JP6762974B2 - Positive electrode grid for lead-acid batteries and lead-acid batteries - Google Patents

Description

The present invention relates to a positive electrode lattice for a lead storage battery and a lead storage battery.

In order to respond to the seriousness of environmental problems and exhaust gas regulations in recent years, automobiles equipped with an idling stop function that temporarily stops the engine when the vehicle is stopped (hereinafter referred to as "ISS vehicle") are becoming widespread. Since the ISS vehicle can suppress fuel consumption due to idling when the vehicle is stopped at a traffic light or the like, fuel efficiency can be improved and the amount of exhaust gas can be reduced.

It is known that the lead-acid battery mounted on the ISS vehicle tends to reach an early life. The reason for this is that in ISS vehicles, lead-acid batteries are used to a deep discharge depth to supply power to devices such as air conditioners, lights, wipers, and car navigation systems when the engine stops due to waiting for traffic lights, etc. It can be mentioned that a large load is applied to the lead-acid battery by repeating discharging for restarting the engine and charging by an alternator or a regenerative brake.

A lead-acid battery is manufactured by storing a group of plates having a laminated structure in an electric tank and then injecting dilute sulfuric acid, which is an electrolytic solution, into the electric tank. In the electrode plate group of the laminated structure, a positive electrode plate and a negative electrode plate in which a lattice body mainly made of lead or a lead alloy is filled with a paste-like active material, and a separator are alternately laminated. The lattice body is known to have a structure having, for example, a frame bone and an internal bone surrounded by the frame bone. The frame bones are the first horizontal frame bones arranged on the upper side and the collecting ears are formed, the second horizontal frame bones arranged on the lower side, and the ends of the first and second horizontal frame bones. It has first and second vertical frame bones to be connected. The internal bone has a plurality of horizontal and vertical crosspieces. The lattice body is filled with active material at least in the opening defined as the area surrounded by the frame bone and the internal bone.

One of the life factors of such a lead-acid battery is the expansion and deformation of the entire positive electrode grid due to the corrosion and expansion of the positive electrode grid. Such deformation of the positive electrode lattice is called growth. When growth occurs, a part of the positive electrode lattice is curved and broken, and the broken end breaks through the separator and comes into contact with the facing negative electrode plate, or expands upward and comes into contact with a part of the negative electrode such as the negative electrode strap. As a result, an internal short circuit may occur, and the lead-acid battery may reach the end of its life at an early stage. In addition, the growth of the positive electrode lattice causes exfoliation or shedding of the positive electrode active material, which causes an early decrease in capacity. Under these circumstances, when designing a lead-acid battery, it is necessary to take measures against the growth of the positive electrode grid.

The mechanism by which growth occurs is considered as follows. In lead-acid batteries, lead or lead alloys that form a positive electrode lattice by charging and discharging react mainly with sulfate ions contained in the electrolytic solution and active material, and PbO _x (x: 1-2) and PbSO ₄ This is due to the oxidation reaction that changes into a multi-layered corrosion reaction product consisting of the above. The corrosion progresses with repeated charging and discharging. At this time, a layer of the corrosion reaction product grows in the vicinity of the surface of the positive electrode lattice in contact with the electrolytic solution. Since the growth of the corrosion reaction product is accompanied by an increase in the volume of the positive electrode lattice, as the corrosion progresses, a large stress is caused by the difference in the degree of expansion between the corrosion reaction product near the surface of the positive electrode lattice and the internal positive electrode lattice itself. Occurs. As a result, the stress becomes a tensile stress that stretches the positive electrode lattice, and growth is generated due to the expansion of the entire positive electrode lattice.

Since the electrode plate group of the lead-acid battery is fixed to the lid or the upper part of the battery case by the electrode column provided so as to extend upward from the strap and the connecting member between the cells, the positive electrode plate is first fixed when growth occurs. It extends to the left and right sides and the bottom side that are not. In the initial growth, the downward growth allowance is often smaller than the lateral extension allowance of the positive electrode plate. This is because the lower end of the electrode plate group is in contact with the bottom surface of the battery case and the saddle provided on the bottom surface in order to support the electrode plate group. Therefore, when growth occurs, the downward extension of the positive electrode plate turns to the upward extension, so that the upper end of the positive electrode plate may come into contact with a part of the negative electrode such as the negative electrode strap to cause an internal short circuit.

As a means for preventing an internal short circuit due to growth to the upper side of the positive electrode lattice, the applicant in Patent Document 1 and Patent Document 2 states that a lead-acid battery in which the saddle of the battery case that holds the electrode plate group is made of sponge or foamable resin. Is proposing. By forming the saddle part of the battery case with a sponge or foamable resin, when the positive electrode lattice grows, the saddle part collapses and absorbs the downward extension, so that the upward extension of the positive electrode lattice is suppressed. Therefore, contact with the negative electrode strap and the like and internal short circuit can be prevented.

On the other hand, various inventions for suppressing an internal short circuit between the positive electrode lattice and the negative electrode lattice have been proposed in a form different from the configurations of Patent Documents 1 and 2. Patent Document 3 discloses a lead-acid battery having a structure in which the positive electrode plate is suspended in the air and the lower side of the positive electrode plate is separated from the bottom of the battery case. In this lead-acid battery, since the positive electrode plate preferentially extends downward when growth occurs, an internal short circuit due to the upward extension and the accompanying contact between the positive electrode plate and the negative electrode plate is suppressed.

In Patent Document 4 and Patent Document 5, as a method of suppressing contact between the positive electrode plate and the negative electrode plate due to growth, a lead-acid battery in which a portion having a weak mechanical strength such as a notch or a constriction is provided in a predetermined portion of the positive electrode lattice. Is disclosed. By forming a portion having a weak mechanical strength in a part of the positive electrode lattice in this way, when growth occurs, the portion having a low mechanical strength is preferentially broken or deformed, and the entire positive electrode lattice is formed. Expansion is suppressed.

In addition to the technology for suppressing the growth of the positive electrode lattice due to corrosion, it is also being studied to prevent deformation due to expansion and contraction of the active material during the charge / discharge cycle and improve the life of the lead storage battery.

Patent Document 6 discloses a lead-acid battery in which the arrangement spacing of the horizontal rails and the vertical rails constituting the inner bone is reduced from the central portion to the peripheral portion in the positive electrode lattice body. By reducing the arrangement spacing of the horizontal rails and the vertical rails from the central portion to the peripheral portion in this way, the horizontal rails and the vertical rails are arranged closer to the peripheral portion of the positive electrode grid, so that the machine of the positive electrode grid Strength is improved. Therefore, when the positive electrode active material expands in the plane direction due to charging, the deformation of the positive electrode lattice body in the lateral direction is suppressed, and the cycle characteristics of the lead storage battery are improved.

Japanese Unexamined Patent Publication No. 2001-351671 Jikkenhei 5-45901 JP 2012-079609 Japanese Patent No. 5103385 Japanese Unexamined Patent Publication No. 2013-16499 Japanese Unexamined Patent Publication No. 2-281563

However, the lead-acid batteries described in Patent Documents 1 to 3 assume a lead-acid battery for a stationary power source used in a stationary state, and are used for applications where violent vibration is expected, for example, a starting power source for an automobile. There was a point to improve the durability. In the lead-acid batteries described in Patent Documents 1 to 3, the heavy electrode plate group is supported and held only by the current collector ear connected to the strap on the upper side. Therefore, when violent vibration is applied, the electrode plate group is supported and held. There is a risk of breakage at the current collector ear.
On the other hand, in the lead-acid batteries described in Patent Documents 4 and 5, since a notch or a constriction is provided in a part of the positive electrode lattice, the electric resistance locally increases in the part and the potential distribution at the time of charging / discharging becomes large. There is a risk that non-uniformity will result in reduced current collection efficiency and lower output characteristics. Further, if the notch or the constricted portion is provided, the shape of the mold used for manufacturing the positive electrode lattice is complicated, which may lead to an increase in manufacturing cost and a deterioration in yield. In particular, in the production of a positive electrode lattice by casting, there is a concern about casting defects such as breakage due to poor running of molten lead or lead alloy in the mold.

When the arrangement spacing of the horizontal rails and the vertical rails constituting the inner bone is reduced from the central portion toward the peripheral portion as in the positive electrode lattice body described in Patent Document 6, the opening located in the peripheral portion of the positive electrode lattice body is formed. Has a smaller area than that located at the center of the positive electrode lattice, and has a larger area of the opening located at the center of the positive electrode lattice. In general, the current density at the time of charging / discharging in the positive electrode lattice is larger as it is located near the upper positive electrode current collecting ear and becomes smaller as it is located on the lower side. Further, expansion and contraction of the positive electrode active material occur with the charge / discharge reaction, and the charge / discharge reaction is proportional to the current density. Therefore, the expansion and contraction of the positive electrode active material is large on the upper side of the positive electrode lattice, and is small on the lower side. As a result, as in Patent Document 6, when the distribution of the area of the opening is point-symmetrical with the central portion of the positive electrode lattice as the base point, the expansion and contraction of the positive electrode active material do not necessarily occur when the distribution of the current density is taken into consideration. It was not the most efficient way to prevent it, and there was room for improvement. Further, as described in Patent Document 6, increasing the number of horizontal rails and vertical rails leads to an increase in the weight of the lead storage battery itself. Therefore, increasing the arrangement spacing of the horizontal rails and the vertical rails to the lower side of the positive electrode grid, which contributes less to the prevention of expansion and contraction of the positive electrode active material, impairs the weight reduction of the lead storage battery.

In addition, the mechanism by which growth is promoted, which was found by the inventors, will be described below. When the positive electrode lattice is deformed by the growth so as to expand, the positive electrode active material is exfoliated from the frame bone and the inner bone, falls off from the opening, and a gap is formed. When the electrolytic solution invades the gap and comes into contact with the positive electrode lattice, corrosion of the positive electrode lattice due to charging and discharging is promoted, so that the growth accelerates. Hereinafter, the remarkable progress of growth accompanying the exfoliation or detachment of the positive electrode active material in contact with the vertical frame bone of the positive electrode lattice is referred to as “accelerated growth”. In general, it is known that the larger the cross-sectional area of the positive electrode lattice, the larger the degree of growth during corrosion. Therefore, when the vertical frame bone of the positive electrode lattice is curved outward and peels off or falls off from the positive electrode active material, not only the battery performance such as discharge capacity and output characteristics deteriorates, but also acceleration in the vertical direction occurs. Invite target growth.

In addition, when the positive electrode active material and the positive electrode lattice are in close contact with each other, a corrosive layer necessary for bonding is formed between the positive electrode active material and the surface of the positive electrode lattice. When a corrosive layer is interposed between the positive electrode active material and the positive electrode lattice, the positive electrode active material exerts a force to pull the positive electrode lattice, so that the growth of the positive electrode lattice is suppressed. However, in the state where peeling or dropping occurs, the above action does not work, and accelerated growth is promoted.

In view of the above circumstances, it is an object of the present invention to provide a positive electrode lattice for a lead storage battery and a lead storage battery which can prevent an internal short circuit due to the growth of the positive electrode lattice and can improve the life of the lead storage battery.

In order to solve the above problems, according to one embodiment, a first horizontal frame bone and a second horizontal frame bone extending in the lateral direction, and a first vertical frame bone and a second vertical frame extending in the vertical direction are used. Rectangular frame-shaped frame bone having a frame bone; internal bone having a plurality of horizontal bars and vertical bars arranged in the frame bone and connected to the frame bone in a grid pattern; frame bone and a plurality of lateral bars A region surrounded by a crosspiece and a vertical rail, and a plurality of openings defined as an area surrounded by a plurality of horizontal rails and a vertical rail; and a positive current collector ear connected to a first horizontal frame bone; The average area of the plurality of openings adjacent to the first vertical frame bone and the plurality of openings adjacent to the second vertical frame bone in plan view is the plane of the remaining plurality of openings excluding the plurality of openings. Smaller than the observed average area, the plurality of openings are the second from the second lateral frame bone side when compared on the same perpendicular line that traverses the first lateral frame bone and the second horizontal frame bone. Provided is a positive electrode lattice body for a lead storage battery, characterized in that the area in plan view is gradually reduced toward the lateral frame bone side of 1.

In order to solve the above-mentioned problems, according to another embodiment, there is provided a lead-acid battery characterized by comprising the above-mentioned positive electrode lattice for a lead-acid battery.

According to the present invention, it is possible to provide a positive electrode lattice and a lead storage battery for a lead storage battery, which can prevent an internal short circuit due to the growth of the positive electrode lattice and can improve the life of the lead storage battery.

FIG. 1 is a plan view of the positive electrode grid body according to the first embodiment. FIG. 2 is a plan view of the positive electrode grid body according to the second embodiment. FIG. 3 is an enlarged plan view showing an opening provided in the positive electrode lattice body according to the third embodiment. FIG. 4 is an enlarged plan view showing an opening provided in the positive electrode lattice body according to the fourth embodiment. FIG. 5 is an enlarged plan view showing a part of the positive electrode lattice body according to the fifth embodiment. FIG. 6 is an enlarged plan view showing a part of the positive electrode lattice body according to the sixth embodiment. FIG. 7 is an enlarged plan view showing a part of the positive electrode lattice body according to the seventh embodiment.

<First Embodiment>
FIG. 1 shows a plan view of a positive electrode lattice body 1 for a lead storage battery according to the first embodiment.

The positive electrode lattice body 1 includes a frame bone, an internal bone arranged in the frame bone, and a positive electrode current collector ear 11A. The frame bone has a rectangular frame shape, and the first horizontal frame bone 13a and the second horizontal frame, which extend in the lateral direction X and are connected to the positive electrode collecting ear 11A at a position deviated from the middle of the lateral direction X, and the second horizontal frame. It includes a bone 13b, a first vertical frame bone 14a extending in the vertical direction Y, and a second vertical frame bone 14b. In the present specification, as shown in FIG. 1, the direction in which the first horizontal frame bone 13a and the second horizontal frame bone 13b extend is the horizontal direction X, the first vertical frame bone 14a and the second vertical frame. The direction in which the bone 14b extends is defined as the longitudinal direction Y. Further, the part where the first horizontal frame bone 13a is arranged is on the upper side, the part where the second horizontal frame bone 13b is arranged is on the lower side, the part where the first vertical frame bone 14a is arranged is on the left side, and the second. The site where the vertical frame bone 14b is placed is defined as the right side.

In the frame bone, an internal bone having a plurality of horizontal bars 15a and vertical bars 15b arranged in a grid pattern connected to the frame bone is arranged. The plurality of cross rails 15a are connected to, for example, the first vertical frame bone 14a and the second vertical frame bone 14b, respectively, and extend in the lateral direction X. Further, the plurality of cross rails 15a are arranged in parallel so as to be separated from each other in the vertical direction Y, for example. The plurality of vertical bars 15b are connected to the first horizontal frame bone 13a and the second horizontal frame bone 13b, respectively, and extend in the vertical direction Y. Further, the plurality of vertical bars 15b are arranged in parallel, for example, separated from each other in the lateral direction X. The plurality of horizontal rails 15a and the plurality of vertical rails 15b are arranged so as to intersect each other at right angles, for example.

In the positive electrode lattice body 1, the plurality of openings 16 are defined by a region surrounded by a frame bone and a plurality of cross rails 15a and a vertical rail 15b, and a region surrounded by a plurality of horizontal rails 15a and a vertical rail 15b. To. Each of the plurality of openings 16 has a rectangular shape, for example.

The plurality of vertical bars 15b include the distance between the vertical bars 15b adjacent to the first and second vertical frame bones 14a and 14b and the first and second vertical frame bones 14a and 14b, respectively, and the other plurality of vertical bars. When comparing the distance between the crosspieces 15b, the distance between the first and second vertical frame bones 14a and 14b and the vertical rails 15b adjacent to them is narrower than the distance between the other plurality of vertical rails 15b. It is arranged in. Therefore, the average area of the plurality of openings 16 adjacent to the first vertical frame bone 14a and the plurality of openings 16 adjacent to the second vertical frame bone 14b in a plan view is a plurality of other openings. It is smaller than the average area of the opening 16 in a plan view.

Further, the plurality of cross rails 15a are stepwise, for example, from the second horizontal frame bone 13b side (that is, the lower side in FIG. 1) to the first horizontal frame bone 13a side (that is, the upper side in FIG. 1). They are arranged so that the intervals are narrow. Therefore, the area of the plurality of openings 16 in a plan view is gradually reduced from the second horizontal frame bone 13b side toward the first horizontal frame bone 13a side. At this time, the area of the plurality of openings 16 in a plan view is the area of the openings 16 on the second horizontal frame bone 13b side from the second horizontal frame bone 13b side toward the first horizontal frame bone 13a side. It is preferable to gradually reduce the size within a range of 0.85 times or more and 0.99 times or more. For example, in the example shown in FIG. 1, the area ratio of one opening 16 located in the y-th row of the same column to the area of the opening 16 located in the y + 1th row counting from the upper side is 0. It is 85 times, and the maximum is 0.99 times.

A positive electrode current collecting ear 11A for connecting the positive electrode lattice body 1 to the outside is connected to the first horizontal frame bone 13a. The positive electrode current collector ear 11A has, for example, a rectangular plate shape, and is connected so as to extend from the right side to the upper side of the first horizontal frame bone 13a in FIG. When the positive electrode plate and the negative electrode plate are laminated to form a electrode plate group as described later, the positive electrode current collecting ear 11A and the negative electrode current collecting ear 11B are the first when viewed in the direction of laminating the electrode plate group. The horizontal frame bones 13a of the above are arranged so as to be offset from each other in the length direction. In the example shown in FIG. 1, the positive electrode current collecting ears 11A and the negative electrode current collecting ears 11B are arranged symmetrically with respect to the center line in the lateral direction X of the positive electrode lattice body 1.

Next, the operation of the positive electrode lattice body 1 according to the first embodiment will be described.

The average area of the plurality of openings 16 adjacent to the first vertical frame bone 14a and the plurality of openings 16 adjacent to the second vertical frame bone 14b in a plan view is the remaining plurality of openings excluding the plurality of openings 16. It is smaller than the average area of the opening 16 of. As described above, the average area of at least the plurality of openings 16 adjacent to the first vertical frame bone 14a and the plurality of openings 16 adjacent to the second vertical frame bone 14b in a plan view is taken from the plurality of openings. By making the area smaller than the average area of the remaining plurality of openings 16 excluding 16, the positive electrode active material filled in the plurality of openings 16 is in contact with the positive electrode lattice 1 per fixed area. It is larger than the positive electrode active material filled in the plurality of openings 16. Therefore, the adhesion between the positive electrode active material filled in the plurality of openings 16 and the positive electrode lattice body 1 is improved as compared with other portions, and peeling or falling off of the positive electrode active material can be suppressed. Therefore, it is possible to suppress deterioration of battery performance such as discharge capacity and output characteristics due to peeling or falling off of the positive electrode active material filled in the plurality of openings 16. At the same time, it is possible to prevent the accelerated growth of the first vertical frame bone 14a and the second vertical frame bone 14b of the positive electrode lattice body 1.

In order to reduce the area of the positive electrode lattice body 1 when the opening 16 is viewed in a plan view, for example, the width of the frame bone, the horizontal rail 15a or the vertical rail 15b forming the opening 16 can be increased, or the same area can be obtained. A method such as increasing the number of horizontal rails 15a or vertical rails 15b in the above can be considered. However, since both of them have a trade-off relationship with the weight increase of the positive electrode lattice body 1, the reduced portion of the average area in plan view of the opening is adjacent to the first vertical frame bone 14a and the second vertical frame bone 14b. It is desirable to limit it to a part.

The plurality of openings 16 are compared from the side of the second horizontal frame bone 13b to the first horizontal frame bone when compared on the same vertical line traversing the first horizontal frame bone 13a and the second horizontal frame bone 13b. The area viewed in a plan view is gradually reduced toward the 13a side. In this way, the opening 16 having a small area located above the positive electrode lattice 1 has a fixed area per positive electrode lattice 1 as compared with the opening 16 having a large area located below the positive electrode lattice 1. The proportion of positive electrode active material in contact with is increased. Therefore, the adhesion between the positive electrode active material filled in the opening 16 and the positive electrode lattice body 1 is improved, and the accelerated growth of the positive electrode lattice body 1 can be prevented. Here, the area ratio of the plurality of vertically continuous openings 16 is within a range in which the area of the upper opening 16 is 0.85 times or more and does not exceed 0.99 times the lower opening 16. , (Upper opening) / (Lower opening) area ratio = 0.85-0.99 times, more desirable in preventing accelerated growth. When the area ratio exceeds 0.99 times, the area difference between the upper side and the lower side of the positive electrode lattice body 1 is small, so that the effect of selectively enhancing the reinforcement of the upper side of the positive electrode lattice body 1 becomes small. Further, when the area ratio is less than 0.85 times, the filling property of the positive electrode active material is improved by reducing the upper opening 16 of the positive electrode lattice body 1, but the area of the lower opening 16 is relative. There is a risk that the output characteristics and the retention of the positive electrode active material will deteriorate.

When the first horizontal frame bone 13a and the second horizontal frame bone 13b are compared on the same vertical line traversing the plurality of openings 16 described above, the first lateral frame bone 13b side to the second horizontal frame bone 13b side. The action of suppressing the growth of the positive electrode lattice body 1 due to the expansion and contraction of the positive electrode active material by gradually reducing the area viewed in plan toward the frame bone 13a side will be described.

When the positive electrode active material expands and contracts due to charging and discharging, the expansion and contraction force is propagated from the central portion to the outer peripheral portion of the positive electrode lattice body 1. According to the research by the inventors, a large elongation is generated especially in the first and second vertical frame bones 14a and 14b as the total sum of the propagations, and in the opening adjacent to the first and second vertical frame bones 14a and 14b. It was found that exfoliation or desorption of the positive electrode active material is likely to occur. Peeling or falling off can be suppressed to some extent by reducing the area of the plurality of openings 16 adjacent to the first and second vertical frame bones 14a and 14b in a plan view. Further, by reducing the area difference (volume difference when the thickness of the positive electrode lattice 1 is constant) in a plan view of the openings 16 which are continuously arranged vertically on the same vertical line, the vertically continuous openings 16 are further reduced. It was found that the difference between the expansion force and the contraction force of the positive electrode active materials 16 can alleviate the interfacial stress generated between the openings 16 and more remarkably suppress the peeling or falling off of the positive electrode active materials.

For this reason, the area of the plurality of openings 16 in plan view is reduced as the lower second horizontal frame bone 13b side approaches the upper first horizontal frame bone 13a side on the same vertical line. Therefore, on the upper side of the positive electrode lattice body 1 where accelerated growth is likely to occur and the expansion and contraction of the positive electrode active material is remarkable, the interfacial stress generated between the surface of the positive electrode lattice body 1 and the positive electrode active material between the openings 16 is relaxed. However, it is possible to prevent the positive electrode active material from peeling off or falling off.

Further, in the above configuration, as the position is located above the positive electrode lattice body 1, the number of horizontal bars 15a and vertical bars 15b occupying the positive electrode lattice 1 is relatively large, so that the mechanical strength of the upper side of the positive electrode lattice 1 is increased. improves. Therefore, even if the growth occurs upward, the horizontal crosspiece 15a located on the upper side of the positive electrode lattice body 1 suppresses the upward curvature, and the upper part of the positive electrode plate and a part of the negative electrode such as the negative electrode plate or the negative electrode strap are connected. Internal short circuit due to contact can be suppressed. Further, since the number of horizontal bars 15a and vertical bars 15b occupying the positive electrode lattice 1 is relatively small on the lower side of the positive electrode lattice 1 which is less affected by the expansion and contraction of the positive electrode active material, the weight of the lead storage battery is reduced. Is not impaired.

The frame bone constituting the positive electrode lattice body 1, the inner bone provided with the plurality of horizontal bars 15a and the vertical bars 15b, and the positive electrode current collecting ear 11A are made of, for example, lead or a lead alloy, and are metal elements added to the lead alloy. Is not limited, and known ones can be used. In particular, when a predetermined amount of Ca, Sn, Al or Ag is added, the mechanical strength and corrosion resistance of the positive electrode lattice 1 can be improved, which is more preferable in suppressing deformation due to growth.

In the above-mentioned positive electrode lattice body 1, for example, Ca is 0.02 to 0.08% by mass, Sn is 0.4 to 2.5% by mass, Al is 0.005 to 0.04% by mass, and Ag is 0.001. It is made of a lead alloy consisting of ~ 0.0049% by mass and the balance consisting of Pb and unavoidable impurities.

Addition of the component elements of Ca, Sn, Al, and Ag in a specific range makes it possible to improve both the corrosion resistance and the mechanical strength of the obtained lead alloy. The addition of Ca improves the mechanical strength of the positive electrode lattice body 1. If the amount of Ca blended is less than 0.02% by mass, the effect is small, and if it exceeds 0.08% by mass, the corrosion resistance may decrease. The addition of Sn improves the flowability of the molten metal of the lead alloy and also improves the mechanical strength of the positive electrode lattice body 1. If the blending amount of Sn is less than 0.4% by mass, the effect is small, and if it exceeds 2.5% by mass, the corrosion resistance may decrease. The addition of Al prevents the loss of Ca due to the oxidation of the molten metal, and further improves the mechanical strength of the positive electrode lattice body 1. If the amount of Al added is less than 0.005% by mass, the effect is small, and if it exceeds 0.04% by mass, Al is likely to precipitate as dross. The addition of Ag improves mechanical strength and especially creep resistance at high temperatures. If the amount of Ag added is less than 0.001% by mass, the effect is small, and if it exceeds 0.0049% by mass, the effect cannot be expected to increase with the increase in the amount added.

The positive electrode lattice body 1 can be produced, for example, by cutting out a punched lattice body or an expanded lattice body of a rolled plate made of lead or a lead alloy, or a rolled plate by a discharge wire cutting method or the like. Further, it may be produced as a cast lattice by a book mold method or the like. In particular, since the growth of the positive electrode lattice 1 is likely to occur in a lattice formed from a rolled plate in which crystal grains containing lead or a lead alloy are oriented, the effect of suppressing the growth is a punched lattice, an expanded lattice, or an electric discharge. In the case of a lattice body made from a rolled plate by a wire cutting method or the like, it is remarkably obtained.

Hereinafter, the positive electrode lattice body 1 according to another embodiment will be described with reference to the drawings. The same components as those in the first embodiment are designated by the same reference numerals, and the description thereof will be omitted.

<Second embodiment>
FIG. 2 is a plan view showing the positive electrode grid body 1 according to the second embodiment. In addition to the configuration described in the first embodiment, the positive electrode lattice body 1 is formed from the central side of the internal bone toward the first vertical frame bone 14a side and from the central side of the internal bone toward the second vertical frame. A plurality of vertical bars 15b are arranged so that the intervals are gradually narrowed toward the bone 14b side. Therefore, the area of the plurality of openings 16 in a plan view is directed from the central side of the internal bone toward the first vertical frame bone 14a side and from the central side of the internal bone toward the second vertical frame bone 14b side. And gradually become smaller.

The positive electrode lattice body 1 according to the second embodiment has the same effect as that of the first embodiment. The stress generated by the expansion and contraction of the positive electrode active material in the positive electrode lattice body 1 is propagated from the central side of the inner bone of the positive electrode lattice body 1 toward the frame bone side. Further, in the lateral direction X of the positive electrode lattice body 1, the area of the plurality of openings 16 in a plan view is gradually reduced from the central side of the inner bone toward the frame bone side, so that the lateral direction of the positive electrode lattice body 1 is gradually reduced. The mechanical strength at X can be improved. As a result, according to the positive electrode lattice body 1 according to the second embodiment, it is possible to more effectively prevent the growth of the positive electrode lattice body 1 in the lateral direction X and the peeling or falling off of the positive electrode active material.

<Third embodiment>
3A and 3B are plan views showing an enlarged opening 16 provided in the positive electrode lattice body 1 according to the third embodiment. As shown in FIG. 3A, rounded R1s are formed at the four corners of the plurality of openings 16 formed in the positive electrode lattice body 1 in a plan view. The magnitude of the roundness R1 may be defined by, for example, the radius of curvature of the roundness R1.

Further, among the plurality of openings 16 adjacent to the frame bone, at least the four corners of the openings 16 located at the four corners of the frame bone in a plan view are larger than the openings 16 located at least at the four corners of the frame bone. At least one roundness R is provided. In the openings 16 located at the four corners of the frame bone, the size of the roundness R of the corner closest to the corner of the frame bone in the opening 16 is maximized. FIG. 3B shows an opening 16 arranged in the upper left corner defined by the first horizontal frame bone 13a and the first vertical frame bone 14a in the positive electrode lattice body 1. The opening 16 arranged in the upper left corner of the frame bone indicates the roundness of the upper left corner closest to the corner of the frame bone as R2, and the roundness of the other three corners in the opening 16 as R1. The magnitude of the roundness R1 and R2 is defined by, for example, the radius of curvature of the roundness R, and the roundness R2 is larger than the roundness R1.

The openings 16 arranged at the other three corners of the frame bone also have a large rounded R2 at the corner closest to the corner of the frame bone, as in FIG. 3B. Except for the openings 16 arranged at the four corners of the frame bone, small rounded R1s are provided at the four corners in the openings 16 as in FIG. 3A.

As described above, in the positive electrode lattice body 1 according to the third embodiment, as shown in FIG. 3A, rounded R1s are formed at the four corners of the opening 16 in a plan view, whereby the positive electrode to the opening 16 is formed. Since the filling property of the active material is improved and the unfilled region is reduced, the adhesion between the positive electrode lattice body 1 and the positive electrode active material can be improved. Further, since the mechanical strength of the four corners in the opening 16 is improved, the growth of the positive electrode lattice body 1 can be prevented, and an internal short circuit due to contact between the positive electrode plate and a part of the negative electrode such as the negative electrode plate or the negative electrode strap, or internal short circuit It is possible to prevent peeling or falling off of the positive electrode active material and the accompanying accelerated growth.

Further, in the positive electrode lattice body 1 shown in FIG. 3B, among the plurality of openings 16, the four corners in the openings 16 arranged at the four corners of the frame bone where the positive electrode active material is easily peeled off or fall off are selectively selected. A large roundness R2 is provided. Therefore, it is possible to more effectively prevent the positive electrode active material from peeling off or falling off from the positive electrode lattice body 1 and the growth of the positive electrode lattice body 1 without causing an unnecessary increase in the weight of the positive electrode lattice body 1.

The roundness R1 provided in the plurality of openings 16 is not limited to the example shown in FIG. 3A, and the arrangement and size thereof are appropriately selected according to the ease of peeling or falling off of the positive electrode active material. You may. Further, although it has been stated that the magnitude of the roundness R1 can be defined by the radius of curvature, the roundness R is not limited to an arc. For example, it may be a polygon close to an arc. The magnitude of the roundness R1 may be defined by, for example, the rate of change in area due to the roundness R1 as compared with the case where the opening 16 has a rectangular shape.

The roundnesses R1 and R2 provided in the plurality of openings 16 are not limited to the example shown in FIG. 3B, and the arrangement and size thereof are appropriately selected according to the ease of peeling or falling off of the positive electrode active material. You may. Further, two or more types of roundness R may be provided at the four corners in the opening 16. For example, among the four corners in the opening 16, the roundness R of one corner and the remaining three corners are different from each other, and the roundness R of the two corners and the two corners of the four corners in the opening 16 are different from each other. Of the four corners, the roundness R of all corners is different from each other, the roundness R of two or three corners of the four corners in the opening 16 is different from each other, and the roundness R is not provided in the remaining one corner or two corners, etc. It may be in the form of. The opening 16 having no rounded R at all four corners may be arranged in a part of the inner bone. It has been stated that the magnitude of the roundness R1 or R2 can be defined by the radius of curvature, but the roundness R1 or R2 is not limited to an arc. For example, it may be a polygon close to an arc. Further, the size of the roundness R1 or R2 may be defined by, for example, how much the area is reduced by the roundness R1 or R2 as compared with the case where the opening 16 has a rectangular shape.

<Fourth Embodiment>
FIGS. 4A and 4B are plan views showing an enlarged opening 16 provided in the positive electrode lattice body 1 according to the fourth embodiment. The positive electrode lattice body 1 according to the fourth embodiment has the same configuration as that of the third embodiment except that the size of the roundness R provided at each of the four corners of the plurality of openings 16 is changed.

In FIG. 4A, in the opening 16 arranged adjacent to the first horizontal frame bone 13a, rounded R3 is provided at two corners adjacent to the first horizontal frame bone 13a, and the other Rounded R1 is provided at the two corners.

FIG. 4B shows an opening 16 arranged in the upper left corner defined by the first horizontal frame bone 13a and the first vertical frame bone 14a in the positive electrode lattice body 1. The opening 16 located in the upper left corner of the frame bone has a rounded R2 in the upper left corner closest to the corner of the frame bone, a rounded R1 in the corner facing the rounded R2, and a rounded R1 in the other two corners. R3 is provided respectively. The magnitude of the roundness R1 to R3 is defined by, for example, the radius of curvature of the roundness R, and increases in the order of R1, R3, and R2.

The opening 16 not adjacent to the frame bone has the same structure as that shown in FIG. 4A. That is, rounded R1s are provided at the four corners not adjacent to the frame bone.

Further, although not shown, the openings 16 arranged at the other three corners of the positive electrode lattice body 1 also have the same configuration as that of FIG. 4B. That is, the four openings arranged at the four corners of the positive electrode lattice body 1 have rounded R2 at the corner closest to the corner of the frame bone, rounded R1 at the corner facing the rounded R2, and rounded R1 at the other two corners. Roundness R3 is provided.

In the positive electrode lattice body 1 according to the fourth embodiment, the same effect as that of the third embodiment can be obtained. In the positive electrode lattice body 1, the positive electrode active material is likely to peel off or fall off at a plurality of openings 16 arranged adjacent to the frame bone, particularly at the openings 16 located at the four corners of the frame bone. Therefore, in the positive electrode lattice body 1 according to the fourth embodiment, the maximum roundness R2 is provided in the corners closest to the corners of the frame bones in the openings 16 located at the four corners of the frame bones. As shown in (a) and (b) of No. 4, a relatively large roundness R3 is also provided at the corner of the opening 16 adjacent to the frame bone. According to such a configuration, the adhesion of the positive electrode active material to the positive electrode lattice body 1 is further improved as compared with the third embodiment, and the positive electrode active material is peeled off or dropped from the positive electrode lattice body 1, and the positive electrode lattice body is formed. It is possible to prevent the internal short circuit accompanying the growth of 1 more effectively.

<Fifth Embodiment>
FIG. 5 is an enlarged plan view showing a part of the positive electrode lattice body 1 according to the fifth embodiment. The positive electrode lattice body 1 according to the fifth embodiment has one opening 16 corresponding to directly below the negative electrode collecting ear 11B among the plurality of openings 16 adjacent to the first horizontal frame bone 13a, that is, the positive electrode plate. And the negative electrode plate are laminated via a separator to form an electrode plate group, and when the electrode plate group is viewed through in the stacking direction, they form a straight line hanging from both ends of the negative electrode collector ear 11B onto the positive electrode lattice body 1, respectively. An auxiliary crosspiece 17 extending in the direction in which the first vertical frame bone 14a and the second vertical frame bone 14b extends, that is, in the vertical direction Y is arranged in the opening 16 that overlaps at least a part of the enclosed area. It has the same configuration as that of the first embodiment except that 16 is divided into two parts. The area of the opening 16 divided by the auxiliary crosspiece 17 in a plan view is about half that of the area of the other adjacent openings 16.

The positive electrode lattice body 1 according to the fifth embodiment can obtain the same effect as the positive electrode lattice body 1 according to the first embodiment. When an upward growth occurs in the positive electrode lattice body 1, one of the negative electrodes such as the negative electrode collecting ear 11B or the negative electrode strap located above the negative electrode lattice body in which the first horizontal frame 13a faces the positive electrode lattice body 1. There is a risk that the lead-acid battery will reach the end of its life early due to internal short-circuiting due to contact with the electrode.

As shown in FIG. 5, among a plurality of openings 16 adjacent to the first horizontal frame bone 13a, an auxiliary crosspiece 17 extending in the vertical direction Y is arranged in the opening 16 corresponding directly below the negative electrode current collecting ear 11B. As a result, the area of the opening 16 in this region becomes smaller, and the number of internal bones occupying the positive electrode lattice body 1 becomes relatively large, so that the mechanical strength of the positive electrode lattice body 1 at that portion increases. As a result, in the opening 16 in which the auxiliary crosspiece 17 is arranged, the adhesion between the positive electrode lattice body 1 and the positive electrode active material is improved, and the positive electrode lattice body 1 is accelerated by peeling or falling off of the positive electrode active material. Growth can be suppressed. Further, since the mechanical strength of the positive electrode lattice 1 is increased in the opening 16 in which the auxiliary crosspiece 17 is arranged, the growth toward the upper side of the positive electrode lattice 1 can be suppressed, and an internal short circuit due to contact between the positive electrode and the negative electrode can be suppressed. Can be effectively suppressed.

The auxiliary rail 17 is not limited to the one that divides the opening 16 in the vertical direction, and the same effect can be obtained even if the opening 16 is divided in the horizontal direction, the diagonal direction, the cross, or the like. Further, the auxiliary crosspiece 17 may not divide the opening 16, and for example, the area of the opening 16 may be reduced by partially increasing the cross-sectional area of the frame bone or the inner bone of the portion. However, the same effect can be obtained.

<Sixth Embodiment>
FIG. 6 is an enlarged plan view showing a part of the positive electrode lattice body 1 according to the sixth embodiment. In the positive electrode lattice body 1 according to the sixth embodiment, among the plurality of openings 16 adjacent to the first horizontal frame bone 13a, the first opening 16 corresponds to the two openings 16 directly below the negative electrode collecting ear 11B. A fifth embodiment other than arranging auxiliary crosspieces 17 extending in the direction in which the vertical frame bone 14a and the second vertical frame bone 14b extend, that is, in the vertical direction Y, and dividing the two openings 16 into two. It has the same configuration as the form. As shown in FIG. 6, the auxiliary crosspiece 17 responds to the need for reinforcement of the positive electrode lattice body 1 in the opening 16 arranged adjacent to the first horizontal frame bone 13a corresponding directly below the negative electrode current collector ear 11B. You may arrange more than one. The area of the opening 16 divided by the auxiliary rail 17 in a plan view is about 1/2 of the area of the other adjacent openings 16.

The same effect as that of the fifth embodiment can be obtained in the positive electrode lattice body 1 according to the sixth embodiment. As in the sixth embodiment, by appropriately arranging a plurality of auxiliary bars 17 at positions corresponding directly under the negative electrode current collector ear 11B, it is possible to suppress the growth of the positive electrode lattice 1 toward the upper side, and the positive electrode can be suppressed. It is possible to more effectively suppress an internal short circuit due to contact between the negative electrode and the negative electrode.

<7th Embodiment>
FIG. 7 is an enlarged plan view showing a part of the positive electrode lattice body 1 according to the seventh embodiment. The positive electrode lattice body 1 according to the seventh embodiment includes not only the opening 16 corresponding directly below the negative electrode collecting ear 11B provided on the negative electrode plate of the lead storage battery, but also the negative electrode strap to which the negative electrode collecting ear 11B is connected. The opening 16 corresponding directly under 12B, that is, the positive electrode plate and the negative electrode plate are laminated via a separator to form a electrode plate group, and when the electrode plate group is viewed through in the stacking direction, they are formed from both ends of the negative electrode strap 12B, respectively. It has the same configuration as that of the fifth embodiment except that the auxiliary crosspiece 17 is arranged for the opening 16 that overlaps at least a part of the region surrounded by the straight line hanging on the positive electrode lattice body 1. The area of the opening 16 divided by the auxiliary crosspiece 17 is about half the area of the other adjacent openings 16.

The same effect as that of the fifth embodiment can be obtained in the positive electrode lattice body 1 according to the seventh embodiment. By arranging a plurality of auxiliary crosspieces 17 in the opening 16 directly below the negative electrode strap 12B as in the seventh embodiment, it is possible to suppress the growth of the positive electrode lattice 1 toward the upper side, and the positive electrode and the positive electrode Internal short circuit due to contact with the negative electrode can be suppressed more effectively.

<8th Embodiment>
Hereinafter, the structure of the lead storage battery according to the eighth embodiment will be described. The configuration of the lead storage battery according to the eighth embodiment is not particularly limited except that the positive electrode lattice plate according to any one of the first to seventh embodiments is used for at least the positive electrode plate.

Although not shown in detail, the lead-acid battery has a monoblock structure in which a group of electrode plates is housed in cell chambers divided into six by a partition wall in an electric tank made of a bottomed square cylinder-shaped resin. In the electrode plate group, a positive electrode plate and a negative electrode plate inserted into a bag-shaped separator are alternately laminated via a retainer mat made of glass fiber or the like. As an example, the electrode plate group has seven positive electrode plates and eight negative electrode plates.

The positive electrode plate is produced by filling the positive electrode lattice body 1 of any one of the first to seventh embodiments described above with a positive electrode active material prepared according to a conventional method, and aging and drying according to a conventional method. The negative electrode plate is manufactured by filling a negative electrode lattice body with a negative electrode active material adjusted according to a conventional method, and aging and drying according to a conventional method. The structure of the negative electrode grid has, for example, a radial shape in which the negative electrode current collector ears 11B are arranged symmetrically with the positive electrode grid described above. In the electrode plate group, the positive electrode current collecting ears 11A of the positive electrode plate and the negative electrode current collecting ears 11B of the negative electrode plate have center lines in the longitudinal direction of the first horizontal frame bone 13a when viewed through in the stacking direction. They are arranged symmetrically with each other as a reference. The electrode plate group is arranged in each of the six cell chambers of the battery case with the positive electrode current collecting ear 11A and the negative electrode current collecting ear 11B facing upward. The negative electrode current collector ears 11B of the plurality of negative electrode plates are electrically connected and fixed by a common negative electrode strap 12B for each electrode plate group. Similarly, the positive electrode current collector ears 11A of the plurality of positive electrode plates are electrically connected and fixed by a common positive electrode strap for each electrode plate group. Further, the positive electrode strap and the negative electrode strap 12B are connected to an inter-cell connecting member provided through a partition wall between cells and connecting a group of electrode plates in series, or a pole column extending upward.

A lid is fitted in the opening 16 of the electric tank in which the electrode plates are housed. Hollow positive electrode terminals and negative electrode terminals are provided at predetermined positions of the lid. The positive electrode strap and the negative electrode strap 12B are connected to and fixed to the positive electrode terminal and the negative electrode terminal via the positive electrode pole pillar and the negative electrode pole pillar. An electrolytic solution consisting of an aqueous sulfuric acid solution (dilute sulfuric acid) having a specific gravity of 1.240 is injected into an electric tank through a pillar liquid port provided on the lid, and the electric tank is formed to supply a voltage between the positive electrode terminal and the negative electrode terminal. It will be possible.

As described above, the lead-acid battery according to the eighth embodiment using the positive electrode lattice according to any one of the first to seventh embodiments has an internal short circuit due to the growth of the positive electrode lattice and the battery capacity. Deterioration is prevented and life is improved.

Further, in each of the first to eighth embodiments, the horizontal frame bones 13a and 13b of the positive electrode lattice body and the plurality of cross rails 15a are arranged in parallel, and the horizontal frame bones 13a and 13b and the plurality of cross rails 15a are arranged. An example in which the vertical frame bones 14a and 14b and a plurality of vertical crosspieces 15b are arranged at right angles has been described, but the present invention is not limited thereto. For example, the horizontal frame bones 13a and 13b and the plurality of horizontal rails 15a may not be arranged in parallel with each other, and may be arranged at a desired angle with each other. Similarly, the vertical frame bones 14a and 14b and the plurality of vertical crosspieces 15b do not have to be arranged in parallel with each other, and may be arranged at a desired angle with each other. Further, the horizontal frame bones 13a and 13b and the vertical frame bones 14a and 14b constituting the frame bones, and the plurality of horizontal rails 15a and the vertical rails 15b constituting the internal bones have been described as an example of being linear. However, the present invention is not limited to this, and it may be curved or polygonal, or may have a branch. In addition, although a plurality of horizontal rails 15a and a plurality of vertical rails 15b having the same thickness are arranged at regular intervals, the thickness and the intervals at which they are arranged are not limited to this. May be changed as appropriate. The same applies to the auxiliary rail 17.

In each embodiment, the shape of the plurality of openings 16 is rectangular or rectangular with rounded corners R, but the present invention is not limited to this. The shape of the plurality of openings 16 may be, for example, another polygonal shape or a circular shape.

Further, in each embodiment, as a method of reducing the area of the opening 16 of the positive electrode lattice, the intervals at which a plurality of horizontal bars 15a and vertical bars 15b constituting the frame bone and the inner bone defining the opening 16 are arranged are arranged. I explained a narrowed version, but it is not limited to this. In order to reduce the area of the opening 16, for example, rounded R may be provided at the four corners of the rectangular opening 16. The area of the opening 16 can be adjusted by appropriately changing the radius of curvature of the roundness R. Alternatively, in order to reduce the area of the opening 16, the thickness of the plurality of horizontal bars 15a and vertical bars 15b constituting the frame bone and the internal bone defining the opening 16 may be increased only in that portion. Further, the above-mentioned methods for reducing the area of the opening 16 may be combined as appropriate.

Further, in each embodiment, an example in which the positive electrode current collector ear 11A has a rectangular plate shape has been described, but the present invention is not limited to this. The shape of the positive electrode current collector ear 11A may be appropriately changed in consideration of current collection performance and strength, and may be, for example, a fan shape, a triangle shape, or a rectangular shape having rounded corners R. Further, the width of the positive electrode current collector ear 11A may be changed as appropriate. The same applies to the negative electrode current collector ear 11B.

The configurations of the positive electrode lattice bodies 1 described in the first to seventh embodiments can be combined with each other. Although each embodiment of the present invention has been specifically described above, the present invention is not limited to these embodiments and examples, and various modifications can be made based on the technical idea of the present invention. ..
Hereinafter, the inventions described in the claims of the original application of the present application will be added.
[1] A positive electrode grid for lead-acid batteries.
A rectangular frame-shaped frame bone having a first horizontal frame bone and a second horizontal frame bone extending in the horizontal direction and a first vertical frame bone and a second vertical frame bone extending in the vertical direction;
An internal bone arranged in the frame bone and having a plurality of horizontal and vertical crosspieces connected to the frame bone and provided in a grid pattern;
A plurality of openings defined by the frame bone and the area surrounded by the horizontal rails and the vertical rails, and the area surrounded by the horizontal rails and the vertical rails;
Positive electrode current collector ear connected to the first horizontal frame bone located on the side of the second vertical frame bone;
With
The average area of the first vertical frame bone and the plurality of openings adjacent to the second vertical frame bone in a plan view is the average area of the remaining plurality of openings excluding the plurality of openings in a plan view. Smaller than
When the area of the plurality of openings in a plan view is compared on the same perpendicular line that vertically traverses the first horizontal frame bone and the second horizontal frame bone, the area from the second horizontal frame bone side to the second. A positive electrode lattice body for a lead storage battery, characterized in that it gradually decreases toward the horizontal frame bone side of 1.
[2] The area of the plurality of openings in a plan view gradually decreases from the central side of the internal bone toward the first vertical frame bone side, and from the central side of the internal bone to the second. The positive electrode lattice body for a lead storage battery according to [1], which is characterized in that the size gradually decreases toward the vertical frame bone side.
[3] In a plurality of openings vertically continuous from the second horizontal frame bone side toward the first horizontal frame bone side, the upper opening with respect to the area of the lower opening in a plan view. The positive electrode lattice body for a lead storage battery according to [1] or [2], wherein the ratio of the areas viewed in plan is 0.85 times or more and not exceeding 0.99 times.
[4] Of the plurality of openings adjacent to the first horizontal frame bone, directly below the negative electrode collecting ear provided on the negative electrode plate of the lead storage battery, or directly below the negative electrode strap to which the negative electrode collecting ear is connected. [1] to [3], the opening corresponding to the above is divided by an auxiliary crosspiece extending in the same direction as the first vertical frame bone and the second vertical frame bone extending. The positive electrode lattice body for a lead storage battery according to any one of the above.
[5] The positive electrode lattice for a lead storage battery according to any one of [1] to [4], wherein the four corners of the plurality of openings in a plan view have rounded R.
[6] Of the plurality of openings adjacent to the frame bone, the four corners of the openings located at least at the four corners of the frame bone in a plan view are compared with the openings located other than the four corners of the frame bone. At least one large roundness R is provided, and in the openings located at the four corners of the frame bone, the size of the roundness R of the corner closest to the corner of the frame bone in the opening is maximized. The positive lattice body for a lead storage battery according to [5].
[7] The positive electrode lattice for a lead storage battery according to any one of [1] to [6], which is a punched lattice of a rolled plate of lead or a lead alloy.
[8] In the lead alloy, Ca is 0.02 to 0.08% by mass, Sn is 0.4 to 2.5% by mass, Al is 0.005 to 0.04% by mass, and Ag is 0.001 to 0.001. The positive electrode lattice for a lead storage battery according to [7], which has a composition of 0.0049% by mass and the balance of Pb and unavoidable impurities.
[9] A lead-acid battery comprising the positive electrode lattice for a lead-acid battery according to any one of [1] to [8].

1 ... Positive electrode lattice, 13a ... 1st horizontal frame bone, 13b ... 2nd horizontal frame bone, 14a ... 1st vertical frame bone, 14b ... 2nd vertical frame bone, 15a ... horizontal crosspiece, 15b ... vertical Rail, 16 ... Opening, R1, R2 ... Rounded R, 17 ... Auxiliary rail, 11A ... Positive electrode collector ear, 11B ... Negative electrode collector ear, 12B ... Negative electrode strap

Claims (9)

A positive electrode grid for lead-acid batteries
When the positive electrode lattice is viewed in a plan view, a first lateral frame bone located at the upper end and a second horizontal frame bone extending in the lateral direction located at the lower end, and a longitudinally extending bone located at the left end . A rectangular frame-shaped frame bone including one vertical frame bone and a second vertical frame bone located at the right end in the vertical direction ;
An internal bone arranged in the frame bone and having a plurality of horizontal and vertical crosspieces connected to the frame bone and provided in a grid pattern;
A plurality of openings defined by the frame bone and the area surrounded by the horizontal rails and the vertical rails, and the area surrounded by the horizontal rails and the vertical rails; and the second. Positive electrode current collector ear connected to the first horizontal frame bone located on the vertical frame bone side;
With
The average area of the first vertical frame bone and the plurality of openings adjacent to the second vertical frame bone in a plan view is the average area of the remaining plurality of openings excluding the plurality of openings in a plan view. Smaller than
The area of the plurality of openings adjacent to the first vertical frame bone in a plan view is gradually reduced from the second horizontal frame bone side toward the first horizontal frame bone side, and the area is described. area in plan view a plurality of said openings adjacent the second vertical frame bone also characterized by comprising reduced stepwise toward the first lateral frame bone side from the front Stories second lateral frame bone side Positive electrode lattice for lead-acid batteries. Area in plan view is a plurality of said apertures, along said transverse direction, stepwise reduced toward the central or al the first vertical frame bone side within said bone, middle of said bone pressurized et the lead-acid battery positive grid of claim 1, characterized by comprising reduced stepwise toward the second vertical frame bone side. In the plurality of openings adjacent to the first vertical frame bone and the plurality of openings adjacent to the second vertical frame bone, the second horizontal frame bone side to the first horizontal frame bone side a plurality of said openings successively vertically toward the upper ratio of the area viewed the opening of 0.85 times or more to the area in plan view the opening in the lower, 0.99 times the The positive lattice body for a lead storage battery according to claim 1 or 2, wherein the size gradually decreases from the second horizontal frame bone side toward the first horizontal frame bone side within a range not exceeding the range. The positive electrode lattice body for a lead storage battery according to any one of claims 1 to 3 , wherein the four corners of the plurality of openings in a plan view have rounded R. Of the plurality of openings adjacent to the frame bone, at least the four corners of the openings located at the four corners of the frame bone in a plan view are larger than the openings located at least at the four corners of the frame bone. At least one roundness R is provided, and in the openings located at the four corners of the frame bone, the size of the roundness R of the corner closest to the corner of the frame bone in the opening is maximized. The positive lattice body for a lead storage battery according to claim 4 . The positive electrode lattice for lead- acid batteries has Ca of 0.02 to 0.08% by mass, Sn of 0.4 to 2.5% by mass, Al of 0.005 to 0.04% by mass, and Ag of 0.001. The positive electrode lattice for a lead storage battery according to any one of claims 1 to 5, wherein the lead alloy is composed of ~ 0.0049% by mass and the balance is composed of Pb and unavoidable impurities. A lead-acid battery equipped with a group of plates
In the electrode plate group, a positive electrode plate having a positive electrode lattice for a lead storage battery according to any one of claims 1 to 6 and a negative electrode plate having a negative electrode lattice having a negative electrode current collecting ear are separated by a separator. Constructed by stacking
The positive electrode current collecting ear and the negative electrode current collecting ear extend upward from the first horizontal frame bone side when the electrode plates are viewed through in the stacking direction, and are arranged so as to be offset from each other in the horizontal direction. A characteristic lead-acid battery. The positive electrode current collector ear and the negative electrode current collector ear are arranged symmetrically with respect to each other with reference to the center line in the lateral direction of the positive electrode lattice body when the electrode plate group is viewed through in the stacking direction. The lead storage battery according to claim 7, wherein the lead storage battery is characterized in that. In the positive electrode lattice, among the plurality of openings adjacent to the first horizontal frame bone, the openings arranged at positions immediately below the negative electrode collecting ears provided on the negative electrode plate are the openings. The lead-acid battery according to claim 7 or 8, wherein the first vertical frame bone and the second vertical frame bone are divided by an auxiliary crosspiece extending in the same direction as the extending direction.

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