhesion to the active material. If the antimony is less than 1000 ppm by mass with respect to the positive electrode lattice mass, application of this technique to the present invention is not excluded.
主な実施例の結果を図１〜図３に示す。各図の中央の正方形は、アンチモンを接続部材に2.5質量％含む従来例（試料A1）の性能を示し、活物質及び電解液でのアンチモン含有量は不純物濃度以下で、アルミニウムイオンもリチウムイオンも無添加である。図１では、接続部材がアンチモンを含まず、負極活物質が100質量ppmのアンチモンを含み、電解液が共に0.2mol/Lのアルミニウムイオンとリチウムイオンとを含む実施例を試料A26とする。次に試料A26から負極活物質のアンチモンを除いた比較例を試料A15、アルミニウムイオンを除いた比較例を試料A11、リチウムイオンを除いた比較例を試料A7とする。また常温寿命性能はアイドリングストップ寿命試験（SBA S 0101:2006の9.5.4）を実施した際の結果を示し、高温寿命性能はこの試験を規定の周囲温度25℃ではなく、周囲温度60℃で行った際の結果を示す。さらに減液性能は減液速度の逆数の比を表したもので、試料A1の減液速度の逆数を100としたときの相対値で示し、試験温度を60℃（高温）と25℃（常温）とでアイドリングストップ寿命試験を行った際の結果である。なおこの明細書において、結果は３個の蓄電池の平均で示し、従来例の蓄電池（試料A1）の性能を100とする相対値で示す。試験条件は以下同様である。 The results of the main examples are shown in FIGS. The center square in each figure shows the performance of the conventional example (sample A1) containing 2.5% by mass of antimony in the connecting member. The antimony content in the active material and the electrolyte is below the impurity concentration, and both aluminum ions and lithium ions No additives. In FIG. 1, an example in which the connecting member does not contain antimony, the negative electrode active material contains 100 mass ppm of antimony, and the electrolytic solution contains both 0.2 mol / L of aluminum ions and lithium ions is designated as sample A26. Next, a comparative example in which antimony of the negative electrode active material is removed from sample A26 is designated as sample A15, a comparative example in which aluminum ions are removed is designated as sample A11, and a comparative example in which lithium ions are removed is designated as sample A7. The normal temperature life performance shows the results when the idling stop life test (SBA S 0101: 2006 9.5.4) is performed. The high temperature life performance shows that this test is performed at an ambient temperature of 60 ° C instead of the specified ambient temperature of 25 ° C. The result when it is performed is shown. Furthermore, the liquid reduction performance represents the ratio of the reciprocal of the liquid reduction rate, and shows the relative value when the reciprocal of the liquid reduction rate of sample A1 is 100. The test temperatures are 60 ° C (high temperature) and 25 ° C (room temperature) ) And idling stop life test results. In this specification, the results are shown as an average of three storage batteries, and are expressed as relative values with the performance of the conventional storage battery (sample A1) as 100. The test conditions are the same below.
図１から高温寿命性能を得るには、負極活物質がアンチモンを含み、電解液がアルミニウムイオンとリチウムイオンとを含むことが必要不可欠であることが分かる。常温の寿命性能では、負極活物質がアンチモンを含み、電解液がアルミニウムイオンを含めば、リチウムイオンを含まないでも、ある程度良好な結果を得ることができる。しかし高温寿命性能では、リチウムイオンを含まない蓄電池の場合、良好な結果を得ることができない。常温の減液性能では、４種類の試料A26,A25,A11,A7は類似の結果を示す。しかし高温の減液性能では、アルミニウムイオンを含まない試料A11では従来例以下の性能となり、高温での減液性能を試料A1以下に保つにはアルミニウムイオンが必要不可欠である。以上のように高温の性能と常温の性能とは異なる性能であり、高温で寿命性能が高く、かつ減液も遅くするためには、負極活物質がアンチモンを含み、電解液がアルミニウムイオンとリチウムイオンとを含むことが必要である。 From FIG. 1, it can be seen that it is indispensable that the negative electrode active material contains antimony and the electrolytic solution contains aluminum ions and lithium ions in order to obtain high-temperature life performance. In the life performance at room temperature, if the negative electrode active material contains antimony and the electrolytic solution contains aluminum ions, good results can be obtained to some extent even without lithium ions. However, in the high temperature life performance, in the case of a storage battery not containing lithium ions, good results cannot be obtained. In the liquid reducing performance at room temperature, the four types of samples A26, A25, A11, and A7 show similar results. However, in the high-temperature liquid reduction performance, the performance of the sample A11 that does not contain aluminum ions is less than that of the conventional example, and aluminum ions are indispensable to keep the liquid reduction performance at high temperatures below the sample A1. As described above, the performance at high temperature is different from the performance at normal temperature, and in order to have high life performance at high temperature and slow down the liquid reduction, the negative electrode active material contains antimony, and the electrolytic solution contains aluminum ions and lithium. It is necessary to contain ions.
図２は接続部材中のアンチモン濃度の影響を示し、接続部材中のアンチモン濃度を増すと、寿命性能が向上して減液性能が低下し（試料A34）、アンチモン濃度をさらに増すと、寿命性能も減液性能も低下する（試料A45）。図３は負極活物質中のアンチモン濃度の影響を示し、負極活物質中のアンチモン濃度を増すと、寿命性能が向上して減液性能が低下し（試料A30）、アンチモン濃度をさらに増すと、寿命性能も減液性能も低下する（試料A49）。一方負極活物質がアンチモンを含まないと、減液性能は実施例と同等であるが、良好な寿命性能が得られない（試料A15）。 Fig. 2 shows the effect of antimony concentration in the connection member. When the antimony concentration in the connection member is increased, the life performance is improved and the liquid reduction performance is lowered (Sample A34), and when the antimony concentration is further increased, the life performance is increased. The liquid reduction performance also decreases (Sample A45). FIG. 3 shows the effect of the antimony concentration in the negative electrode active material. When the antimony concentration in the negative electrode active material is increased, the life performance is improved and the liquid reduction performance is lowered (Sample A30). When the antimony concentration is further increased, Both life performance and liquid reduction performance decrease (Sample A49). On the other hand, if the negative electrode active material does not contain antimony, the liquid reduction performance is equivalent to that of the example, but good life performance cannot be obtained (Sample A15).
正極活物質あるいは電解液にアンチモンを添加しても、アンチモンは負極活物質に析出するので、その効果は負極活物質に添加した場合と同様である（表２）。従って、アンチモンは負極活物質、正極活物質、電解液のいずれかに添加されれば良く、その合計量が重要である。 Even if antimony is added to the positive electrode active material or the electrolytic solution, since antimony is deposited on the negative electrode active material, the effect is the same as when added to the negative electrode active material (Table 2). Therefore, antimony may be added to any one of the negative electrode active material, the positive electrode active material, and the electrolytic solution, and the total amount is important.
アンチモンは鉛よりも水素過電圧の低い元素であり、充電受入性を改善する。例えば図３で、負極活物質がアンチモンを含まない試料A15は、高温でも常温でも寿命性能が低い。アンチモンと同等の作用をする元素として、ニッケル、銀、モリブデン、銅、及びテルルがあり、これらの適正添加量はニッケル、銀、モリブデンでアンチモンの1/10、銅でアンチモンの1/5、テルルでアンチモンの1/20である。またニッケル、銀、モリブデン、銅、及びテルルでも、負極活物質の代わりに、正極活物質あるいは電解液に添加しても良い。アンチモンを活物質あるいは電解液に添加した際の結果を表１，表２に示し、ニッケル、銀、モリブデン、銅、あるいはテルルを活物質あるいは電解液に添加した際の結果を表３〜表１２に示す。 Antimony is an element with a lower hydrogen overvoltage than lead and improves charge acceptance. For example, in FIG. 3, the sample A15 in which the negative electrode active material does not contain antimony has low life performance at both high temperature and room temperature. There are nickel, silver, molybdenum, copper, and tellurium as elements that have the same effect as antimony. The appropriate addition amount of nickel, silver, and molybdenum is 1/10 of antimony, copper is 1/5 of antimony, and tellurium. It is 1/20 of antimony. Nickel, silver, molybdenum, copper, and tellurium may also be added to the positive electrode active material or the electrolytic solution instead of the negative electrode active material. Tables 1 and 2 show the results when antimony is added to the active material or the electrolytic solution, and Tables 3 to 12 show the results when nickel, silver, molybdenum, copper, or tellurium is added to the active material or the electrolytic solution. Shown in
この発明では、高温でも常温でもアイドリングストップ寿命性能に優れ、かつ減液速度が接続部材が2〜5質量%程度のアンチモンを含む従来の液式鉛蓄電池以下である鉛蓄電池が得られる。 According to the present invention, a lead storage battery having excellent idling stop life performance at a high temperature and a normal temperature and having a liquid reduction rate equal to or lower than a conventional liquid lead storage battery containing antimony whose connection member is about 2 to 5% by mass can be obtained.
この明細書で、アルミニウムイオン，リチウムイオンの濃度は電解液1L当たりのアルミニウムイオンとリチウムイオンの濃度（mol/L）で表す。なおアルミニウムイオンの１モルは、硫酸アルミニウム（Al2(SO4)3）の171.05gに相当する。また活物質の組成は水と硫酸とを除いて示し、負極活物質の質量は化成後の負極板を水洗乾燥し、負極活物質と負極格子とを分離して測定する。 In this specification, the concentration of aluminum ions and lithium ions is expressed as the concentration (mol / L) of aluminum ions and lithium ions per liter of electrolyte. One mole of aluminum ions corresponds to 171.05 g of aluminum sulfate (Al 2 (SO 4 ) 3 ). The composition of the active material is shown excluding water and sulfuric acid, and the mass of the negative electrode active material is measured by washing and drying the formed negative electrode plate, separating the negative electrode active material and the negative electrode lattice.
以下に、本願発明の最適実施例を示す。本願発明の実施に際しては、当業者の常識及び先行技術の開示に従い、実施例を適宜に変更できる。 Hereinafter, an optimum embodiment of the present invention will be described. In carrying out the present invention, the embodiments can be appropriately changed in accordance with common sense of those skilled in the art and disclosure of prior art.
鉛蓄電池の製造
JIS D 5301に準拠した55B24形の液式鉛蓄電池（公称電圧12V、５時間率定格容量は36Ah）を製造した。正極格子は0.07質量%のCaと1.5質量%のSnと不可避不純物とを含み残余がPbの合金で、負極格子は0.05質量%のCaと0.5質量%のSnと不可避不純物とを含み残余がPbの合金である。各格子はエキスパンド格子であり、サイズは共に高さが115mm、幅が100mm、厚さが1mmである。格子の形状はエキスパンド格子に限らず任意であり、また、サイズも任意である。
Manufacture of lead-acid batteries
A 55B24 type liquid lead-acid battery (nominal voltage 12V, 5 hour rate rated capacity 36Ah) in accordance with JIS D 5301 was manufactured. The positive electrode lattice is an alloy of 0.07% by mass of Ca, 1.5% by mass of Sn and unavoidable impurities, and the balance is Pb, and the negative electrode lattice is of 0.05% by mass of Ca, 0.5% by mass of Sn and unavoidable impurities, and the balance is Pb. Alloy. Each lattice is an expanded lattice, the size of which is 115 mm in height, 100 mm in width, and 1 mm in thickness. The shape of the lattice is not limited to the expanded lattice, and may be any size.
負極活物質として、ボールミル法の鉛粉に、リグニン0.15質量%、カーボンブラック0.2質量%、硫酸バリウム0.5質量%、0.1質量%のアクリル繊維、及びアンチモンを含む場合には三酸化アンチモンを加え、鉛粉との合計を100質量%とした。この混合物100質量%に、水13質量%と20℃で比重1.40の希硫酸10質量%とを混合し、負極活物質とした。正極活物質として、ボールミル法の鉛粉に、0.1質量%のアクリル繊維、及びアンチモンを含む場合には三酸化アンチモンを加え、合計を100質量%とした。この混合物100質量%に、水13質量%と20℃で比重1.40の希硫酸10質量%とを混合し、正極活物質とした。なお鉛粉はボールミル法に限らず、バートン法等によるものでも良い。アクリル繊維に代えて他の合成樹脂繊維を加えても良く、また合成樹脂繊維を加えなくても良い。また、アンチモンの添加形態は三酸化アンチモンに限らず、金属アンチモンや硫酸アンチモンとして添加しても良い。正極と負極格子とに１枚当たり50gの活物質ペーストを充填し、各々50℃相対湿度50%で48時間熟成し、次いで50℃の乾燥雰囲気で24時間乾燥させ未化成の正負極板を得た。 As a negative electrode active material, if it contains 0.15% by mass of lignin, 0.2% by mass of carbon black, 0.5% by mass of barium sulfate, 0.1% by mass of acrylic fiber, and antimony, lead powder of the ball mill method is added with antimony trioxide, lead The total with the powder was 100% by mass. To 100% by mass of this mixture, 13% by mass of water and 10% by mass of diluted sulfuric acid having a specific gravity of 1.40 at 20 ° C. were mixed to obtain a negative electrode active material. As a positive electrode active material, when 0.1% by mass of acrylic fiber and antimony were contained in the ball mill lead powder, antimony trioxide was added to make the total to 100% by mass. To 100% by mass of this mixture, 13% by mass of water and 10% by mass of diluted sulfuric acid having a specific gravity of 1.40 at 20 ° C. were mixed to obtain a positive electrode active material. The lead powder is not limited to the ball mill method, but may be a Barton method. Another synthetic resin fiber may be added instead of the acrylic fiber, or the synthetic resin fiber may not be added. The addition form of antimony is not limited to antimony trioxide, but may be added as metal antimony or antimony sulfate. Filling positive electrode and negative electrode grid with 50g of active material paste, aged for 48 hours at 50 ° C and 50% relative humidity respectively, then dried in dry atmosphere at 50 ° C for 24 hours to obtain unformed positive and negative plates It was.
微孔性のポリエチレンシートを２つ折りにして両側端をメカニカルシールした袋からなるセパレータに、未化成の負極板を収容した。セパレータは、ポリエチレン以外にも硫酸中で安定で、絶縁性の素材のものであれば良い。さらにガラス繊維シートをセパレータとしても良い。セパレータは、袋状でもリーフ状のものでも良い。 A non-chemically formed negative electrode plate was accommodated in a separator made of a bag in which a microporous polyethylene sheet was folded in two and both ends were mechanically sealed. The separator may be made of an insulating material that is stable in sulfuric acid other than polyethylene. Further, a glass fiber sheet may be used as the separator. The separator may be a bag or a leaf.
未化成の正極板7枚と未化成の負極板8枚とをセパレータを介して交互に積層し、キャストオンストラップ法（ＣＯＳ法）により、同極性の極板同士を接続し、ストラップとセル間接続導体及び極柱からなる接続部材を形成して極板群とした。接続部材はアンチモン含有量が0〜5000質量ppmの鉛−アンチモン合金、もしくはアンチモン含有量が0〜5000質量ppmの３成分系、もしくは４成分系等の鉛合金からなる。３成分系の鉛合金は例えば鉛−0.1質量％カルシウム−アンチモン合金、あるいは鉛−1.5質量%スズ−アンチモン合金等があり、カルシウム含有量とスズ含有量等は特に限定する必要はない。ただし、カルシウムを含有する場合は腐食しやすい金属間化合物Ca3Sb2を生成するため、接続部材のアンチモン含有量は100質量ppm以下であることが望ましい。得られた極板群を６個ポリプロピレン製の電槽に収納して直列に接続するように、セル間接続導体の位置で溶接し、蓋溶着を実施した後に正負の極柱を鉛蓄電池の出力端子に接続した。負極側の接続部材と正極側の接続部材は、アンチモン含有量が共に0〜5000質量ppmであれば、組成が異なっても良い。 7 unformed positive plates and 8 unformed negative plates are stacked alternately via separators, and the same polarity plates are connected to each other by the cast-on-strap method (COS method). A connecting member composed of a connecting conductor and a pole column was formed to form an electrode plate group. The connecting member is made of a lead-antimony alloy having an antimony content of 0 to 5000 mass ppm, or a ternary or quaternary lead alloy having an antimony content of 0 to 5000 mass ppm. Examples of ternary lead alloys include lead-0.1 mass% calcium-antimony alloy or lead-1.5 mass% tin-antimony alloy, and the calcium content and tin content need not be particularly limited. However, since the intermetallic compound Ca 3 Sb 2 that easily corrodes is generated when calcium is contained, the antimony content of the connecting member is preferably 100 ppm by mass or less. The obtained electrode plate group is housed in a battery case made of polypropylene and connected in series so that it is welded at the position of the inter-cell connection conductor, and after the lid is welded, the positive and negative pole columns are output from the lead-acid battery. Connected to the terminal. The negative electrode side connecting member and the positive electrode side connecting member may have different compositions as long as the antimony content is 0 to 5000 ppm by mass.
20℃で比重が1.230の希硫酸に所定量の硫酸アルミニウムと硫酸リチウムとを添加した電解液を注入し、25℃の水槽内で電槽化成を行って、55B24形の鉛蓄電池とした。電解液の量はセル当たりで、450mLであった。アルミニウム源とリチウム源は任意で、例えば水酸化アルミニウムと水酸化リチウム等の形態で添加しても良い。電解液にアンチモンを添加する場合、酸化アンチモンや硫酸アンチモン等の任意の形態で添加する。 An electrolytic solution in which a predetermined amount of aluminum sulfate and lithium sulfate was added to dilute sulfuric acid having a specific gravity of 1.230 at 20 ° C. was injected, and a battery was formed in a water bath at 25 ° C. to obtain a 55B24 type lead acid battery. The amount of the electrolytic solution was 450 mL per cell. The aluminum source and the lithium source are optional, and may be added in the form of, for example, aluminum hydroxide and lithium hydroxide. When antimony is added to the electrolyte, it is added in any form such as antimony oxide or antimony sulfate.
アンチモンに代えて、ニッケル、銀、モリブデン、銅あるいはテルルを添加しても良く、アンチモン及びこれらの元素は、負極活物質、正極活物質、電解液のいずれかに加える。添加形態は金属、酸化物、硫酸塩等任意である。これらの元素はいずれの位置に添加しても、最終的には負極活物質に析出し、最初から負極活物質に添加した場合と同様に作用する。またこれらの個別の元素の量よりも、これらの元素の合計量が重要である。以下、試作した鉛蓄電池で添加量０は各元素の濃度が不純物として含まれる濃度と同等であることを意味し、０以外の添加量の場合、添加量は不純物に由来するものも含んでいる。一般に、鉛及び鉛合金の不純物はアンチモンで30質量ppm、ニッケルで5質量ppm、銀で5質量ppm、モリブデンで5質量ppm、銅で10質量ppm、テルルで1質量ppmである。電解液中のこれらの元素の不純物濃度は一般に1mg/L以下である。負極活物質の質量は、化成後の負極板を水洗乾燥し、負極活物質と負極格子とを分離して測定する。 Instead of antimony, nickel, silver, molybdenum, copper, or tellurium may be added, and antimony and these elements are added to any of the negative electrode active material, the positive electrode active material, and the electrolytic solution. The addition form is arbitrary such as metal, oxide, sulfate. Even if these elements are added at any position, they are finally deposited on the negative electrode active material and act in the same manner as when added to the negative electrode active material from the beginning. The total amount of these elements is more important than the amount of these individual elements. Hereinafter, in the prototype lead-acid battery, the addition amount 0 means that the concentration of each element is equivalent to the concentration contained as an impurity, and in the case of an addition amount other than 0, the addition amount includes those derived from impurities. . Generally, impurities in lead and lead alloys are 30 mass ppm for antimony, 5 mass ppm for nickel, 5 mass ppm for silver, 5 mass ppm for molybdenum, 10 mass ppm for copper, and 1 mass ppm for tellurium. The impurity concentration of these elements in the electrolyte is generally 1 mg / L or less. The mass of the negative electrode active material is measured by washing and drying the formed negative electrode plate and separating the negative electrode active material and the negative electrode lattice.
試験法
各鉛蓄電池に対し、常温（25℃）でのアイドリングストップ寿命試験（SBA S 0101:2006の9.5.4）を行うと共に、周囲温度を60℃に変更してアイドリングストップ寿命試験（SBA S 0101:2006の9.5.4）を行った。試料数は各３で、結果は３個の試料の平均値を従来例の試料A1の性能を100とする相対値で示す。結果を表１〜表１４に示す。
Test method For each lead-acid battery, an idling stop life test (SBA S 0101: 2006 9.5.4) at normal temperature (25 ° C) was performed, and the idling stop life test (SBA S) was performed by changing the ambient temperature to 60 ° C. 0101: 2006, 9.5.4). The number of samples is 3, and the result is an average value of the three samples as a relative value with the performance of the sample A1 of the conventional example as 100. The results are shown in Tables 1-14.
結果
表１は負極活物質にアンチモンを添加した際の結果で、表２は負極活物質、正極活物質あるいは電解液にアンチモンを添加した際の結果である。負極活物質に添加しても、正極活物質あるいは電解液に添加しても、結果は同等である。表３、表４はニッケルを添加した際の結果で、負極活物質に添加しても、正極活物質あるいは電解液に添加しても良く、その効果はアンチモンと同等で添加量はアンチモンの場合の1/10とすると良い。表５、表６は銀を添加した際の結果で、効果はアンチモンと同等で、添加量はアンチモンの場合の1/10とすると良い。表７、表８は銅を添加した際の結果で、効果はアンチモンと同等で、添加量はアンチモンの場合の1/5とすると良い。表９、表１０はモリブデンを添加した際の結果で、効果はアンチモンと同等で、添加量はアンチモンの場合の1/10とすると良い。表１１、表１２はテルルを添加した際の結果で、効果はアンチモンと同等で、添加量はアンチモンの場合の1/20とすると良い。銀、銅、モリブデン、テルルのいずれの場合も、負極活物質に添加するか、正極活物質に添加するか、あるいは電解液に添加するかは問題ではないことが分かる。
Results Table 1 shows the results when antimony was added to the negative electrode active material, and Table 2 shows the results when antimony was added to the negative electrode active material, the positive electrode active material, or the electrolytic solution. The result is the same whether it is added to the negative electrode active material or the positive electrode active material or the electrolytic solution. Tables 3 and 4 show the results when nickel is added, and may be added to the negative electrode active material, the positive electrode active material or the electrolytic solution. The effect is the same as that of antimony, and the addition amount is antimony. It should be 1/10 of. Tables 5 and 6 show the results when silver is added. The effect is equivalent to that of antimony, and the addition amount is preferably 1/10 that of antimony. Tables 7 and 8 show the results when copper is added. The effect is equivalent to that of antimony, and the addition amount is preferably 1/5 that of antimony. Tables 9 and 10 show the results when molybdenum is added. The effect is equivalent to that of antimony, and the addition amount is preferably 1/10 that of antimony. Tables 11 and 12 show the results when tellurium is added. The effect is equivalent to that of antimony, and the addition amount is preferably 1/20 that of antimony. In any case of silver, copper, molybdenum, and tellurium, it is understood that it does not matter whether it is added to the negative electrode active material, the positive electrode active material, or the electrolyte solution.
アンチモン、ニッケル、銀、銅、モリブデン、テルルを組み合わせて添加した際の結果を表１３に示し、アンチモン、ニッケル、銀、銅、モリブデン、テルルの合計添加量が重要で、ニッケル、銀、モリブデンの場合は添加量を10倍し、銅の場合は5倍し、テルルの場合は20倍したものをアンチモンの添加量と加算したものが意味を持つ。表１４は接続部材の材質を鉛−アンチモン合金から、鉛−0.1質量％カルシウム−アンチモン合金あるいは鉛−1.5質量％スズ−アンチモン合金に変更した例を示し、接続部材が鉛−アンチモン合金か、鉛−カルシウム−アンチモン合金あるいは鉛−スズ−アンチモン合金かは問題ではないことが分かる。 The results of adding antimony, nickel, silver, copper, molybdenum, and tellurium are shown in Table 13, and the total amount of antimony, nickel, silver, copper, molybdenum, and tellurium is important. In the case, the addition amount is 10 times, in the case of copper, 5 times, and in the case of tellurium, the addition of the addition amount of antimony is significant. Table 14 shows an example in which the material of the connecting member is changed from lead-antimony alloy to lead-0.1 mass% calcium-antimony alloy or lead-1.5 mass% tin-antimony alloy. It can be seen that it does not matter whether it is a calcium-antimony alloy or a lead-tin-antimony alloy.
表１に戻り、各添加元素の作用を検討する。接続部材中のアンチモン濃度を低下させると、減液速度が低下する。接続部材中のアンチモン濃度を低下させ、活物質等にアンチモンを添加すると、常温でのアイドリングストップ寿命性能は向上するが、高温での減液が著しくなる。活物質等にアンチモンを添加する他に、アルミニウムイオンを電解液に添加すると常温、高温共に減液速度は試料A1以下となり、常温でのアイドリングストップ寿命性能も向上する。適正量のアルミニウムイオンを添加すると、高温での減液性能を改善し、さらに高温でも常温でもアイドリングストップ寿命性能を若干向上することができる。しかし高温でのアイドリングストップ寿命性能の改善効果は常温の場合と同等にまでは達しない。そして活物質等にアンチモンを添加する他に、アルミニウムイオンとリチウムイオンとを電解液に添加すると、高温と常温でのアイドリングストップ寿命性能に優れ、高温でも常温でも減液速度が試料A1以下となる鉛蓄電池が得られる。 Returning to Table 1, the effect of each additive element will be examined. When the antimony concentration in the connecting member is lowered, the liquid reduction rate is lowered. When the antimony concentration in the connecting member is lowered and antimony is added to the active material or the like, the idling stop life performance at room temperature is improved, but the liquid reduction at high temperature becomes remarkable. In addition to adding antimony to the active material, etc., when aluminum ions are added to the electrolyte, the rate of liquid reduction will be less than sample A1 at both room temperature and high temperature, and the idling stop life performance at room temperature will be improved. When an appropriate amount of aluminum ions is added, the liquid reduction performance at high temperatures can be improved, and the idling stop life performance can be slightly improved at both high temperatures and normal temperatures. However, the effect of improving the idling stop life performance at high temperature does not reach the same level as at normal temperature. In addition to adding antimony to the active material, etc., adding aluminum ions and lithium ions to the electrolyte provides excellent idling stop life performance at high and normal temperatures, and the rate of liquid reduction is less than sample A1 at both high and normal temperatures. A lead acid battery is obtained.
接続部材でのアンチモン濃度が10000質量ppmと過剰な場合、高温でのアイドリングストップ寿命性能と、高温及び常温での減液速度が試料A1より速くなる。負極活物質等でのアンチモン濃度が2000質量ppmと過剰な場合、高温及び常温での減液速度が試料A1より速くなる。接続部材でのアンチモン濃度が5000質量ppmと10000質量ppmとの性能差は大きく、また負極活物質等でのアンチモン濃度が1000質量ppmと2000質量ppmとでの性能差も大きい。また接続部材及び負極活物質等でのアンチモン濃度が適正でも、電解液中のアルミニウムイオンが0.3mol/Lと過剰、あるいは電解液中のリチウムイオンが0.3mol/Lと過剰な場合、高温、常温ともにアイドリングストップ寿命性能が低下する。以上のように、接続部材中のアンチモン濃度を5000質量ppm以下とし、負極活物質、正極活物質、及び電解液でのアンチモンの合計含有量を、負極活物質との質量比で100〜1000質量ppmとし、電解液中のアルミニウムイオン濃度とリチウムイオン濃度を各0.02〜0.2mol/Lとすることには相乗効果があり、この範囲内でのみ高温と常温で優れたアイドリングストップ寿命性能が得られ、高温と常温で減液速度を許容範囲内に保つことができる。これらの結果は、活物質あるいは電解液に、アンチモンに代えて、ニッケル、銀、モリブデン、銅、もしくはテルルを添加する場合も同様である。 When the antimony concentration in the connecting member is excessive as 10000 ppm by mass, the idling stop life performance at high temperature and the liquid reduction rate at high temperature and normal temperature are faster than those of the sample A1. When the antimony concentration in the negative electrode active material or the like is excessive as 2000 ppm by mass, the liquid reduction rate at high temperature and room temperature is faster than that of the sample A1. The performance difference between the antimony concentration in the connecting member between 5000 mass ppm and 10000 mass ppm is large, and the performance difference between the antimony concentration in the negative electrode active material or the like between 1000 mass ppm and 2000 mass ppm is also large. Also, even if the antimony concentration in the connecting member and the negative electrode active material is appropriate, if the aluminum ion in the electrolyte is excessive at 0.3 mol / L or the lithium ion in the electrolyte is excessive at 0.3 mol / L, the In both cases, the idling stop life performance is reduced. As described above, the antimony concentration in the connecting member is set to 5000 mass ppm or less, and the total content of antimony in the negative electrode active material, the positive electrode active material, and the electrolytic solution is 100 to 1000 mass by mass ratio with the negative electrode active material. There is a synergistic effect when the aluminum ion concentration and the lithium ion concentration in the electrolyte solution are 0.02 to 0.2 mol / L, respectively, and excellent idling stop life performance can be obtained at high and normal temperatures only within this range. The liquid reduction rate can be kept within an allowable range at high and normal temperatures. These results are the same when nickel, silver, molybdenum, copper, or tellurium is added to the active material or electrolyte instead of antimony.
Claims (5)
接続部材は鉛を主成分とし、かつアンチモン含有量が5000質量ppm以下で、
負極活物質、正極活物質、及び電解液の少なくともいずれかが、アンチモン、ニッケル、銀、モリブデン、銅、及びテルルからなる群の少なくとも一員の元素を含有し、
負極活物質、正極活物質、及び電解液での、アンチモンの含有量と、ニッケル、銀、モリブデンの含有量の10倍と、銅の含有量の5倍と、テルルの含有量の20倍との和が、負極活物質との質量比で100〜1000質量ppmであり、
電解液はアルミニウムイオンとリチウムイオンとを各0.02〜0.2mol/L含有することを特徴とする、液式鉛蓄電池。 A liquid lead storage battery comprising a positive electrode lattice made of a lead-calcium-tin alloy, a negative electrode lattice made of a lead-calcium-tin alloy, a positive electrode active material, a negative electrode active material, an electrolytic solution, and a connecting member,
The connecting member is composed mainly of lead, and the antimony content is 5000 mass ppm or less,
At least one of the negative electrode active material, the positive electrode active material, and the electrolytic solution contains at least one member of the group consisting of antimony, nickel, silver, molybdenum, copper, and tellurium,
Antimony content in negative electrode active material, positive electrode active material, and electrolyte, 10 times the content of nickel, silver, molybdenum, 5 times the content of copper, and 20 times the content of tellurium Is a mass ratio of 100 to 1000 mass ppm with the negative electrode active material,
A liquid lead acid battery characterized in that the electrolytic solution contains 0.02 to 0.2 mol / L of aluminum ions and lithium ions.
接続部材は鉛を主成分とし、かつアンチモン含有量が5000質量ppm以下で、
負極活物質、正極活物質、及び電解液の少なくともいずれかが、アンチモンを含有し、
負極活物質、正極活物質、及び電解液でのアンチモンの合計含有量が、負極活物質との質量比で100〜1000質量ppmであり、
電解液はアルミニウムイオンとリチウムイオンとを各0.02〜0.2mol/L含有することを特徴とする、液式鉛蓄電池。 A liquid lead storage battery comprising a positive electrode lattice made of a lead-calcium-tin alloy, a negative electrode lattice made of a lead-calcium-tin alloy, a positive electrode active material, a negative electrode active material, an electrolytic solution, and a connecting member,
The connecting member is composed mainly of lead, and the antimony content is 5000 mass ppm or less,
At least one of the negative electrode active material, the positive electrode active material, and the electrolytic solution contains antimony,
The total content of antimony in the negative electrode active material, the positive electrode active material, and the electrolyte is 100 to 1000 ppm by mass with respect to the negative electrode active material,
A liquid lead acid battery characterized in that the electrolytic solution contains 0.02 to 0.2 mol / L of aluminum ions and lithium ions.
接続部材は鉛を主成分とし、かつアンチモン含有量が5000質量ppm以下で、
負極活物質、正極活物質、及び電解液の少なくともいずれかが、ニッケル、銀、モリブデンからなる群の少なくとも一員の元素を含有し、
負極活物質、正極活物質、及び電解液での、前記少なくとも一員の元素の合計含有量が、負極活物質との質量比で10〜100質量ppmであり、
電解液はアルミニウムイオンとリチウムイオンとを各0.02〜0.2mol/L含有することを特徴とする、液式鉛蓄電池。 A liquid lead storage battery comprising a positive electrode lattice made of a lead-calcium-tin alloy, a negative electrode lattice made of a lead-calcium-tin alloy, a positive electrode active material, a negative electrode active material, an electrolytic solution, and a connecting member,
The connecting member is composed mainly of lead, and the antimony content is 5000 mass ppm or less,
At least one of the negative electrode active material, the positive electrode active material, and the electrolytic solution contains at least one element of the group consisting of nickel, silver, and molybdenum,
In the negative electrode active material, the positive electrode active material, and the electrolytic solution, the total content of the at least one member element is 10 to 100 ppm by mass with respect to the negative electrode active material,
A liquid lead acid battery characterized in that the electrolytic solution contains 0.02 to 0.2 mol / L of aluminum ions and lithium ions.
接続部材は鉛を主成分とし、かつアンチモン含有量が5000質量ppm以下で、
負極活物質、正極活物質、及び電解液の少なくともいずれかが、銅を含有し、
負極活物質、正極活物質、及び電解液での銅の合計含有量が、負極活物質との質量比で20〜200質量ppmであり、
電解液はアルミニウムイオンとリチウムイオンとを各0.02〜0.2mol/L含有することを特徴とする、液式鉛蓄電池。 A liquid lead storage battery comprising a positive electrode lattice made of a lead-calcium-tin alloy, a negative electrode lattice made of a lead-calcium-tin alloy, a positive electrode active material, a negative electrode active material, an electrolytic solution, and a connecting member,
The connecting member is composed mainly of lead, and the antimony content is 5000 mass ppm or less,
At least one of the negative electrode active material, the positive electrode active material, and the electrolytic solution contains copper,
The total content of copper in the negative electrode active material, the positive electrode active material, and the electrolytic solution is 20 to 200 ppm by mass with respect to the negative electrode active material,
A liquid lead acid battery characterized in that the electrolytic solution contains 0.02 to 0.2 mol / L of aluminum ions and lithium ions.
接続部材は鉛を主成分とし、かつアンチモン含有量が5000質量ppm以下で、
負極活物質、正極活物質、及び電解液の少なくともいずれかが、テルルを含有し、
負極活物質、正極活物質、及び電解液でのテルルの合計含有量が、負極活物質との質量比で5〜50質量ppmであり、
電解液はアルミニウムイオンとリチウムイオンとを各0.02〜0.2mol/L含有することを特徴とする、液式鉛蓄電池。 A liquid lead storage battery comprising a positive electrode lattice made of a lead-calcium-tin alloy, a negative electrode lattice made of a lead-calcium-tin alloy, a positive electrode active material, a negative electrode active material, an electrolytic solution, and a connecting member,
The connecting member is composed mainly of lead, and the antimony content is 5000 mass ppm or less,
At least one of the negative electrode active material, the positive electrode active material, and the electrolytic solution contains tellurium,
The total content of tellurium in the negative electrode active material, the positive electrode active material, and the electrolyte is 5 to 50 ppm by mass with respect to the negative electrode active material,
A liquid lead acid battery characterized in that the electrolytic solution contains 0.02 to 0.2 mol / L of aluminum ions and lithium ions.
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