CN211320252U

CN211320252U - Lead-acid battery

Info

Publication number: CN211320252U
Application number: CN202020166069.2U
Authority: CN
Inventors: 赤阪有一; 西村章宏; 佐藤笃志; 小野祐太朗; 若梅一真
Original assignee: Furukawa Battery Co Ltd
Current assignee: Furukawa Battery Co Ltd
Priority date: 2019-04-05
Filing date: 2020-02-13
Publication date: 2020-08-21
Anticipated expiration: 2030-02-13
Also published as: JP6982593B2; JP2020170681A

Abstract

The utility model provides a novel lead storage battery, even also can expect the fracture of ear and the suppression of the moisture reduction in the electrolyte under the condition of using with partial state of charge. The lead storage battery includes: a battery cell chamber; a plate group (3) housed in the cell chamber; and an electrolyte (5) injected into the cell chamber, wherein the plurality of negative electrode plates (31) and the plurality of positive electrode plates (32) that form the electrode plate group (3) each have: substrates (311, 321) that hold active materials; and current collecting lug parts (312, 322) projecting upward from the substrate, the lug parts (312, 322) being connected by a negative electrode bus bar (310) and a positive electrode bus bar (320), respectively, and the ratio (We/Wp) of the total mass (We) of the electrolyte held by the plurality of negative and positive electrode plates to the total mass (Wp) of the plurality of negative and positive electrode plates being 0.04 to 0.12 inclusive.

Description

Lead-acid battery

Technical Field

The utility model relates to a lead storage battery.

Background

In recent years, in order to reduce environmental load, vehicles have been rapidly driven by electric power, and idling stop vehicles and hybrid vehicles have appeared. Hybrid vehicles include micro hybrid vehicles, mild hybrid vehicles, and strong hybrid vehicles, and the popularity of relatively inexpensive micro hybrid vehicles and mild hybrid vehicles has risen.

In the above-described micro hybrid vehicle, mild hybrid vehicle, a lead storage battery for idle stop is used for engine start and restart. In the idle stop function, when deterioration of the battery has progressed to a certain extent, the function is stopped by control on the vehicle side, but a lead storage battery may be used as it is for starting. Even in such a case, it is necessary to avoid the occurrence of a problem that the engine cannot be started due to a sudden decrease in voltage.

In connection with this, patent document 1 describes a liquid lead acid storage battery as a lead acid storage battery for an idle stop vehicle, the liquid lead acid storage battery including a negative electrode plate filled with a negative electrode active material in a negative electrode grid obtained by spreading or punching a rolled sheet of a Pb — Ca — Sn alloy, a positive electrode plate, a negative electrode busbar to which a plurality of lug portions of the negative electrode plate are welded, and a positive electrode busbar. In addition, the following are described: when the lead-acid battery is used in an insufficiently charged state as in an idling stop vehicle, the lug portion of the negative electrode grid is thinned to reach the end of the life; and in order to suppress the ear thinning of the negative electrode grid, a ratio L2/L1 of a total thickness L2 of the ear portions of the plurality of negative electrode plates to a dimension L1 of the negative electrode bus bar is set to be 0.22 or more and 0.34 or less.

Patent document 2 describes the following: in a vehicle such as an idling stop vehicle or a vehicle mounted with a regenerative braking system, that is, in a use environment where soc (state of charge) is deeper and charge/discharge frequency is higher, a problem arises in that corrosion progresses at the negative electrode grid ear portion, and as a result, the thickness of the negative electrode grid ear portion decreases, current collection efficiency of the negative electrode decreases, and the service life decreases.

As one of the causes of corrosion of the negative grid ear portion, the following is described: even in a state where the electrode holder and the negative electrode grid lug part are immersed in the electrolyte solution, Sb disposed on the positive electrode grid, and Sb contained in the lead alloy connecting member such as the positive electrode holder, the positive electrode post, and the positive electrode connector dissolve into the electrolyte solution, and deposit on the surface of the negative electrode grid lug part in a slight amount. In addition, the following are described: in order to prevent corrosion of the anode grid lug portions, the anode grid, the anode connecting member, the cathode grid, and the anode connecting member are formed of lead or a lead alloy that does not contain Sb. The negative electrode grid is a pull-out grid, the negative electrode grid ribs are provided with pull-out meshes and framework ribs connected with the pull-out meshes, the negative electrode grid ears are integrally provided with the framework ribs, and when the height dimension of the negative electrode grid ears is Lt and the height dimension of the framework ribs is Lf, the ratio (Lt/Lf) is 2.2-15.0.

Patent document 3 describes the following: a lead-acid battery which can perform high-rate discharge even in a state of a shallow depth of charge (SOC) and has a long service life is realized by optimizing the arrangement relationship and the electrical connection relationship between the unit batteries, and optimizing the arrangement of the positive electrode plate and the negative electrode plate, the relative relationship between the cross-sectional areas and the thicknesses of the lug parts of the positive electrode plate and the negative electrode plate, and the like.

Patent document 4 describes the following: in the valve-regulated lead-acid battery, since the welded portion between the lug portion of the negative electrode plate and the bus bar is exposed from the electrolyte, even during charging, the welded portion is higher than the equilibrium potential of lead, and therefore, there is a problem that the weld interface is broken due to corrosion progressing at the lug portion and the bus bar by sulfuric acid that has climbed to the lug portion and the bus bar and oxygen generated from the positive electrode. In addition, the following are described: if the ratio (d/l) of the thickness (d) of the lug portion of the negative electrode plate to the length (l) of the lug portion in the height direction is small, the lug portion thickness is thin relative to the lug portion length, and therefore breakage due to corrosion easily occurs.

On the other hand, by suppressing the reduction of the moisture in the electrolytic solution, the frequency of maintenance for supplying water to the electrolytic cell of the lead acid battery can be reduced. Further, the higher the temperature, the more likely the moisture in the electrolyte decreases. Therefore, since micro hybrid vehicles and mild hybrid vehicles are expected to rapidly spread in southeast asia, which is a high-temperature area, in the future, it can be said that the performance capable of suppressing the reduction of moisture in the electrolyte is one of important performances of the lead-acid storage battery for an idling stop vehicle.

Patent document 5 describes a liquid lead-acid battery using grids of a Pb — Ca alloy for a positive electrode and a negative electrode in order to suppress a decrease in moisture in an electrolyte. In addition, the following are described: in order to improve the charge acceptance of the lead-acid battery and improve the life characteristics, the mass ratio (SA/PAM) of the mass (SA) of sulfuric acid to the positive electrode active material (PAM) of the electrolyte held in the positive electrode active material and the mass ratio (SB/PAM) of the mass (SB) of sulfuric acid to the positive electrode active material (PAM) of the electrolyte present between the positive electrode plate and the negative electrode plate are specified.

However, patent documents 1 to 5 do not describe the relationship between the total mass Wp of the positive and negative electrode plates constituting the lead-acid battery and the total mass We of the electrolyte held by the negative and positive electrode plates.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 5772497

Patent document 2: japanese patent No. 4892827

Patent document 3: japanese patent No. 5106712

Patent document 4: japanese patent No. 6070684

Patent document 5: japanese patent No. 4857894

SUMMERY OF THE UTILITY MODEL

Problem to be solved by the utility model

The present invention addresses the problem of providing a novel lead-acid battery that can be expected to suppress breakage of the ear and reduction in moisture in the electrolyte even when used in a partially charged State (PSOC).

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 (1) to (5).

(1) The disclosed device is provided with: an electrolytic cell having a plurality of cell chambers partitioned by partition walls; a plurality of electrode plate groups respectively housed in the plurality of battery cell chambers; and an electrolyte injected into the plurality of cell compartments.

(2) The electrode plate group comprises: a plurality of positive electrode plates and negative electrode plates arranged alternately; a separator disposed between the positive electrode plate and the negative electrode plate; and a positive electrode bus bar and a negative electrode bus bar arranged above the plurality of positive electrode plates and the plurality of negative electrode plates. The positive electrode bus bar connects the plurality of positive electrode plates to each other at different positions in the width direction of the positive electrode plates in the thickness direction of the positive electrode plates. The negative electrode bus bar connects the plurality of negative electrode plates to each other at different positions in the width direction of the negative electrode plates in the thickness direction of the negative electrode plates.

(3) A positive electrode intermediate post that rises from a positive electrode bus bar of an electrode plate group disposed in one of two adjacent battery cell chambers and a negative electrode intermediate post that rises from a negative electrode bus bar of an electrode plate group disposed in the other battery cell chamber are connected by a metal portion embedded in a through hole formed in a partition wall.

(4) The positive electrode plate and the negative electrode plate each have: a substrate that holds a mixture containing an active material; and a current collecting lug projecting upward from the outer frame of the substrate. The lug portions of the positive electrode plate are connected by a positive electrode bus bar. The lug portions of the negative electrode plates are connected by a negative electrode bus bar.

(5) The ratio (We/Wp) of the total mass We of the electrolyte held by the plurality of positive and negative electrode plates to the total mass Wp of the plurality of positive and negative electrode plates is 0.04 to 0.12, for each cell.

The lead-acid battery of the second mode of the present invention is characterized in that, in the lead-acid battery of the first mode of the present invention,

x is 50mm calculated by the following expression (1) using a dimension L (mm) of the ear portion in a height direction, a dimension W (mm) of the ear portion in the width direction, and a dimension T (mm) of the ear portion in the thickness direction^-1Above and 500mm^-1In the following, the following description is given,

X＝L³/(W×T³)……(1)。

a lead-acid battery according to a third aspect of the present invention is characterized in that, in the lead-acid battery according to the first or second aspect of the present invention,

a plurality of the battery cell compartments are arranged in one direction,

the electrode plate group disposed in the battery cell chamber at one end in the arrangement direction has a positive electrode intermediate terminal rising from the positive electrode bus bar and a negative electrode terminal rising from the negative electrode bus bar, and the electrode plate group disposed in the battery cell chamber at the other end in the arrangement direction has a positive electrode terminal rising from the positive electrode bus bar and a negative electrode intermediate terminal rising from the negative electrode bus bar,

the liquid level height of the electrolyte in the cell chamber is different between the cell chamber located at both ends in the arrangement direction and the other cell chambers.

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,

the liquid level of the electrolyte in the cell chambers located at both ends in the arrangement direction is higher than the liquid level of the electrolyte in the other cell chambers.

Effect of the utility model

The utility model discloses a lead accumulator is neotype lead accumulator, according to the utility model discloses a lead accumulator even under the condition with partial state of charge use, also can expect the fracture of ear and the suppression of the moisture reduction in the electrolyte.

Drawings

Fig. 1 is a partial sectional view showing a lead-acid battery according to an embodiment.

Fig. 2 is a plan view showing an electrolytic cell having a plurality of battery cell chambers partitioned by partition walls and a bus bar of an electrode plate group arranged in the battery cell chambers in the lead-acid storage battery according to the embodiment.

Fig. 3 is a perspective view illustrating a dimension L, W, T of an ear portion of each of the positive and negative electrode plates constituting the electrode plate group of the lead-acid battery according to the embodiment, and a dimension L indicates a dimension of a portion below the bus bar in a state of being connected by the bus bar (the same as in fig. 1).

Description of the symbols

1 electrolytic cell

13 bulkhead

13a through hole of partition wall

2 cover

3 polar plate group

31 negative electrode plate

311 negative electrode base plate (base plate of negative plate)

312 negative plate ear

310 cathode bus bar

310a cathode intermediate pole

361 negative terminal pole

32 positive plate

321 positive electrode base plate (base plate of positive plate)

322 positive plate ear

320 positive electrode bus bar

320a anode middle pole

362 positive terminal post

330a buried in the through hole

41 cell chamber at one end of arrangement direction

46 in the other end of the arrangement direction

42-45 other battery cell chambers

5 electrolyte solution

L₃₁₀Center line of negative electrode bus bar in width direction

L₃₂₀The width direction center line of the positive electrode bus bar.

Detailed Description

[ study ]

As to the above-described cause of breakage of the ear portion, the inventors of the present invention made various studies and, as a result, found that: in addition to the fact that the ear part is easily thinned due to corrosion in the positive electrode due to use under PSOC in the negative electrode, vibration caused by frequent restart after idle stop peculiar to the idle stop vehicle is also one of causes of breakage of the ear part. In addition, the reason why ear thinning easily occurs in the negative electrode under PSOC is that: the negative electrode is easily sulfated under PSOC, and if used in a sulfated state, the ear portion is activated and eventually falls off.

In addition, the inventors of the present invention have made various studies considering that the weight of the electrode plate seems to affect the breakage of the ear in the lead-acid battery in which the ear thinning has been started. As a result, it was found that when the ratio (We/Wp) of the total mass (We) of the electrolyte solution held by the positive electrode plate and the negative electrode plate to the total mass (Wp) of the positive electrode plate and the negative electrode plate is 0.04 or more and 0.12 or less, breakage of the ear portion is suppressed, and a battery having excellent water reducing characteristics is obtained.

In the case where the ratio (We/Wp) is less than 0.04, it is considered that the load on the ear portion is increased due to the heavy pole plate, so that the ear portion becomes easily broken. When the ratio (We/Wp) is greater than 0.12, it is considered that the electrolyte solution held by the electrode plate is large, and even if the electrolyte solution is reduced due to deterioration of the electrode plate (in a state of large lead sulfate), a state of high concentration (specific gravity) of the electrolyte solution continues, and thus corrosion of the ear portion easily progresses.

When the ratio (We/Wp) is larger than 0.12, the amount of moisture reduction in the electrolyte solution increases. The reason for this is not clear, but is considered to be: for the above reasons, even if the electrode plate is deteriorated, the specific gravity is not easily lowered, and the liquid resistance is low, so that the charging current easily flows, and thus the electrolysis of water easily progresses during the charging.

The lead-acid battery of one embodiment preferably has the following structure (11).

(11) X calculated by the following expression (1) using a dimension l (mm) of the ear in the height direction, a dimension w (mm) of the ear in the width direction (same as the width direction of the positive and negative electrode plates), and a dimension t (mm) of the ear in the thickness direction (same as the thickness direction of the positive and negative electrode plates) is 50mm^-1Above and 500mm^-1The following.

X＝L³/(W×T³)……(1)

It can be presumed that: the lead storage battery in one mode has a size of 50mm^-1≤X≤500mm^-1In the case of the ear portion of (3), resonance caused by individual vibration of each battery cell chamber is suppressed, and thus breakage of the ear portion is suppressed. The expression (1) is obtained by focusing on the calculation formula of the deflection of the plate spring, and if it does not satisfy 50mm^-1≤X≤500mm^-1It is presumed that the ear portion is not properly flexed and the vibration cannot be suppressed.

When the lead-acid battery of one embodiment has the following structure (12), it preferably has the following structure (13).

(12) The plurality of battery cell chambers are arranged in one direction, the electrode group arranged in the battery cell chamber at one end in the arrangement direction has a positive electrode intermediate terminal rising from the positive electrode bus bar and a negative electrode terminal rising from the negative electrode bus bar, and the electrode group arranged in the battery cell chamber at the other end in the arrangement direction has a positive electrode terminal rising from the positive electrode bus bar and a negative electrode intermediate terminal rising from the negative electrode bus bar.

(13) The liquid level of the electrolyte in the cell chamber is different between the cell chamber at both ends in the arrangement direction and the other cell chambers.

In the case where the lead-acid battery of one embodiment has the above-described configuration (12), the electrode group housed in the cell chamber at both ends and the electrode group housed in the other cell chamber are different in the state of fixation to the electrolytic cell.

Specifically, in the electrode plate group housed in the battery cell chambers at both ends, the intermediate pole standing from one of the positive electrode bus bar and the negative electrode bus bar and the intermediate pole in the adjacent battery cell chamber are fixed by a metal portion buried in a through hole formed in a partition wall of the electrolytic bath, and the terminal pole standing from the other is inserted into a through hole of a sleeve made of a lead alloy formed integrally with a lid by, for example, insert molding, and fixed. In the electrode plate group housed in another battery cell chamber, the intermediate pole standing from both the positive electrode bus bar and the negative electrode bus bar and the intermediate pole in the adjacent battery cell chamber are fixed by a metal portion buried in a through hole formed in a partition wall of the electrolytic cell.

It is presumed that, due to such a difference in the fixed state, the behavior of vibration differs between the electrode group housed in the battery cell chamber at both ends and the electrode group housed in the other battery cell chamber. Based on this, the inventors of the present invention have studied and, as a result, have obtained the following presumptions that: if the liquid level of the electrolyte in the cell chambers at both ends is different from that in the other cell chambers, the resonance point of the electrode group due to vibration is shifted, and resonance can be suppressed, whereby breakage of the ear portion can be suppressed.

That is, when the lead-acid battery of one embodiment has the above-described structure (12), it is considered that the effect of suppressing breakage of the ear portion is increased by having the above-described structure (13).

In addition, when the lead-acid battery of one embodiment has the above-described structure (12), it is considered that the effect of suppressing breakage of the ear portion is further enhanced by having the following structure (14).

(14) The liquid level of the electrolyte in the cell chambers is higher in the cell chambers located at both ends in the arrangement direction than in the other cell chambers.

For the battery cell compartments located at both ends in the arrangement direction, there are adjacent battery cell compartments in one direction of the arrangement direction, but there are no battery cell compartments in the other direction. For the other battery cell compartments (battery cell compartments other than both ends in the arrangement direction), there are adjacent battery cell compartments in both directions in the arrangement direction. Therefore, the cell chambers at both ends press the stacked body formed of the positive electrode plates, the negative electrode plates, and the separators of the electrode plate groups present inside less strongly than the other cell chambers, and gas is likely to accumulate in the space between the stacked body and the cell chambers. Therefore, the liquid level of the electrolyte in the cell chambers at both ends is easily raised.

Therefore, if the liquid level of the electrolyte in the cell chambers at both ends is made lower than the liquid level of the electrolyte in the other cell chambers in the initial state, the liquid level of the electrolyte in the cell chambers at both ends may rise during use of the lead-acid battery, and may become the same as the liquid level of the electrolyte in the other cell chambers. In addition, even if the liquid level of the electrolyte in the battery cell chambers at both ends rises as described above in the normal use state, it cannot be considered that the liquid level of the electrolyte in the battery cell chambers at both ends falls.

Therefore, if the liquid level of the electrolyte in the cell chambers at both ends is made higher than the liquid level of the electrolyte in the other cell chambers in the initial state, the liquid level of the electrolyte in the cell chambers will continue to be different between the cell chambers at both ends in the arrangement direction and the other cell chambers during use of the lead acid battery.

In this way, the lead-acid battery according to one embodiment having the above-described configuration (12) has the above-described configuration (14), and thus, in the process of using the lead-acid battery, the liquid level height of the electrolyte in the cell chamber continues in a state where the cell chamber at both ends in the arrangement direction is different from the other cell chamber. As a result, it is presumed that the resonance is suppressed by the shift of the resonance point of the electrode group due to the vibration, and the effect of suppressing the breakage of the ear portion is further increased.

[ 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.

As shown in fig. 1 and 2, the lead acid battery of the embodiment includes a conventional and well-known monolithic electrolytic cell 1, a lid 2, and six electrode plate groups 3. The electrolytic cell 1 is divided into six cell chambers 41 to 46 by partition walls 13. The six cell chambers 41 to 46 are arranged in the longitudinal direction (one direction) of the electrolytic cell 1. One electrode plate group 3 is disposed in each of the cell chambers 41 to 46. An electrolyte 5 is injected into each of the cell chambers 41 to 46.

< Structure common to multiple cell compartments >

As shown in fig. 1, the electrode plate group 3 includes: a plurality of positive and

negative electrode plates

32 and 31, a separator 33, a positive electrode bus bar 320, and a negative electrode bus bar 310.

In fig. 1, the number of positive electrode plates 31 and the number of negative electrode plates 32 constituting one electrode plate group 3 are the same, but the number of positive electrode plates 31 may be one more than the number of negative electrode plates 32, or the number of negative electrode plates 32 may be one more than the number of positive electrode plates 31. In fig. 1 to 3, the arrangement direction of the battery cell chambers 41 to 46 is represented as the X direction, the height direction is represented as the Z direction, and the direction perpendicular to the X direction and the Z direction is represented as the Y direction.

As shown in fig. 1 and 3, the positive electrode plate 32 includes: a positive electrode substrate 321 that holds a mixture containing a positive electrode active material; an ear portion 322 protruding upward from the positive electrode substrate 321; a leg (not visible in fig. 3, but corresponding to the leg 313 of the negative electrode plate 31) projecting downward from the positive electrode substrate 321. The negative electrode plate 31 has: a negative electrode substrate 311 holding a mixture containing a negative electrode active material; an ear portion 312 protruding upward from the negative electrode substrate 311; and a leg portion 313 protruding downward from the negative electrode substrate 311. The plurality of positive electrode plates 32 and negative electrode plates 31 are alternately arranged with separators 33 interposed therebetween. The negative electrode plate 31 may be placed in a separator that is folded into two pieces and folded downward, and then may be stored in a bag-shaped separator in which left and right ends of each separator are sealed by a gear seal or the like.

As shown in fig. 1, the positive electrode bus bar 320 and the negative electrode bus bar 310 are disposed above all the positive electrode plates 32 and the negative electrode plates 31 in one battery cell compartment, the positive electrode bus bar 320 connects the lug portions 322 of all the positive electrode plates 32 in the thickness direction (X direction), and the negative electrode bus bar 310 connects the lug portions 312 of all the negative electrode plates 31 in the thickness direction (X direction). In fig. 1, a dimension L in the height direction (Z direction) of the

ear portions

312, 322 is shown.

As shown in fig. 3, the ear portions 322 of the positive electrode plate 32 and the ear portions 312 of the negative electrode plate 31 are disposed at different positions in the width direction (the direction in the Y direction when entering the battery cell chamber).

In fig. 3, only the width-direction center line L of the positive electrode bus bar 320 is described for the positive electrode bus bar 320 and the negative electrode bus bar 310 that connect the lug portions 322 of the positive electrode plate and the lug portions 312 of the negative electrode plate 31, respectively₃₂₀And the width-direction center line L of the cathode bus bar 310₃₁₀。

That is, the positive electrode plate 32 is connected to the negative electrode plate 31 at different positions in the width direction (the direction in the Y direction when the positive electrode plate is inserted into the cell compartment) via the positive electrode bus bar 320 and the negative electrode plate 31 is connected to the negative electrode bus bar 310.

Fig. 3 shows a portion of the electrode plate group 3 shown in fig. 1 on the lower side than the positive electrode bus bar 320 and the negative electrode bus bar 310. In fig. 3, a dimension L in the height direction Z, a dimension W in the width direction (direction Y perpendicular to the arrangement direction of the cell chambers), and a dimension T in the thickness direction (arrangement direction X of the cell chambers) of the

ear portions

312, 322 are shown for the negative electrode plate 31 and the positive electrode plate 32 at this portion. Further, the

ear portions

312 and 322 satisfy 50mm in X calculated by the following expression (1) using the dimension L (mm), the dimension W (mm), and the dimension T (mm), respectively^-1Above and 500mm^-1The following.

X＝L³/(W×T³)……(1)

The positive electrode substrate 321, the lug portions 322, and the leg portions are integrally formed of a lead alloy, and the content of antimony (Sb) in the metal forming the lug portions 322 is 50ppm or less. The negative electrode substrate 311, the ear portion 312, and the leg portion 313 are integrally formed of a lead alloy, and the content of antimony (Sb) in the metal forming the ear portion 312 is 50ppm or less.

< relationship of multiple cell compartments >

In fig. 1, the upper side portion of a cell chamber 41 at one end in the arrangement direction and a cell chamber (other cell chamber) 42 adjacent thereto are mainly shown. That is, fig. 1 corresponds to a sectional view a-a of fig. 2. The negative electrode intermediate terminal 310a rising from the right end of the negative electrode bus bar 310 in one (left) cell chamber 41 and the positive electrode intermediate terminal 320a rising from the left end of the positive electrode bus bar 320 in the other (right) cell chamber 42 are connected by a metal portion 330a embedded in the through hole 13a formed in the partition wall 13. The metal portion 330a is a metal portion generated in the through-hole 13a by sandwiching the portion of the partition wall 13 where the through-hole 13a is formed between the negative electrode intermediate electrode post 310a and the positive electrode intermediate electrode post 320a, and resistance-welding the two intermediate electrode posts to each other.

As shown in fig. 2, the electrode plate group 3 in the battery cell chamber 41 disposed at one end in the arrangement direction has a negative electrode intermediate electrode post 310a rising from the negative electrode bus bar 310 and a positive electrode terminal electrode post 362 rising from the positive electrode bus bar 320. The electrode group 3 disposed in the battery cell chamber 46 at the other end in the arrangement direction has a positive electrode intermediate terminal 320a rising from the positive electrode bus bar 320 and a negative electrode terminal 361 rising from the negative electrode bus bar 310. The positive terminal post 362 and the negative terminal post 361 are formed on the tab portions 35 extending in the Y direction from the positive bus bar 320 and the negative bus bar 310, respectively.

In each of the cell chambers 41 to 46, the ratio (We/Wp) of the total mass We of the electrolyte held by the plurality of positive electrode plates 32 and negative electrode plates 31 to the total mass Wp of the plurality of positive electrode plates 32 and negative electrode plates 31 is 0.04 or more and 0.12 or less.

As shown in FIG. 1, the liquid level H1 of the electrolyte 5 in the cell chamber 41 at one end in the arrangement direction is higher than the liquid level H2 of the electrolyte 5 in the cell chambers 42 to 45 at the other ends. The liquid level of the electrolyte 5 in the cell chamber 46 at the other end in the arrangement direction is the same as the liquid level H1 in the cell chamber 41 and is higher than the liquid level H2 of the electrolyte 5 in the cell chambers 42 to 45 not located at the both ends.

< action, Effect >

In the lead-acid battery of this embodiment, the ratio (We/Wp) is 0.04 or more and 0.12 or less per cell chamber 41 to 46, and therefore, even when the lead-acid battery is used in a partially charged state, breakage of the

ear portions

312 and 322 can be suppressed, and reduction in the amount of the electrolytic solution 5 can also be suppressed. In addition, in the lead-acid battery of this embodiment, X calculated by the expression (1) using the dimension L, W, T of the

ear portions

312 and 322 satisfies 50mm^-1Above and 500mm^-1The following relation H1 is satisfied>H2, the breakage suppression effect of the

ear portions

312 and 322 is high, and the reduction suppression effect of the electrolyte 5 is also high.

< preparation method >

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

First, a positive electrode plate and a negative electrode plate are produced before formation of an electrode plate group. At this time, the dimension L in the height direction of the ear, the dimension W in the width direction of the ear, and the dimension T in the thickness direction of the ear of the negative electrode plate ear 312 and the positive electrode plate ear 322 are determined so that X calculated by the equation (1) satisfies 50mm^-1Above and 500mm^-1The following. The particle size of the active material used is adjusted so that the ratio (We/Wp) in each cell chamber 41-46 is 0.04-0.12. The particle size of the active substance is controlled by the formation temperature. It is known that the larger the formation temperature, the larger the size of the positive and negative electrode active materials.

Next, the positive electrode plates and the negative electrode plates before formation are alternately stacked with separators made of polyethylene or the like interposed therebetween, thereby obtaining a stacked body. The separator may be formed into a bag-like separator by disposing the positive electrode plate or the negative electrode plate in a separator which is folded into two pieces and has folds facing downward, and then sealing the left and right ends of each separator by gear sealing or the like.

Next, a positive electrode bus bar 320 connecting the lug portions 322 of the positive electrode plates, a negative electrode bus bar 310 connecting the lug portions 311 of the negative electrode plates, a positive electrode intermediate post and a positive electrode terminal post standing from the positive electrode bus bar 320, and a negative electrode intermediate post 310a and a negative electrode terminal post 361 standing from the negative electrode bus bar are formed on the laminate using a COS (case-on strap) casting apparatus to obtain an electrode plate group 3, and then the electrode plate group 3 is housed in each cell chamber of the electrolytic cell.

Next, in a state where the electrode group is housed in each battery cell chamber of the electrolytic cell 1, the positive electrode intermediate electrode 320a and the negative electrode intermediate electrode 310a adjacent to each other with the partition wall 13 between the battery cell chambers interposed therebetween are resistance-welded, and the adjacent battery cell chambers are electrically connected in series. Next, the upper surface of the electrolytic cell 1 and the lower surface of the lid 2 are melted with heat and the lid 2 is placed on the electrolytic cell 1, and the lid 2 is fixed to the electrolytic cell 1 by thermal fusion. When the lid is placed in the electrolytic cell, the negative electrode terminal post 310a and the positive electrode terminal post 320a are inserted into through holes of a lead alloy sleeve (not shown) formed integrally with the lid 2 by insert molding, and are welded and integrated to form a terminal.

Then, an electrolyte (containing aluminum ions by adding aluminum sulfate to the sulfuric acid aqueous solution) 5 is injected into the cell chambers from injection ports (not shown) provided in the lid 2 as holes communicating with the cell chambers. Then, a normal process such as closing the pouring port with a port plug (not shown) is performed, whereby an unfinished lead acid battery is assembled. Then, the formation of the electrolytic cell was carried out under ordinary conditions.

Then, the electrolyte 5 is added to the cell chamber 41 at one end and the cell chamber 46 at the other end in the arrangement direction, and the liquid level of the electrolyte 5 is made higher than the liquid level of the electrolyte 5 in the other cell chambers 42 to 45, thereby producing a finished product.

[ examples ] A method for producing a compound

< production of test Battery >

As a lead-acid battery having the same structure as that of the lead-acid battery of the embodiment, sample nos. 1 to 90 were produced.

The lead-acid batteries of sample nos. 1 to 90 are liquid lead-acid batteries for idle stop of type D23, and have the same configuration in all respects except that the ratios (We/Wp), the value of X relating to the size of the ear portion, and whether or not the liquid level height of the electrolyte is different between the cell chambers at both ends and the other cell chambers (hereinafter referred to as "liquid level height relationship") are different as shown in table 1 and table 2.

The positive and negative electrode plates of the lead-acid batteries constituting the respective samples had the same value of X. That is, X shown in the table shows the values of both the positive electrode plate and the negative electrode plate.

First, a base material having a shape in which a grid-like substrate, a current collecting lug portion, and a leg portion extending downward from the grid-like substrate are integrated before a mixture containing an active material is held is produced using a Pb — Ca — Sn-based alloy having an antimony content of 50ppm or less. At this time, in the negative electrode and the positive electrode, X was changed by changing the thickness (dimension T) of the ear portion by fixing the width (dimension W) of the ear portion and fixing the height (dimension L) of the ear portion (13mm), respectively.

Reference numeral 43 denotes a reference sample, and in the positive electrode plate of reference numeral 43, X calculated by substituting T of 1.04mm, L of 13mm, and W of 13mm into the formula (1) is substantially 150mm^-1. In the negative electrode plate of No. 43, X calculated by substituting T of 1.02mm, L of 13mm, and W of 14mm into expression (1) is approximately 150mm^-1。

A punched substrate having a JIS-D size was used as the positive electrode base material, and a continuously cast substrate having a JIS-D size was used as the negative electrode base material. In addition, the grid design of the substrate is determined by current/potential analysis simulation in consideration of the ease of manufacturing the base material and the amount of lead so that the potential distribution is as uniform as possible. Specifically, the amount of lead in the portion around the ear where the current is concentrated is increased, and a grid design is made such that the grid is radial from the ear as a base point.

Next, a substrate of the positive electrode base material (positive electrode substrate) was filled with a mixture containing a positive electrode active material (positive electrode mixture) prepared by a usual method using the following composition. The composition for the positive electrode mixture is a composition obtained by mixing lead powder containing lead monoxide as a main component with compound particles containing red lead, polyester fibers (for example, tiolon (registered trademark)), bismuth, or antimony. After the filling, a normal treatment was performed to obtain a positive electrode plate before formation. A substrate of the negative electrode substrate (negative electrode substrate) is filled with a mixture containing a negative electrode active material (negative electrode mixture) prepared by a usual method, and the mixture is cured and dried to obtain a negative electrode plate before chemical conversion.

Next, 7 positive electrode plates and 8 negative electrode plates were alternately stacked with a polyethylene separator interposed therebetween, thereby obtaining a stacked body. Six of these laminates were prepared, and a COS (Cast-on strap) casting apparatus was used to form a strap and an intermediate pole or a strap and a terminal pole on the positive electrode plate and the negative electrode plate of each laminate, and then the laminates were stored in the cell chambers of the electrolytic cell. The pressing force of the laminate in the battery cell chamber was about 10 kPa.

Next, the D23 type liquid lead storage battery for idle stop was assembled by performing ordinary steps such as resistance welding of the intermediate electrode posts between the adjacent battery cell chambers, thermal welding of the electrolytic cell and the lid, injection of the electrolytic solution into each battery cell chamber from the injection port, and closing of the injection port with the port plug. Thereafter, the specific gravity after formation of the electrolytic cell was 1.285(20 ℃ C. equivalent) by formation of the electrolytic cell by a usual method.

Next, after the formation was completed and left for 48 hours, the liquid level height of the electrolyte in all the cell chambers was first adjusted to be the same. Then, in the numbers 6 to 10, 21 to 25, 36 to 40, 51 to 55, 66 to 70, and 81 to 85, the electrolyte was taken out from the

cell chambers

41, 46 at both ends, and the liquid level was 3mm lower than the liquid level of the other cell chambers 42 to 45. In addition, in the numbers 11 to 15, 26 to 30, 41 to 45, 56 to 60, 71 to 75, and 86 to 90, the electrolyte was added to the

cell chambers

41 and 46 at both ends so that the liquid level was 3mm higher than the liquid level of the other cell chambers 42 to 45. Thus, the lead-acid batteries of sample nos. 1 to 90 were completed.

Further, since the electrolyte is held in the space of the porous body formed of the active material held by the substrate, the volume V of the space is examined for the positive electrode plate and the negative electrode plate, and the total value thereof is calculated as We. Specifically, the porosity of the active material-containing mixture obtained by a mercury porosimeter (AutoPore IV of micromeritics) is multiplied by the volume of the electrode plate to obtain a space volume. We is obtained by adding the space volumes of the positive and negative electrodes in parts.

In addition, if the value of X is different, the volume of the ear is different, and thus the value of Wp varies. Therefore, in the groups (numbers 1 to 15, numbers 16 to 30, numbers 31 to 45, numbers 46 to 60, numbers 61 to 75, and numbers 76 to 90) in which the values of X are the same, the ratio (We/Wp) is changed by changing We using the positive electrode plate and the negative electrode plate having different volumes V.

< test and evaluation >

The lead-acid batteries thus obtained were each tested in the following manner.

As the PSOC life test, after an idle stop life test of SBAS 0101(2014) of 30000 cycles was performed, EN 50342-1: "Vibration resistance standard V4(Vibration resistance Level V4)" in 2015. Then, the lead-acid battery was disassembled, and the state of the ear portion was visually confirmed with respect to all the positive and negative electrode plates of the electrode plate group taken out from the one-end cell chamber 41 and the cell chambers 43 adjacent to the one-end cell chamber with a space therebetween. The percentage of the value obtained by dividing the number of broken ear portions by 30, which is the total number of electrode plates, was calculated as "ear portion breakage ratio (%)".

Additionally, the treatment was carried out for 42 days in EN 50642-1: the "water consumption test (Waterconsumption test)" described in 2015 was performed to measure how much the total amount of the electrolyte solution in the six battery cell chambers was reduced (water reduction amount). For each measured value of the obtained reduced water amount, the result of sample No. 43 was calculated as a relative value of 100.

The test results are shown in tables 1 and 2 together with the structure of the lead-acid battery (relationship between We/Wp, X and liquid level height).

[ TABLE 1 ]

[ TABLE 2 ]

As shown in Table 1 and Table 2, in each group (No. 1 to 5, No. 6 to 10, No. 11 to 15, No. 16 to 20, No. 21 to 25, No. 26 to 30, No. 31 to 35, No. 36 to 40, No. 41 to 45, No. 46 to 50, No. 51 to 55, No. 56 to 60, No. 61 to 65, No. 66 to 70, No. 71 to 75, No. 76 to 80, No. 81 to 85, No. 86 to 90) in which X and the liquid surface height have the same relationship, the samples satisfying the first aspect of the present invention, wherein the ratio (We/Wp) is 0.04 or more and 0.12 or less (No. 2 to 4, No. 7 to 9, No. 12 to 14, No. 17 to 19, No. 22 to 24, No. 27 to 29, No. 32 to 34, No. 37 to 39, No. 42 to 44, No. 47 to 49, No. 52 to 54, No. 57 to 59, No. 62 to 64, No. 69, No. 74 to 72 to 74 to 72), No. 77-79, No. 82-84, No. 87-89: example), the ear portion breakage ratio was smaller than that of the sample not satisfying the above conditions, and in terms of the water-reducing rate, although there were also some samples in which no difference was seen, a lower tendency was observed as a whole.

Samples having the ratios (We/Wp) of sample numbers 1 to 90 of 0.04 to 0.12 were taken out and summarized in tables 3 to 5 below for each relationship of the liquid surface height in the battery cell chamber. In each table, the difference in test results due to the difference in the X value can be observed for each ratio (We/Wp).

Table 3 is a table in which samples having the same liquid level height are collected.

[ TABLE 3 ]

Table 4 is a table in which samples having lower ends are collected for the liquid level.

[ TABLE 4 ]

Table 5 is a table in which samples having higher ends are collected for the liquid level height.

[ TABLE 5 ]

As can be seen from these tables, in the samples classified as examples, the passing thickness of 50mm was satisfied^-1≤X≤500mm^-1Thereby further reducing the ear breakage ratio and the water reduction rate as a whole.

The values of X for samples having sample numbers 1 to 90 in which the ratio (We/Wp) was 0.04 or more and 0.12 or less are shown in tables 6 and 7 below. In each table, differences in test results due to differences in the relationship between the liquid level levels in the battery cell chambers can be seen for each ratio (We/Wp).

Table 6 shows the values 40, 50, 150mm for X^-1Table summarizing the samples.

[ TABLE 6 ]

Table 7 is the values 350, 500, 510mm for X^-1Table summarizing the samples.

[ TABLE 7 ]

As can be seen from these tables, the thickness of the film satisfies 50mm^-1≤X≤500mm^-1In the case of (3), the liquid level of the electrolyte is set to be at a high levelThe battery cell chambers at both ends are higher than the other battery cell chambers, and the ear breakage ratio can be set to 0. The value of the ratio (We/Wp) at which the ear portion breakage ratio becomes 0 can be varied depending on the value of X.

Claims

1. A lead-acid battery is characterized by comprising:

an electrolytic cell having a plurality of cell chambers partitioned by partition walls;

a plurality of electrode plate groups respectively housed in the plurality of battery cell chambers; and

an electrolyte injected into the plurality of cell chambers,

the electrode plate group comprises: a plurality of positive electrode plates and negative electrode plates arranged alternately; a separator disposed between the positive electrode plate and the negative electrode plate; and a positive electrode bus bar and a negative electrode bus bar that are disposed above the plurality of positive electrode plates and the plurality of negative electrode plates, and that respectively connect the plurality of positive electrode plates and the plurality of negative electrode plates to each other at different positions in the width direction of the positive electrode plates and the negative electrode plates in the thickness direction of the positive electrode plates and the negative electrode plates,

a positive electrode intermediate post that rises from the positive electrode bus bar of the electrode plate group disposed in one of the two adjacent battery cell chambers, and a negative electrode intermediate post that rises from the negative electrode bus bar of the electrode plate group disposed in the other battery cell chamber, are connected by a metal portion embedded in a through hole formed in the partition wall,

the positive electrode plate and the negative electrode plate each have: a substrate holding a mixture; and current collecting lug portions protruding upward from the substrate, the lug portions being connected to the positive electrode bus bar and the negative electrode bus bar, respectively.

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

the ratio of the total mass We of the electrolyte retained by the plurality of positive and negative electrode plates to the total mass Wp of the plurality of positive and negative electrode plates, that is, We/Wp, is 0.04 to 0.12 for each of the cell compartments.

3. The lead-acid battery according to claim 1,

the composition comprises an active substance.

4. The lead-acid battery according to claim 2,

x is 50mm calculated by the following expression (1) using a dimension L of the ear portion in a height direction, a dimension W of the ear portion in the width direction, and a dimension T of the ear portion in the thickness direction^-1Above and 500mm^-1In the following, wherein the units of L, W and T are mm,

X＝L³/(W×T³)……(1)。

5. lead-acid battery according to claim 2 or 4,

a plurality of the battery cell compartments are arranged in one direction,

6. The lead-acid battery according to claim 5,