JP2010102916A - Method for manufacturing positive electrode plate for lead-acid battery, method for manufacturing lead-acid battery, and lead-acid battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve problems in which when the drying temperature is raised in order to shorten aging and drying time, tetrabasic lead sulfate is formed in a positive electrode active material and the battery capacity is reduced. <P>SOLUTION: After lignin or bisphenol, and formaldehyde condensed product of sulfite or amino acid is added into a positive electrode paste for a lead-acid battery, and in an aging and drying process, especially in the drying process, the time required for aging and drying is shortened remarkably by setting the drying temperature to 65°C or more preferably 67°C or more, and 100°C or less preferably 98°C or less, and since the formation of tetrabasic lead sulfate is suppressed which is conventionally formed at such a drying temperature, the lead-acid battery having high capacity is obtained, that is, both the shortening of the aging and drying time and the high capacity of the lead-acid storage battery are made compatible, which are mutually incompatible conventionally. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a positive electrode plate for a lead storage battery, a method for manufacturing a lead storage battery using the positive electrode plate, and a lead storage battery.

As electrode plates for lead-acid batteries, paste-type electrode plates dominate except for some industrial lead-acid batteries. As a manufacturing method of the paste type electrode plate, lead powder (PbO powder, mixed powder of PbO and Pb, or a mixture of these powders with Pb ₃ O ₄ powder) is diluted with dilute sulfuric acid or water. A current collector formed from a paste kneaded with dilute sulfuric acid using lead or a lead alloy, or titanium having sulfuric acid resistance and oxidation resistance, and conductivity, or a conductive titanium oxide. It fills the body and aged and dried.

3PbO · PbSO ₄ (tribasic lead sulfate) is mainly produced in the electrode plate during aging and drying, and the electrode plate is electrolytically oxidized (chemically formed) to convert the tribasic lead sulfate into a positive electrode active material for a lead storage battery. Lead dioxide (PbO ₂ ) is obtained, and the electrode plate is subjected to electrolytic reduction (chemical conversion) to obtain a porous spongy Pb which is a negative electrode active material of the lead storage battery.

In particular, with respect to aging drying of the positive electrode plate, the temperature of the positive electrode plate in the maturation drying (more strictly, a temperature of the paste in the maturation drying) exceeds 65 ° C., in addition to _{3PbO · PbSO 4, 4PbO · PbSO} 4 ( Tetrabasic lead sulfate). Since this tetrabasic lead sulfate has a coarse crystal grain size compared to tribasic lead sulfate, the electrolytic oxidation reaction to PbO ₂ is difficult to proceed, and the chemical conversion efficiency is extremely reduced. As a result, there has been a problem that the capacity of the lead storage battery is greatly reduced.

  The above-described maturing and drying of the positive electrode plate is one of the important processes that determine the capacity performance of the lead storage battery among the manufacturing processes of the lead storage battery. Therefore, in consideration of the above-mentioned decrease in capacity performance, the maximum temperature in the aging drying process has been controlled to be at least less than 65 ° C.

  Due to the limitation of the maximum temperature in aging drying as described above, the time required for aging drying is extremely long, and it is related to the thickness of the filled paste. As a time required for setting it to 3.0 mass% or less which is a standard, an extremely long time of 30 to 40 hours is required, which has been an obstacle to shortening the lead time for producing lead-acid batteries.

As a technique for shortening the aging drying time of the positive electrode plate for a lead storage battery, Patent Document 1 discloses a technique for promoting the evaporation of moisture in the paste by reducing the pressure inside the aging drying furnace from atmospheric pressure. Proposed.
Japanese Patent Laid-Open No. 2008-4401

Since the above-mentioned Patent Document 1 promotes moisture evaporation of the paste by decompression, the aging drying temperature of the positive electrode plate can be kept low. As the aging drying furnace, an oven chamber having airtightness, Pump is required. Further, the furnace chamber needs to have sufficient strength not to be damaged by the atmospheric pressure even during decompression, and the decompression pump has a large volume (for example, 90 to 200 m ³ ). The inside of the volume must have a pressure-reducing capability sufficient to promote the evaporation of moisture in the paste, and the equipment cost is extremely high compared to a conventional aging drying furnace, In view of the use of a pressure-reducing furnace that can enter the interior, it is undesirable from the viewpoint of work safety.

  Therefore, the technique disclosed in Patent Document 1 prepares a plurality of small-sized ones in such a volume that an operator cannot enter the interior in consideration of work safety. Therefore, in the end, although it is a relatively easy method in the laboratory, the above-mentioned facility restrictions are extremely large when mass-producing the positive electrode plate for a lead storage battery.

  In the present invention, when the aging drying is performed at a high temperature by using an aging drying furnace without using the decompression furnace shown in Patent Document 1 as described above, the capacity of the lead storage battery is reduced due to the positive electrode. It solves the conflicting problem that occurs. That is, the object of the present invention is to produce a positive electrode plate for a lead storage battery that does not cause a decrease in the capacity of the battery even if the aging drying time is shortened by increasing the drying temperature, and the positive electrode plate for the lead storage battery The present invention provides a method for producing a lead-acid battery using a battery, and uses this positive electrode plate to provide a high-capacity lead-acid battery with a reduced production lead time.

  In order to solve the above-mentioned problem, the invention according to claim 1 of the present invention is a method in which lead powder is mixed with dilute sulfuric acid or pasty active material kneaded with water and dilute sulfuric acid, and then aged and dried. A lead plate for a positive electrode plate, wherein the lead powder contains 0.03 parts by mass and 0.8 parts by mass or less when the mass of lead contained in the lead powder is 100 parts by mass. The manufacturing method of the positive electrode plate for lead acid batteries characterized by including the process of adding the quantity of lignin and making the temperature of the said positive electrode plate 65 degreeC or more in the said aging drying process.

  Further, the invention according to claim 2 of the present invention is a positive electrode for a lead storage battery, in which lead powder is filled in a current collector with a paste-like active material kneaded with dilute sulfuric acid or water and dilute sulfuric acid, and then aged and dried. A method for producing a plate, wherein the lead powder contains 0.01 mass part or more and 0.8 mass part or less of bisphenols and sulfites or amino acids when the mass of lead contained in the lead powder is 100 mass parts A method for producing a positive electrode plate for a lead-acid battery, comprising adding a formaldehyde condensate and a step of setting the temperature of the positive electrode plate to 65 ° C. or higher in the aging and drying step.

  The invention according to claim 3 of the present invention is a lead storage battery characterized in that the positive electrode plate obtained in any one of claim 1 or claim 2 and the negative electrode plate are combined to form a lead storage battery. A manufacturing method is shown, and the invention according to claim 4 of the present invention shows a lead storage battery obtained by the manufacturing method of the lead storage battery shown in claim 3.

  According to the present invention described above, when the positive electrode plate for lead storage battery is aged and dried, even if the aging drying temperature exceeds 65 ° C., the production of tetrabasic lead sulfate that causes a decrease in the capacity of the lead storage battery is remarkable. Since it is suppressed, it is possible to obtain a lead storage battery in which the decrease in capacity is suppressed, and the aging drying temperature can be set higher than before, so that the aging drying time can be shortened. Accordingly, a positive electrode plate and a lead-acid battery for a high-capacity lead-acid battery that can solve the conflicting problem that the battery capacity is reduced by shortening the required time by increasing the aging and drying temperature, and without impairing productivity. Can be obtained.

  Hereinafter, the manufacturing method of the positive electrode plate for lead acid batteries by the embodiment of the present invention, the manufacturing method of lead acid battery, and the lead acid battery using this are explained.

(First embodiment)
As a first embodiment according to the present invention, lead powder obtained by a conventionally known ball mill method, Burton pot method or the like is prepared. The lead powder is a mixed powder of 10% by mass to 30% by mass of metallic lead and 70% by mass to 90% by mass of lead oxide (PbO), although it varies depending on the production method. In addition, as is conventionally known, lead tan (Pb ₃ O ₄ ) may be added to the lead powder for the purpose of improving chemical conversion efficiency. However, although the chemical conversion efficiency is improved by the addition of the red lead to the lead powder, thereby improving the initial capacity of the lead storage battery, the binding force between the positive electrode active materials decreases, and with the increase of the addition amount, Since the tendency for a deep discharge lifetime to fall is recognized, it is preferable that the addition amount of a red lead shall make an upper limit 25 mass parts with respect to 100 mass parts of lead contained in lead powder.

  In this invention, 0.03 mass part or more and 0.8 mass part or less lignin are added per 100 mass parts of lead contained in the lead powder of this lead powder. Then, after adding water and kneading with water, dilute sulfuric acid having a density of about 1.100 to 1.400 at 20 ° C. is added, and sulfuric acid kneading is performed to prepare a positive electrode paste.

  This positive electrode paste had conductivity such as lead or lead alloy, and also titanium metal having acid resistance and alkali resistance, conductive titanium oxide layer, or other conductive metal oxide layer. The current collector is filled with the desired amount and aged and dried.

  In this invention, the drying process performed after an aging process of an aging drying process includes the process which makes the maximum temperature of a positive electrode plate 65 degreeC or more. According to the present invention, even when the aging drying step includes a step in which the temperature of the positive electrode plate exceeds 65 ° C., the growth of coarse crystals of tetrabasic lead sulfate is remarkable due to the addition of lignin into the positive electrode paste. Since it is suppressed, a high capacity positive electrode plate for a lead storage battery can be obtained. Moreover, a high capacity lead acid battery can be obtained by using the positive electrode plate for a lead acid battery obtained by the present invention.

  In the aging and drying step of the present invention, in the so-called initial aging process, as conventionally known, for example, aging is performed under conditions of a temperature of 40 ° C. and a humidity of 60 to 100 RH%, and then 65 ° C. As described above, the temperature inside the aging drying furnace is raised and dried in a short time. The time required for the aging process varies depending on the thickness of the electrode plate, but can be set to about 4 to 12 hours for a normal electrode plate having a paste thickness of about 1.0 to 4.0 mm.

  The drying process performed subsequent to the aging process is different from the electrode plate thickness and the drying temperature (corresponding to the maximum temperature in the aging drying process), but is at least 65 ° C. or higher. The upper limit of the drying temperature is 110 ° C., preferably 100 ° C. or less. In particular, when the aging drying step includes a step in which the temperature of the positive electrode plate exceeds 110 ° C., the rapid drying of the positive electrode plate expands the difference in the dry state between the positive electrode surface and the positive electrode plate, Since the paste on the surface of the positive electrode plate is drastically dried, a gap is formed between the current collector and the paste, or cracks are generated in the paste itself, so that the positive electrode paste from the current collector (after aging and drying) The current collection efficiency of the current collector decreases due to the loss of adhesion or the decrease in the adhesion between the positive electrode pastes (after aging and drying) or between the positive electrode paste (after aging and drying) and the current collector. This is because the capacity of the lead storage battery is reduced.

  In Table 1, 0.03 parts by mass of lignin is added to 100 parts by mass of lead contained in the lead powder, and a paste obtained by mixing with water and dilute sulfuric acid is filled into a lead alloy current collector. After aging at 35 ° C. and 80 RH% for 6 hours, the moisture content in the positive electrode paste when the drying temperature was set at 60 ° C., 65 ° C., 67 ° C., 80 ° C., 98 ° C., 100 ° C., 110 ° C. Time to reach 3.0 mass% and 0.5 mass% is shown. In the drying process, no humidification is performed. Table 1 shows an example in which the current collector has a lattice shape, and the maximum thickness (electrode plate thickness) of the positive electrode paste at the lattice grid portion is 2.0 mm.

  As shown in Table 1, by setting the temperature during the drying time to 65 ° C. or more, more preferably 67 ° C. or more, the moisture content in the positive electrode paste, which is a measure of completion of drying, is 3.0 mass. % Can be significantly shortened. In the present invention, it is essential that the temperature during the drying time is 65 ° C. or higher, but the upper limit is 110 ° C., preferably 100 ° C. or lower, more preferably 98 ° C. or lower, as described above. To do. For example, at 98 ° C. and 100 ° C., there is a significant difference in the occurrence of cracks in the positive electrode paste (less at 98 ° C. and significantly more at 100 ° C.), but also the drying time (water content 3.0). This is because there is almost no difference in mass%). Therefore, it is not desirable to include a stage in which the positive electrode plate temperature becomes 100 ° C. or higher in the aging drying process, and the temperature should be less than 100 ° C., for example, 98 ° C. or lower.

  Next, in this embodiment, although the example which mixes the lead powder containing lignin with water and dilute sulfuric acid was shown, the water kneading may be omitted and the lead powder containing lignin may be mixed only with dilute sulfuric acid.

  In addition, lignin may be added at a stage prior to the start of mixing of water and dilute sulfuric acid or dilute sulfuric acid, at the point when the addition of dilute sulfuric acid is completed, or by kneading with water. May be added at the stage of starting the process and before the start of the addition of dilute sulfuric acid. Further, lignin dispersed in water or dilute dilute sulfuric acid may be added at any one of the above time points.

  As lignin, for example, Sun Extract P252 (sodium lignin sulfonate), vaniol (modified sodium lignin sulfonate), vanillex (partially desulfonated sodium) or Pearl Rex NP (high molecular weight lignin sulfone) manufactured by Nippon Paper Chemicals Co., Ltd. Acid sodium) (above, all are trade names), Vanperser A (sodium salt of modified oxylignin) manufactured by Borregaard LignoTech, or Vanisserse HT-1 (highly modified sodium lignin sulfonate) (all are trade names) However, it is not limited to these.

  As described above, the amount of lignin added is 0.03 parts by mass or more with 100 parts by mass of lead contained in the lead powder. When the amount of lignin added exceeds 0.80 parts by mass, for example, 1.0 parts by mass, the capacity of the lead storage battery tends to decrease as shown in the examples described later. The upper limit is preferably 0.80 parts by mass or less when the lead contained in the lead powder is 100 parts by mass.

  And according to the 1st Embodiment of this invention, the process which temperature exceeds 65 degreeC is included in the aging drying process of the positive electrode plate for lead acid batteries. More preferably, a stage of 67 ° C. or higher is included. Such an expression includes a stage of raising the temperature from 40 ° C. to 65 ° C., which is a ripening temperature when moving from the aging step to the drying step. This is because it is practically impossible.

  Then, in the lead powder as a raw material of the positive electrode paste, or at each stage in the middle of the production of the positive electrode paste, by adding the above amount of lignin, coarse tetrabasic during the aging and drying process Formation of lead sulfate crystals is suppressed, and as a result, a high capacity positive electrode plate for a lead storage battery can be obtained. And, by combining the positive electrode plate for a lead storage battery obtained by the present invention with a known negative electrode plate and a separator and assembling the lead storage battery by a known method, the time required for production of a high capacity lead storage battery is shortened. There is a remarkable effect that it can be obtained.

(Second Embodiment)
Next, the manufacturing method of the positive electrode plate for lead acid batteries by the 2nd Embodiment of this invention, the manufacturing method of lead acid batteries, and a lead acid battery using the same are demonstrated.

  In the second embodiment of the present invention, instead of adding lignin in at least one of the stages in the production of the lead powder or the positive electrode paste in the first embodiment of the present invention described above, A formaldehyde condensate (hereinafter referred to as condensate) of bisphenols and sulfites or amino acids is added in at least one stage in the lead powder or each stage during the production of the positive electrode paste. However, the amount of the condensate added to the lead powder is 0.01% by mass or more with respect to 100 parts by mass of lead in the lead powder, unlike the various lignins shown in the first embodiment.

  Moreover, it is preferable that the upper limit of the said condensate shall be 0.8 mass part or less with respect to 100 mass parts of lead in lead powder for the same reason as what was shown in 1st Embodiment.

  In the first embodiment of the present invention and the second embodiment of the present invention, whether the additive to lead powder is lignin, or a formaldehyde condensate of bisphenols and sulfites or amino acids. It ’s the difference, and everything else remains the same.

  According to the second embodiment of the present invention, as in the first embodiment of the present invention described above, when the positive electrode plate of the lead storage battery is aged and dried, in particular, even if the temperature in the drying process is set to 65 ° C. or higher, the lead Since the production of coarse tetrabasic lead sulfate, which causes a reduction in the capacity of the storage battery, is significantly suppressed, a high capacity positive electrode plate for a lead storage battery can be obtained while significantly reducing the time required for the aging and drying process. Can do.

  The upper limit of the temperature in the drying step is 110 ° C. or less, preferably 100 ° C. or less, more preferably less than 100 ° C., for example 98 ° C. or less, for the same reason as described in the first embodiment. Moreover, the temperature in a drying process includes the stage of 65 degreeC or more, More preferably, 67 degreeC or more. As described in the first embodiment, such a representation includes a stage of raising the temperature from 40 ° C. to 65 ° C., which is an aging temperature, when the aging process is shifted to the drying process. Because of.

  As the formaldehyde condensate of bisphenols and sulfites or amino acids used in the second embodiment of the present invention, for example, Bispaz P121, P125 and P215 (trade names) manufactured by Nippon Paper Chemical Co., Ltd. are used. Can do. In addition, as an addition point of these additives, lead powder may be added at a stage before the start of mixing of water and dilute sulfuric acid or dilute sulfuric acid. The kneading may be added at the time when kneading is started and before the addition of dilute sulfuric acid is started. Further, a product obtained by dispersing a formaldehyde condensate of bisphenols and sulfites or amino acids in water or very dilute dilute sulfuric acid may be added at any one of the above time points.

  Then, a lead storage battery is assembled by combining a positive electrode plate for a lead storage battery according to the present invention, a known negative electrode plate, and a separator by a known method, thereby obtaining a high capacity lead storage battery with a reduced production time. It has a remarkable effect of being able to.

  Next, the effect of the present invention will be described with reference to examples.

  The lignin shown in the first embodiment or the bisphenols and sulfites or formaldehyde condensates of amino acids shown in the second embodiment were added to the lead powder by the ball mill method in various addition amounts. In addition, lead powder is PbO which has a tetragonal structure called 75 mass% PbO (red-PbO (R-PbO), and is used for active materials for lead storage batteries such as Barton pot method lead powder and ball mill method lead powder. PbO contained in commercially produced lead powder) and the remaining 25% by mass is composed of metal Pb.

  As the lignin, a partially desulfurized sodium lignin sulfonate powder, which is Vanillex (trade name) manufactured by Nippon Paper Chemicals Co., Ltd., which is shown in the first embodiment, is called Vanillex N among them. In addition, as a formaldehyde condensate of bisphenols and sulfites or amino acids, powder of Bisperz P215 (trade name) manufactured by Nippon Paper Chemical Co., Ltd. as shown in the second embodiment was added.

These lead powder added with various addition amounts of Vanillex N or Bisperz P215, and for comparison, lead powder without addition of these additives, water and dilute sulfuric acid (density 1.300 g / cm ^{3 at} 20 ° C.) The various positive electrode pastes were prepared by mixing with the above. Next, these various positive electrode pastes were filled in an expanded lattice body made of a Pb-0.06 mass% Ca-1.60 mass% Sn alloy to obtain a positive electrode plate. The filling amount of the positive electrode paste was finely adjusted so that the amount of lead contained in the positive electrode paste filled in one positive electrode plate was constant in each electrode plate. In addition, the thickness of each positive electrode plate including the expanded lattice after finely adjusting the positive electrode paste filling amount in this way is 2.0 ± 0.07 mm, and is not significantly affected by the additive amount. It was. In addition, aging drying was performed in a state in which thin paper called paste paper was pasted on both surfaces of the positive electrode plate, and in this state, 60 positive electrodes were stacked together (ie, in a stacked state).

  The various positive electrode plates using these various positive electrode pastes are aged in a humidified and heated state of 40 ° C. and 85 RH% for 12 hours, and then dried by changing the temperature to perform an aging drying step. I did it. The positive electrode plate being dried was sampled at intervals of 0.5 hours, the water content contained in the positive electrode paste was measured, and the water content in the positive electrode paste was less than 3.0% by mass. The aging drying process was completed.

  Tables 2 and 3 show the addition amount of Vanillex N or Bisperz P215 in the lead powder, the temperature conditions in the drying step, and the time required for drying. In addition, both the addition amount of Vanillex N and Bisper P215 were shown by the mass part when the mass of the lead contained in lead powder was 100 mass parts.

  From Table 2 and Table 3, the drying temperature is 65 ° C. or more and the drying time is drastically shortened to 67 ° C. regardless of the presence or absence of addition of Vanillex N or Bisperz P215 to the lead powder and the amount of addition. With the above, it is shortened more rapidly. When switching from aging (40 ° C.) to drying (60 ° C. to 100 ° C.), the temperature is raised from the aging temperature (40 ° C.) to the drying temperature (60 ° C. to 100 ° C.) for 0.5 hours to 1.5 hours. It took time, and thereafter, the temperature was maintained at the set drying temperature until the end of drying. The temperature rise time during the transition from aging to drying depends on the amount of heat supplied per hour in the aging drying oven, so if a larger capacity drying oven is used, the temperature raising time can be further shortened. It becomes.

  Next, an unformed active material is sampled from each positive electrode plate shown in Table 2 and Table 3, and each unformed active material is converted into tetrabasic lead sulfate ( Hereinafter, qualitative analysis of 4BS) was performed. As the X-ray diffractometer, RINT2200 manufactured by Rigaku Co., Ltd. is used. As the X-ray generator, Cu-Kα rays generated at an X-ray tube voltage of 40 kV and an X-ray tube current of 40 mA are used. The peak intensity I (4BS) of the peak (2θ = 27.6 °) that appears characteristically in 4BS when the measurement angle 2θ is scanned between 20 ° and 40 ° and PbO (in this example, R The ratio K (= I (4BS) / I (R-PbO)) of the peak intensity I (R-PbO) of the peak (2θ = 28.7 °) characteristically appearing in -PbO) was determined.

  Furthermore, using each positive electrode plate shown in Table 2 and Table 3 and a known negative electrode plate, 55D23 having a nominal voltage of 12 V and a rated capacity of 48 Ah of 48 Ah as shown in JIS D5301: 2006 (lead storage battery for starting). A battery (hereinafter referred to as a battery) was prepared.

  Each of these batteries was the same as the negative electrode plate, the separator, the electrolytic solution, and other component materials constituting the battery except that the positive electrode plate was different. As for the negative electrode plate, water and dilute sulfuric acid are added to the same ball mill type lead powder as previously used for the positive electrode plate, with the addition of vanillax N, barium sulfate and carbon as previously known. The negative electrode paste obtained by mixing was filled in an expanded lattice body made of a Pb-0.07 mass% Ca-0.25 mass% Sn alloy, and aged and dried.

And 5 sheets of each positive electrode plate and 6 said common negative electrode plates were combined, and it was set as the single cell. In addition, as a separator, the negative electrode plate is accommodated in the thing processed into the bag shape of the well-known microporous polyethylene separator (Including polyethylene, a silica, carbon, and the oil as an antioxidant). Then, in the following, six of these single cells are housed in the cell chamber of the battery case by a known method, each cell is connected in series, the battery case is covered, terminal welding is performed, and the battery is connected. After assembling and injecting dilute sulfuric acid electrolyte into each cell, conducting energization, and after energizing, adjusting the electrolyte density (converted to 20 ° C) of each battery to 1.285 g / cm ³ Was set at a position 30 mm above the upper surfaces of the positive and negative straps (not shown).

  And after leaving each battery in 25 degreeC atmosphere, it discharged to the discharge end voltage 10.5V with the constant current of 9.6A in the same 25 degreeC atmosphere, and calculated | required the 5-hour rate discharge capacity of each battery. .

  In the X-ray diffraction of the unformed active material of each positive electrode plate, the peak intensity I (4BS) of a peak (2θ = 27.6 °) characteristically appearing in 4BS and PbO (in this example, R-PbO) The ratio K (= I (4BS) / I (R-PbO)) of the peak intensity I (R-PbO) of the peak (2θ = 28.7 °) characteristically shown in FIG. Tables 4 and 5 show the measurement results of the 5-hour rate capacity of each battery. Table 4 shows the results of adding no additive to lead powder or adding only Vanillex N as an additive, and Table 5 shows the result of adding only Bispraz P215 as an additive to lead powder. Indicated. Each battery symbol was the same as the symbol of the positive electrode plate used.

  As shown in Tables 4 and 5, with respect to the batteries A1 to A6 in which neither Vanillex N nor Bisper P215 was added to the positive electrode paste, the battery A1 having a drying temperature of 60 ° C. contained tetrabasic sulfuric acid in the positive electrode plate. Lead cannot be detected, and it can be seen that the battery capacity has a margin with respect to the rated capacity (48 Ah). However, this specification is longer than other types having a drying time of 65 ° C. or higher and is extremely inferior in productivity.

  Next, when the drying temperature is set to 65 ° C., the production of tetrabasic lead is confirmed in the positive electrode, and the battery capacity is also reduced as compared with A1. Further, when the drying temperature is increased from 67 ° C to 100 ° C, the drying time is shortened, but the production of tetrabasic lead is promoted, and at the same time, the battery capacity is reduced. As a result, the capacity of 48 Ah was interrupted.

  On the other hand, when Vanillex N is added in an amount of 0.03 to 0.8 parts by mass with respect to 100 parts by mass of lead in the lead powder, tetrabasic lead sulfate cannot be detected even when the drying temperature is 65 ° C. or higher. The battery capacity was sufficient for the rated value. However, in the example where the drying temperature is 100 ° C., although the battery capacity is equal to or higher than the rated value, a tendency to decrease as compared with the case where the drying temperature is 65 ° C. to 98 ° C. was recognized. Therefore, the drying temperature is preferably less than 100 ° C., for example, 98 ° C. or less as in the examples. In addition, such a drying temperature can suppress cracks in the active material itself, or a gap between the active material and the lattice, and can significantly shorten the time until the end of drying. Can be obtained.

  When the drying temperature is set to 100 ° C., cracks in the active material and generation of gaps between the active material and the lattice are remarkable compared with those having a drying temperature of 98 ° C. or less, which decreases the positive electrode capacity. It is estimated that the battery capacity has decreased.

  On the other hand, the addition of 1.0 part by mass of Vanillex N to 100 parts by mass of lead in the lead powder, although tetrabasic lead sulfate cannot be detected even when the drying temperature is 65 ° C. or higher, the battery capacity is Compared with what added amount was 0.03 mass part-0.8 mass part or less, it was falling clearly. This is presumed that the conductive network between the active materials was inhibited due to the excessive addition amount of Vanillex N, and / or the amount of chemical electricity was consumed by the oxidation reaction of Vanillex N, resulting in a decrease in capacity.

  Next, regarding the battery to which Bisperz P215 was added, the same behavior as the battery to which Vanillex N was added was shown. Like Vanillex N, for the reasons described above, the addition amount of Bispraz P215 is preferably 0.01 parts by mass to 0.8 parts by mass with respect to 100 parts by mass of lead in the lead powder. In particular, when comparing Vispers P215 and Vanillex N, the addition of Bispurs P215 in the drying temperature range of 65-98 ° C is superior in capacity characteristics compared to the battery added with Vanillex N. The most favorable results were obtained in the examples. In addition, the time to completion of drying is not changed compared to Vanillex N, and even when aging drying at a high temperature in a short time, the formation of tetrabasic lead sulfate is suppressed. As a result, aging drying is performed. The remarkable effect of obtaining a high-capacity lead-acid battery while significantly shortening the time required was obtained.

  In this embodiment, an example in which powdered vanillex N or bispraz P215 is added to lead powder and then mixed with water and dilute sulfuric acid has been described. The effect was obtained. Further, the effect of the present invention was obtained even when the additive was added after mixing with water or after mixing with dilute sulfuric acid. In addition, when adding an additive to mixing with dilute sulfuric acid, in order to improve the dispersibility of an additive, it is preferable to continue mixing after adding an additive.

  Further, in this example, an example in which powdery Vanillex N or Bisper P215 was added was shown. However, these powdery additives are previously dispersed in a solvent such as water, and at any stage of paste mixing. Even if it adds to a mixture, the effect of this invention can be acquired. Further, the present invention is not limited to Vanillex N or Bispaz P215, and by using the various lignins and condensates shown in the first and second embodiments of the present invention, the same effects of the present invention as shown in the examples can be obtained. Obtainable.

  As described above, according to the present invention, it is possible to shorten the time required for the ripening drying process, which has been extremely long in the past, and to generate when the drying temperature is 65 ° C. or higher in order to shorten the time required for the process. Since the growth of coarse tetrabasic lead sulfate crystals can be suppressed, it is possible to achieve both the shortening of the time required for the aging drying process and the high capacity of the battery, both of which have been impossible in the past. Play.

  The present invention is also preferable in that it does not require a special apparatus such as a decompression furnace or a decompression apparatus as disclosed in Patent Document 1, and can be handled by a conventional aging drying furnace.

  The present invention can be applied to lead storage batteries for various uses, including the liquid lead and control valve types, including the solid lead storage battery for starting in the embodiments.

Claims (4)

A method for producing a positive electrode plate for a lead-acid battery, in which lead powder is mixed with dilute sulfuric acid or a paste-like active material kneaded with water and dilute sulfuric acid and then aged and dried, which is included in the lead powder When the lead mass to be added is 100 parts by mass, 0.03 parts by mass and 0.8 parts by mass or less of lignin is added to the lead powder, and in the aging drying step, the temperature of the positive electrode plate is adjusted. The manufacturing method of the positive electrode plate for lead acid batteries characterized by including the process made into 65 degreeC or more. A method for producing a positive electrode plate for a lead-acid battery, in which lead powder is mixed with dilute sulfuric acid or a paste-like active material kneaded with water and dilute sulfuric acid and then aged and dried, which is included in the lead powder When the lead mass to be added is 100 parts by mass, a bisphenol and a sulfite or a formaldehyde condensate of amino acids in an amount of 0.01 parts by mass or more and 0.8 parts by mass or less are added to the lead powder, and the aging The method for producing a positive electrode plate for a lead storage battery, comprising a step of setting the temperature of the positive electrode plate to 65 ° C. or higher in the drying step. A method for producing a lead storage battery, comprising combining the positive electrode plate obtained in any one of claims 1 and 2 and a negative electrode plate into a lead storage battery. The lead acid battery obtained by Claim 3.