JP5532245B2 - Lead-acid battery and method for manufacturing the same - Google Patents

Description

  The present invention relates to a lead storage battery and a method for manufacturing the same.

  In lead-acid batteries, a positive electrode active material or negative electrode active material, water and dilute sulfuric acid are mixed into a positive electrode grid or negative electrode grid, respectively, and the positive electrode plate and the negative electrode plate obtained by chemical conversion of these pastes are diluted. Contact with an electrolyte composed of sulfuric acid. Here, Patent Document 1: JP2010-67522A discloses a positive electrode active material raw material in which antimony is added to a mixture of a lead tan powder and a lead powder having a low lead tanning rate. And patent document 1 is disclosing that the lead capacity battery with a large initial capacity by this type | system | group and being hard to soften a positive electrode active material is obtained. Patent Document 3: JP2008-276980A discloses a method for measuring the content of red lead in lead powder.

  Patent Document 2: WO2007 / 36979 discloses that a positive electrode active material is prepared by a conventional method, and lithium ions such as 0.02 mol / L and aluminum ions such as 0.1 mol / L are added to an electrolytic solution. Patent Document 2 discloses that the idling stop life is improved by adding aluminum ions to the electrolytic solution, and that the 5-hour rate capacity is improved by adding lithium ions.

The inventor of these prior arts
・ There is an interaction between lithium ions in the electrolyte and antimony in the positive electrode active material.
More than the configuration disclosed in the patent literature by adding a predetermined amount of red lead (Pb ₃ O ₄ ) and antimony to the cathode active material raw material, and further including lithium ions in the electrolyte 5 hour rate capacity is large,
・ High rate discharge characteristics are large,
-It has been found that a lead-acid battery can be obtained, which can suppress softening of the positive electrode active material and hardly reduce the capacity even after repeated deep charge and discharge. And it discovered that said effect was acquired only in the range of predetermined | prescribed antimony content, predetermined | prescribed lithium content, and predetermined | prescribed red lead content, and came to this invention.

JP2010-67522A WO2007 / 36979 JP2008-276980A

  An object of the present invention is to provide a lead-acid battery and a method for manufacturing the same, which are excellent in initial 5-hour rate capacity and high rate discharge characteristics, and have a high capacity retention even after repeated deep charge and discharge.

This invention is a lead storage battery comprising a positive electrode plate obtained by filling a paste obtained by kneading a positive electrode active material raw material, water and dilute sulfuric acid into a positive electrode grid, and forming this, and an electrolyte solution comprising dilute sulfuric acid. The positive electrode active material material has a lead (Pb ₃ O ₄ ) content of 10 to 30% by mass, 0.01 to 0.2% by mass of metal antimony or antimony compound in terms of antimony element, and 0.02 to 0.2% in the electrolyte. It contains mol / L lithium ion.

The present invention also provides a lead-acid battery comprising a positive electrode plate obtained by filling a paste obtained by kneading a positive electrode active material raw material, water and dilute sulfuric acid into a positive electrode grid, and forming the paste, and an electrolyte comprising dilute sulfuric acid. The positive electrode active material raw material has a lead content (Pb ₃ O ₄ ) content of 10 to 30% by mass, metal antimony or antimony compound is added in an amount of 0.01 to 0.2% by mass in terms of antimony element, It is characterized by adding 0.02 to 0.2 mol / L of lithium ions to the electrolytic solution.

The content of lead (Pb ₃ O ₄ ) in the positive electrode active material raw material is preferably adjusted by changing the mixing ratio of normal lead powder consisting of a mixture of Pb and PbO and lead red powder. The lead tan powder is, for example, a lead tan powder having a low lead tanning rate of 30 to 80% by mass, but may be a lead tan powder having a high lead tanning rate of 98% by mass or the like. Or you may use only the lead tan powder of the ultra-low lead tanning rate whose lead tanning rate is 10-30 mass%, for example, without mixing lead powder and lead tan powder. Lead powder is obtained by firing lead powder at 350 to 450 ° C, and the lead tanning rate of lead powder is adjusted by converting only a part of the lead powder to Pb ₃ O _4. To do. The lead tanning rate is the ratio (mass%) of the mass of Pb ₃ O ₄ to the total mass of the lead tan powder. The method for measuring the lead tanning rate is disclosed in Patent Document 3, and the lead tan powder is converted to acetic acid. -Dissolve completely in a solution of ammonium acetate solution and 0.1 mol / L sodium thiosulfate, and titrate the remaining amount of thiosulfate ions with 0.05 mol / L iodine solution using starch solution as an indicator. The amount of iodine solution consumed in the empty sample required to appear purple due to the iodine starch reaction is b ′ (mL), and the amount of iodine solution consumed in the sample for measurement in which lead powder is dissolved is b ( mL), where the mass of the sample for measurement is S (g) and the factor of the iodine solution is f, the lead tanning rate (mass%) is given by (0.3428 (b'-b) f / S) x 100 It is done.

Antimony is added to the positive electrode active material as, for example, antimony trioxide (Sb ₂ O ₃ ) or antimony sulfate (Sb ₂ (SO ₄ ) ₃ ), but may be added as a metal powder. Further, the Pb—Sb alloy may be pulverized, and a part thereof may be added as an oxidized powder to the positive electrode active material raw material. Lithium ions and aluminum ions are added to the electrolyte as, for example, lithium sulfate (Li ₂ SO ₄ ) or aluminum sulfate (Al ₂ (SO ₄ ) ₃ ). For example, in the case of a compound such as hydroxide or carbonate, or aluminum May be added as a metal.

In the present invention, when the content and addition amount are expressed as “A to B”, the lower limit A and the upper limit B are included. In this specification, the concentration of lithium ions and aluminum ions is expressed as the concentration of ions per mol of electrolyte (mol / L). One mole of aluminum ions corresponds to 171.05 g of aluminum sulfate (Al ₂ (SO ₄ ) ₃ ). In the present invention, the positive electrode active material raw material contains lead powder, lead powder, and antimony or a compound thereof.

  Water and sulfuric acid are added to the positive electrode active material raw material to fill the positive electrode grid as a positive electrode active material paste. The positive electrode lattice is, for example, a Pb—Ca alloy, more preferably a Pb—Ca—Sn alloy. An unformed positive electrode plate group and an unformed negative electrode plate prepared by a conventional method are alternately combined through, for example, a separator, and the same polarity electrode plates are welded together to form an unformed electrode plate group. Next, after inserting the unformed electrode plate group into the battery case, the cells are connected, the lid is welded, the terminals are welded to assemble the unformed battery, the dilute sulfuric acid is injected, and the battery case is formed. Thus, the battery of the present invention can be obtained. The formation is not limited to battery case formation, but may be tank formation.

  In the present invention, lithium ions and aluminum ions may be added to dilute sulfuric acid at the time of battery case formation, or after forming a formed battery by battery case formation or other methods, it is added to the electrolytic solution. May be. In this specification, the description regarding the lead storage battery also applies to the manufacturing method of the lead storage battery, and the description regarding the manufacturing method of the lead storage battery also applies to the lead storage battery. Preferably, the electrolytic solution further contains 0.02 to 0.2 mol / L of aluminum ions.

As shown in Tables 1 and 2, in the present invention, the positive electrode active material raw material containing 10-30% by mass of lead (Pb ₃ O ₄ ) and 0.01-0.2% by mass of antimony in terms of elements is used. The produced positive electrode plate is combined with an electrolytic solution containing 0.02 to 0.2 mol / L of lithium ions. Only in this range, a lead-acid battery having excellent 5-hour rate capacity and high rate discharge characteristics and high capacity retention when repeated deep charge / discharge is obtained.

Each of the above numerical limited ranges has a critical significance. For example, when the content of lead (Pb ₃ O ₄ ) is increased from 30% by mass to 40% by mass, an appropriate amount of antimony and lithium ions are added, Softening of the positive electrode active material becomes significant, and the capacity retention rate decreases rapidly. For example, when the antimony content is increased from 0.2% by mass to 0.3% by mass, the 5-hour rate capacity and the high rate discharge characteristics are significantly reduced. When the lithium ion content is increased from, for example, 0.2 mol / L to 0.3 mol / L, the high rate discharge characteristics are remarkably deteriorated. A positive electrode plate was prepared using a positive electrode active material material containing 10% by weight of red lead (Pb ₃ O ₄ ) and antimony, and 0.01% by weight of antimony. Even a lead storage battery containing 0.02 mol / L lithium ion can greatly improve the 5-hour rate capacity and the high rate discharge characteristics, and increase the capacity retention ratio against repeated deep charge and discharge.

  The details of the interaction between antimony in the positive electrode active material and lithium ions in the electrolyte are unknown, but it is related to the fact that lithium ions inhibit the aggregation of lead sulfate particles produced on the positive electrode by discharge Can be estimated. Figure 1 shows the lead sulfate produced on the positive electrode active material side after the fifth 5 hour rate capacity test after repeating the 5 hour rate capacity test and full charge four times in an electrolyte solution containing 0.2 mol / L of lithium ion. FIG. 2 is an electron micrograph of lead sulfate produced on the positive electrode active material side after the same test in an electrolyte containing no lithium ions. Compared to FIG. 2, aggregation of lead sulfate particles is suppressed in the electrolytic solution containing lithium ions (FIG. 1).

The significance of adding antimony to the positive electrode active material is to suppress the softening of the active material (Patent Document 1, etc.). By the way, the positive electrode active material is composed of a network of secondary particles in which primary particles of PbO ₂ are aggregated, and pores between the secondary particles are called micropores, and large pores between the skeletons of the network are called macropores. The antimony effect occurs only when antimony remains in the micropores when PbO ₂ is reduced to lead sulfate. When PbO ₂ is reduced to lead sulfate, part of the antimony is eluted into the electrolyte as ions such as SbO ₂ ⁺ . At this time, if the aggregation of the lead sulfate particles is large, the micropores are compressed and lost, and the eluted antimony is pushed out into the macropores, so even if the lead sulfate is oxidized to PbO ₂ again by charging, PbO by antimony _{2 The} effect of binding the secondary particles cannot be obtained, and the softening of the active material proceeds. Now possible to suppress the aggregation of lead sulfate as in FIG. 1, antimony eluted when the PbO ₂ is reduced to lead sulfate remains in the micropores, since hardly impaired binding between PbO ₂ 2 primary particles, It is considered that the softening of the active material can be suppressed and the capacity is unlikely to decrease.

  The effect of the combination of antimony and lithium ions occurs when the positive electrode active material raw material contains 10% by mass or more of red lead, and does not occur, for example, when it does not contain red lead. Furthermore, the effect of the combination of red lead, antimony and lithium ions occurs only in a specific numerical range, and the cause is unknown.

  When aluminum ions are further added to the electrolyte, the capacity reduction due to repeated deep charge and discharge can be reduced, and this effect becomes significant when the aluminum ion content is 0.02 mol / L or more, and is saturated near 0.2 mol / L. Or it becomes maximum, and at 0.3 mol / L, the high rate discharge characteristic is remarkably lowered. It should be noted that it is not harmful to contain aluminum ions less than 0.02 mol / L and not to contain aluminum ions. For example, many of the examples do not contain aluminum ions. The aluminum ion content is 0 to 0.2 mol / L, preferably 0.02 to 0.2 mol / L.

Although the details of the reason why aluminum ions exhibit the effect of reducing the decrease in capacity are unknown, it is presumed that they inhibit the diffusion of ions such as SbO ₂ ⁺ . When PbO ₂ changes to lead sulfate, sulfate ions in the electrolytic solution are consumed, and the pH of the electrolytic solution on the surface of lead sulfate in the micropores temporarily approaches neutrality. At this time, since Al ³⁺ ions are changed to Al ₂ O ₃ .3H ₂ O and the like to form a sol-like substance, it is considered that this prevents the diffusion of ions such as SbO ₂ ⁺ . As a result, it is considered that the capacity retention can be improved by an appropriate amount of aluminum ions.

Electron micrograph of lead sulfate formed on the cathode active material side in an electrolyte solution containing 0.2 mol / L of lithium ion Electron micrograph of lead sulfate produced on the positive electrode active material side in an electrolyte that does not contain lithium ions

  Hereinafter, an optimum embodiment of the present invention will be described. In carrying out the present invention, the embodiments can be appropriately changed within the scope of the claims in accordance with common sense and prior art of those skilled in the art.

Best practice

Manufacture of lead-acid batteries
A 34B19L lead acid battery that conforms to JIS D 5301 was manufactured. Nominal voltage 12V, 5 hour rate rated capacity is 27Ah. As a positive electrode grid material, a slab containing 0.07% by mass of Ca, 1.5% by mass of Sn and unavoidable impurities and the balance of Pb is rolled and a sheet having a thickness of 1.0 mm is used. Created. The positive grid has a height of 115 mm, a width of 100 mm, and a thickness of 1.4 mm. In addition to the mesh, the positive grid has upper and lower edges and ears. The composition of the Pb—Ca—Sn alloy of the positive electrode lattice can be changed as appropriate, and the size of the positive electrode lattice is arbitrary. As a negative electrode grid, a slab containing 0.05% by mass of Ca, 0.5% by mass of Sn, and unavoidable impurities and the balance of Pb is rolled and a sheet with a thickness of 0.8mm is used to create a negative electrode grid by the rotary expand method. did. The negative grid has a height of 115 mm, a width of 100 mm, a thickness of 1.2 mm, and similarly has ears and upper and lower edges. The material and structure of the positive and negative grids are arbitrary, and may be manufactured by a casting method instead of the expanding method.

As a positive electrode active material raw material, a lead powder produced by a ball mill method was baked at 450 ° C. in an oxygen-containing atmosphere such as air, for example, to obtain a low lead tanning powder having a lead tanning ratio of 50 mass%. Low lead tanning rate Lead tan powder and lead powder produced by the ball mill method are mixed, and Sb ₂ O ₃ is mixed into the mixed powder whose content of lead tan (Pb ₃ O ₄ ) is adjusted. did. The composition of the positive electrode active material is 10-30% by weight of lead (Pb ₃ O ₄ ), 0.012-0.24% by weight of Sb ₂ O ₃ (0.01-0.2% by weight in terms of antimony element), and the remainder is lead powder. This is the portion of the lead powder that has not been lead tanned. Further, 0.1 part by mass of acrylic fiber as a binder was mixed with 100 parts by mass of the positive electrode active material raw material, and further 13 parts by mass of water and 11 parts 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 paste. The lead powder is not limited to the ball mill method, but may be a Barton method. Antimony may be added in the form of antimony sulfate (Sb ₂ (SO ₄ ) ₃ ). Moreover, the kind of binder is not limited to acrylic fiber, and any binder may be added.

In the present invention, it was confirmed that the ratio of the lead tan in the positive electrode active material raw material was important, and the lead tanning rate of the lead tan powder itself was not important. That is, battery No. 13 (Table 1) described later has a red lead content of 20% by mass, an antimony content of 0.2% by mass, and a lithium ion content of 0.2 mol / L. While maintaining the lead content in the positive electrode active material at 20% by mass, a low lead content rate of 50% by mass, and 30% by mass and 80% by mass. Although it changed to the low lead tanning rate lead tan powder, the result was equivalent. Furthermore, a lead tan powder having a lead tanning rate of 98% by mass and a normal lead powder were mixed to obtain a positive electrode active material material having a lead tan content of 20% by mass, but the results were almost the same. In the present invention, it was confirmed that the proportion of the antimony element in the positive electrode active material material is important, and the composition of the antimony component to be added is not important. That is, Sb ₂ O ₃ was replaced with metal antimony and Sb ₂ (SO ₄ ) ₃ while keeping the antimony content in the positive electrode active material raw material in battery No. 13 (Table 1) described later at 0.2% by mass in terms of antimony element. Changed to Due to the difference in the molecular weight of the antimony component, the ratio of lead powder (Pb ₃ O ₄ ) and lead powder excluding the antimony component in the cathode active material raw material increased by 0.04% by mass in the case of metal antimony, and Sb ₂ (SO ₄ ) _In the case of ₃ , it decreased by 0.2% by mass, but the change in the total mass was slight, and the performance of the battery was equivalent. Therefore, the results are shown below for a positive electrode active material raw material composed of a mixture of a low lead tanning rate lead tan powder having a lead tanning rate of 50 mass%, Sb ₂ O ₃ and lead powder.

  As a negative electrode active material raw material, 0.15% by mass of lignin, 0.2% by mass of carbon black, and 0.5% by mass of barium sulfate were added to lead powder produced by a ball mill method, and the total amount with lead powder was 100% by mass. To 100 parts by mass of this mixture, 0.1 part by mass of acrylic fiber, 11 parts by mass of water, and 7 parts by mass of dilute sulfuric acid having a specific gravity of 1.40 at 20 ° C. were mixed to obtain a negative electrode active material paste. The lead powder is not limited to the ball mill method, but may be a Barton method or the like, and the composition of the negative electrode active material paste itself is arbitrary.

  70g of positive electrode active material paste per positive grid and 57g of negative active material paste per negative grid, each aged 48 hours at 40 ° C and 50% relative humidity, then 24 hours in dry atmosphere at 50 ° C By drying, an unformed positive electrode plate and negative electrode plate were obtained. An unformed negative electrode plate was accommodated in a bag-like polyethylene separator, four positive electrode plates and five negative electrode plates were alternately laminated, and electrode plates of the same polarity were welded together to form an electrode plate group. Six obtained electrode plate groups are housed in a polypropylene battery case separated by a partition wall, welded so that 6 cells are connected in series, a lid is welded, and terminals are welded to form an unformed battery. Obtained. An electrolyte obtained by dissolving a predetermined amount of lithium sulfate in dilute sulfuric acid having a specific gravity of 1.230 at 20 ° C. was injected into this unformed battery so that the lithium ion content was 0.02 to 0.2 mol / L. . Alternatively, a predetermined amount of lithium sulfate and aluminum sulfate are added to dilute sulfuric acid having a specific gravity of 1.230 at 20 ° C. so that the contents of lithium ions and aluminum ions are 0.02 to 0.2 mol / L, respectively, in the unformed battery. An electrolytic solution obtained by dissolution was injected. After injection of the electrolytic solution, the battery was formed in a 25 ° C. water tank to obtain a 34B19L type lead acid battery. In addition, when the antimony content of the positive electrode active material after chemical conversion was measured, it was 0.009 to 0.18% by mass.

  The types of the lithium ion source and the aluminum ion source are arbitrary, and any material that dissolves in dilute sulfuric acid and dissociates into lithium ions and aluminum ions, such as lithium carbonate and lithium hydroxide, may be used. Further, it may be formed by dilute sulfuric acid containing no lithium ion source or aluminum ion source, and these may be added after the formation.

  In the same manner as described above, batteries of comparative examples having different lead content and antimony content in the positive electrode active material material and different lithium ion and aluminum ion contents in the electrolytic solution were prepared.

Test method Each lead-acid battery was subjected to a 5-hour rate capacity test (JIS D 5301: 2006 9.5.2b)) and a high rate discharge characteristic test (JIS D 5301: 2006 9.5.3b)). The 5-hour rate capacity test and full charge were repeated 5 times, and the ratio of the 5 hour rate capacity to the 5th time with respect to the first time was defined as the capacity retention rate. The capacity retention rate represents durability against deep charge / discharge, and the main cause of the decrease in the capacity retention rate is softening of the positive electrode active material. The number of samples is 3, and the results are shown as average values.

  Tables 1 to 3 show the results. Based on battery No. 1 (comparative example) to which no lead, antimony, or lithium ion is added, high rate discharge duration, first 5 hour rate capacity, capacity retention Examples that exceeded battery No. 1 in all points of rate were taken as examples. High rate discharge duration is shown in Battery No. 1 is a relative value with 100%, and a 5-hour rate capacity is a relative value with the first capacity of battery No. 1 being 100%.

As is clear from Table 1,
i The positive electrode active material material contains 10-30% by weight of red lead,
ii In the cathode active material raw material, 0.01 to 0.2% by mass of antimony in terms of antimony element is contained,
iii When 0.02 to 0.2 mol / L lithium ion is contained in the electrolyte,
A lead storage battery having a long high rate discharge duration, a large 5-hour rate capacity, and a high capacity retention rate is obtained.

  On the other hand, if any of the above conditions i to iii is absent, the lead storage battery is equivalent to or lower than the battery No. 1 of the comparative example in any respect. For example, a battery No. with 0.3% by mass of antimony added. 14 and 15 have an adequate lead content of 30% by mass, a low lithium ion content of 0.02 or 0.2 mol / L, and a low high rate discharge duration and 5 hour capacity, and an antimony content. There is a critical change between 0.2% and 0.3% by weight. Battery Nos. 24-26, which do not contain red lead, did not give good results even when the antimony content and lithium ion content were changed. Batteries lacking antimony (batteries Nos. 27 and 29) were able to obtain only a low capacity retention rate even if other conditions were appropriate. In addition, the batteries lacking lithium ions corresponding to the configuration of Patent Document 1 (batteries Nos. 28 and 30) could obtain only a low capacity retention rate even if other conditions were appropriate. Even with No. 31 battery with excess of red lead, only low capacity retention was obtained. There is also a critical difference between the lead content of 40% by mass (battery No. 31) and 30% by mass (batteries No. 16-23). In addition, in batteries Nos. 32 and 33 with excessive lithium ions, the high rate discharge duration was short. There is also a critical difference between the lithium ion content of 0.2 mol / L (battery No. 13 etc.) and 0.3 mol / L.

  Battery No. 9 (Example) and Battery No. 28 (Comparative Example) were decomposed four times after the 5-hour rate capacity test and full charge, and were produced in the positive electrode active material after the fifth 5-hour rate capacity test. An electron micrograph of the lead sulfate was taken. In the examples, many micropores are observed in the lead sulfate, while in the comparative example, there are few micropores. In the examples having lithium ions, the micropores are maintained, and antimony that strengthens the bond between the positive electrode active materials and suppresses softening stays in the micropores and functions again after charging, whereas in the comparative example without lithium ions, the micropores remain. It is believed that the pores are not maintained and that antimony is pushed from the micropores to the macropores and loses function.

  The capacity retention could be further improved by adding aluminum ions to the electrolyte. The results are shown in Table 3. Capacity retention could be improved by including 0.02 to 0.2 mol / L of aluminum ions in the electrolyte with respect to a wide range of lead content, antimony content, and lithium ion content. However, when 0.3 mol / L of aluminum ions were contained, the high rate discharge characteristics deteriorated.

Although it is difficult to quantitatively explain the role of aluminum ions, it can be qualitatively estimated as follows. When PbO ₂ changes to lead sulfate, sulfate ions in the electrolytic solution are consumed, and the pH of the electrolytic solution on the surface of lead sulfate in the micropores temporarily approaches neutrality. At this time, since Al ³⁺ ions are changed to Al ₂ O ₃ .3H ₂ O and the like to form a sol-like substance, it is considered that this prevents the diffusion of ions such as SbO ₂ ⁺ . This effect is presumed to maintain the effect of antimony that prevents softening of the positive electrode active material.

The material of the negative electrode active material and the negative electrode lattice is arbitrary. In addition to sulfuric acid, lithium ions, and aluminum ions, the electrolyte solution includes sodium ions derived from lignin in the negative electrode active material, and third ions such as potassium ions and magnesium ions contained as impurities in the lithium ion source and aluminum ion source. It may contain a small amount of ingredients. The positive electrode active material may contain a small amount of a lead compound such as PbO ₂ and a third component such as iron, nickel, bismuth, tin contained as an impurity of lead powder in addition to antimony and binder.

In the example,
i The positive electrode active material material contains 10-30% by weight of red lead,
ii In the cathode active material raw material, 0.01 to 0.2% by mass of antimony in terms of antimony element is contained,
iii By containing 0.02 to 0.2 mol / L lithium ion in the electrolyte,
The high rate discharge duration, the initial value of the 5-hour rate capacity, and the capacity retention rate can be improved. Moreover, the capacity retention can be further improved by containing 0.02 to 0.2 mol / L of aluminum ions in the electrolytic solution.

Claims (4)

In a lead storage battery comprising a positive electrode plate obtained by filling a positive electrode grid with a paste obtained by kneading a positive electrode active material raw material, water and dilute sulfuric acid, and forming the paste, and an electrolyte comprising dilute sulfuric acid, the positive electrode active material The raw material has a lead content (Pb ₃ O ₄ ) of 10 to 30% by mass, contains 0.01 to 0.2% by mass of metal antimony or antimony compound in terms of antimony element, and further contains 0.02 to 0.2 mol / L in the electrolyte. A lead-acid battery comprising lithium ions.   The lead-acid battery according to claim 1, wherein the electrolyte further contains 0.02 to 0.2 mol / L of aluminum ions. A method for producing a lead storage battery comprising a positive electrode plate obtained by filling a paste obtained by kneading a positive electrode active material raw material, water and dilute sulfuric acid into a positive electrode lattice, and forming this, and an electrolytic solution comprising dilute sulfuric acid, The positive electrode active material raw material has a lead (Pb ₃ O ₄ ) content of 10 to 30% by mass, 0.01 to 0.2% by mass of metal antimony or antimony compound in terms of antimony element added, and 0.02 to A method for producing a lead-acid battery, comprising adding 0.2 mol / L of lithium ions.   The method for producing a lead storage battery according to claim 3, wherein 0.02 to 0.2 mol / L of aluminum ions is further added to the electrolytic solution.