JP4904658B2 - Method for producing lead-acid battery - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a method for manufacturing a lead storage battery.
[0002]
[Prior art]
  Among lead-acid batteries, control valve-type lead-acid batteries are particularly characterized by having no leakage and no maintenance characteristics. The leak-free liquid is a structure in which the electrolytic solution is impregnated and held only in the separator and no flowing electrolytic solution is present, and there is no leakage of the electrolytic solution even when the storage battery is placed horizontally. Non-maintenance refers to a characteristic in which maintenance is not required such as a replacement liquid because gas is not generated during normal charging due to the sealed reaction function that is a characteristic of the storage battery, and there is almost no decrease in the electrolyte.
[0003]
  Due to the excellent characteristics as described above, in recent years, the use of control valve type lead-acid batteries has been expanded in various fields. Accordingly, demands for high reliability, high energy density, and long life have been increasing.
[0004]
  The sealing reaction in the above-described control valve type lead-acid battery includes the following (1), (2) and (3)
It is shown by the formula.
(Positive electrode) H₂O = 1 / 2O₂+ 2H⁺+ 2e⁻・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (1)
(Negative electrode) Pb + 1 / 2O₂+ 2H⁺+ SO₄ ^2-= PbSO₄+ H₂O (2)
PbSO₄+ 2e⁻= Pb + SO₄ ^2-(3)
  As above, water (H₂O) is decomposed and oxygen gas (O₂However, as described above, the storage battery has a structure in which the electrolytic solution is impregnated and held only in the separator and the flowing electrolytic solution does not exist.₂Easily moves to the negative electrode through the separator and reacts with Pb to form PbSO₄And H₂O is generated. That is, H lost in equation (1)₂Since O is regenerated by the formula (2), the electrolyte does not decrease as a whole.
[0005]
  In addition, PbSO generated by the equation (2)₄Is reduced to Pb by the negative electrode charging reaction as shown in formula (3), and no hydrogen gas (H2) is generated during charging at the negative electrode. That is, neither oxygen gas nor hydrogen gas is generated during charging.
[0006]
  However, when self-discharge of the negative electrode increases, excessive hydrogen gas is generated, and H in accordance with the above formulas (1), (2) and (3)₂When the balance of the O regeneration cycle is lost and the negative electrode becomes insufficiently charged, and this continues, the negative electrode becomes PbSO₄A so-called sulfation phenomenon occurs, resulting in a short life.
[0007]
  Therefore, Pb, Pb—Ca alloy or Pb—Ca—Sn alloy having a small amount of self-discharge is usually adopted for the positive / negative grid in the control valve type lead storage battery.
[0008]
  However, the above grid has no problem when using a trickle or float that is used while being constantly charged, but it is used in a cycle where charging / discharging is repeated continuously, especially in a usage state where the discharge amount is small and overcharged. Since oxidation proceeds too much, the portion is preferentially discharged at the time of discharge, and an insulating layer of lead sulfate is formed at the interface between the positive electrode lattice and the active material, so that the capacity is reduced early (early capacity reduction, or premature capacity loss). (Abbreviated as PCL for short) occurs.
[0009]
  Regarding the above-mentioned early capacity reduction, not only the control valve type lead storage battery, but also an open type in which Pb, Pb-Ca or Pb-Ca-Sn alloy lattice not containing Sb is used for the positive and negative electrodes, and the electrolyte is sufficiently present. A similar phenomenon is seen in lead-acid batteries.
[0010]
  As one of the above measures, Pb, Pb—Ca alloy or Pb—Ca—Sn alloy is used for the negative electrode lattice, and the Sb concentration is 0.5 mass% or more and 1.5 mass% or less for the positive electrode. A method using a Pb—Sb alloy lattice having a low concentration (referred to as low antimony) has been proposed. Due to the presence of Sb in the positive electrode, the cause is not clear, but the above-described early capacity reduction in cycle use does not occur. However, if the Sb is eluted from the positive electrode into the electrolyte and deposited on the negative electrode, the hydrogen overvoltage of the negative electrode is lowered, the generation of hydrogen gas is promoted, the balance of the above-described sealed reaction cycle is lost, and the function of the control valve type lead-acid battery is reduced. The lost negative electrode plate becomes insufficiently charged and the storage battery performance deteriorates. Even in an open-type storage battery, there is a problem that the charging efficiency is lowered due to a decrease in hydrogen overvoltage, the decrease in the electrolyte is accelerated, and the performance is deteriorated.
[0011]
[Problems to be solved by the invention]
  In a lead-acid battery having a positive electrode lattice made of a Pb—Sb-based alloy having an Sb concentration of 0.5% by mass or more and 1.5% by mass or less, early capacity reduction is prevented by the presence of Sb, and Sb to the negative electrode An object of the present invention is to provide a lead-acid storage battery manufacturing method and a lead-acid storage battery that have an excellent cycle life while suppressing adverse effects as much as possible.
[0012]
[Means for Solving the Problems]
  As a means for solving the problem, according to claim 1, in a method for producing a lead-acid battery having a positive electrode lattice made of a Pb—Sb-based alloy having an Sb concentration of 0.5 mass% or more and 1.5 mass% or less. In the negative electrode active material, 0.3 mass% or more and 0.7 mass% or less of oil with respect to the mass of the negative electrode active material is added, and the electrolyte specific gravity is in the range of 1.29 to 1.4. The amount of Sn is less than 1.5% by mass, the amount of lignin in the negative electrode active material is in the range of 0.3 to 0.8% by mass, and the ratio of the negative electrode active material amount (g) to the positive electrode active material amount (g) is It is characterized by being 0.6 or more per cell.
[0013]
  In a lead-acid battery, particularly a control valve-type lead-acid battery, when a Pb—Sb alloy having a Sb concentration of 0.5% by mass or more and 1.5% by mass or less is used for the positive electrode lattice, the cycle of the battery is caused by the presence of Sb. Although the early capacity drop during use can be suppressed, when Sb elutes in the electrolyte and deposits on the negative electrode, the hydrogen overvoltage is lowered, the generation of hydrogen gas is promoted, the balance of the above-mentioned closed reaction cycle is lost, and the negative electrode plate is charged. There was a problem that it became insufficient, and it was sulphated and the performance deterioration of the storage battery was promoted. As one of the means for suppressing the harmful effects of Sb, it has been found that the oil added to the negative electrode active material has the effect of suppressing the precipitation of Sb eluted from the positive electrode on the negative electrode, and the present invention has found that It is based on. When the amount added is less than 0.3% by mass, the function of supplementing Sb of the oil is not sufficient, and when it exceeds 0.7% by mass, the oil covers the surface of the negative electrode plate and the performance of the negative electrode plate deteriorates. It turned out to be undesirable. Therefore, 0.3 mass% or more and 0.7 mass% or less are suitable.
[0014]
  The oil here means oil obtained by producing petroleum (crude oil). As a result of testing various oils, the inventors of the present application have found that paraffinic hydrocarbon oils having a chain structure are particularly effective for the purpose of the present invention.
[0015]
  In addition, the present invention is characterized in that a positive electrode plate containing Sn in the positive electrode active material is used.
[0016]
  That is, when Sn is contained in the positive electrode active material, Sb and Sn eluted from the positive electrode lattice produce an Sb-Sn compound, and Sb stays in the positive electrode active material and suppresses precipitation on the negative electrode. I found it effective.
[0017]
  The appropriate amount of Sn is related to the amount of Sb contained in the positive electrode lattice. The amount of Sb contained in the positive electrode lattice is S (mass%), and the amount of Sn contained in the positive electrode active material is T (mass%). It was found that by maintaining the relationship of 1.5> T ≧ 0.15 × S + 0.05, Sn effectively acts and suppresses elution of Sb. That is, it is necessary to suppress the Sn amount to a mass% smaller than the maximum Sb content of 1.5 mass% contained in the positive electrode lattice at the maximum. When the Sn amount is 1.5% or more, the adverse effect of Sn appears regardless of the presence of Sb, and the performance of the storage battery is degraded. Further, the lower limit value of the addition amount is related to the Sb concentration in the positive electrode lattice, and it was found from the test results that the relationship of T ≧ 0.15 × S + 0.05 needs to be maintained.
[0018]
  It was also found that the above relationship functions effectively when the positive electrode lattice mass (g) / positive electrode active material amount (g) is in the range of 0.5 to 1.2.
[0019]
  The present invention is also characterized in that a negative electrode plate containing lignin in the negative electrode active material is used.
[0020]
  The amount of lignin in the negative electrode active material is preferably in the range of 0.3 to 0.8% by mass. In addition, the quantity of lignin here says the value measured by the ultraviolet absorption spectrum method.
[0021]
  That is, when Sb eluted from the positive electrode was deposited on the negative electrode, it was found that the lignin captures Sb, thereby suppressing the adverse effects of Sb. However, if the amount of lignin is more than 0.8% by mass, the lignin covers the surface of the negative electrode plate, resulting in performance deterioration of the negative electrode plate. On the other hand, if the amount is less than 0.3% by mass, the ability to capture Sb is reduced, and the effect cannot be obtained. Therefore, it turned out that the range of 0.3-0.8 mass% is preferable.
[0022]
  Further, the present invention provides a method for producing a lead-acid battery having a positive electrode lattice made of a Pb—Sb-based alloy having an Sb concentration of 0.5% by mass or more and 1.5% by mass or less, and a negative electrode with respect to the positive electrode active material amount (g). The ratio of the amount of active material (g) is preferably maintained at 0.6 or more per cell.
[0023]
  Here, the ratio of the amount of the negative electrode active material to the amount of the positive electrode active material per cell is PbO which is the positive electrode active material.₂The mass ratio between the mass of the negative electrode active material and the mass containing Pb and various additives.
[0024]
  In the present invention, the positive electrode active material density is 3.1 g / cm.³3.8 g / cm³The following is preferable.
[0025]
  That is, the positive electrode active material is a porous material, and a high-porosity, that is, low-density active material has many voids in the active material and is highly reactive with sulfuric acid. Rises. On the other hand, since the bonding force between the active materials is weakened, the cycle life performance is inferior. On the other hand, Sb has a function of increasing the bonding strength between the positive electrode active materials, so 3.1 g / cm.³3.8 g / cm³Even in the following low-density active materials, a storage battery having excellent capacity and excellent life even in cycle use can be obtained.
[0026]
[Reference example]
  First, as a reference example, as described above, by using a Pb—Sb alloy having a Sb concentration of 0.5% by mass or more and 1.5% by mass or less for the positive electrode lattice, the control valve does not contain Sb in the positive electrode lattice. The results of tests conducted to clarify that the battery has an excellent cycle life performance compared to a lead-acid battery. At that time, the effect of the specific gravity of the electrolyte used on the life performance was also tested.
[0027]
  A cast grid made of six types of Pb—Sb alloys containing zero Sb in the positive grid was prepared, and a normal paste was filled into the grid and dried to prepare a positive plate. For the negative electrode plate, a Pb-0.07 mass% Ca-1.3 mass% Sn alloy cast grid was used, and the grid was filled with a normal paste and dried, and then used. Three positive electrode plates and four negative electrode plates are alternately laminated through fine glass fiber separators, inserted into a battery case, and a predetermined amount of dilute sulfuric acid having a concentration such that the final specific gravity is 1.25 to 1.44. After injecting the solution, chemical conversion was performed in the battery case, and a control valve type lead storage battery having a rated capacity of about 7 Ah (20 hR), a nominal voltage, and 12 V with a normal control valve mounted thereon was manufactured. In this example, the amount of oil in the negative electrode active material was 0% by mass, the amount of Sn in the positive electrode active material was 0% by mass, the amount of lignin in the negative electrode active material was 0.3% by mass, and the negative electrode active material per cell. Substance amount / positive electrode active material amount is 0.8, positive electrode active material density is 3.2 g / cm³Applied.
[0028]
  The storage battery was subjected to a cycle life test under the following conditions.
[0029]
(Cycle life test conditions)
After discharging at 1.75 A (0.25 CA) and final discharge voltage: 1.7 V / cell, charging is performed at a maximum current of 1.4 A (0.2 CA), and the storage battery voltage reaches 2.4 V / cell. At that time, switching to constant current charging of 0.35 A (0.05 CA) was performed up to 110% of the discharge amount. The test atmosphere temperature was 25 ° C., and the capacity under the above discharge conditions was confirmed every about 100 cycles, and the time when the capacity decreased to the initial 50% was regarded as the life.
[0030]
  In this test, the addition amount of oil, 0 mass%, the addition amount of Sn, 0 mass%, the negative electrode active material amount / the positive electrode active material amount, 0.8, the positive electrode active material density, 3.2 g / cm.³Respectively.
[0031]
  The test results are shown in FIG.
[0032]
  As shown in FIG. 1, a storage battery with a Sb content in the positive electrode grid in the range of 0.5 to 1.5 mass% showed a life of about 670 to 800 cycles, whereas a 2 mass% storage battery It decreased to 400 cycles or less. The reason is that the amount of Sb is large and deposited on the negative electrode plate, and the negative electrode plate deteriorated early. On the other hand, the 0.3 mass% storage battery did not show the effect of Sb, showed the same characteristics as the storage battery using a lattice with 0 mass% Sb, and had a short life.
[0033]
  Regarding the electrolyte concentration (specific gravity) used for the storage battery, when it was lower than 1.29, the life was shortened. The reason is that when the electrolyte specific gravity is low, the solubility of Sb in dilute sulfuric acid increases, the amount deposited on the negative electrode plate increases, and the negative electrode plate is deteriorated. On the other hand, when the specific gravity of the electrolyte was higher than 1.4, the life was shortened. This is because the positive electrode active material was softened and dropped due to the high specific gravity.
[0034]
  As described above, in the control valve type lead-acid battery, when using a positive electrode grid containing Sb in order to improve the short life in cycle use, the Sb content is preferably in the range of 0.5 to 1.5 mass%. I understand that. In addition, using an electrolyte having a specific gravity of 1.29 or more is effective in suppressing the elution of Sb, but if the specific gravity is too high, the positive electrode active material is softened, so 1.4 can be said to be the limit.
[0035]
【Example】
  Next, in order to clarify the effect of the present invention, it explains in detail based on an example.
[0036]
Example 1
  In Example 1, the results of tests conducted to clarify that the oil added to the negative electrode active material has a function of suppressing the precipitation of Sb eluted from the positive electrode lattice onto the negative electrode plate will be described.
[0037]
  6 types of positive plates including zero amount of Sb in the positive electrode lattice were prepared, and these were combined with 8 types of plate including zero amount of oil in the negative electrode active material. A control valve type lead-acid battery having a rated capacity of about 7 Ah and a nominal voltage of 12 V was prepared according to the same formulation as the example. As the oil, an oil based on a paraffinic hydrocarbon having a chain structure was used. The electrolyte specific gravity is 1.32 (20 ° C.), the Sn amount in the positive electrode active material is 0% by mass, the lignin amount in the negative electrode active material is 0.3% by mass, the negative electrode active material amount per cell / positive electrode Active material amount is 0.8, positive electrode active material density is 3.2 g / cm³Respectively.
[0038]
  The above-mentioned storage battery was subjected to a cycle life test under the same conditions as in the reference example. The result is shown in FIG.
[0039]
  As shown in FIG. 2, the cycle life of a storage battery having an Sb content in the positive electrode lattice in the range of 0.5 to 1.5 mass% and an oil content of 0 mass% was about 700 cycles, A storage battery having an oil addition amount of 0.3 mass% or more and 0.7 mass% showed a life of 800 to 1000 cycles, and the effect of oil was recognized. However, the lifetime was reduced at 0.8% by mass. The reason is considered to be that there was too much oil to cover the surface of the negative electrode plate, and the negative electrode plate did not function sufficiently. A storage battery having an Sb content of 2.0 mass% was greatly affected by Sb, and the negative electrode plate deteriorated and reached the end of its life regardless of the amount of oil added. On the other hand, in a storage battery having an Sb content of 0 or 0.3% by mass, the life of the positive electrode plate was shortened due to the deterioration of the positive electrode plate because Sb did not function sufficiently or not at all regardless of the amount of oil.
[0040]
  As described above, by adding 0.3% by mass or more and 0.7% by mass or less of oil to the negative electrode active material, it is possible to suppress Sb that has been eluted from the positive electrode plate from being precipitated on the negative electrode. It was found that the deterioration of the negative electrode was prevented and the life performance was improved.
[0041]
(Example 2)
  In Example 2, when Sn is present in the positive electrode active material, it is clearly shown that it has an effect of forming a compound with Sb eluted from the positive electrode lattice and suppressing the dissolution of Sb into the electrolyte. The results of the tests conducted for this purpose will be described.
[0042]
  Six kinds of positive plates including zero in the positive electrode lattice including zero are prepared, and these electrode plates are combined with nine kinds of positive plates including the amount of Sn added in the positive electrode active material. Produced a control valve type lead-acid battery having a rated capacity of about 7 Ah and a nominal voltage of 12 V according to the same formulation as the reference example. The positive electrode lattice mass (g) / positive electrode active material amount (g) was set to 1.0.
[0043]
  In this case, the oil amount is 0.3 mass%, the electrolyte specific gravity is 1.32 (20 ° C.), the negative electrode active material amount / positive electrode active material amount per cell is 0.8, and the positive electrode active material density is 3. 2g / cm³Respectively.
[0044]
  The above-mentioned storage battery was subjected to a cycle life test under the same conditions as in the reference example. The result is shown in FIG.
[0045]
  As shown in FIG. 3, in the storage battery in which the amount of Sb in the positive electrode lattice is in the range of 1.0 mass% to 1.5 mass%, the amount of Sn in the positive electrode active material is 1.5> T (Sn mass%) ≧ In the range satisfying 0.15 × S (Sb mass%) + 0.05, the effect of Sn functions effectively, and combined with the effect of the oil added to the negative electrode active material, excellent life performance of 1000 cycles or more showed that. In this prescription, the effect of suppressing the harmful effects of Sb is great, and the cycle life performance is greatly improved. Therefore, a storage battery with an Sb content of 0.5% by mass has a negative effect on the cycle life due to low Sb, Due to the deterioration of the positive electrode plate, it remained at about 900 cycles.
[0046]
  Regarding the influence of the Sn amount, when it was 1.5% by mass or more, the cycle life was greatly reduced regardless of the Sb amount in the positive electrode lattice. This is considered to be because when the amount of Sn is large, a local battery is formed between the positive electrode and Sn and self-discharge increases.
[0047]
  Further, when the amount of Sb in the positive electrode lattice was 2.0% by mass, the effect of Sb exceeded the effect of Sn, and the life was short.
[0048]
  In this example, the amount of oil added was fixed at 0.3% by mass, but the same cycle life tendency was obtained when the amount added was in the range of 0.3 to 0.7% by mass.
[0049]
  Further, it was confirmed by other tests that Sn effectively acts in the range of positive electrode lattice mass (g) / positive electrode active material mass (g) of 0.5 to 1.2.
[0050]
(Example 3)
  In Example 3, it is clear that when the amount of lignin added to the negative electrode plate is increased, Sb eluted from the positive electrode plate is captured, and the Sb has a function of suppressing adverse effects on the negative electrode plate. The results of tests conducted to make this
[0051]
  Six types of positive plates including zero Sb in the positive electrode lattice were prepared, and these plates were combined with six types of plates with different amounts of lignin in the negative electrode active material. A control valve type lead-acid battery having a rated capacity of about 7 Ah and a nominal voltage of 12 V was produced.
[0052]
  In this case, the amount of oil added is 0.3% by mass, the amount of Sn in the positive electrode active material is 0% by mass, the specific gravity of the electrolyte is 1.32 (20 ° C.), the amount of negative electrode active material per cell / positive electrode Active material amount is 0.8, positive electrode active material density is 3.2 g / cm³Respectively.
[0053]
  The above-mentioned storage battery was subjected to a cycle life test under the same conditions as in the reference example. The result is shown in FIG.
[0054]
  As shown in FIG. 4, the storage battery in which the amount of Sb in the positive electrode lattice is 0.5 to 1.5 mass% and the amount of lignin in the negative electrode plate is 0.3 to 0.8 mass% is good cycle life performance. showed that. When the amount of lignin was more than 0.8% by mass, the lignin covered the surface of the negative electrode plate, the negative electrode plate did not perform its original function, and the cycle life decreased rapidly. When the amount of lignin added was less than 0.3% by mass, the Sb trapping function of lignin was lowered, and the cycle life was poor regardless of the amount of Sb in the positive electrode.
[0055]
  Further, when the amount of Sb in the positive electrode lattice was 2% by mass, the adverse effect of Sb exceeded the effect of lignin and the life was short.
[0056]
  In this example, the amount of oil in the negative electrode active material was fixed at 0.3% by mass, and the amount of Sn in the positive electrode active material was fixed at 0% by mass. However, the amount of oil added was 0.2% by mass or more, 0.7 mass% or less, Sn amount in the positive electrode active material, and 1.5> T (mass% of Sn) ≧ 0.15 × S (mass% of Sb) +0.05 each independently Or even when applied in combination, the same life tendency was obtained.
[0057]
Example 4
  In Example 4, in a valve-regulated lead-acid battery containing Sb in the positive electrode grid, a test was conducted to examine the degree of adverse effects of Sb on the negative electrode when the ratio of the negative electrode active material amount to the positive electrode active material amount was changed. We will describe the results.
[0058]
  5 types of negative electrode plates having a constant amount of positive electrode active material, 6 types of positive electrode plates including zero amount of Sb in the positive electrode lattice, and different ratios of the amount of negative electrode active material to the amount of positive electrode active material, In combination, a control valve type lead-acid battery having a rated capacity of about 7 Ah and a nominal voltage of 12 V was prepared in the same manner as in the reference example.
[0059]
  In contrast, the amount of oil added is 0.3% by mass, the amount of Sn in the positive electrode active material is 0% by mass, the amount of lignin in the negative electrode active material is 0.3% by mass with respect to the negative electrode material, and the specific gravity of the electrolyte 1.32 (20 ° C.), positive electrode active material density is 3.2 g / cm³Respectively.
[0060]
  The above-mentioned storage battery was subjected to a cycle life test under the same conditions as in the reference example. The result is shown in FIG.
[0061]
  As shown in FIG. 5, in the storage battery in which the amount of Sb in the positive electrode lattice is in the range of 0.5 to 1.5% by mass, if the negative electrode active material amount / the positive electrode active material amount is 0.6 or more, a good cycle Although the lifetime was shown, when it was smaller than 0.6, even if the Sb amount range was 0.5 to 1.5% by mass, which showed a good cycle life, the negative electrode was deteriorated early, so that the lifetime was shortened. It was. A storage battery having an Sb content of 2.0 mass% has a large negative effect of Sb, so that the cycle life performance was not improved even when the negative electrode active material amount / positive electrode active material amount was 0.6 or more.
[0062]
  In this example, the amount of oil added is 0.3% by mass, the amount of Sn in the positive electrode active material is 0% by mass, and the amount of lignin in the negative electrode active material is fixed at 0.3% by mass. However, the amount of oil added, 0.2% by mass or more and 0.7% by mass or less, the Sn amount in the positive electrode active material, the range in which 1.5> T ≧ 0.15 × S + 0.05 is applied, the negative electrode When the amount of lignin in the active material, 0.3% by mass or more and 0.8% by mass or less, was applied individually or in combination, the same trend of life performance was obtained.
[0063]
(Example 5)
  As is well known, when a low-density active material is applied to the positive electrode plate, the utilization factor of the positive electrode active material is improved and the capacity is increased. When Sb is contained in the positive electrode lattice, the Sb has a function of increasing the bonding force between the positive electrode active materials, and a control valve type lead-acid battery having good initial performance and excellent life performance can be obtained. The results of tests conducted to clarify this will be described.
[0064]
  A storage battery was produced by combining six types of positive electrode lattices including zero positive electrode lattices and seven types of positive electrode plates having different active material densities. The amount of oil added is 0% by mass, the amount of Sn in the positive electrode active material is 0% by mass, the amount of lignin in the negative electrode active material is 0.3% by mass, the electrolyte specific gravity is 1.32 (20 ° C.), The negative electrode active material amount / positive electrode active material amount per cell was 0.8.
[0065]
  The initial capacity of the storage battery was evaluated and a cycle life test was performed under the same conditions as in the reference example. The results are shown in FIGS. 6 and 7, respectively.
[0066]
  As shown in FIG. 6, the storage battery having Sb concentrations of 0 and 0.3% by mass has a density of the positive electrode active material amount of 3.3 g / cm 3.³The capacity decreased at the following, whereas when the Sb concentration was 0.5% by mass or more, the binding force of the positive electrode active material was increased and 3.1 g / cm 3.³Such a low-density positive electrode active material showed excellent capacity. However, the positive electrode active material density is 3 g / cm³Then, even when the Sb concentration was 0.5% by mass or more, a decrease in capacity was inevitable.
[0067]
  FIG. 7 shows the results of subjecting the storage battery to a cycle life test. As described above, the positive electrode active material density is 3 g / cm.³This battery was not subjected to the test because its capacity was low from the beginning.
[0068]
  As shown in FIG. 7, the storage battery with zero or 0.3 mass% Sb has a positive electrode active material density of 3.5 g / cm.³In contrast, the cycle life performance has been reduced, whereas a storage battery with an Sb content of 0.5 to 1.5 mass% is 3.1 g / cm.³But it had excellent cycle life performance.
[0069]
  However, a storage battery having an Sb amount of 2.0 mass% has a short life due to the harmful effects of Sb for the same reason as described above.
[0070]
  On the other hand, the storage batteries with Sb amounts of 0 and 0.3% had a short life when the positive electrode active material had a low density, but 3.8 g / cm³At the above, the cycle life performance improved. This is considered to be due to the fact that the bonding strength between the active materials is improved due to the high density.
[0071]
  In this example, the amount of oil added in the negative electrode active material is 0% by mass, the amount of Sn in the positive electrode active material is 0% by mass, the amount of lignin in the negative electrode active material is 0.3% by mass, and per cell. The amount of negative electrode active material / the amount of positive electrode active material was described as being fixed to 0.8. However, the amount of oil added was 0.2% by mass or more and 0.7% by mass or less, and the amount of Sn added and the amount of Sb Range in which relation 1.5> T ≧ 0.15 × S + 0.05 is applied [positive electrode lattice mass (g) / positive electrode active material mass (g): 1.0], lignin amount, 0.3 mass% or more, The same life performance tendency was obtained when 0.8% by mass or less and the amount of negative electrode active material per cell / positive electrode active material amount of 0.6 or more were used alone or in combination.
[0072]
  In the examples, the control valve type lead storage battery has been described. However, a positive electrode lattice made of a Pb—Sb alloy having an Sb concentration of 0.5% by mass or more and 1.5% by mass or less and Pb, Pb—Ca or Pb. -A lead storage battery having a negative electrode lattice made of a Ca-Sn alloy, and even in an open type lead storage battery in which an electrolyte is sufficiently present, the amount of oil added, 0.2 mass% or more, 0.7 mass% or less, positive electrode Relationship between Sn addition amount in active material and Sb amount in positive electrode lattice 1.5> T ≧ 0.15 × S + 0.05 applicable range, lignin amount in negative electrode active material, 0.3 mass% or more 0.8 mass% or less, negative electrode active material amount per cell / positive electrode active material amount 0.6 or more, positive electrode active material density 3.1 g / cm³3.8 g / cm³Although the absolute value differs by applying the following, it confirmed that the effect similar to a control valve type lead acid battery was acquired.
[0073]
【The invention's effect】
  In a lead-acid battery using positive / negative electrode plates that do not contain Sb in the positive / negative electrode grid, an early capacity decrease occurs depending on charge / discharge conditions in cycle use. As a countermeasure, the above problem can be solved by using a Pb—Sb alloy having a Sb concentration of 0.5% by mass or more and 1.5% by mass or less for the positive electrode lattice. If it deposits on the negative electrode, the hydrogen overvoltage of the negative electrode is lowered, hydrogen gas is generated, the balance of the sealing reaction function that is characteristic of the control valve type lead storage battery is lost, the function is lost, and the performance of the negative electrode plate deteriorates. It was. In contrast, a certain amount of oil is added to the negative electrode active material, a certain amount of Sn is added to the positive electrode active material, a certain amount of lignin is added to the negative electrode active material, and / or the amount of the negative electrode active material per cell / By making the ratio of positive electrode active material amount 0.6 or more, the above-mentioned adverse effects of Sb are suppressed, and the excellent cycle life performance inherent in control valve type lead-acid batteries or open-type lead-acid batteries can be obtained. Is extremely large.
[Brief description of the drawings]
FIG. 1 is a diagram showing the relationship between Sb concentration and electrolyte specific gravity in a positive grid and cycle life in a control valve type lead-acid battery.
FIG. 2 is a graph showing the relationship between the amount of oil added (mass%) in the negative electrode active material of Example 1 and the cycle life.
3 is a graph showing the relationship between the Sn amount (% by mass) in the positive electrode active material of Example 2 and the cycle life. FIG.
4 is a graph showing the relationship between the amount of lignin (mass%) in the negative electrode active material of Example 3 and the cycle life. FIG.
5 is a graph showing the relationship between the amount of negative electrode active material per cell (g) / the amount of positive electrode active material (g) and the cycle life in Example 4. FIG.
6 is a graph showing the influence of the amount of Sb (mass%) in the positive electrode lattice in the relationship between the positive electrode active material density and the storage battery capacity in Example 5. FIG.
7 is a graph showing the influence of the amount of Sb (% by mass) in the positive electrode lattice in the relationship between the positive electrode active material density of Example 5 and the cycle life of the storage battery. FIG.

Claims (1)

In the method for producing a lead-acid battery having a positive electrode lattice made of a Pb—Sb-based alloy having an Sb concentration of 0.5% by mass or more and 1.5% by mass or less, 0.3% of the negative electrode active material mass in the negative electrode active material More than mass% and less than 0.7 mass% oil is added, the electrolyte specific gravity is in the range of 1.29 to 1.4, the amount of Sn in the positive electrode active material is less than 1.5 mass %, The amount of lignin in the range of 0.3 to 0.8 mass %, and the ratio of the amount of negative electrode active material (g) to the amount of positive electrode active material (g) is 0.6 or more per cell. Production method.

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