WO2014097516A1

WO2014097516A1 - Lead storage battery

Info

Publication number: WO2014097516A1
Application number: PCT/JP2013/005563
Authority: WO
Inventors: 下田　一彦; 中嶋　孝; 小島　優; 亮太菊池; 健治泉
Original assignee: パナソニック株式会社
Priority date: 2012-12-21
Filing date: 2013-09-20
Publication date: 2014-06-26
Also published as: CN104067414B; CN104067414A

Abstract

A lead storage battery provided with a plurality of polar plate groups in which a plurality of positive plates and negative plates are stacked together interposed by separators, and a plurality of cell chambers accommodating the polar plate group together with an electrolyte, wherein the polar plates having the same polarity in the polar plate group are connected together through a polar plate-connecting plate, the multiple cell chambers are adjacently arrayed, and the polar plate groups accommodated in adjacent cell chambers are connected together in series through a connection body connected to the polar plate-connecting plate. Among the polar plate-connecting plates connected to the polar plate groups accommodated in the cell chambers located at the edges, one polar plate-connecting plate is connected to a polar column connected with an external terminal. The polar plate-connecting plate, the connection body and the polar column comprise a lead alloy not containing Sb but containing Sn. The connection body and/or the polar column has a greater content ratio of Sn than the polar plate-connecting plate.

Description

Lead acid battery

The present invention relates to a lead storage battery used in an idling stop vehicle.

The idling stop vehicle can improve fuel efficiency by stopping the engine while it is stopped. However, since the lead storage battery supplies all electric power such as an air conditioner and a fan during idling stop, the lead storage battery tends to be insufficiently charged. Therefore, the lead storage battery is required to have a high charge acceptability capable of being charged more in a short time in order to solve the shortage of charging. Further, since the idling stop vehicle frequently repeats on / off of the engine, the next discharge is performed immediately before the lead sulfate generated by the discharge is restored to lead dioxide and lead by charging. Therefore, the life of the lead storage battery is likely to decrease. For this reason, lead storage batteries are also required to have high durability in order to eliminate the decrease in life.

Also, a member called a connecting body that connects the electrode plate groups between the cell chambers and a pole column that is an intermediary member with the external terminal are subjected to great stress due to vehicle vibration. Therefore, it is conceivable to use antimony-containing lead having high strength for these members. However, when antimony is contained, the corrosion resistance against charge / discharge reaction is poor. Especially in the idling stop vehicle, compared with the vehicle without the idling stop function, the number of times of switching from charging to discharging and discharging and charging and the amount of charge / discharge electricity are greatly increased, so not only the electrode plate due to the charging / discharging reaction, A portion called a so-called ear of the electrode plate that connects the electrode plate and the connecting body / pole column also easily corrodes.

In order to improve the charge acceptability of a lead storage battery, Patent Document 1 describes a lead storage battery in which aluminum ions are contained in an electrolytic solution. Aluminum ions have the effect of suppressing the coarsening of the lead sulfate crystals produced at the positive and negative electrodes during discharge, thereby improving the charge acceptance performance of the lead storage battery.

In order to improve the durability of the lead storage battery, Patent Document 2 describes a lead storage battery in which a lead alloy layer containing antimony is provided on the surface of a negative electrode lattice not containing antimony. The lead alloy layer containing antimony has an effect of efficiently charging and recovering the negative electrode plate, and thereby the durability of the lead storage battery can be improved.

Patent Document 3 discloses that a negative electrode lattice not containing antimony is filled with a negative electrode active material to which antimony is added, and the mass ratio of the negative electrode active material to the positive electrode active material is in the range of 0.7 to 1.3. A lead acid battery is described. Antimony added to the negative electrode active material has an effect of lowering the hydrogen overvoltage of the negative electrode, whereby the charge acceptability of the negative electrode active material can be improved. Furthermore, by setting the mass ratio of the negative electrode active material to the positive electrode active material in the range of 0.7 to 1.3, when the lead storage battery is overdischarged, antimony is eluted from the negative electrode active material into the electrolytic solution, Precipitation on the negative electrode ear can be suppressed, and thereby corrosion of the negative electrode ear can be suppressed.

JP 2006-4636 A JP 2006-156371 A JP 2006-114417 A International Publication WO2012 / 120768

鉛 Lead-acid batteries used in idling stop vehicles tend to be undercharged. Therefore, for the purpose of preventing overdischarge of the lead storage battery, the idling stop vehicle may be provided with a fail-safe mechanism that does not discharge the lead storage battery when the state of charge (SOC) becomes a predetermined value (for example, 60%) or less. is there.

FIG. 1 is a graph schematically showing a state of charge (SOC) when a lead-acid battery is repeatedly discharged and charged in an idling stop vehicle. The line graph shown in FIG. 1 shows a pattern in which the lead storage battery is discharged while the vehicle is stopped, the SOC decreases, the vehicle travels again, the lead storage battery is charged, the SOC is recovered, and this is repeated. It is shown.

If the lead-acid battery has a high charge acceptance, the lead-acid battery recovers to about 100% while the car is running. Therefore, even if the idling stop car is run for a long time as shown in the line graph A in FIG. The charge / discharge of the lead storage battery can be repeated.

However, if the lead-acid battery is not highly charge-acceptable, as shown by the line graph B in FIG. . When the vehicle is stopped in a state where the SOC does not recover to 100%, the decrease in the SOC due to the discharge becomes large. When such charging / discharging is repeated, the SOC gradually decreases. In this case, when the fail-safe mechanism is provided in the idling stop vehicle, the fail-safe mechanism is activated and the discharge is stopped when the SOC becomes a predetermined value (for example, 60%) or less.

In particular, when a ride with a short mileage is repeatedly performed (hereinafter, such a ride method is referred to as “choy ride”), charging during running cannot be sufficiently performed and the SOC does not recover to 100%. The safe mechanism is frequently operated. In addition, when driving on weekends without driving on weekdays, the SOC decreases due to self-discharge and dark current when stopping on weekdays. The situation where the mechanism operates becomes more prominent. However, sufficient charge acceptance and durability that can be applied to idling stop vehicles that are conventionally used in such “choy riding” mode and at low frequency (life characteristics, vibration resistance characteristics of connectors and poles) ) Was not included in the lead storage battery.

The present invention has been made in view of such a problem, and its main purpose is sufficient charge acceptance and durability (life characteristics, connection body) that can be applied to an idling stop vehicle used in the “choi riding” mode.・ To provide a lead-acid battery that has both the anti-vibration characteristics of the poles).

A lead storage battery according to the present invention is a lead comprising a plurality of electrode plate groups in which a plurality of positive electrode plates and negative electrode plates are laminated via separators, and a plurality of cell chambers for accommodating each of the electrode plate groups together with an electrolytic solution. In the storage battery, electrode plates of the same polarity in the electrode plate group are connected to each other by electrode plate connection plates, and the plurality of cell chambers are arranged adjacent to each other and are accommodated between the adjacent cell chambers. The electrode plate groups are connected in series by a connection body connected to the electrode plate connection plate, and the electrode plates connected to the electrode plate group housed in the cell chamber located at the end. Of the connection plates, the electrode plate connection plate that is not connected to the connection body is connected to a pole column connected to an external terminal, and the electrode plate connection plate, the connection body, and the pole column do not contain antimony. It consists of a lead alloy containing tin, and the tin content is Wherein said that towards the at least one connection member and the electrode post is larger than the electrode plate connecting plate.

In a preferable embodiment, the content ratio of tin in the electrode plate connection plate is 1.5% by mass or more and 3.5% by mass or less, and the content ratio of tin in at least one of the connection body and the pole column is It is 3 mass% or more and 10 mass% or less.

In a preferred embodiment, the connection body is integrally connected to the electrode plate connection plate in a stacking direction of the electrode plates and on a line extending from the electrode plate connection plate.

In a preferred embodiment, the proportion of tin contained in the pole column is larger in the upper part connected to the external terminal than in the lower part connected to the electrode plate connection plate. It is preferable that the tin content of the polar column gradually increases from the lower part to the upper part.

In a preferred embodiment, when the distance inside the cell chamber in the stacking direction of the electrode plate group is L, and the total thickness of the plurality of positive electrode plates and negative electrode plates in one electrode plate group is W, W / L is: It is in the range of 0.50 or more and 0.80 or less.

According to the present invention, a lead storage battery having sufficient charge acceptance and durability (life characteristics, connection body / vibration resistance characteristics of a pole pole) that can be applied to an idling stop vehicle used in the “choi riding” mode. Can be provided.

It is the graph which showed typically a charge condition (SOC) when discharging and charge of a lead acid battery in an idling stop car are repeated. 1 is an overview diagram schematically showing a configuration of a lead storage battery in an embodiment of the present invention. It is sectional drawing which showed the structure of the electrode group accommodated in the cell chamber. It is a typical perspective view which shows the shape of a connection component. It is a typical perspective view which shows the shape of another connection component. It is a typical perspective view which shows the shape of another connection component.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited to the following embodiment. Moreover, it can change suitably in the range which does not deviate from the range which has the effect of this invention. Furthermore, combinations with other embodiments are possible.

FIG. 2 is an overview diagram schematically showing the configuration of the lead storage battery 1 in one embodiment of the present invention.

As shown in FIG. 2, the lead storage battery 1 has an electrode plate group 5 in which a plurality of positive electrode plates 2 and negative electrode plates 3 are laminated via a separator 4, and the electrode plate group 5 is a cell together with an electrolyte. It is accommodated in the chamber 6.

Here, the positive electrode plate 2 includes a positive electrode lattice (not shown) and a positive electrode active material (not shown) filled in the positive electrode lattice, and the negative electrode plate 3 fills the negative electrode lattice (not shown) and the negative electrode lattice. A negative electrode active material (not shown). The positive electrode lattice and the negative electrode lattice in this embodiment are both made of lead or a lead alloy containing no antimony (Sb), for example, a Pb—Ca alloy, a Pb—Sn alloy, or a Pb—Ca—Sn alloy. The fact that it does not contain antimony means that antimony is not added as an alloy component. If the raw material contains a small amount of antimony as an impurity and it takes a large cost to remove this antimony, it means that no antimony is contained. That is, when antimony is an unavoidable impurity, the present invention does not contain antimony.

The plurality of positive electrode plates 2 are connected in parallel to each other by the positive electrode straps (electrode plate connection plates) 7 at the ears 9 of the positive electrode lattice. The plurality of negative electrode plates 3 are connected in parallel to each other by negative electrode straps (electrode plate connection plates) 8 at the ends 10 of the negative electrode lattice. Further, the plurality of electrode plate groups 5 accommodated in each cell chamber 6 are connected in series by a connection body 11. The connection body 11 is electrically connected to the positive strap 7 or the negative strap 8. Each of the positive strap 7 and the negative strap 8 in the cell chambers 6 at both ends is not connected to the electrode plate group 5 of the adjacent cell chamber 6 and is connected to an external terminal. That is, the pole columns are welded to the positive strap 7 and the negative strap 8 in the cell chambers 6 at both ends, and the respective pole columns are welded to the positive terminal 12 and the negative terminal 13 disposed on the lid 14, respectively. ing.

In this embodiment, the electrode plate connection plate (positive electrode strap 7, negative electrode strap 8), connection body 11, and electrode column are formed of a Pb—Sn alloy containing no antimony. These electrode plate connection plate, connection body and pole column are collectively referred to as connection parts.

The connection parts of this embodiment are shown in FIGS. As shown in FIG. 4A, the electrode plate connection plate 50 and the connection body 51 are supplied as separate members, and are connected together with the ears 60 by welding as shown in FIG. 4B. Further, the pole column 53 and the electrode plate connecting plate 50 are supplied as separate members as shown in FIG. 5A, and are connected together with the ears 60 as shown in FIG. 5B by welding. In the present embodiment, the connection body 51 is connected to the electrode plate connection plate 50 via the connection interposition member 52, and the pole column 53 is also connected to the electrode plate connection plate 50 via the connection interposition member 54.

Here, a plurality of positive plates 2 or negative plates 3 hang from the connection body 51 and the pole column 53, and the connection body 51 is fixed to each other, or the pole column 53 and the external terminal are fixed. . When the lead storage battery is vibrated, the stress is most applied in the vicinity of these fixed portions. Therefore, if all the connection parts are made of the same material and have the same strength, the connection body 51 and the pole column 53 are first damaged. In order to withstand such vibration, it is effective to use a Pb—Sb alloy having high strength as a constituent material. However, as described in Patent Document 4, when antimony is included, Since the corrosiveness with respect to the electrolytic solution is inferior, it is considered to use an alloy containing Sn. In particular, when charging / discharging is performed in the “choi riding” mode in an idling stop vehicle application, charging is insufficient and a discharge product is formed even in the ear portion, so further measures are required.

However, simply using a lead alloy containing Sn will affect the cost and the “choy ride” mode. Therefore, as a result of examining the raw material composition of the connecting part in the “choi riding” mode, which has not been studied so far, the present inventors used a Pb—Sn alloy containing no antimony for the connecting part, and At least one of the connection body 51 and the pole column 53 has a higher Sn content than the electrode plate connection plate 50. The reason why Sn is also contained in the electrode plate connecting plate 50 is that stress is also applied to the electrode plate connecting plate 50 due to vibration, and the above-described configuration is adopted according to the magnitude of stress and the charge / discharge mode / number of times. did.

The connection body 51 and the pole column 53 have a larger Sn content than the electrode plate connection plate 50, and the electrode plate connection plate 50 contains Sn in an amount of 1.5 mass% to 3.5 mass%. It is more preferable that at least one of the connection body 51 and the pole column 53 contains Sn in an amount of 3% by mass to 10% by mass.

In addition, regarding the pole column 53, the stress applied to the tip (upper part) connected to the external terminal is larger than that of the lower part connected to the electrode plate connection plate 50, so the Sn content in the upper part is increased. Is more preferable.

Further, in this embodiment, a method (COS: Cast on Strap) in which the connection parts are not connected to each other by welding but connected to the ears by casting is adopted as a more preferable example. Did. In this case, the connection body and the pole column may be manufactured by a method in which a member having a high Sn content is prepared in advance and put in a mold, or the connection body and the pole column are injected with a molten material having a high Sn content. Alternatively, a method for manufacturing may be used.

When the connection part is produced by casting, as shown in FIG. 6, the connection body 55 can be positioned on a line in which the electrode plate connection plate 50 extends (in the stacking direction of the electrode plates). When a connection part is produced by welding, it is very difficult to position the connection body 51 on a line on which the electrode plate connection plate 50 extends in order to ensure the connection between the ear portion 60 and the electrode plate connection plate 50. For this reason, in the connection component shown in FIG. 4, the current flows more linearly in the connection component of FIG. Therefore, even if it is applied to an idling stop vehicle that is improved in charge acceptance and used in the “choy ride” mode, the operation of the fail-safe mechanism can be more effectively suppressed. However, the COS is heavier than the connection part produced by welding.

In this embodiment, when the distance between the inner walls of the cell chamber 6 in the stacking direction of the electrode plate group 5 is L, and the total thickness of the plurality of positive plates 2 and negative plates 3 housed in the cell chamber 6 is W. , W / L is preferably in the range of 0.50 to 0.80. The value of W / L is an index of the size of the gap between the positive electrode plate 2 and the negative electrode plate 3, in other words, the amount of wraparound of the electrolyte, and the value of W / L is 0.50 to 0.80. If it is within the range, the charge acceptability of the lead storage battery 1 is further improved, and the operation of the fail-safe mechanism can be more effectively suppressed even when applied to an idling stop vehicle used in the “choy ride” mode.

In this embodiment, a surface layer (not shown) made of a lead alloy containing antimony is formed on the surface of the negative electrode lattice. The lead alloy containing antimony has an effect of lowering the hydrogen overvoltage, whereby the charge acceptability of the lead storage battery 1 can be improved. The surface layer is preferably made of a Pb—Sb alloy having an antimony content of 1.0 to 5.0 mass%.

In the present embodiment, the electrolytic solution contains 0.01 to 0.45 mol / L, more preferably 0.03 to 0.28 mol / L of sodium ions. The sodium ions in the electrolyte have the effect of improving the overdischarge recovery, which further improves the charge acceptance of the lead storage battery 1 and is applied to an idling stop vehicle used in the “choi ride” mode. However, the operation of the fail-safe mechanism can be more effectively suppressed.

In the present embodiment, the negative electrode plate 3 is disposed on both sides of the electrode plate group 5, and the negative electrode plate 3 is accommodated in a bag-like separator 4, It is preferable that a plurality of ribs 15 forming a certain gap be provided between the negative electrode plate 3 and the separator 4. As a result, the electrolyte solution can also flow into the negative electrode plates 3 arranged on both sides of the electrode plate group 5, so that the charge acceptance of the lead storage battery 1 is further improved, and the idling stop used in the “choi riding” mode. Even when applied to a vehicle, the operation of the fail-safe mechanism can be more effectively suppressed.

In addition, if the separator 4 that accommodates the negative electrode plate 3 disposed at least on both sides of the electrode plate group 5 is provided with a plurality of ribs 15, the above-described effects can be exhibited. Of course, all the negative electrode plates 3 are accommodated. The separator 4 may be provided with a plurality of ribs 15. When the lead storage battery 1 has only one cell chamber 6, the battery case of the lead storage battery 1 may also serve as the cell chamber 6.

Further, in the present embodiment, when the mass of the positive electrode active material per cell chamber 6 and _{M P,} the mass of the negative electrode active material and _{M N,} the mass ratio _M N / _{M P} of both 0.70 and 1. It is preferably set in the range of 10, more preferably in the range of 0.80 to 1.0. When the mass ratio M _{N /} M _P of the negative electrode active material for the positive electrode active material is in this range, while maintaining the life characteristics, improved charge acceptance of the lead storage battery 1, the idling stop to be used in the "Choi ride" mode This is because even when applied to a car, the operation of the fail-safe mechanism can be further suppressed.

The positive electrode active material density is preferably 3.6 to 4.8 g / ml. This is because the charge acceptability of the lead storage battery 1 is improved while maintaining the life characteristics, and the operation of the fail-safe mechanism can be further suppressed even when applied to an idling stop vehicle used in the “choy ride” mode. .

Hereinafter, the configuration and effects of the present invention will be further described with reference to examples of the present invention. The present invention is not limited to these examples.

(1) Production of lead acid battery The lead acid battery 1 produced in the present example is a liquid lead acid battery having a D23L type size defined in JIS D5301. Each cell chamber 6 accommodates seven positive electrode plates 2 and eight negative electrode plates 3, and the negative electrode plate 3 is accommodated in a bag-like polyethylene separator 4. On the inner surface of the bag of the separator 4, a plurality of ribs 15 that form a certain gap with the negative electrode plate 3 are provided.

Table 1 shows the configurations and battery characteristics of the batteries 1 to 16 according to the examples and the batteries A and B according to the comparative example.

The configuration common to each battery other than the configuration shown in Table 1 will be described below.

The positive electrode plate 2 was prepared by kneading lead oxide powder with sulfuric acid and purified water to prepare a paste, and filling this into an expanded lattice made of a lead alloy containing calcium and tin.

The negative electrode plate 3 is prepared by adding an organic additive to lead oxide powder, kneading with sulfuric acid and purified water to create a paste, and filling this into an expanded lattice made of a lead alloy containing calcium and tin. Made.

The negative electrode lattice is composed of an expanded lattice of Pb-1.2Sn-0.1Ca, and the surface layer is composed of Pb-3 mass% Sb foil.

The positive electrode lattice is an expanded lattice of Pb-1.6Sn-0.1Ca, and no surface layer is provided.

After the produced positive electrode plate 2 and negative electrode plate 3 are aged and dried, the positive electrode plates 2 and the negative electrode plates 3 are alternately stacked via the separators 4, and the seven positive electrode plates 2 and the eight negative electrode plates 3 are separated. The electrode plate group 5 laminated through 4 was produced. At this time, the positive electrode active material density was 4.2 g / ml. The electrode plate group 5 was accommodated in each of the six cell chambers 6, and lead storage batteries according to Examples and Comparative Examples in which six cells (electrode plate group 5) were connected in series by connecting parts were produced.

An electrolytic solution made of dilute sulfuric acid having a density of 1.28 g / cm ³ was put into this lead storage battery, and a battery case was formed to obtain a 12V48Ah lead storage battery.

(2) Characteristic evaluation of lead storage battery (2-1) Evaluation of life characteristics Evaluation of life characteristics of lead storage batteries by repeatedly charging and discharging the prepared lead storage battery assuming idling stop as described below. Went.

The test of the life characteristics was performed under the conditions shown below, almost compliant with the battery industry association standard (SBA S 0101). The ambient temperature was 25 ° C. ± 2 ° C.

(A) After discharging at a discharge current of 45A for 59 seconds, discharge at 300A for 1 second.

(B) Thereafter, the battery is charged for 60 seconds at a charge voltage of 14.2 V (limit current 100 A).

(C) Charge / discharge of (A) and (B) is set as one cycle, and after leaving for 48 hours every 3600 cycles, the cycle is started again.

The above cycle was repeated and the number of cycles when the discharge voltage was less than 7.2 V was defined as the life characteristic. In the above test, water replenishment was not performed until 30000 cycles.

(2-2) Characteristic Evaluation of “Choide Ride” Mode For the produced lead storage battery 1, charge / discharge assuming the “Choide Ride” mode as described below is repeated, and the “choi ride” of the lead storage battery is repeated. The mode characteristics were evaluated. The ambient temperature was 25 ° C. ± 2 ° C.

(A) Discharge at 9.6 A for 2.5 hours and leave for 24 hours.

(B) Next, the battery is discharged at a discharge current of 20 A for 40 seconds.

(C) Next, the battery is charged for 60 seconds with a charge voltage of 14.2 V (limit current 50 A).

After charging and discharging (D), (B), and (C) 18 times, the battery is discharged at a discharge current of 20 mA for 83.5 hours.

(E) Charge / discharge of (B) to (D) is one cycle, and 20 cycles are repeated.

The state of charge (SOC) of the lead storage battery after the above 20 cycles was measured, and this value was taken as the “choy ride” mode characteristic.

(2-3) Vibration resistance The vibration resistance was evaluated by the following method. The basic evaluation method conformed to the vibration resistance described in Japanese Industrial Standard JIS D5301. However, since this method can only determine whether the standard is good or bad, the vibration time is fixed at 2 hours in the standard, but the vibration time is arbitrary. In addition, the standard is that the discharge current is discharged at a 5-hour rate current, but it was changed to a 20-hour rate current assuming that the vibration time becomes longer. The vibration test was performed under such conditions, the behavior of the discharge current was observed sequentially, and the time when the abnormality appeared in the current behavior was regarded as the vibration resistance of the corresponding battery. That is, the longer the vibration time, the higher the vibration resistance.

(Sn content of pole pole and connector)
In the batteries 1 to 8 and the batteries A and B, the Sn contents of the pole column and the connection body were changed as parameters, and the other conditions were the same, and the battery characteristics were compared.

As shown in Table 1, at least one of the pole column and the connecting body has a life characteristic of 35,000 times or more in the batteries 1 to 8 having a Sn content larger than that of the electrode plate, and the “choy ride” mode characteristic. It can also be seen that the SOC is 75% or more and the vibration resistance is 800 minutes or more. Lead-acid batteries that satisfy these values can maintain sufficient vibration resistance even when the idling stop vehicle is used in the “choi ride” mode, and have excellent life characteristics, and can operate the fail-safe mechanism. Can be suppressed. In particular, the battery 3 in which the Sn content of the electrode plate connecting plate is 2.0% by mass, and both the pole column and the connected body have the Sn content in the range of 5.0% by mass to 8.0% by mass. ~ 5 has a lifespan of 35,000 times or more, “choy ride” mode characteristics, SOC is 75% or more, and vibration resistance is more than 1200 minutes, and all three are excellent, and idling stop in “choy ride” mode When using a car, it has suitable performance.

Moreover, the Sn content of the electrode plate connecting plate is 2.0% by mass, and both the pole column and the connected body have the Sn content of 3.0% by mass or 10.0% by mass. Although the vibration resistance is slightly inferior to those of the batteries 3 to 5, it has a practically sufficient performance.

On the other hand, in the battery A in which all of the electrode plate connection plate, the pole column, and the connection body have an Sn content of 2.0 mass%, the “choy ride” mode characteristics and the life characteristics are excellent, but the vibration resistance Sex is as low as 300 minutes. This is thought to be because the strength is low in the pole column and connection body, where stress is relatively large, because it has the same Sn content as the electrode plate connection plate.

In addition, the battery B in which 3.8% by mass of Sb is contained in all of the electrode plate connecting plate, the pole column, and the connected body has excellent vibration resistance of 1200 minutes or more, but has a life characteristic of 18,000 times. And inferior. This is because Sb is contained in the connecting part, so that the strength of the part is improved and the vibration resistance is improved, but the life of the connecting part is shortened due to corrosion by the charge / discharge reaction. it is conceivable that.

In addition, the battery 7 has a Sn content of 2.0 mass%, which is the same as that of the electrode plate connection plate, and an Sn content of 6.0 mass% in the polar column. The battery 7 has excellent life characteristics, “choi riding” mode characteristics and life characteristics, but has a vibration resistance of 900 minutes, which is practically sufficient but slightly lower. On the other hand, the battery 8 has the same Sn content as the electrode plate connecting plate and the Sn content of 2.0% by mass and the connected body has the Sn content of 6.0% by mass. Although the life characteristics are excellent, the vibration resistance is 800 minutes and there is no practical problem, but it is lower than the battery 7. This is probably because the stress applied to the pole column is larger when the connecting body and the pole column are compared, and therefore the vibration resistance is improved by increasing the Sn content in the pole column.

(Connecting parts form)
The battery 9 of the example is used as a base to produce a connecting part by casting, and the battery 9 having the shape of FIG. 6 and the battery 2 of the example are used as a base to produce a connecting part by casting, and the shape of FIG. Then, a battery 10 having a Sn content at the tip (upper part) of the pole column (upper part) as high as 6.0% by mass was fabricated and evaluated.

Both the

batteries

9 and 10 have greatly improved “choi riding” mode characteristics compared to the

batteries

2 and 4. This is thought to be because the

batteries

9 and 10 have a shape of connecting parts with less current detour compared to the

batteries

2 and 4 that are bent until the current flow path reaches the connecting body from the electrode plate connecting plate. . In addition, the battery 10 has improved vibration resistance compared to the battery 2 because the upper Sn content, which is considered to have the highest stress in the pole column, is larger than that in the pole column lower part. Conceivable.

(Ratio between cell chamber width and total electrode plate thickness)
Based on the battery 4 of the example, when the distance inside the cell chamber in the stacking direction of the electrode plate group is L, and the total thickness of the plurality of positive and negative electrode plates is W, W / L is 0.45. Batteries 11 to 16 were prepared in the range of ˜0.85, and the life characteristics, “choy ride” mode characteristics and vibration resistance of each battery were evaluated.

FIG. 3 is a cross-sectional view of the cell chamber 6, where L is the distance between the inner walls in the stacking direction of the electrode plate group accommodated in the cell chamber 6, and the thickness W 1 of the positive electrode plate 2 and the negative electrode plate 3 The thickness W2 is the total thickness (W1 × 7 + W2 × 8) of the positive electrode plate 2 and the negative electrode plate 3.

As shown in Table 1, in the

batteries

4 and 12 to 15 having W / L in the range of 0.50 to 0.80, the life characteristic is 35,000 times or more and the SOC indicating the “choi riding” mode characteristic is 70. It can be seen that the vibration resistance is excellent at 1200 minutes or more. A lead storage battery satisfying these values can suppress the operation of the fail-safe mechanism while maintaining sufficient life characteristics and vibration resistance even when the idling stop vehicle is used in the “choy ride” mode. In particular, the

batteries

4, 13 and 14 having a W / L in the range of 0.60 to 0.70 have a life characteristic of 35,000 times or more, a vibration resistance of 1200 minutes or more, and a “choy ride” mode characteristic. The SOC is 75% or more, all three are excellent, and when the idling stop vehicle is used in the “choi ride” mode, it has a suitable performance.

On the other hand, in the battery 11 with W / L of 0.45, the life characteristic is 36,000 times and the vibration resistance is 1200 minutes or more, but the “choy ride” mode characteristic is 66% SOC. I'm low. This is thought to be due to the lack of active material, which reduced charge acceptance.

The battery 16 with W / L of 0.85 also has a life characteristic of 36,000 times and a vibration resistance of 1200 minutes or more. However, the “choy ride” mode characteristic has a low SOC of 66%. It has become. This is presumably because the electrolyte solution could not move sufficiently and the charge acceptance was reduced.

From the above results, by setting W / L to 0.50 to 0.80, more preferably 0.60 to 0.70, the charge acceptability is further improved and the idling used in the “choi riding” mode. Even when applied to a stop vehicle, the operation of the fail-safe mechanism can be more effectively suppressed.

As mentioned above, although this invention has been demonstrated by suitable embodiment, such description is not a limitation matter and of course various modifications are possible.

For example, tin sulfate may be added to the positive electrode. It is preferable to add tin sulfate to the positive electrode because the discharge capacity is improved.

When connecting parts are made by casting, a Pb-Sn alloy with a high Sn content is put in advance in the mold part corresponding to the upper part of the pole column, and the temperature conditions are adjusted so that the upper part of the pole column is moved to the lower part. The Sn content may be gradually lowered.

The present invention is useful for a lead storage battery used in an idling stop vehicle.

DESCRIPTION OF SYMBOLS 1 Lead acid battery 2 Positive electrode plate 3 Negative electrode plate 4 Separator 5 Electrode plate group 6 Cell chamber 7 Positive electrode strap 8

Negative electrode strap

9, 10 Ear part 11 Connection body 12 Positive electrode terminal 13 Negative electrode terminal 14 Lid 15 Rib 50 Electrode plate connection plate 51 Connection object 53 poles 55 connectors

Claims

A plurality of electrode plate groups in which a plurality of positive electrode plates and negative electrode plates are laminated via separators,
A lead storage battery comprising a plurality of cell chambers for accommodating each of the electrode plate groups together with an electrolyte,
The plates of the same polarity in the electrode plate group are connected to each other by a plate connection plate,
A plurality of the cell chambers are arranged adjacent to each other,
The electrode plate groups accommodated between the adjacent cell chambers are connected in series by a connection body connected to the electrode plate connection plate,
Of the electrode plate connection plates connected to the electrode plate group housed in the cell chamber located at the end, the electrode plate connection plate not connected to the connector is connected to an electrode column connected to an external terminal. And
The electrode plate connection plate, the connection body and the pole column do not contain antimony and are made of a lead alloy containing tin,
The content rate of tin is a lead acid battery in which at least one of the connection body and the pole column is larger than the electrode plate connection plate.
The tin content in the electrode plate connection plate is 1.5% by mass or more and 3.5% by mass or less,
The lead acid battery according to claim 1, wherein a content ratio of tin of at least one of the connection body and the pole column is 3% by mass or more and 10% by mass or less.
The lead-acid battery according to claim 1 or 2, wherein the connection body is integrally connected to the electrode plate connection plate on a line in which the electrode plate connection plate extends in the stacking direction of the electrode plates.
The lead storage battery according to any one of claims 1 to 3, wherein a tin content ratio of the pole column is larger in an upper part connected to the external terminal than in a lower part connected to the electrode plate connection plate.
The lead acid battery according to claim 4, wherein a tin content ratio of the polar column is gradually increased from the lower part to the upper part.
When the distance inside the cell chamber in the stacking direction of the electrode plate group is L, and the total thickness of the plurality of positive and negative electrode plates in one electrode plate group is W, W / L is 0.50. The lead acid battery according to any one of claims 1 to 5, which is in the range of 0.80 or less.
W / L is a lead acid battery of Claim 6 which exists in the range of 0.60 or more and 0.70 or less.