JP2012138331A - Lead storage battery and idling stop vehicle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lead storage battery having a positive electrode grid composed of a lead-calcium-tin based alloy, and a negative electrode grid composed of a lead-calcium based alloy or a lead-calcium-tin based alloy provided, on the surface of the lug, with a lead-tin-X based alloy, where X represents at least one kind of element in a group consisting of arsenic, silver, and selenium.SOLUTION: Thinning of the lug of a negative electrode is suppressed by suppressing the roughening of a tin-rich β phase in a lead-tin based alloy on the surface at the lug of a negative electrode in a lead storage battery.

Description

  The present invention relates to a lead-acid battery and an idling stop vehicle using the same, and particularly to suppression of corrosion of a negative electrode ear.

  It is known that when a lead-acid battery is used for an idling stop vehicle, the negative electrode may be burnt. In this regard, Patent Document 1 (WO2010 / 32782A) discloses that the potential at which the negative electrode ear is placed is important. Like conventional lead-acid batteries, under conditions where the battery is fully charged after discharge and the negative electrode ear is sufficiently reduced, the lead sulfate produced in the negative electrode ear is reduced to metallic lead, resulting in ear burn Absent. However, under conditions where the amount of charge is insufficient and only a portion of the lead sulfate is reduced, porous lead sulfate gradually accumulates, and dilute sulfuric acid penetrates into the accumulated lead sulfate. Proceed to. Moreover, when the charge amount is insufficient, sulfation in which the negative electrode active material is changed to lead sulfate which is difficult to reduce also proceeds. In the idling stop mode, the lead-acid battery may become insufficiently charged, and the life of the lead-acid battery will be reached due to thinning due to corrosion of the negative electrode ear and sulfation of the negative electrode active material.

  In Patent Document 1, a lead-tin alloy layer is provided on the surface of the negative electrode ear portion, thereby reducing the speed of the negative electrode. The tin concentration in the lead-tin alloy layer is 5 to 40% by mass. Further, in order to suppress sulfation of the negative electrode active material, 0.25 to 0.75% by mass of carbon is added to the negative electrode active material. Carbon forms a conductive path in the negative electrode active material, facilitating reduction of lead sulfate. Further, Patent Document 1 points out that carbon in the negative electrode active material suppresses the burning of the negative electrode. Patent Documents 2 and 3 disclose that a lead-tin alloy layer is formed on the surface of the negative electrode ear in order to suppress the corrosion of the joint between the negative electrode ear and the strap.

  By the way, the lead-tin alloy is composed of a eutectic structure of a lead-rich α phase and a tin-rich β phase. The inventors have studied the ear-burning mechanism of a negative electrode provided with a lead-tin alloy layer, and the tin-rich β phase changed over time from a fine structure to a coarse structure. It has been found that the effect of suppressing is reduced. In other words, the β-phase is finely dispersed in the lead-tin alloy layer, thereby increasing the effect of preventing the negative electrode from being burnt. Moreover, the coarsening of the β phase tends to proceed under high temperature conditions.

WO2010 / 32782A JP2009-193693 JP2009-146872

The basic problem of the present invention is to suppress the tinting of the negative electrode by suppressing the coarsening of the tin-rich β phase in the lead-tin alloy on the surface of the negative electrode ear of the lead-acid battery.
An additional problem in the present invention is to suppress the accumulation of lead sulfate as a negative electrode active material and to improve the low-temperature high-rate discharge performance.
Another object of the present invention is to improve the storage battery performance of an idling stop vehicle.

  The present invention provides a lead-acid battery in which a positive electrode plate and a negative electrode plate are immersed in an electrolyte solution, wherein the negative electrode plate has a negative electrode ear provided on an upper part of a negative electrode grid, and the negative electrode ear is a lead- A lead-tin-X alloy layer (where X represents at least one element of the group consisting of arsenic, silver, and selenium) is formed on the surface of the base made of a calcium alloy or lead-calcium-tin alloy. It is characterized by having.

The present invention also includes a positive electrode lattice made of a lead-calcium-tin alloy, a negative electrode lattice made of a lead-calcium alloy or a lead-calcium-tin alloy, a positive electrode ear provided on top of the positive electrode lattice, A positive electrode grid holding a positive electrode active material, a negative electrode grid holding a negative electrode active material, and a positive electrode grid and a positive electrode ear, and a negative electrode grid and a negative electrode ear. In lead-acid batteries that are immersed in the electrolyte,
The negative electrode ear has a lead-tin-X alloy layer (where X is arsenic, silver, and selenium) on the surface of the base made of lead-calcium alloy or lead-calcium-tin alloy. It represents a kind of element).

  In this invention, a lead-tin-X alloy layer is provided on the surface of the ear portion of the negative electrode, and the tin-rich β phase in the alloy layer is finely dispersed in the α phase. For this reason, a structure in which the β phase is finely dispersed in the α phase is maintained, and the negative electrode can be prevented from being burnt.

  Preferably, a lead-tin-X alloy layer is provided on the surface of the ear portion and the upper edge portion of the negative electrode. If it does in this way, the thinning of an upper edge can also be controlled.

  Preferably, the tin content in the lead-tin-X alloy layer is 5% by mass or more and 40% by mass or less. By setting the tin content to 5% by mass or more, it is possible to suppress the burning of the negative electrode. Further, the alloy layer containing excessive tin brings about a decrease in the electrolyte by reducing the hydrogen overvoltage. In contrast, when the tin content is 40% by mass or less, it is possible to suppress an increase in the liquid reduction rate.

  Preferably, the sum of the arsenic content and the silver content and 10 times the selenium content in the lead-tin-X alloy layer is 0.01% by mass or more and 1% by mass or less. By setting the sum to 0.01% by mass or more, the effect of suppressing the earburn of the negative electrode is increased, and the effect of suppressing the earring is saturated at 1% by mass. Accordingly, it is possible to effectively suppress the ear burn in the range of 0.01% by mass or more and 1% by mass or less.

  Preferably, the electrolytic solution contains 0.02 mol / L or more and 0.2 mol / L or less aluminum ions and 0.02 mol / L or more and 0.2 mol / L or less lithium ions. Under these conditions, accumulation of lead sulfate as the negative electrode active material can be suppressed, and the low-temperature high-rate discharge performance important as the performance of the lead storage battery can be improved.

The present invention further resides in an idling stop vehicle using the above lead storage battery. As described above, in the lead storage battery of the present invention, the negative electrode is prevented from being burnt down, so that a highly reliable idling stop vehicle can be obtained.

Front view of negative electrode grid in Example This is a characteristic diagram of a lead-acid storage battery with lead-tin-selenium alloy layers on both the front and back surfaces of the negative electrode ear and upper edge. This is the negative electrode when the SBA-IS life test was conducted after leaving at 75 ° C for 1 month. Shows the amount of ear thinning. FIG. 6 is a characteristic diagram showing the amount of ear fining in a lead storage battery in which the alloy layer is a lead-tin-arsenic alloy, and the measurement conditions are the same as in FIG. FIG. 6 is a characteristic diagram showing the amount of harshness of the negative electrode ear in a lead-acid battery whose alloy layer is a lead-tin-silver alloy, and the measurement conditions are the same as in FIG.

  Hereinafter, embodiments of the present invention will be described using examples. In carrying out the present invention, the embodiments can be appropriately changed according to the common sense of those skilled in the art and the disclosure of the prior art, and the present invention is not limited to the embodiments.

  A lead storage battery includes a negative electrode plate made of a negative electrode lattice and a negative electrode active material, a positive electrode plate made of a positive electrode lattice and a positive electrode active material, and an electrolyte, and the plurality of negative electrode plates and the plurality of positive electrode plates have separators. Are stacked alternately to form a group of electrode plates, and the electrode plates of the same polarity are connected by a strap. The negative electrode strap and the positive electrode strap are connected between the cells, the pole column is connected to the positive electrode strap and the negative electrode strap at the end, and connected to the external terminal. The negative electrode plate and the positive electrode plate are immersed in an electrolytic solution containing dilute sulfuric acid.

  FIG. 1 shows the configuration of the negative electrode lattice 2, and 4 is a mesh portion, which is formed by a rotary expanding method here, but may be formed by a reciprocating expanding method, a punching method, a casting method, or the like. 6 is an upper edge, 8 is a lower edge, and 10 is an ear. The main material of the negative electrode grid 2 includes 0.06 to 0.09 mass% calcium and 0.01 to 0.03 mass% aluminum in the case of lead-calcium alloy, and 0.06 to 0.09 mass% calcium and tin in the case of lead-calcium-tin alloy. It contains 0.35 to 0.5 mass%, aluminum 0.01 to 0.03 mass%, and the remainder is lead. The impurity concentration may be about 0.005% by mass of tin, about 0.003% by mass of arsenic, about 0.003% by mass of silver, and about 0.0003% by mass of selenium.

  The mesh part 4 and the lower edge part 8 are comprised with the main material of a negative electrode grid. The ear portion 10 and the upper edge portion 6 are provided with a lead-tin-X-based alloy layer on the surface of the plate member made of the main material, preferably on both the front and back surfaces, where X is arsenic, silver and selenium. At least one of the group consisting of: The thickness of the alloy layer is preferably 10 to 100 μm, and here it is 30 μm. The composition of the alloy layer is 5 mass% or more and 40 mass% or less of tin. The effects of arsenic, silver, and selenium all suppress the phenomenon that the ear part 10 or the ear part 10 and the upper edge part 6 are corroded and become thin. Arsenic and silver have almost the same effect per content when the content is expressed in mass%, and selenium has an effect per content that is about 10 times that of arsenic and silver. Therefore, the selenium content is 10 times and the total content of arsenic and silver is 0.01% by mass or more and 1% by mass or less. When arsenic or silver is contained alone, the content is from 0.01% by mass to 1% by mass, and when selenium is contained alone, the content is from 0.001% by mass to 0.1% by mass. The alloy layer can be formed by simultaneously rolling the alloy layer at the positions corresponding to the ear portion 10 and the upper edge portion 6 of the slab before rolling when the negative electrode lattice 2 is produced by, for example, the rotary expanding method. . In the case of a casting method or the like, it can be formed by immersing the ear portion 10 and the upper edge portion 6 in a molten bath having a composition of lead-tin-X. The shape of the positive electrode lattice is similar to that of the negative electrode lattice 2, and the main material of the positive electrode lattice includes 0.065% by mass of calcium, 1.3% by mass of tin, and 0.03% by mass of aluminum, and the impurity concentration is about 0.003% by mass for arsenic and 0.003% for silver. About mass%, selenium is about 0.0003 mass%, the remainder is lead, and the ear portion and the upper edge portion are not provided with an alloy layer.

  The mesh part 4 of the negative electrode is filled with a negative electrode active material paste, and the negative electrode active material paste includes lead powder, carbon black, graphite, expanded graphite, carbon fiber, etc., lignin, barium sulfate, synthetic resin fiber, dilute sulfuric acid, It was obtained by mixing water. The mesh portion of the positive electrode is filled with a positive electrode active material paste, and the positive electrode active material paste is obtained by mixing lead powder, synthetic resin fiber, dilute sulfuric acid, and water, but may not contain synthetic resin fiber. .

The electrolytic solution contains aluminum ions and lithium ions, and the content of aluminum ions and lithium ions is 0.02 mol / L or more and 0.2 mol / L or less, respectively, lead ions eluted from the negative electrode plate and the positive electrode plate, tin ions, Contains calcium ions, carbon, lignin, etc. One mole of aluminum ions corresponds to 171.05 g of aluminum sulfate (Al ₂ (SO ₄ ) ₃ ).

Manufacture of lead-acid batteries
A lead-acid battery (N-55 type, nominal voltage 12 V, 5 hour rate rated capacity 36 Ah) for idling stop vehicles compliant with SBA S 0101 was manufactured. The positive grid is an alloy with 0.065 wt% calcium, 1.3 wt% tin and unavoidable impurities and the balance is lead, and the negative grid is 0.09 wt% calcium, 0.35 wt% tin and unavoidable impurities and the balance is lead The lead-tin-X alloy layer (30 μm thick) is provided on both the front and back surfaces of the negative electrode ear 10 and the upper edge 6 of the negative electrode. Both the positive electrode plate and the negative electrode plate 2 have a height of 115 mm, a width of 100 mm, a thickness of 1.5 mm for the positive electrode plate and 1.2 mm for the negative electrode plate, and the height is the height excluding the ears. As comparative examples, the alloy layer has a lead-tin composition with no X element, the X element is excessive, the lead-X composition has no tin, and the lead-tin-X composition has tin. Was produced in excess.

  The negative electrode active material paste is based on 100% by mass of lead powder of the ball mill method, 0.2% by mass of lignin, 0.3% by mass of carbon black, 0.6% by mass of barium sulfate, 0.1% by mass of acrylic fiber, 11% by mass of water and 20 ° C. And 7% by mass of dilute sulfuric acid having a specific gravity of 1.40. In addition to this, an unformed negative electrode active material paste was prepared in the same manner as in Examples except that it did not contain carbon black. The positive electrode active material paste was obtained by adding 0.1% by mass of acrylic fiber to 100% by mass of lead powder of the ball mill method, and mixing 13% by mass of water and 6% by mass of dilute sulfuric acid having a specific gravity of 1.40 at 20 ° C. The lead powder is not limited to the ball mill method, but may be a Barton method. Filled with 55g of active material paste per positive grid and 52g per negative grid, aged for 48 hours at 50 ° C and 50% relative humidity respectively, then dried in a dry atmosphere at 50 ° C for 24 hours. A positive and negative electrode plate was obtained.

A non-chemically formed negative electrode plate was accommodated in a bag-like separator in which a microporous polyethylene sheet was folded in two and closed at both ends with mechanical seals. The separator may be made of a material that is stable, insulating and porous in dilute sulfuric acid in addition to polyethylene. For example, a glass fiber sheet may be used as the separator. The separator may be a bag or a leaf. Seven unformed positive plates and 8 unformed negative plates contained in a bag-like separator are laminated alternately, and the same polarity plates are connected to each other by the cast-on strap method (COS method). A connecting member composed of columns and inter-cell connecting members was formed to form an electrode plate group. The material of the strap, the pole column, and the inter-cell connecting member is a lead-antimony alloy, a lead-tin alloy, or the like, but a lead-antimony alloy is preferable in order to withstand vibration when mounted on an automobile. 6 pieces of the obtained electrode plate group were accommodated in a battery case made of polypropylene and connected in series so that they were welded at the position of the inter-cell connecting member, and after the lid was welded, the positive and negative electrode poles were connected to the lead-acid battery. Connected to the output terminal. An N-55 type lead-acid battery was formed by injecting an electrolyte solution containing a predetermined amount of aluminum sulfate and lithium sulfate into dilute sulfuric acid with a specific gravity of 1.230 at 20 ° C and forming a battery case in a 25 ° C water tank. . The aluminum source and the lithium source are optional, and may be added in the form of, for example, lithium aluminate AlLiO ₂ , aluminum hydroxide and lithium hydroxide, or lithium carbonate. In addition, a lead storage battery was prepared using the same electrolyte solution that did not contain aluminum ions or lithium ions.

From experiments conducted for each test method, it was confirmed that the lead-15 mass% tin-based alloy layer on the surface of the negative electrode ears was coarsened at high temperatures and the eutectic structure changed. Therefore, each lead storage battery was left at 75 ° C. for one month as an accelerated test of the environment where the lead storage battery for automobiles is placed. Next, in order to confirm the life performance in the idling stop mode, an idling stop life test (SBA S 0101: 9.4.5 in 2006) was performed. Idling stop life test conditions were as follows: in a 25 ° C air tank, a cycle consisting of 59 seconds of discharge at 45A, 1 second of discharge at 300A, and 60 seconds of charge at 14V (maximum 100A) was repeated every 3600 cycles. For about 2 days, and discharge life is less than 7.2V. However, in Tables 1 to 5, the batteries were disassembled after the elapse of 4 weeks from the start of the test before reaching the end of life, and the amount of thinning of the negative electrode ear was measured. For example, an ear thinning amount of 100% means that the remaining amount of the ear portion is 0%, and an ear thinning amount of 40% means that the residual amount of the ear portion is 60%. The target for ear loss was 40% or less. In the tests of Table 1, Table 2, and Table 3, the electrolytic solution does not contain aluminum ions and lithium ions. In each test, the number of samples is 3, and the results are shown as average values. The results are shown in Table 1 (lead-tin-selenium), Table 2 (lead-tin-arsenic), and Table 3 (lead-tin-silver).

  In order to evaluate the initial performance, a low-temperature high-rate discharge test (JIS D 5301: 2006, 9.5.3b)) was conducted before leaving at 75 ° C. In the low-temperature high-rate discharge test, 300 A was discharged in an atmosphere at -15 ° C., the discharge time until the terminal voltage decreased to 6 V was determined, and the relative value of this time was defined as the low-temperature high-rate discharge performance. After that, it was left at 75 ° C. for 1 month, and then the amount of lead sulfate accumulated in the negative electrode active material after 4 weeks from the start of the idling stop life test was measured. In the test of Table 4, the concentration of aluminum ions and lithium ions in the electrolyte was changed from 0 to 0.2 mol / L. In the test of Table 5, the concentration of aluminum ions and lithium ions in the electrolyte was 0.1 mol / L. A battery not containing carbon black was also included. In each test, the number of samples is 3, and the results are shown as average values. The results are shown in Tables 4 and 5.

Results Table 1 shows the effect of selenium addition to the lead-tin alloy layer, and FIG. 2 shows the results when the tin concentration was 5, 15, and 40% by mass. When tin is not contained, since there is no tin-rich β phase, the presence or absence of selenium does not affect the amount of ear burn. When the tin content is 5% by mass or more and 40% by mass or less, by adding 0.001% by mass or more of selenium, the earburning amount satisfies the target value, and even if it exceeds 0.1% by mass, Since the amount does not decrease any more, the upper limit of the selenium content was set to 0.1% by mass. Assuming that the liquid reduction rate in a battery without an alloy layer is 100, when an alloy layer is provided, the tin content is 5% by mass, the liquid reduction rate is 101, 15% by mass and the liquid reduction rate is 102, 40% by mass. Therefore, the tin content in the alloy layer was set to 40% by mass or less. In addition, since content of X element was slight, it did not affect the liquid reduction rate.

  Table 2 shows the effect of arsenic addition to the lead-tin alloy layer, and the results at tin concentrations of 5, 15, and 40% by mass are shown in FIG. The effect of arsenic addition is similar to the effect of selenium addition. When tin is not contained, the presence or absence of arsenic does not affect the amount of ear burn. In addition, when the tin content is 5 to 40% by mass, by adding 0.01% by mass or more of arsenic, the earburning amount satisfies the target value, and even if it exceeds 1% by mass, It will not decrease any more. Therefore, the arsenic content was set to 0.01% by mass or more and 1% by mass or less. Further, from the balance between the liquid reduction rate and the amount of ear burn, the tin content was set to 5 mass% to 40 mass%.

  Table 3 shows the effect of adding silver to the lead-tin alloy layer, and the results at tin concentrations of 5, 15, and 40% by mass are shown in FIG. The effect of silver addition is equivalent to the effect of arsenic addition, and the effect is equivalent if the content is the same. When tin is not contained, the presence or absence of silver does not affect the amount of ear thinning. When the tin content is 5 to 40% by mass, by adding 0.01% by mass or more of silver, the amount of ear thinning satisfies the target value, and even if the content exceeds 1% by mass, the amount of ear thinning is more than that Does not decrease. Therefore, the silver content is set to 0.01% by mass or more and 1% by mass or less. Further, from the balance between the liquid reduction rate and the amount of ear burn, the tin content was set to 5 mass% to 40 mass%. When both selenium, arsenic and silver are added, the effect is determined by the sum of the selenium content and the total content of arsenic and silver.

  The results in Tables 1 to 3 are the results of providing the lead-tin-X alloy layer on the negative electrode ear surface and the upper edge surface, but the lead-tin-X alloy layer is only on the negative electrode ear surface. The same test was conducted with respect to the case where the lead electrode was provided. As for the thinning amount of the negative electrode ear, the lead-tin-X alloy was also used when the lead-tin-X alloy layer was provided only on the surface of the negative electrode ear. Similar results were obtained when the layer was provided on the surface of the ear and the upper edge of the negative electrode. In addition, it is more preferable that the lead-tin-X-based alloy layer is provided on the surface of the ear portion and the upper edge portion of the negative electrode because it is possible to prevent the upper frame from being thinned.

  Table 4 shows the low-temperature high-rate discharge performance and the amount of lead sulfate accumulated in the negative electrode active material after 4 weeks from the start of the idling stop life test. The accumulated amount of lead sulfate and the low-temperature high-rate discharge performance are shown as relative values with the battery A1 of the comparative example containing no X element, aluminum ions, and lithium ions as 100. In the samples shown in Table 4, the harshness of the negative electrode was determined by tin and X element in the alloy layer, and no influence of aluminum ion concentration and lithium ion concentration in the electrolyte was observed. Therefore, aluminum ions and lithium ions do not have to be included from the problem of suppressing the burn-up of the negative electrode. Furthermore, the composition of the alloy layer did not affect the amount of lead sulfate accumulation and the low-temperature high-rate discharge performance. In addition, it has been confirmed from tests conducted separately that aluminum ions suppress the accumulation of lead sulfate and lithium ions improve low-temperature high-rate discharge performance. From Table 4, aluminum ions are contained in an amount of 0.02 mol / L or more and 0.2 mol / L or less, and lithium ions are contained in an amount of 0.02 mol / L or more and 0.2 mol / L or less. It turns out that the lead storage battery excellent in the high-rate discharge performance is obtained. Battery A2 containing 0.01 mol / L of aluminum ions has a slightly large lead sulfate accumulation of 90, and battery A7 containing 0.01 mol / L of lithium ions has a low-temperature high-rate discharge performance of 100 and no improvement is seen. .

  Table 5 shows that the tin content in the alloy layer is 15% by mass, the selenium content is 0.01% by mass, the arsenic content and the silver content are 0% by mass, and both the aluminum ion concentration and the lithium ion concentration are 0.1 mol. The result when the content of carbon black of the negative electrode active material is changed is shown as / L, and the measurement method is the same as in Table 4. Carbon not only suppresses the accumulation of lead sulfate as the negative electrode active material, but also reduces the negativeness of the negative electrode. This effect can be obtained with other carbons such as carbon fiber, graphite, expanded graphite in addition to carbon black. Therefore, it is preferable to contain 0.25 mass% or more and 0.75 mass% or less of carbon in the negative electrode active material.

From the above embodiment, the following can be said.
1) By suppressing the coarsening of the tin-rich β phase in the alloy layer on the surface of the ear part and the surface of the upper edge part of the negative electrode lattice, the ear burn of the negative electrode is suppressed. This effect is particularly important in environments where lead storage batteries are placed at high temperatures.
2) Aluminum ions in the electrolyte suppress the accumulation of lead sulfate as the negative electrode active material, and lithium ions improve the low-temperature high-rate discharge performance.
3) The carbon in the negative electrode active material is effective in suppressing lead sulfate accumulation and also in suppressing the negative ear burn.

2 Negative electrode grid 4 Mesh portion 6 Upper edge portion 8 Lower edge portion 10 Ear portion

Claims (8)

In a lead storage battery in which a positive electrode plate and a negative electrode plate are immersed in an electrolyte solution,
The negative electrode plate has a negative electrode ear provided on an upper part of a negative electrode grid,
The negative electrode ear has a lead-tin-X alloy layer (where X represents at least one element of the group consisting of arsenic, silver, and selenium) on the surface of the base, Lead acid battery. A positive grid made of a lead-calcium-tin alloy, a negative grid made of a lead-calcium alloy or a lead-calcium-tin alloy, a positive ear provided on the positive grid, and an upper part of the negative grid The positive electrode grid holds the positive electrode active material, the negative electrode grid holds the negative electrode active material, and the positive electrode grid, the positive electrode ear, the negative electrode grid, and the negative electrode ear are in the electrolyte. In lead-acid batteries immersed in
The negative electrode ear has a lead-tin-X alloy layer (where X is at least one of the group consisting of arsenic, silver, and selenium) on the surface of a base portion made of lead-calcium alloy or lead-calcium-tin alloy. Lead acid battery, characterized by comprising a single element).   3. The lead acid battery according to claim 1, wherein the lead-tin-X alloy layer is provided on a surface of an ear portion and an upper edge portion of a negative electrode lattice.   The lead acid battery according to any one of claims 1 to 3, wherein a tin content in the lead-tin-X alloy layer is 5 mass% or more and 40 mass% or less.   The sum of the arsenic content and the silver content and 10 times the selenium content in the lead-tin-X alloy layer is 0.01% by mass or more and 1% by mass or less. The lead acid battery in any one of Claims 1-4.   The lead acid battery according to claim 1, wherein the electrolytic solution contains aluminum ions and lithium ions.   The said electrolyte solution contains 0.02 mol / L or more and 0.2 mol / L or less aluminum ion, and 0.02 mol / L or more and 0.2 mol / L or less lithium ion, It is characterized by the above-mentioned. Lead acid battery in any one of. An idling stop vehicle using the lead storage battery according to any one of claims 1 to 7.

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