JP2010170939A - Lead storage battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a long-life lead storage battery capable of restraining stratification of an electrolyte since a Pb-Ca-Sn-Ba system lead-based alloy board is used and a positive electrode plate is stored in a bag-shaped separator and ribs with thickness of 3.0-7.0 mm are arranged on an inner wall and/or a partition wall of a battery case. <P>SOLUTION: In the lead storage battery wherein the Pb-Ca-Sn-Ba system lead-based alloy board is used for a positive electrode and a negative electrode plate and a positive electrode plate stored in the bag-shaped separator are set up to be a group of electrode plates by alternately laminating these and at least one of an end plate of the group of electrode plates is set up to be a negative electrode plate and the group of electrode plates is stored in the battery case and the electrolyte is poured into the battery case while chemical conversion is carried out, the ribs extending to a horizontal direction against a laminated direction of at least the group of electrode plates are arranged in the inner wall and the partition wall forming the battery case, and height of the ribs is set up to be 3.0-7.0 mm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a lead storage battery including a positive electrode plate housed in a bag-shaped separator and provided with ribs on the inner wall and partition wall of a battery case, and more particularly to an improvement of the lead storage battery for the purpose of improving cycle life characteristics.

Liquid lead-acid batteries are used for vehicle engine starting and backup power supplies. Among them, since the liquid lead-acid storage battery for start-up has different start-up frequencies, electrical component loads, etc., the deterioration modes leading to the battery life are different. As an example, an idling stop start (ISS) in which start-stop is frequently repeated for energy saving and environmental measures is performed in business vehicles such as delivery vehicles and delivery vehicles (taxi, bus, etc.). In particular, urban vehicles have many shops and narrow intervals, so the travel distance is short, and frequent start and stop are repeated. In such a vehicle, charging by an alternator is not sufficient, and a liquid lead acid battery is used on the discharge side.

The idle stop start (ISS) has a problem that a stratification phenomenon is likely to occur because the deep discharge and charging are repeated so as not to be compared with the conventional SLI (starting / lighting / ignition) application. The charge prevention system has a problem that the stratification phenomenon is difficult to be solved because the electrolyte solution is not stirred by a large amount of gas generated during overcharge.

The stratification phenomenon is a phenomenon in which sulfuric acid generated during charging settles in the lower part of the battery cell, and the electrolytic solution in the battery cell becomes thicker in the lower part and thinner at the upper part. The sulfation in which lead sulfate accumulates at the lower part of the electrode plate progresses due to a decrease in charging efficiency, and a concentration battery is formed, and self-discharge proceeds rapidly. As a result, the life of the lead storage battery is significantly shortened.

Therefore, as a method for suppressing the stratification phenomenon and improving the life characteristics of the lead-acid battery, the separator is a sheet bent in a V shape, and the negative electrode plate is accommodated inside the sheet, and the left and right side edges are opened. As a lead storage battery used for a method of covering the left and right side edges of the positive electrode plate and the left and right side edges of the positive electrode plate (Patent Document 1) or a delivery vehicle or the like, Pb-Ca- Using Sn—Ba alloy, positive electrode plates and negative electrode plates housed in a bag-like separator are alternately laminated to form an electrode plate group, and at least one of the end plates of the electrode plate group is used as a negative electrode plate, and the electrode plate group A lead storage battery (Non-Patent Document 1) or the like is proposed in which a battery is stored in a battery case and an electrolytic solution is injected into the battery case to form a chemical.

JP 2002-270216 A

FB Technical News NO. 63 (2007.11)

  In the method described in Patent Document 1, the electrode plate is accommodated in a bag-like separator, and the bag-like separator is provided with a plurality of longitudinally parallel ribs to prevent stratification and charge / discharge cycle life. It is possible to provide a lead storage battery having excellent characteristics.

However, in general, the Pb—Ca—Sn alloy substrate has less self-discharge and less electrolyte reduction, while the substrate is easily softened, while the Pb—Sb alloy substrate is less likely to be softened. There is a lot of self-discharge, and there is a lot of electrolyte reduction. Therefore, in Patent Document 1 in which a Pb—Ca—Sn alloy substrate is used as a substrate, it is considered that the cause of lifetime is not due to lattice corrosion but due to softening, and it is desirable to improve the lifetime of the alloy substrate itself. It is. In addition, there is no mention of the height and shape of the ribs. Depending on the height of the ribs, it is considered that there is almost no effect of suppressing the stratification phenomenon. Furthermore, depending on the shape of the ribs (the tip is sharp) There is a risk of damaging the separator.

Moreover, although the method described in Non-Patent Document 1 uses a Pb—Ca—Sn—Ba high corrosion resistance alloy for the positive electrode plate, and further uses a bag-like separator, it is said to have excellent long life and liquid reduction characteristics. However, little consideration has been given to the suppression of the oxygen gas absorption reaction and stratification phenomenon, and considering the outflow of gas and the stratification phenomenon, a gap may be provided between the electrode plate group and the inner wall and partition wall of the battery case. Therefore, it does not lead to a long-life lead-acid battery that satisfies the current market.

In addition, as a method of providing a rib between the electrode plate and the battery case, for example, there is JP-A-2002-260717, which is that at least one of the electrode plates located at both ends of the electrode plate group is a negative electrode plate. , A control valve type lead-acid battery (only the electrolyte is immersed in the lower part of the negative electrode plate), characterized in that a space is formed between the negative electrode plate and the battery case wall. It suppresses dendrite shorts, improves oxygen absorption capacity and rapid discharge characteristics, and does not consider stratification. That is, the stratification phenomenon is caused by the difference in concentration between the upper and lower portions of the electrolytic solution as described above, and hardly causes a problem in a control valve type lead storage battery in which almost no electrolytic solution exists.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a lead-acid battery that suppresses the stratification phenomenon and has a long life.

  The present invention uses a Pb-Ca-Sn-Ba-based lead-based alloy substrate for the positive electrode, and alternately laminates the negative electrode plate and the positive electrode plate housed in the bag-shaped separator to form an electrode plate group. In a lead storage battery in which at least one of the end plates is a negative electrode plate, the electrode plate group is housed in a battery case, and an electrolytic solution is injected into the battery case to perform conversion, an inner wall and a partition wall constituting the battery case Among them, at least ribs protruding in the horizontal direction with respect to the stacking direction of the electrode plate group are provided, and the height of the ribs is set to 3.0 to 7.0 mm.

The lead-acid battery of the present invention uses a Pb—Ca—Sn—Ba-based lead-based alloy substrate, houses a positive electrode plate in a bag-like separator, and laminates at least an electrode plate group among an inner wall and a partition wall constituting a battery case. By providing a rib of 3.0 to 7.0 mm in the horizontal direction with respect to the direction, it is possible to suppress a decrease in the stratification of the electrolytic solution and to provide a long-life lead-acid battery.
Moreover, since the active material can be prevented from falling off by storing the positive electrode plate in a bag-like separator, a short circuit between the electrode plates can be prevented, and a Pb—Ca—Sn—Ba based lead-based alloy substrate is used for the positive electrode. By using it, it is possible to improve the mechanical strength and reduce the amount of liquid reduction.

It is a perspective view of the electrode group which accommodated the positive electrode plate in the bag-shaped separator which shows one Example of this invention. It is a perspective view of a lead acid battery showing one example of the present invention. FIG. 3 is a sectional view taken along line AA ′ of FIG. 2 showing an embodiment of the present invention. FIG. 3 is a cross-sectional view corresponding to the line AA ′ of FIG. 2, showing another embodiment of the present invention.

  FIG. 1 is a perspective view of an electrode plate group 1 in which a positive electrode plate 2 is accommodated in a bag-like separator 4 according to an embodiment of the present invention. Reference numeral 2 denotes a positive electrode plate housed in a bag-like separator 4 made of synthetic resin such as polyethylene, and 3 denotes a negative electrode plate. Both end portions of the bag-like separator 4 are welded by a heat seal or an adhesive, or are joined by a mechanical seal. The positive electrode plate 2 and the negative electrode plate 3 are separated by the bag-like separator 4, and a predetermined number of the positive electrode plates 2 and the negative electrode plates 3 are alternately stacked to constitute the electrode plate group 1. The same polarity ears 2 ′ and 3 ′ of the positive and negative electrode plates 2 and 3 are welded by a positive strap 5 and a negative strap 6, respectively. The electrode plate group 1 formed by alternately combining the positive electrode plates 2 and the negative electrode plates 3 was inserted into a 6-cell monoblock battery case 7 to obtain a lead storage battery shown in FIG. In FIG. 2, 9 is a lid, 10 is a liquid spout, and 11 and 12 are a positive terminal and a negative terminal, respectively.

  FIG. 3 is a cross-sectional view taken along line AA ′ of the lead storage battery shown in FIG. 2 showing an embodiment of the present invention. As shown in FIG. 3, a plurality of ribs 8 having a desired shape are provided on the inner wall 71 and the partition wall 72 of the battery case 7 so as to be perpendicular to the inner wall 71 and the partition wall 72 by integral formation when the battery case is formed. The ribs 8 have a rectangular shape, each having a desired height h and width W, and the ribs 8 are formed at a constant interval. As described above, 2 is a positive electrode plate and is accommodated in a bag-like separator 4 made of a synthetic resin such as polyethylene, and 3 is a negative electrode plate, which are alternately stacked to constitute the electrode plate group 1. .

Here, in the present invention, among the inner wall 71 and the partition wall 72 constituting the battery case 7, at least the rib 8 protruding in the horizontal direction with respect to the stacking direction of the electrode plate group 1 is provided. This is because the end plate of the electrode plate group 1 and the battery case 1 come into contact with each other to prevent the suppression of the stratification phenomenon.

In consideration of oxygen gas absorption reaction and prevention of stratification, for example, a plurality of ribs 8 having a width of about 5.0 mm are preferably provided at intervals of about 5.0 to 10.0 mm. If the width W of the rib is narrow, that is, if the rib is thin and linear (1.0 mm or less), the bag-shaped separator may be damaged, and if the rib interval is wide (20.0 mm or more), the electrode plate There is a possibility that the escape of gas generated from the gas will worsen, and the effect of preventing stratification may be reduced. Accordingly, the rib width W is preferably 5.0 to 10.0 mm.

Moreover, it is preferable that the total length of the ribs in the battery case height direction is not less than 50% and not more than 100% in the height direction of the positive electrode plate or the negative electrode plate constituting the electrode plate group. When the total length of the ribs is short, there may occur a portion where the end plate of the electrode plate group and the battery case or / and the partition wall come into contact with each other, and there is a possibility that stratification cannot be prevented. The total length in the present invention is good even if one rib is continuously protruding and formed discontinuously. In the case of discontinuity, the total length of each rib is added. However, it is preferably 50% or more and 100% or less in the height direction of the positive electrode plate or the negative electrode plate constituting the electrode plate group.

The rib height h is preferably 3.0 to 7.0 mm. When the height of the rib is less than 3.0 mm, the effect is hardly seen. Conversely, when it exceeds 7.0 mm, it becomes difficult to produce a lead-acid battery having the same volume and capacity, and the dropped active life. The substance is likely to be electrodeposited on the upper part of the electrode plate group due to the convection of the electrolyte, and there is a risk of short circuit.

More preferably, by setting the rib height h to 4.0 to 6.0 mm, it is possible to prevent stratification of the electrolytic solution and to suppress a decrease in life due to electrodeposition on the upper part of the electrode plate group.

In addition, the shape of the rib is not particularly limited, but in consideration of damage such as a bag-like separator, the shape of the rib is not sharp, such as an arc shape, a semi-track shape, a square shape, or a trapezoid shape. It is preferable.

Moreover, it is preferable that at least one of the ribs provided on the inner wall or / and the partition wall of the battery case is a surface facing the negative electrode plate, that is, at least one is a negative electrode end plate. This suppresses the deformation of the negative electrode end plate during the use period, and by ensuring a space for gas diffusion between the negative electrode end plate and the inner wall of the battery case, the negative electrode end plate is also involved in the gas absorption reaction. This is because an appropriate oxygen gas absorption reaction occurs as a whole.

In the present invention, the positive electrode plate is accommodated in the bag-shaped separator in order to prevent internal short circuit at the bottom edge and side edge due to the dropping of the active material from the positive electrode plate and the generation of dendrite from the negative electrode plate. .

Conventionally, there has been a problem that the separator is damaged due to the elongation of the positive electrode substrate, and eventually leads to an internal short circuit. The problem can be solved.

In the Pb—Ca—Sn—Ba based lead-based alloy substrate in the present invention, calcium is 0.02 mass% or more and less than 0.05 mass%, tin is 0.4 mass% or more and 4.0 mass% or less, aluminum The alloy substrate is preferably 0.04 mass% or less, barium is 0.002 mass% or more and 0.014 mass% or less, and the balance is composed of lead and inevitable components.

Here, the addition of calcium is to improve the mechanical strength. When the amount of calcium added is less than 0.02% by mass, the effect is small, and the amount of calcium added is 0.05% by mass or more. It is difficult to obtain a good cast product at a low casting temperature, and conversely, when the casting temperature is increased, oxidation occurs and the loss of calcium increases. Also, tin is added to improve the hot water flow and mechanical strength of the alloy. When the amount of tin added is less than 0.4% by mass, the effect is small and exceeds 4.0% by mass. In this case, the crystal grains become coarse and intergranular corrosion proceeds. Aluminum is added to prevent calcium loss due to oxidation of the molten metal and improve mechanical strength. When the amount of aluminum exceeds 0.04% by weight, it tends to precipitate as dross. Further, the addition of barium is to improve the mechanical strength. If the barium content is less than 0.002% by weight, the above effect is not sufficient. Not so much.

Furthermore, 0.005% by mass or more and 0.07% by mass or less silver, 0.01% by mass or more and 0.01% by mass or less bismuth, 0.001% by mass or more and 0.05% by mass or more on the lead-based alloy substrate. At least one selected from thallium of mass% or less, and / or 0.01 mass%
The corrosion resistance can be further improved by adding at least one selected from copper, potassium, lithium, magnesium, sodium, phosphorus, antimony, selenium, and tellurium in an amount of 0.1% by mass or less.

  Hereinafter, the present invention will be specifically described by way of examples.

  A Pb-Ca alloy containing 0.04 mass% Ca, 1.0 mass% Sn, 0.015 mass% Al, and 0.008 mass% Ba, with the balance being Pb and inevitable impurities and having excellent corrosion resistance and gloss resistance. Was cast into a grid plate at a rate of 15 sheets per minute, and then the grid plate was heat treated (age hardening) at 120 ° C. for 3 hours to produce a positive electrode substrate.

On the other hand, antimony pentoxide (Sb2O5) was added to the lead powder for the positive electrode (active material) at 350 ppm in terms of metal antimony and mixed, and 10 parts by weight of ion-exchanged water was added to the mixed powder, followed by a specific gravity of 1.27. A positive electrode paste having a cup density of 140 g / 2 in 3 is prepared by adding 10 parts by weight of dilute sulfuric acid to prepare a positive electrode paste.
Then, it was aged for 24 hours in an atmosphere with a humidity of 95% and dried to produce a positive electrode unformed sheet.

Next, on the five positive electrode unformed plates, a plurality of negative electrode unformed plates (electrode plate number configuration: the same number) produced by a known method are alternately stacked, and the same electrode plates of this laminate are COS. The electrode plate group was welded by the method. The positive electrode non-formed sheet was prepared by folding a microporous sheet mainly composed of a synthetic resin sheet made of polyethylene having a thickness of 0.25 mm into two in a substantially V shape and welding the left and right side edges. It was stored in a synthetic resin bag-like separator. Next, the electrode plate group is inserted into a battery case made of polypropylene (total height: 225 mm, width: 170 mm, length: 260 mm), the battery case is covered with a heat seal, and an electrolyte is injected from the liquid port of the cover. Then, the battery case after the liquid injection was put into a 40 ° C. water tank, overcharged by 200% of the theoretical capacity to form a battery case, and a D23 size 12V liquid lead acid battery having a 5-hour rate capacity of 50 Ah was manufactured.

Of the inner wall and partition wall of the battery case, a plurality of ribs are provided at the time of battery case forming only in the stacking direction of the electrode plate group (see FIG. 3). The square shape was 0 mm, and the rib interval was 5.0 mm.
The total length of the ribs in the battery case height direction was 100 mm (Invention 1).

  A D23 size 12V liquid lead-acid battery having a 5-hour rate capacity of 50 Ah was manufactured in the same manner as in Example 1 except that the height of the rib was set to 4.0 mm (Invention 2).

A D23 size 12V liquid lead acid battery having a 5-hour rate capacity of 50 Ah was manufactured in the same manner as in Example 1 except that the rib height was set to 5.0 mm (Invention 3).

A D23 size 12V liquid lead-acid battery having a 5-hour rate capacity of 50 Ah was manufactured in the same manner as in Example 1 except that the rib height was 6.0 mm (Invention 4).

A D23 size 12V liquid lead acid battery having a 5-hour capacity of 50 Ah was manufactured in the same manner as in Example 1 except that the rib height was 7.0 mm (Invention 5).

A D23 size 12V liquid lead acid battery with a 5-hour capacity of 50 Ah is manufactured in the same manner as in Example 1 except that a plurality of ribs are provided on the inner wall and partition wall of the battery case when the battery case is formed (see FIG. 4). (Invention 6).

A plurality of ribs are provided on the inner wall and partition wall of the battery case at the time of forming the battery case (see FIG. 4), and the 5-hour rate capacity is 50 Ah as in Example 1 except that the height of the ribs is 7.0 mm. A D23 size 12V liquid lead acid battery was manufactured (Invention 7).

D23 size with a 5-hour rate capacity of 50 Ah as in Example 1 except that the height of the rib is 3.0 mm and the number of plates is 5 positive plates, 6 negative plates and 1 negative plate. Of 12V liquid type lead-acid battery (Invention 8).

D23 size with a 5-hour rate capacity of 50 Ah as in Example 1 except that the height of the rib is 5.0 mm and the number of plates is 5 positive plates, 6 negative plates and 1 negative plate. 12V liquid lead acid battery (Invention 9).

D23 size with a 5-hour capacity of 50 Ah, as in Example 1, except that the rib height is 7.0 mm and the number of electrode plates is 5 positive plates, 6 negative plates and 1 negative plate. Of 12V liquid type lead acid battery (Invention 10).

A plurality of ribs are provided on the inner wall and partition wall of the battery case when forming the battery case (see FIG. 4), the height of the ribs is 3.0 mm, the number of electrode plates is 5 positive plates, 6 negative plates and 6 negative electrodes A D23 size 12V liquid lead acid battery having a 5-hour rate capacity of 50 Ah was manufactured in the same manner as in Example 1 except that the number of plates was increased by one (Invention 11).

A plurality of ribs are provided on the inner wall and partition wall of the battery case when the battery case is formed (see FIG. 4), the height of the ribs is 7.0 mm, the number of electrode plates is 5 positive plates, 6 negative plates and the negative electrode A D23 size 12V liquid lead acid battery having a 5-hour rate capacity of 50 Ah was manufactured in the same manner as in Example 1 except that the number of plates was increased by one (Invention 12).

(Comparative Example 1)
A D23 size 12V liquid lead acid battery having a 5-hour capacity of 50 Ah was manufactured in the same manner as in Example 1 except that the rib height was 1.0 mm (Comparative Example 1).
(Comparative Example 2)
A D23 size 12V liquid lead acid battery having a 5-hour rate capacity of 50 Ah was manufactured in the same manner as in Example 1 except that the rib height was set to 2.0 mm (Comparative Example 2).
(Comparative Example 3)
A D23 size 12V liquid lead acid battery having a 5-hour capacity of 50 Ah was manufactured in the same manner as in Example 1 except that the rib height was 8.0 mm (Comparative Example 3).
(Comparative Example 4)
A D23 size 12V lead-acid battery with a 5-hour rate capacity of 50 Ah was manufactured in the same manner as in Example 1 except that the rib height was 9.0 mm (Comparative Example 4).
(Comparative Example 5)
D23 size with a 5-hour rate capacity of 50 Ah, as in Example 1, except that the height of the rib is 2.0 mm and the number of plates is 5 positive plates, 6 negative plates and 1 negative plate. 12V liquid lead acid battery was manufactured (Comparative Example 5).
(Comparative Example 6)
D23 size with a 5-hour rate capacity of 50 Ah, as in Example 1, except that the height of the ribs was 8.0 mm and the number of electrode plates was 5 positive plates, 6 negative plates and 1 negative plate. 12V liquid lead acid battery was manufactured (Comparative Example 6).
(Comparative Example 7)
D23 size with a 5-hour rate capacity of 50 Ah as in Example 1 except that the height of the rib was 3.0 mm, the number of plates was 6 positive plates, 5 negative plates and 1 positive plate were added. 12V liquid lead acid battery was manufactured (Comparative Example 7).
(Comparative Example 8)
D23 size with a 5-hour rate capacity of 50 Ah as in Example 1 except that the rib height is 5.0 mm and the number of electrode plates is 6 positive plates, 5 negative plates and 1 positive plate. 12V liquid lead acid battery was manufactured (Comparative Example 7).
(Comparative Example 9)
D23 size with a 5-hour capacity of 50 Ah, as in Example 1, except that the rib height is 7.0 mm, the number of electrode plates is 6 positive plates, 5 negative plates and 1 positive plate. 12V liquid lead acid battery was manufactured (Comparative Example 9).
(Comparative Example 10)
A D23 size 12V liquid lead acid battery with a 5-hour rate capacity of 50 Ah was obtained in the same manner as in Example 1 except that the height of the rib was 2.0 mm and the negative electrode unformed plate was housed in a synthetic resin bag-like separator. Manufactured (Comparative Example 10).
(Comparative Example 11)
A D23 size 12V liquid lead-acid battery with a 5-hour rate capacity of 50 Ah is the same as in Example 1 except that the height of the rib is 3.0 mm and the negative electrode unformed plate is housed in a synthetic resin bag-like separator. Manufactured (Comparative Example 11).
(Comparative Example 12)
A D23 size 12V liquid lead acid battery with a 5-hour rate capacity of 50 Ah was obtained in the same manner as in Example 1 except that the rib height was 5.0 mm and the negative electrode unformed plate was housed in a synthetic resin bag-like separator. Manufactured (Comparative Example 12).
(Comparative Example 13)
A D23 size 12V liquid lead acid battery with a 5-hour rate capacity of 50 Ah was obtained in the same manner as in Example 1 except that the height of the rib was 7.0 mm and the negative electrode unformed plate was housed in a synthetic resin bag-like separator. Manufactured (Comparative Example 13).
(Comparative Example 14)
A D23 size 12V liquid lead acid battery with a 5-hour rate capacity of 50 Ah was obtained in the same manner as in Example 1 except that the height of the rib was 8.0 mm and the negative electrode unformed plate was housed in a synthetic resin bag-like separator. Manufactured (Comparative Example 14).
(Comparative Example 15)
The height of the rib is 2.0 mm, the negative electrode unformed plate is housed in a synthetic resin bag-like separator, and the number of electrode plates is 5 positive plates, 6 negative plates and 1 negative plate. In the same manner as in Example 1, a D23 size 12 V liquid lead acid battery having a 5-hour capacity of 50 Ah was manufactured (Comparative Example 15).
(Comparative Example 16)
The height of the rib is 3.0 mm, the negative electrode unformed plate is housed in a synthetic resin bag-like separator, and the number of electrode plates is 5 positive plates, 6 negative plates and 1 negative plate. In the same manner as in Example 1, a D23 size 12V liquid lead acid battery having a 5-hour capacity of 50 Ah was manufactured (Comparative Example 16).
(Comparative Example 17)
The height of the rib is 7.0 mm, the negative electrode unformed plate is housed in a synthetic resin bag-like separator, and the number of electrode plates is 5 positive plates, 6 negative plates and 1 negative plate. In the same manner as in Example 1, a D23 size 12V liquid lead acid battery having a 5-hour capacity of 50 Ah was manufactured (Comparative Example 17).
(Comparative Example 18)
The height of the rib is 8.0 mm, the negative electrode unformed plate is accommodated in a synthetic resin bag-like separator, and the number of electrode plates is 5 positive plates, 6 negative plates and 1 negative plate. In the same manner as in Example 1, a D23 size 12V liquid lead acid battery having a 5-hour capacity of 50 Ah was manufactured (Comparative Example 18).
(Comparative Example 19)
The height of the rib is 2.0 mm, the negative electrode non-formed plate is housed in a synthetic resin bag-like separator, and the number of electrode plates is 6 positive plates, 5 negative plates and 1 positive plate. In the same manner as in Example 1, a D23 size 12V liquid lead acid battery having a 5-hour capacity of 50 Ah was manufactured (Comparative Example 19).
(Comparative Example 20)
The height of the rib is set to 3.0 mm, the negative electrode unformed plate is accommodated in a synthetic resin bag-like separator, and the number of electrode plates is 6 positive plates, 5 negative plates and 1 positive plate. In the same manner as in Example 1, a D23 size 12V liquid lead acid battery having a 5-hour capacity of 50 Ah was manufactured (Comparative Example 20).
(Comparative Example 21)
The height of the rib is 7.0 mm, the negative electrode non-formed plate is housed in a synthetic resin bag-like separator, and the number of electrode plates is six positive plates, five negative plates and one positive plate. In the same manner as in Example 1, a D23 size 12V liquid lead acid battery having a 5-hour capacity of 50 Ah was manufactured (Comparative Example 21).
(Comparative Example 22)
The height of the rib is 8.0 mm, the negative electrode unformed plate is accommodated in a synthetic resin bag-like separator, and the number of electrode plates is 6 positive plates, 5 negative plates and 1 positive plate. In the same manner as in Example 1, a D23 size 12V liquid lead acid battery having a 5-hour capacity of 50 Ah was manufactured (Comparative Example 22).

(Conventional example)
The 5-hour rate capacity is 50 Ah as in Example 1 except that a Pb—Ca-based alloy substrate containing 0.06 mass% Ca and 1.0 mass% Sn, the balance being Pb and inevitable impurities is used, and no rib is provided. The D23 size 12V liquid lead acid battery was manufactured (conventional example).

Each liquid lead acid battery (Invention 1-12, Comparative Examples 1-22, Conventional Example) produced was subjected to a JIS light load test to examine the cycle life. Test condition is test temperature 80 ℃
, Discharge 25A x 4 minutes, charge 25A x 10 minutes CC / CV charge (constant current / constant voltage charge), judgment discharge at 356A every week, when the voltage at 30 seconds reaches 7.2V Was defined as the lifetime.

Table 1 shows the rib height of the battery case and the electrode plate (positive electrode plate or negative electrode plate) stored in the bag-shaped separator in each of the liquid lead-acid batteries produced (Examples 1 to 12, Comparative Examples 1 to 22, and conventional example). ), Number of electrode plates, life performance (number of cycles and ratio), confirmation of stratification, presence / absence of short circuit, amount of liquid reduction, and overall evaluation.
Here, the number of electrode plates is “the same number” when the number of the positive and negative electrode plates is the same when the positive electrode plate and the negative electrode plate are alternately laminated to form the electrode plate group, and one negative electrode plate. Many samples were described as “one negative electrode”, and one positive electrode plate was described as “one positive electrode”.
Moreover, the ratio in life performance represents the cycle life of each lead-acid battery as a ratio when the number of cycle lives in the conventional example is 100%.
In addition, the stratification phenomenon was confirmed. To confirm the stratification phenomenon, the JIS light load test was temporarily stopped after 50,000 cycles of each of the liquid lead-acid batteries produced (invention 1 to 8, comparative examples 1 to 22, and conventional example) for 1 hour. After standing, the electrolyte specific gravity measurement of the upper part and the lower part was performed with a specific gravity measuring instrument. As an evaluation, the case where the electrolyte specific gravity difference was less than 0.01 was evaluated as ◯, the case where the electrolytic solution specific gravity difference was 0.01 or more and less than 0.02 was evaluated as △, and the case where the electrolyte specific gravity difference was 0.02 or more was evaluated as ×. .
Moreover, the presence or absence of the short circuit was performed by the permeation short circuit test. In the present invention, the osmotic short-circuit test means that a half of a predetermined amount of injected sulfuric acid is first poured into a storage battery and left for 24 hours, and then the remaining half is poured into the storage battery again. Then, energization, that is, battery case formation is performed, and after completion, the storage battery is disassembled to investigate the state and degree of lead penetration and short circuit. As an evaluation, no short circuit was present, and no short circuit was confirmed (including a short circuit).
Moreover, the amount of liquid reduction is the value when the liquid reduction amount of the conventional example is set to 100% when 50,000 cycles have elapsed for the lead storage batteries (Invention 1 to 12, Comparative Examples 1 to 22, Conventional Example). Each liquid reduction amount is expressed as a ratio.
In addition, the overall evaluation is that the lifetime performance is one point for less than 70,000 cycles, two points for 70,000 cycles or more and less than 80,000 cycles, and 80,000 cycles or more and less than 90,000 cycles. 3 points, 4 points for 90,000 cycles or more and less than 100,000 cycles, 5 points for those with 100,000 cycles or more, and for stratification confirmation, x is 1 point, Δ is 2 points, ○ is 3 As for the presence / absence of a short circuit, there are 2 points when there is no short circuit, 1 point when there is a short circuit, and the liquid reduction amount is 1 point for 80% or more, 2 points for 70% to less than 80%, 70% Less than 3 points were multiplied by each value, the total score was less than 10 points, x was 10 points or more and less than 50 points, and 50 point or more was rated ◯.

As is apparent from Table 1, the height of the battery case rib is 3.0 to 7.0 mm, the positive electrode plate is accommodated in a bag-shaped separator, and the positive electrode plate and the negative electrode plate are alternately stacked. Examples 1 to 12 (examples of the present invention) in which at least one end plate of the plate group was a negative electrode plate showed good cycle characteristics. This is thought to be because by providing ribs in the battery case, a space was provided between the battery case and the electrode plate group to improve the escape of gas generated from the electrode plate surface and to suppress the stratification phenomenon. It is done.
Furthermore, by using a Pb—Ca—Sn—Ba-based lead-based alloy substrate, it is possible to suppress mechanical strength and corrosion resistance, and to reduce softening and to suppress softening.
Therefore, a Pb—Ca—Sn—Ba-based lead-based alloy substrate is used, the height of the battery case rib is set to 3.0 to 7.0 mm, the positive electrode plate is accommodated in the bag-shaped separator, and the positive electrode plate and the negative electrode plate By using at least one end plate of a group of electrode plates alternately laminated as a negative electrode plate, it is possible to improve the cause of the conventional life due to the stratification phenomenon, and long-life liquid lead A storage battery can be provided.

Conventional examples and comparative examples 1, 2, and 5 showed low values of the cycle life because the height of the ribs was low, and the escape of gas generated from the electrode plate was poor, making it difficult to suppress the stratification phenomenon.
In Comparative Examples 3, 4, and 6, although the escape of gas is good, the height of the ribs is high, so that the dropped active material is easily electrodeposited on the upper part of the electrode plate group by the convection of the electrolytic solution. A short circuit occurred and suddenly reached the end of its life.
In Comparative Examples 7 to 9, the positive electrode plate is stored in the bag-shaped separator, and the number of electrode plates is one more than that of the negative electrode plate. It is considered that the cycle characteristics were deteriorated because the absorption reaction was not performed well.
Further, Comparative Examples 10 to 22 in which the negative electrode plate was accommodated in the bag-like separator reduced the amount of electrolyte compared to the case where the positive electrode plate was accommodated in the bag-like separator even when the height of the ribs and the number of electrode plates were varied. The amount of liquid was large, and a short-circuit occurred due to dropping of the active material, which was inferior to Examples 1-12.

In the present invention, the Pb—Ca—Sn—Ba based lead-based alloy substrate contains Ca 0.06 mass%, Sn 1.0 mass%, Al 0.015 mass%, Ba 0.008 mass%, with the balance being Pb and inevitable impurities. A Pb—Ca—Sn—Ba based lead-based alloy substrate made of the following was used, but calcium was 0.02% by mass or more and less than 0.05% by mass, and tin was 0.4% by mass or more and 4.0% by mass or less. If aluminum is 0.04 mass% or less and barium is 0.002 mass% or more and 0.014 mass% or less, the same effect can be obtained. Moreover, 0.005 mass% on the alloy substrate
At least one selected from 0.07% by mass or less of silver, 0.01% by mass to 0.01% by mass of bismuth, 0.001% by mass to 0.05% by mass of thallium, And / or 0.01 mass%
The corrosion resistance can be further improved by adding at least one selected from copper, potassium, lithium, magnesium, sodium, phosphorus, antimony, selenium, and tellurium in an amount of 0.1% by mass or less.
Further, in the present embodiment, the rib has a rectangular shape, but the same effect can be obtained even when the tip of the rib is not sharp, such as an arc shape.

DESCRIPTION OF SYMBOLS 1 Electrode plate group 2 Positive electrode plate 3 Negative electrode plate 4 Bag-shaped separator 5 Positive electrode strap 6 Negative electrode strap 7 Battery case 71 Inner wall 72 Partition wall 8 Rib 9 Lid 10 Liquid stopper 11 Positive electrode terminal 12 Negative electrode terminal

Claims (1)

  A Pb—Ca—Sn—Ba-based lead-based alloy substrate is used for the positive electrode, and the negative electrode plate and the positive electrode plate accommodated in the bag-like separator are alternately laminated to form an electrode plate group, and at least of the end plates of the electrode plate group One of the negative electrode plates, the electrode plate group is housed in a battery case, and in a lead storage battery formed by injecting an electrolyte into the battery case and performing chemical conversion, at least of an inner wall and a partition wall constituting the battery case, A liquid lead-acid battery characterized in that a rib projecting in a horizontal direction with respect to the stacking direction of the electrode plate group is provided, and the height of the rib is 3.0 to 7.0 mm.