CN211320251U - Lead-acid battery - Google Patents

Abstract

The utility model provides a novel lead storage battery, the internal resistance that makes and arouses by the gas that produces in the battery rises and has obtained the suppression. The lead storage battery is provided with an electrolytic cell (1) and an electrode group, wherein the electrolytic cell (1) comprises a battery cell chamber (2) having two parallel wall surfaces (21, 22) that face each other, the electrode group is housed in the battery cell chamber together with an electrolyte, the electrode group comprises a laminate body composed of positive and negative electrode plates that are alternately arranged and a separator arranged between the positive and negative electrode plates, and the laminate body is arranged in the battery cell chamber such that a direction perpendicular to the wall surfaces coincides with a stacking direction of the laminate body. A first rib (31) protrudes from one of the two wall surfaces, a second rib (32) protrudes from the other wall surface, the stacked body is in contact with the first rib and the second rib, and a maximum protruding dimension X of the first rib, a maximum protruding dimension Y of the second rib, and a dimension Z between the two opposing wall surfaces satisfy the following expression (1): Z/(X + Y) is more than or equal to 12.5 and less than or equal to 21.0 … … (1).

Description

Lead-acid battery

Technical Field

The utility model relates to a lead storage battery.

Background

Among lead-acid batteries are a liquid lead-acid battery including an electrolytic cell having a cell chamber and an electrode group housed in the cell chamber together with an electrolytic solution, the electrode group including a laminate body including positive electrode plates and negative electrode plates alternately arranged and separators arranged between the positive electrode plates and the negative electrode plates, and a valve-regulated lead-acid battery.

In recent years, many of domestic newly-sold automobiles are replaced with ISS (idle stop and Start) vehicles from existing engine vehicles, and it is predicted that the demand for lead-acid batteries for ISS will further increase in response to the control of these vehicles in the future.

The vehicle control method of the ISS differs from vehicle manufacturer to vehicle manufacturer, but the starting condition of the ISS during actual running is generally a method of determining the state of charge and the state of deterioration of the lead storage battery, and one of the determination criteria at this time is the internal resistance of the lead storage battery as one of important items. In lead-acid batteries for ISS mounted on vehicles, internal resistance generally increases when the state of charge is insufficient in actual use or when the battery itself deteriorates due to aging. Therefore, in a "healthy lead acid battery" which is not aged over time and has a sufficient state of charge, it is essential to perform control so that the ISS control of the vehicle functions normally without increasing the internal resistance to a certain value or more.

In general, the largest factor determining the initial internal resistance of a lead-acid battery immediately after manufacture is the mass (resistance) of lead members used in the battery, such as bus bars, poles, and terminals (sleeves), that is, the portion resulting from the design of the battery, and research into these design items is indispensable for suppressing the initial internal resistance to a low level.

On the other hand, in the lead-acid battery, since self-discharge is continuously generated until the battery is manufactured (before the control of charging and discharging is started by actual running) in a period from when the self-discharge is not prevented from being generated in a static state to when the battery is mounted on a vehicle, the generated gas is accumulated in the battery, and therefore, the internal resistance of the battery may be continuously increased. When such a state is reached, although the battery itself is almost fully charged and in a healthy state, since only the internal resistance is high, there is a possibility that the vehicle side determines that "the state of charge is insufficient" or "the battery itself is deteriorated", and the control to stop the ISS itself is activated, that is, there is a possibility that "a trouble not performing the idle stop" is intermittently generated.

The most effective means for solving these problems is to eliminate self-discharge of the lead-acid battery or to reduce the amount of self-discharge, but these means reverse the principle of the lead-acid battery itself and are not realistic means. The following means can be mentioned as a practical solution: the mass of lead parts represented by busbars and poles is increased, and the initial internal resistance is suppressed to be low; further, the battery is formed into a structure or the like in which the gas generated by self-discharge is not easily accumulated in the battery and is efficiently and easily released to the outside of the battery by changing various designs of the battery (not including the size of the ribs of the electrolytic bath).

However, increasing the weight of the lead member naturally increases the weight of the lead storage battery itself, and is contrary to the recent vehicle design concept in which improvement in fuel efficiency is sought. In addition, various designs of the battery are changed to a structure in which gas generated by self-discharge is not easily accumulated in the battery, and various characteristics of the battery may be adversely affected.

Patent document 1 describes the following: in the step of inserting the electrode group into the monolithic electrolytic cell, ribs are provided on the inner portion of the cell partition wall or the short side surface of the electrolytic cell of the monolithic lead-acid battery so that the electrode group is not inserted in a state of being inclined or in a state of being displaced from the center of the electrolytic cell.

Patent document 2 describes the following: in a valve-regulated lead-acid battery in which at least one end plate of an electrode group formed by a positive electrode plate and a negative electrode plate with a separator interposed therebetween is a negative electrode plate and the electrode group is housed in a cell chamber of an electrolytic cell, a plurality of linear ribs are provided in parallel on a wall surface of the cell chamber facing the negative electrode plate serving as the end plate.

However, patent documents 1 and 2 do not describe the relationship between the protruding dimension of the rib and the dimension between the wall surfaces of the battery cell chamber.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2003-257381

Patent document 2: japanese patent laid-open No. 2006-114316

SUMMERY OF THE UTILITY MODEL

Problem to be solved by the utility model

The utility model aims to provide a novel lead storage battery, which restrains the internal resistance rise caused by the gas generated in the battery.

Means for solving the problems

In order to solve the above problem, a lead acid battery according to a first aspect of the present invention has the following configurations (a) to (c).

(a) The lead-acid battery includes an electrolytic cell including a cell chamber having two parallel wall surfaces facing each other, and an electrode group housed in the cell chamber together with an electrolytic solution. The electrode group includes a laminate composed of positive and negative electrode plates alternately arranged and separators arranged between the positive and negative electrode plates. The laminate is disposed in the battery cell chamber such that a direction perpendicular to the wall surface of the battery cell chamber coincides with the lamination direction of the laminate.

(b) A first rib protrudes from one of two wall surfaces of the battery cell chamber, a second rib protrudes from the other wall surface, and the stacked body is in contact with the first rib and the second rib.

(c) The maximum projection dimension X of the first rib, the maximum projection dimension Y of the second rib, and the dimension Z between the two opposing wall surfaces satisfy the following expression (1):

12.5≤Z/(X+Y)≤21.0……(1)。

the lead-acid battery of the second aspect of the present invention is the lead-acid battery of the first aspect of the present invention, wherein the value of Z/(X + Y) is 12.5 or more and 16.0 or less in formula (1).

A lead-acid battery according to a third aspect of the present invention is the lead-acid battery according to the first or second aspect, further comprising the following structures (d) and (e).

(d) The positive electrode plate has: a positive electrode current collector having a rectangular grid-shaped substrate and lug portions protruding upward from the grid-shaped substrate; and a positive electrode mixture held by the grid-like substrate,

the negative electrode plate has: a negative electrode current collector having a rectangular grid-shaped substrate and lug portions protruding upward from the grid-shaped substrate; and a negative electrode mixture held by the grid-like substrate.

(e) The first and second ribs are constituted by a vertical portion extending vertically upward from the bottom surface of the electrolytic cell, and an inclined portion extending obliquely from the upper end of the vertical portion toward the wall surface,

a ratio (L1/L2) of a height L1 of the vertical portion from the bottom surface to a dimension L2 of the grid-shaped substrate of the positive electrode plate and the negative electrode plate in a height direction of the electrolytic cell is 4/5 or more.

The lead-acid battery according to the fourth aspect of the present invention is characterized in that, in the lead-acid battery according to the third aspect of the present invention,

an angle θ formed by the inclined surface of the inclined portion and a perpendicular surface of the vertical portion with respect to the bottom surface is 5 ° or more and 30 ° or less.

Effect of the utility model

According to the present invention, a novel lead-acid battery can be provided, in which an increase in internal resistance caused by gas generated in the battery can be suppressed.

Drawings

Fig. 1 is a plan view illustrating an electrolytic cell constituting a lead-acid battery according to an embodiment.

Fig. 2 is a plan view illustrating the lead-acid battery according to the embodiment.

Fig. 3 is a sectional view illustrating the lead acid storage battery of the first embodiment, and is a view corresponding to the section a-a in fig. 2.

Fig. 4 is a sectional view illustrating a lead acid storage battery according to a second embodiment, and corresponds to a section a-a in fig. 2.

Description of the symbols

1 electrolytic cell

2 cell compartment

21. 22 two parallel wall surfaces opposite to each other

31 first rib

32 second rib

4 polar plate group

41 bus bar

42 middle pole

43 laminated body

D1 direction perpendicular to the wall (arrangement direction of cell compartments)

D2 lamination direction of the laminate.

Detailed Description

[ lead storage battery according to one embodiment of the present invention ]

The lead-acid battery according to one embodiment of the present invention preferably has the following structures (d) (e).

(d) The positive plate has: a positive electrode current collector having a rectangular grid-like substrate and lug portions protruding upward from the grid-like substrate; and a positive electrode mixture held on the grid-like substrate, wherein the negative electrode plate has: a negative electrode collector having a rectangular grid-like substrate and lug portions protruding upward from the grid-like substrate; and a negative electrode mixture held on the grid-like substrate.

(e) The first rib and the second rib are each composed of a vertical portion extending vertically upward from the bottom surface of the electrolytic cell, and an inclined portion extending obliquely from the upper end of the vertical portion toward the wall surface, and the ratio (L1/L2) of the height L1 of the vertical portion from the bottom surface to the dimension L2 of the grid-shaped substrate of the positive electrode plate and the negative electrode plate in the height direction of the electrolytic cell is 4/5 or more.

In the lead-acid battery according to one aspect of the present invention, when the structure (d) or (e) is provided, an angle θ formed by the inclined surfaces of the inclined portions of the first rib and the second rib and a perpendicular surface of the perpendicular portion with respect to the bottom surface of the electrolytic bath is preferably 5 ° or more and 30 ° or less.

[ embodiment ]

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the embodiments described below. In the embodiments described below, a technically preferable restriction for carrying out the present invention is given, but the restriction is not an essential element of the present invention.

[ description of the overall Structure ]

The lead-acid battery of this embodiment has a monolithic electrolytic cell, a lid, and six plate groups. The electrolytic cell is divided into six cell compartments by partition walls. Six cell compartments are arranged along the length direction of the electrolytic bath. One electrode plate group is disposed in each battery cell chamber. Each of the electrode groups has a laminate body including a plurality of positive electrode plates and negative electrode plates arranged alternately, and separators arranged between the positive electrode plates and the negative electrode plates.

The positive plate has: a positive electrode current collector having a rectangular grid-like substrate and lug portions protruding upward from the grid-like substrate; and a positive electrode mixture held on the grid-like substrate. The negative electrode plate has: a negative electrode collector having a rectangular grid-like substrate and lug portions protruding upward from the grid-like substrate; and a negative electrode mixture held on the grid-like substrate. The plurality of positive and negative electrode plates are alternately arranged with separators interposed therebetween. The number of negative electrode plates constituting the laminate may be one more than the number of positive electrode plates, or may be the same.

The negative electrode plate is housed in the bag-like separator. The separator is disposed between the positive electrode plate and the negative electrode plate by alternately overlapping the positive electrode plate and the bag-like separator in which the negative electrode plate is incorporated. The positive electrode plate may be housed in the pouch separator so as to be alternately overlapped with the negative electrode plate.

Further, each of the electrode plate groups has: a positive electrode bus bar and a negative electrode bus bar that connect the positive electrode plate and the negative electrode plate of the laminate at different positions in the width direction; and a positive electrode intermediate post and a negative electrode intermediate post respectively rising from the positive electrode bus bar and the negative electrode bus bar. The positive electrode bus bar and the negative electrode bus bar are respectively connected with the lug parts of the positive electrode plate and the negative electrode plate. Positive electrode posts and negative electrode posts serving as external terminals through small pieces are formed on the positive electrode bus bars and the negative electrode bus bars in the battery cell chambers disposed at both ends in the cell arrangement direction, respectively.

[ concerning the relationship between the cell compartment and the laminate of the electrolytic cell ]

As shown in fig. 1, the electrolytic cell 1 includes a battery cell chamber 2, and the battery cell chamber 2 has two parallel wall surfaces 21 and 22 facing each other. In the battery cell chambers 2 at both ends in the longitudinal direction of the electrolytic cell 1, the inner surface of the outer wall forming the end surface (short side surface) in the longitudinal direction and the surface of the partition wall 11 opposed thereto correspond to the wall surfaces 21, 22. In the other battery cell chambers 2, the surfaces of the partition walls 11 constituting the battery cell chambers 2 correspond to the wall surfaces 21 and 22. A first rib 31 projects from one wall surface 21 and a second rib 32 projects from the other wall surface 22.

The first ribs 31 and the second ribs 32 are stripe-shaped projections extending from the bottom surface toward the upper surface of the electrolytic cell 1, and are arranged in plural in the width direction H of the partition wall 11 (the direction perpendicular to the arrangement direction of the cell chambers). The plurality of first ribs 31 and the plurality of second ribs 32 are respectively disposed in the center portion in the width direction H of the partition wall 11 and portions (bus bar peripheral portions) that become both sides of the bus bar 41 and the intermediate pole 42 when the electrode plate group is disposed.

The first ribs 31 and the second ribs 32 may be disposed at equal intervals in the width direction H of the partition wall 11. Alternatively, the arrangement interval between the adjacent first ribs 31 or the arrangement interval between the adjacent second ribs 32 may be set so that the vicinity of the center of the partition wall 11 in the width direction H is larger than the vicinity of the end of the partition wall 11 in the width direction H.

The maximum projection dimension X of the first rib 31, the maximum projection dimension Y of the second rib 32, and the dimension Z between the facing wall surfaces 21, 22 satisfy the following expression (1).

12.5≤Z/(X+Y)≤21.0……(1)

As shown in fig. 2, the stacked body 43 of the electrode group 4 is disposed in the cell chamber 2 such that a direction D1 perpendicular to the wall surfaces 21 and 22 (an arrangement direction of the cell chambers) coincides with a stacking direction D2 of the stacked body 43. The stacked body 43 is in contact with the first rib 31 and the second rib 32. The electrolyte enters each cell chamber 2. In the state before insertion into the battery cell chamber 2, the dimension (B) of the stacked body 43 in the stacking direction D2 is smaller than the distance a between the opposing first rib 31 and second rib 32. In a state where the electrolyte solution has entered the battery cell chamber 2 and has undergone the chemical conversion treatment, the stacked body 43 expands and comes into contact with the first ribs 31 and the second ribs 32. That is, by setting a > B, the laminate 43 is designed not to be damaged when the laminate 43 is inserted into the battery cell chamber 2.

In the first embodiment, as shown in fig. 3, the first rib 31 and the second rib 32 are constituted only by vertical portions extending vertically upward from the bottom surface of the electrolytic cell 1. Each of the positive and negative electrode plates constituting the laminate 43 includes a current collector composed of a rectangular grid-like substrate 51 and lug portions 52 projecting upward from the grid-like substrate 51. An active material mixture is held on the grid-like substrate 51 of the current collector.

The height of the first rib 31 and the second rib 32 from the bottom surface of the electrolytic cell 1 is the same as the dimension L2 of the grid-shaped substrate 51 in the height direction T of the electrolytic cell 1. In other words, the upper ends of the first rib 31 and the second rib 32 are located at substantially the same positions as the upper surface of the grating substrate 51 (the boundary line with the ear portion 52).

In the second embodiment, as shown in fig. 4, the first rib 31 and the second rib 32 are composed of vertical portions 31a and 32a extending vertically upward from the bottom surface of the electrolytic cell 1, and inclined portions 31b and 32b extending obliquely from the upper ends of the vertical portions 31a and 32a toward the wall surfaces 21 and 22. The angle θ formed by the inclined surfaces of the inclined portions 31b and 32b and the vertical surfaces (surfaces parallel to the wall surfaces 21 and 22) of the vertical portions 31a and 32a is 5 ° or more and 30 ° or less.

The ratio (L1/L2) of the height L1 of the vertical portions 31a, 32a to the dimension L2 of each of the grid-like substrates 51 constituting the positive and negative electrode plates of the stacked body 43 in the height direction T of the electrolytic cell 1 is 4/5 or more.

< production method >

The lead-acid battery according to the embodiment can be manufactured by a conventionally known method, for example, the following method.

In the laminate before formation, first, a positive electrode bus bar connecting the lug portions of the positive electrode plates and a negative electrode bus bar connecting the lug portions of the negative electrode plates were formed using a casting apparatus of COS (Cast-on strap) system, and a positive electrode intermediate post, a negative electrode intermediate post, a positive electrode post, and a negative electrode post were formed, thereby obtaining six electrode plate groups. Next, the obtained six electrode plate groups were arranged in the respective battery cell chambers of the electrolytic cell.

Next, the positive electrode intermediate terminals or the negative electrode intermediate terminals between the adjacent battery cells are resistance-welded to each other, whereby the adjacent battery cells are electrically connected in series. Next, the upper surface of the electrolytic bath and the lower surface of the lid are melted with heat and the lid is placed on the electrolytic bath, and the lid is fixed to the electrolytic bath by thermal fusion. When the lid is placed in the electrolytic cell, the positive electrode pole and the negative electrode pole are inserted into the through-hole of the sleeve formed by insert molding. Then, the positive electrode pole and the negative electrode pole, which are respectively protruded from the through-hole of the sleeve, are heated by a burner or the like and integrated with the sleeve, thereby forming a positive electrode terminal and a negative electrode terminal.

Then, the electrolyte (containing aluminum ions by adding aluminum sulfate to sulfuric acid) is injected into the cell chamber through an injection hole provided as a hole penetrating the lid, and then a normal process such as blocking the injection hole is performed, thereby completing the assembly of the lead storage battery. Then, the electrolytic cell formation is performed under normal conditions, thereby obtaining a lead storage battery.

[ operation and Effect of the embodiment ]

In the lead-acid battery of this embodiment, the maximum protrusion X of the first rib 31, the maximum protrusion Y of the second rib 32, and the dimension Z between the facing wall surfaces 21 and 22 satisfy the above expression (1), that is, the value of Z/(X + Y) is 12.5 or more and 21.0 or less, and therefore, while excellent battery performance is ensured (the battery capacity per unit volume is sufficiently large), an increase in internal resistance due to self-discharge caused by gas generated in the battery is suppressed.

When the value of Z/(X + Y) is greater than 21.0, that is, when the ratio of the total value (X + Y) of the projection heights of the first rib 31 and the second rib 32 with respect to the width of the cell chamber (the dimension Z between the wall surfaces 21 and 22) is extremely small, the distance between the stacked body 43 and the wall surfaces 21 and 22 of the cell chamber 2 becomes small, and the liquid space formed therebetween becomes small, and a sufficient liquid space cannot be secured.

Therefore, when gas generated from the positive electrode plate and the negative electrode plate, particularly from the electrode plate (the end plate of the laminate is the negative electrode plate in the present embodiment) present at the lamination end of the laminate 43 is released to the outside from the laminate 43, the gas stays in a narrow liquid space and becomes an inhibiting component that inhibits the reaction between the electrode plate and the electrolyte, and the internal resistance is greatly increased with the increase in the staying gas.

As the value of Z/(X + Y) is smaller, that is, the ratio of the total value (X + Y) of the projection heights of the first rib 31 and the second rib 32 with respect to the width of the cell chamber (the dimension Z between the wall surfaces 21, 22) is larger, the distance between the stacked body 43 and the wall surfaces 21, 22 of the cell chamber 2 becomes larger, and the liquid space formed therebetween becomes larger, and a sufficient liquid space is secured.

Therefore, even when gas generated from the positive and negative electrode plates, particularly from the electrode plate (negative electrode plate in the present embodiment) present at the lamination end of the laminate 43 is released to the outside from the laminate 43, the gas does not stay in the liquid space, but rises in the electrolyte as needed, and after being released to the space above the cell chamber, is discharged to the outside of the battery through the gas outlet provided in the lid. Therefore, the generated gas does not interfere with the reaction between the electrode plate and the electrolyte, and thus the increase in internal resistance can be suppressed.

In addition, the maximum projection dimension X of the first ribs and the maximum projection dimension Y of the second ribs are preferably equal to make the exhaust from the end plates of the stacked body uniform on both sides.

As described above, the smaller the value of Z/(X + Y), the higher the effect of suppressing the increase in internal resistance, but if Z/(X + Y) is less than 12.5, the battery performance may be degraded. This will be explained below.

As a method of designing to reduce the value of Z/(X + Y), there are, for example, a method of increasing the total protrusion size (X + Y) of the first rib and the second rib without changing the size Z of the existing product, and a method of setting the total protrusion size (X + Y) to a normal value by making the size Z smaller than the existing product.

In the method of increasing the total protrusion dimension (X + Y) of the first ribs and the second ribs without changing the dimension Z of the conventional product, a sufficient liquid space can be secured on both sides (between the end plate and each wall surface) of the laminate, but in the case of using a laminate having the same structure as the conventional product, if Z/(X + Y) is extremely small and less than 12.5, the laminate may be in an excessively compressed state. As a result, the liquid space between the positive electrode plate and the negative electrode plate decreases, the amount of electrolyte present between the positive electrode plate and the negative electrode plate decreases, and the charge/discharge efficiency between the positive electrode plate and the negative electrode plate decreases, which may cause a decrease in battery performance such as a decrease in battery capacity.

In the method of increasing the total protrusion dimension (X + Y) of the first ribs and the second ribs without changing the dimension Z of the conventional product, when the number of positive electrode plates and negative electrode plates constituting the laminate is reduced as compared with the conventional product in order to prevent the laminate from being excessively compressed, if Z/(X + Y) is extremely small and less than 12.5, the battery capacity per unit volume of the lead-acid battery is significantly reduced as compared with the conventional product.

In the method of setting the dimension Z to be smaller than the conventional product and setting the total protrusion dimension (X + Y) to a normal value, if Z/(X + Y) is extremely small and smaller than 12.5, the battery capacity per cell is significantly reduced as compared with the conventional product when the number of positive and negative plates constituting the laminate is reduced as compared with the conventional product in accordance with the dimension Z.

In addition, as a method for producing an electrolytic cell in which Z/(X + Y) satisfies formula (1), there is a method in which a mold used when molding the electrolytic cell with a synthetic resin is designed to have respective values corresponding to Z, X, Y. Alternatively, the following can be dealt with: after the molding is performed by using the mold in which X and Y are designed to be large, X, Y is reduced by scraping the first rib and the second rib with a chisel or the like. Alternatively, the following can be dealt with: the cell compartments are formed by partition walls having no ribs on the wall surfaces, and the ribbed spacers are fixed to the wall surfaces.

[ examples ] A method for producing a compound

< test 1>

[ production of test Battery ]

As a lead-acid battery having the same configuration as that of the lead-acid battery of the first embodiment, lead-acid batteries of sample nos. 1-1 to 1-12 were produced by a conventionally known method described in the embodiments. That is, in the lead-acid batteries of sample nos. 1-1 to 1-12, as shown in fig. 3, the first ribs 31 and the second ribs 32 are constituted only by vertical portions and do not have inclined portions.

The lead-acid batteries of sample Nos. 1-1 to 1-6 were M-42 type liquid lead-acid batteries for ISS, and lead-acid batteries having a capacity of 35Ah for 20 hours and an operating voltage of 12V were produced. An electrolytic cell having all the cell chambers of 27.0mm in dimension Z and ribs on the opposing walls was prepared, and the ribs were scraped with a chisel or the like (the protruding dimension of the ribs was different for each sample), thereby obtaining an electrolytic cell for each sample.

As shown in Table 1, the lead-acid batteries of sample Nos. 1-1 to 1-6 have different values of Z/(X + Y), and have the same structure in other respects. In all samples, X ═ Y was defined.

The lead-acid batteries of sample Nos. 1-7 to 1-12 were Q-85 type liquid lead-acid batteries for ISS, and lead-acid batteries having a capacity of 61Ah for 20 hours and an operating voltage of 12V were produced. An electrolytic cell having all the cell compartments of 35.0mm in dimension Z and ribs on the opposing walls was prepared, and the ribs were scraped with a chisel or the like (the protruding dimension of the ribs was different for each sample), thereby obtaining an electrolytic cell for each sample.

As shown in Table 1, the lead-acid batteries of sample Nos. 1-7 to 1-12 have different values of Z/(X + Y), and have the same structure in other respects. In all samples, X ═ Y was defined.

[ test and evaluation ]

The obtained lead-acid batteries of Nos. 1-1 to 1-12 were allowed to stand at 25 ℃ for 48 hours, and then the internal resistance was measured, and the measured value was used as the initial value of the internal resistance. Next, each lead storage battery was left to stand in an atmosphere at a temperature of 25 ℃ for 30 days, and then the internal resistance was measured. The measured value was set as the internal resistance value after self-discharge. Next, these values are substituted into an equation of an internal resistance increase rate (%) shown below, and the internal resistance increase rate is calculated.

Internal resistance increase rate (%) ((internal resistance value after self-discharge-initial value of internal resistance)/initial value of internal resistance) × 100

If the internal resistance increase rate is 10% or less, it can be determined that the increase suppression effect of the internal resistance is obtained. When the initial value of the internal resistance is 5.0m Ω or more, the reference is not satisfied, and therefore it can be determined that the internal resistance is defective.

The results of these tests are shown in table 1 together with the values of Z, X ═ Y and Z/(X + Y).

[ TABLE 1 ]

As shown in Table 1, the lead-acid batteries of Nos. 1-1 to 1-3 and 1-7 to 1-9 had an internal resistance increase rate of 5% or less (. circleincircle.). In the lead-acid batteries of nos. 1 to 4 and 1 to 10, the internal resistance increase rate was 10% or less (. smallcircle.). In the other lead-acid battery, the internal resistance increase rate was a value (x) of more than 10%. In addition, the lead-acid batteries of nos. 1-1 and 1-7 do not satisfy the rated capacity (x).

From these results, it is understood that by setting the value of Z/(X + Y) to 12.5 or more and 21.0 or less, a lead-acid battery can be obtained in which the increase in internal resistance due to self-discharge caused by gas generated in the battery is suppressed while ensuring excellent battery performance (the battery capacity per unit volume is sufficiently large).

In addition, of lead-acid batteries in which the value of Z/(X + Y) is 12.5 or more and 21.0 or less, the lead-acid battery in which the value of Z/(X + Y) is 12.5 or more and 16.0 or less has a particularly high effect of suppressing an increase in internal resistance. Therefore, the value of Z/(X + Y) is preferably 12.5 or more and 16.0 or less.

< test 2>

[ production of test Battery ]

As a lead-acid battery having the same configuration as that of the lead-acid battery of the second embodiment, lead-acid batteries of sample No. 2-1 to No. 2-4 were produced by a conventionally known method described in the embodiments. That is, in the lead-acid batteries of sample nos. 2-1 to 2-4, as shown in fig. 4, the first ribs 31 and the second ribs 32 are constituted by the vertical portions 31a, 32a and the inclined portions 31b, 32 b.

The lead-acid batteries of sample Nos. 2-1 to 2-2 were M-42 type liquid lead-acid batteries for ISS, and lead-acid batteries having a capacity of 35Ah for 20 hours and an operating voltage of 12V were produced. An electrolytic cell having all the cell chambers of 27.0mm in dimension Z and ribs on the opposing walls was prepared, and the ribs were scraped with a chisel or the like (the protruding dimension of the ribs was different for each sample), thereby obtaining an electrolytic cell for each sample.

As shown in Table 2, the lead-acid batteries of sample Nos. 2-1 and 2-2 have different values of the ratio (L1/L2) and have the same structure in other respects. L1 was changed by setting L2 to be fixed, so that the ratios (L1/L2) were 3/4 and 4/5.

The lead-acid batteries of sample Nos. 2-3 to 2-4 were Q-85 type liquid lead-acid batteries for ISS, and lead-acid batteries having a capacity of 61Ah for 20 hours and an operating voltage of 12V were produced. An electrolytic cell having all the cell compartments of 35.0mm in dimension Z and ribs on the opposing walls was prepared, and the ribs were scraped with a chisel or the like (the protruding dimension of the ribs was different for each sample), thereby obtaining an electrolytic cell for each sample.

As shown in Table 2, the lead-acid batteries of sample Nos. 2-3 and 2-4 have different values of the ratio (L1/L2) and have the same structure in other respects. L1 was changed by setting L2 to be fixed, making the ratios (L1/L2) 3/4 and 4/5.

In all samples, X is equal to Y and θ is equal to 60 °.

[ test and evaluation ]

The internal resistance of the obtained lead-acid batteries of nos. 2-1 to 2-4 was measured by the same method as in test 1, and then the rate of increase in the internal resistance was calculated and evaluated by the same method.

Further, the lead-acid batteries of nos. 2-1 to 2-4 and the lead-acid batteries of nos. 1-3 and 1-9 of test 1 were evaluated as to whether or not the laminate 43 could be inserted smoothly without being caught by the first rib 31 and the second rib 32 when the laminate 43 was inserted (group insertion property). In this evaluation, a case where the laminate 43 can be inserted without being caught by the first ribs 31 and the second ribs 32, and a flaw (for example, a dent such as a streak) caused by the first ribs 31 or the second ribs 32 cannot be visually recognized on the surface of the positive electrode plate or the negative electrode plate or the separator located at the outermost side of the laminate 43 when the laminate 43 is taken out is referred to as "group insertability: "group insertion property" means a case where, although the stacked body 43 is caught by the first ribs 31 and the second ribs 32, a flaw (for example, a dent such as a streak) cannot be visually recognized on the surface of the positive electrode plate or the negative electrode plate or the separator located at the outermost side of the stacked body 43: "group insertion property" is a property in which the laminate 43 is caught by the first ribs 31 and the second ribs 32, and a flaw (for example, a dent such as a streak) can be visually recognized on the surface of the positive electrode plate or the negative electrode plate or the separator located outermost in the laminate 43: and (delta).

The test results are shown in table 2 together with values of Z, X ═ Y, Z/(X + Y), θ, and the ratio (L1/L2).

[ TABLE 2 ]

As shown in table 2, the lead-acid batteries of nos. 2-1 to 2-4 having the inclined portions 31b, 32b above the vertical portions 31a, 32a were better in group insertion property than the lead-acid batteries of nos. 1-3 and 1-9 having no inclined portions in the first rib 31 and the second rib 32.

The lead-acid batteries of nos. 2-1 and 2-3 having a ratio (L1/L2) of 4/5 had an internal resistance increase rate (circleincircle) equivalent to that of the lead-acid batteries of nos. 1-3 and 1-9 having no inclined portion of the first rib 31 and the second rib 32. On the other hand, the lead-acid batteries of nos. 2-2 and 2-4 having a ratio (L1/L2) of 3/4 had higher internal resistance increase rates (O) than the lead-acid batteries of nos. 1-3 and 1-9.

As is apparent from the above description, by providing the inclined portions in the first rib and the second rib, the group insertion property becomes good, and by setting the ratio (L1/L2) to 4/5 when the angle of the inclined portions is 60 °, it is possible to obtain a lead acid storage battery in which the increase in internal resistance due to self-discharge caused by gas generated in the battery is suppressed while the group insertion property is kept good.

< test 3>

[ production of test Battery ]

As a lead-acid battery having the same configuration as that of the lead-acid battery of the second embodiment, lead-acid batteries of sample No. 3-1 to 3-4 were produced by a conventionally known method described in the embodiments. That is, in the lead-acid batteries of sample nos. 3-1 to 3-4, as shown in fig. 4, the first ribs 31 and the second ribs 32 are constituted by the vertical portions 31a, 32a and the inclined portions 31b, 32 b.

The lead-acid batteries of sample Nos. 3-1 and 3-2 were M-42 type liquid lead-acid batteries for ISS, and lead-acid batteries having a capacity of 35Ah for 20 hours and an operating voltage of 12V were produced. An electrolytic cell having all the cell chambers of 27.0mm in dimension Z and ribs on the opposing walls was prepared, and the ribs were scraped with a chisel or the like (the protruding dimension of the ribs was different for each sample), thereby obtaining an electrolytic cell for each sample.

As shown in Table 3, the lead-acid batteries of sample Nos. 3-1 and 3-2 have different values of θ and have the same structure in other respects.

The lead-acid batteries of sample Nos. 3-3 and 3-4 were Q-85 type liquid lead-acid batteries for ISS, and lead-acid batteries having a capacity of 61Ah for 20 hours and an operating voltage of 12V were produced. An electrolytic cell having all the cell compartments of 35.0mm in dimension Z and ribs on the opposing walls was prepared, and the ribs were scraped with a chisel or the like (the protruding dimension of the ribs was different for each sample), thereby obtaining an electrolytic cell for each sample.

As shown in Table 3, the lead-acid batteries of sample Nos. 3-3 and 3-4 have different values of θ and have the same structure in other respects.

In all samples, X is set to Y, and the ratio (L1/L2) is set to 4/5.

[ test and evaluation ]

The obtained lead-acid batteries of Nos. 3-1 to 3-4 were evaluated for group insertion by the same method as in test 2.

The test results are shown in table 3 together with the values of Z, X ═ Y, Z/(X + Y), ratio (L1/L2), and θ. For comparison, the results of evaluation of the battery insertability of the lead-acid batteries of nos. 2-2 and 2-4 in test 2 are also shown in table 3.

[ TABLE 3 ]

As is clear from the results in table 3, the lead-acid batteries of nos. 3-2 and 3-4, in which θ is 30 °, are particularly excellent in battery insertion performance. In addition, it is presumed that when θ is less than 30 °, the group insertion property is particularly excellent. From this, it is understood that particularly excellent group insertion properties can be obtained by setting θ to 30 ° or less.

Claims (4)

1. A lead-acid battery is characterized in that,

the electrolytic cell is provided with a cell chamber having two parallel wall surfaces facing each other, and an electrode group housed in the cell chamber together with an electrolytic solution,

the electrode plate group has a laminate composed of positive electrode plates and negative electrode plates arranged alternately, and separators arranged between the positive electrode plates and the negative electrode plates,

the stacked body is disposed in the battery cell chamber so that a direction perpendicular to the wall surface and a stacking direction of the stacked body coincide with each other,

a first rib is projected from one of the two wall surfaces, and a second rib is projected from the other wall surface,

the stacked body is in contact with the first rib and the second rib,

the maximum protrusion dimension X of the first rib, the maximum protrusion dimension Y of the second rib, and the dimension Z between the two opposing wall surfaces satisfy the following expression (1):

12.5≤Z/(X+Y)≤21.0……(1)。

2. the lead-acid battery according to claim 1,

in the formula (1), the value of Z/(X + Y) is 12.5 or more and 16.0 or less.

3. Lead storage battery according to claim 1 or 2,

the positive electrode plate has: a positive electrode current collector having a rectangular grid-shaped substrate and lug portions protruding upward from the grid-shaped substrate; and a positive electrode mixture held by the grid-like substrate,

the negative electrode plate has: a negative electrode current collector having a rectangular grid-shaped substrate and lug portions protruding upward from the grid-shaped substrate; and a negative electrode mixture held by the grid-like substrate,

the first and second ribs are constituted by a vertical portion extending vertically upward from the bottom surface of the electrolytic cell, and an inclined portion extending obliquely from the upper end of the vertical portion toward the wall surface,

L1/L2, which is a ratio of a height L1 of the vertical portion from the bottom surface to a dimension L2 of the grid-shaped substrate of the positive and negative electrode plates in the height direction of the electrolytic cell, is 4/5 or more.

4. The lead-acid battery according to claim 3,

an angle θ formed by the inclined surface of the inclined portion and a perpendicular surface of the vertical portion with respect to the bottom surface is 5 ° or more and 30 ° or less.

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