JPWO2019224946A1 - Lattice and lead-acid battery - Google Patents

Abstract

A lead-containing lattice used for a lead-acid battery electrode, which includes a first surface and a second surface parallel to each other, and a plurality of through holes penetrating the first surface and the second surface. , A lattice body in which the opening area on the first surface and the opening area on the second surface are different in at least one of the plurality of through holes.

Description

The present invention relates to a lattice body and a lead storage battery.

Lead-acid batteries are widely used for industrial and consumer purposes due to their reliability and low price, and there is a particularly large demand for lead-acid batteries for automobiles (so-called batteries).

Patent Document 1 describes a lead storage battery including a positive electrode plate and a negative electrode plate. In this lead-acid battery, each of the positive electrode plate and the negative electrode plate is configured by filling a lead alloy lattice with an active material. Then, the positive electrode plate and the negative electrode plate are alternately laminated via the separator, the current collecting portion of the positive electrode plate and the negative electrode plate is collectively welded to the strap for each polarity, and the cell-cell connection portion or the pole column is connected to the strap. , The electrode plate group is composed.

Japanese Unexamined Patent Publication No. 2012-230838

By the way, in recent years, the load on batteries of automobiles has increased due to the increase in electrical components. As a result, the amount of battery discharge is large. As an index of the discharge amount of the battery, there is a discharge depth DOD (Dept of Discharge). The discharge depth DOD indicates that the larger the value, the larger the discharge amount. When the battery is charged and discharged under a condition where the DOD is large, mud-like formation (softening phenomenon) in which the bonds between the active materials are weakened on the positive electrode plate progresses, and the active materials gradually fall off from the lattice. Moreover, since the lead-acid battery mounted on the automobile is exposed to a large vibration for a long time, the active material is significantly dropped from the lattice body. When the active material falls off from the lattice body, there arises a problem that the life of the electrode plate (particularly the positive electrode plate) is shortened.

Therefore, one aspect of the present invention is to provide a lattice body and a lead storage battery capable of suppressing the falling off of the active material.

The lattice body according to one aspect of the present invention is a lattice body containing lead used for the electrode plate of a lead storage battery, and penetrates the first surface and the second surface parallel to each other and the first surface and the second surface. The opening area on the first surface and the opening area on the second surface are different in at least one of the plurality of through holes.

In this lattice, when used for the electrode plate of a lead-acid battery, the active material is retained on the first surface, the second surface, and a plurality of through holes, but the first surface and the second surface are parallel to each other. Therefore, the active material easily falls off from the first surface and the second surface. However, in at least one of the plurality of through holes penetrating the first surface and the second surface, the opening area on the first surface and the opening area on the second surface are different, so that the active material is difficult to fall out from the through holes. .. Thereby, the dropout of the active material can be suppressed.

In all of the plurality of through holes, the opening area on the first surface and the opening area on the second surface may be different. In this lattice body, since the opening area on the first surface and the opening area on the second surface are different in all of the plurality of through holes, the shedding of the active material can be further suppressed.

In all of the plurality of through holes, the opening area on the first surface may be larger than the opening area on the second surface. In this lattice body, since the opening area on the first surface is larger than the opening area on the second surface in all of the plurality of through holes, the lattice body can be easily formed and the active material can be formed from the first surface side. By filling the mixture, the filling property of the active material with respect to the lattice body is improved.

The total opening area of the plurality of through holes on the first surface may be larger than the total opening area of the plurality of through holes on the second surface. In this lattice body, since the total opening area of the plurality of through holes on the first surface is larger than the total opening area of the plurality of through holes on the second surface, it is difficult for the active material to fall out of the through holes as a whole.

A recess may be formed in at least one inner wall surface of the plurality of through holes. In this lattice body, since a recess is formed in at least one inner wall surface of the plurality of through holes, the active material enters the recess. As a result, it is possible to further suppress the active material from falling off.

Recesses may be formed on all inner wall surfaces of the plurality of through holes. In this lattice body, since recesses are formed on all the inner wall surfaces of the plurality of through holes, the active material enters the recesses. As a result, it is possible to further suppress the active material from falling off.

At least one of the plurality of through holes may have a first tapered portion that extends to the first surface and a second tapered portion that expands to reach the second surface. In this lattice body, since each of the plurality of through holes has a first tapered portion and a second tapered portion, the active material filled in the through holes has a shape that spreads on both sides of the first surface and the second surface. That is, the active material has a shape that sandwiches the lattice body from both sides of the first surface and the second surface. Therefore, it is possible to further suppress the active material from falling off.

Each of the plurality of through holes may have a first tapered portion that extends to the first surface and a second tapered portion that expands to reach the second surface. In this lattice body, since each of the plurality of through holes has a first tapered portion and a second tapered portion, the active material filled in the through holes has a shape that spreads on both sides of the first surface and the second surface. That is, the active material has a shape that sandwiches the lattice body from both sides of the first surface and the second surface. Therefore, it is possible to further suppress the active material from falling off.

In the lead storage battery according to one aspect of the present invention, any of the above grids is used as at least one of the grids of the positive electrode plate and the negative electrode plate. In this lead-acid battery, since any of the above lattices is used as at least one of the positive electrode plate and the negative electrode plate, it is possible to prevent the active material from falling off.

By the way, in the positive electrode lattice, mudification (softening phenomenon) in which the bonds between active materials are weakened by repeating charging and discharging progresses. Therefore, the lattice body may be a positive electrode lattice body used for the positive electrode plate. As a result, it is possible to efficiently prevent the active material from falling off.

According to the present invention, it is possible to suppress the dropout of the active material.

It is a perspective view which shows the whole structure and the internal structure of the lead storage battery which concerns on one Embodiment. It is a perspective view which shows the electrode group of the lead storage battery shown in FIG. It is a front view which shows the positive electrode plate (negative electrode plate). FIG. 3 is a cross-sectional view taken along the line IV-IV of FIG. It is a front view which shows the lattice body which concerns on one Embodiment. It is a schematic cross-sectional view which shows a part of the lattice body shown in FIG. It is a schematic cross-sectional view which shows a part of the lattice body of the modification. It is a schematic cross-sectional view which shows a part of the lattice body of the modification. It is a schematic cross-sectional view which shows a part of the lattice body of the modification.

Hereinafter, preferred embodiments of the lead-acid battery according to one aspect of the present invention will be described in detail with reference to the drawings. In all the drawings, the same or corresponding parts are designated by the same reference numerals. In addition, the numerical range indicated by using "~" indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively. Further, "A or B" may include either A or B, and may include both.

<Lead-acid battery>
FIG. 1 is a perspective view showing the overall configuration and internal structure of the lead-acid battery 1 according to the embodiment. As shown in FIG. 1, the lead-acid battery 1 includes an electric tank 2 having an open upper surface and a lid 3 that closes the opening of the electric tank 2. The battery case 2 and the lid 3 are made of polypropylene, for example. The lid 3 is provided with a positive electrode terminal 4, a negative electrode terminal 5, and a liquid port plug 6 for closing the liquid injection port provided in the lid 3.

Inside the battery case 2, an electrode group 7, a positive electrode column 8 connecting the electrode group 7 to the positive electrode terminal 4, a negative electrode column (not shown) connecting the electrode group 7 to the negative electrode terminal 5, dilute sulfuric acid, etc. Electrolyte and is stored.

FIG. 2 is a perspective view showing the electrode group 7. As shown in FIG. 2, the electrode group 7 includes a positive electrode plate 9, a negative electrode plate 10, and a separator 11 arranged between the positive electrode plate 9 and the negative electrode plate 10.

FIG. 3 is a front view showing the positive electrode plate 9 (negative electrode plate 10), and FIG. 4 is a cross-sectional view taken along the line IV-IV of FIG. As shown in FIGS. 3 and 4, the positive electrode plate 9 has a positive electrode lattice body (positive electrode current collector) 12 and a positive electrode active material (positive electrode material) 13. The positive electrode lattice body 12 is a lattice body of the positive electrode plate 9, and has a lattice portion 12a and an ear portion 12b that is integrally formed with the lattice portion 12a and protrudes from one end of the lattice portion 12a. The positive electrode active material 13 is an active material of the positive electrode plate 9, and is held by the positive electrode lattice body 12. The negative electrode plate 10 has a negative electrode lattice body (negative electrode current collector) 14 and a negative electrode active material (negative electrode material) 15. The negative electrode lattice body 14 is a lattice body of the negative electrode plate 10, and has a lattice portion 14a and an ear portion 14b that is integrally formed with the lattice portion 14a and protrudes from one end of the lattice portion 14a. The negative electrode active material 15 is an active material of the negative electrode plate 10 and is held by the negative electrode lattice body 14. The positive electrode lattice body 12 and the negative electrode lattice body 14 are made of a lead alloy. The lead alloy may be an alloy containing tin, calcium, antimony, selenium, silver, bismuth and the like in addition to lead. Specifically, for example, an alloy containing lead, tin and calcium (Pb-Sn). -Ca-based alloy).

The electrode group 7 has a structure in which a plurality of positive electrode plates 9 and negative electrode plates 10 are alternately laminated in a direction substantially parallel to the opening surface of the battery case 2 via a separator 11. That is, the positive electrode plate 9 and the negative electrode plate 10 are arranged so that their main surfaces extend in the direction perpendicular to the opening surface of the battery case 2. In the electrode group 7, the ears 12b of each of the positive electrode lattices 12 of the plurality of positive electrode plates 9 are collectively welded by the positive electrode side strap 16. Similarly, the ears 14b of each of the negative electrode lattices 14 of the plurality of negative electrode plates 10 are collectively welded by the negative electrode side strap 17. The positive electrode side strap 16 and the negative electrode side strap 17 are connected to the positive electrode terminal 4 and the negative electrode terminal 5 via the positive electrode column 8 and the negative electrode column, respectively.

Subsequently, a method for manufacturing the lead storage battery 1 will be described. The method for manufacturing the lead-acid battery 1 includes an electrode plate manufacturing step for obtaining the electrode plates (positive electrode plate 9 and the negative electrode plate 10) and an assembly step for assembling the constituent members including the electrode plates to obtain the lead-acid battery 1.

In the electrode plate manufacturing process, for example, for each of the positive electrode plate 9 and the negative electrode plate 10, the electrode material paste (negative electrode material paste and positive electrode material paste) was held by the lattice bodies (positive electrode material lattice body 12 and negative electrode material lattice body 14) ( After (filling), aging and drying are performed to obtain an unchemical electrode plate.

The positive electrode material paste can be obtained, for example, by adding an additive (reinforcing short fibers, etc.) and water to a raw material (lead powder, lead tan (Pb3O4), etc.) of the positive electrode active material, and then adding dilute sulfuric acid and kneading. Be done. After the positive electrode material paste is held (filled) in the positive electrode lattice body 12, it is aged for 15 to 60 hours in an atmosphere of, for example, a temperature of 35 to 85 ° C. and a humidity of 50 to 98 RH%, and 15 to 80 ° C. at a temperature of 45 to 80 ° C. By drying for 30 hours, an unchemical positive electrode plate is obtained.

The negative electrode material paste is a dry type, for example, by adding an additive (carbon material, barium sulfate, reinforcing short fibers, a resin having a sulfonic acid group and / or a sulfonic acid base, etc.) to a raw material (lead powder, etc.) of the negative electrode active material. After obtaining a mixture by mixing, it is obtained by adding dilute sulfuric acid and water and kneading. After the negative electrode material paste is held (filled) in the current collector, it is aged for 15 to 30 hours in an atmosphere of, for example, a temperature of 45 to 65 ° C. and a humidity of 70 to 98 RH%, and aged at a temperature of 45 to 60 ° C. for 15 to 30. By drying for a time, an unchemical negative electrode plate is obtained.

In the assembly process, for example, the unchemical negative electrode plate and the unchemical positive electrode plate are alternately laminated via the separator 11, and the ear portions 12b of the positive electrode lattice body 12 are connected (welded, etc.) by the positive electrode side strap 16. At the same time, the ear portions 14b of the negative electrode lattice body 14 are connected (welded or the like) with the negative electrode side strap 17 to obtain the electrode group 7. The electrode group 7 is arranged in the battery case 2 to produce a non-chemical battery. Next, after injecting an electrolytic solution (dilute sulfuric acid or the like) into a non-chemical battery, a direct current is applied to form an electric tank. The lead storage battery 1 can be obtained by adjusting the specific gravity of the electrolytic solution after chemical conversion to an appropriate specific density.

The chemical conversion conditions and the specific gravity of sulfuric acid can be adjusted according to the properties of the electrode active material. Instead of being carried out after the assembly step, the chemical conversion treatment may be carried out by immersing a large number of electrode plates after aging and drying in the electrode plate manufacturing step together in a chemical conversion tank (tank chemical conversion).

<Lattice body>
Subsequently, the positive electrode lattice body 12 and the negative electrode lattice body 14 used for the positive electrode plate 9 and the negative electrode plate 10 of the lead storage battery 1 described above will be described in more detail. Since the positive electrode lattice body 12 and the negative electrode lattice body 14 have basically the same shape in the present embodiment, the positive electrode lattice body 12 and the negative electrode lattice body 14 will be described together as the lattice body 21 below.

FIG. 5 is a front view showing a lattice body according to an embodiment. FIG. 6 is a schematic cross-sectional view showing a part of the lattice body shown in FIG. As shown in FIGS. 3 to 6, the lattice body 21 (positive electrode lattice body 12 and negative electrode lattice body 14) is formed integrally with the lattice portion 22 (lattice portion 12a and lattice portion 14a) and the lattice portion 22, and is a lattice. It has an ear portion 23 (ear portion 12b and ear portion 14b) protruding from one end of the portion 22. The lattice body 21 corresponds to each of the positive electrode lattice body 12 and the negative electrode lattice body 14, the lattice portion 22 corresponds to each of the lattice portion 12a and the lattice portion 14a, and the selvage portion 23 corresponds to the selvage portion 12b and the ear. Corresponds to each of the parts 14b.

The lattice portion 22 is formed in a substantially rectangular thin plate shape, and has a first surface 22a and a second surface 22b parallel to each other, and a plurality of through holes 22c penetrating the first surface 22a and the second surface 22b. I have. Therefore, when the lattice portion 22 is used for the electrode plates (positive electrode plate 9 and negative electrode plate 10) of the lead-acid battery 1, the active material (positive electrode active material 13 and negative electrode active material 15) is the first surface of the lattice portion 22. It is held in 22a, a second surface 22b, and a plurality of through holes 22c. The active material is not retained on the upper part of the lattice portion 22 (the upper part of the first surface 22a and the second surface 22b). There is no distinction between the first surface 22a and the second surface 22b, and either surface of the lattice portion 22 may be the first surface 22a or the second surface 22b. The number, shape, size, etc. of the through holes 22c formed in the lattice portion 22 are not particularly limited, and are appropriately set as long as the active material can be appropriately held.

In the lattice portion 22, the opening area on the first surface 22a and the opening area on the second surface 22b are different in at least one of the plurality of through holes 22c. In this case, the lattice portion 22 may be formed with a through hole 22c in which the opening area on the first surface 22a and the opening area on the second surface 22b are the same. Further, the opening area on the first surface 22a and the opening area on the second surface 22b may be either large or small.

Here, the opening area on the first surface 22a and the opening area on the second surface 22b are defined as follows. The surface of the first surface 22a is designated as the first reference plane, and the surface of the second surface 22b is designated as the second reference plane. Since the first surface 22a and the second surface 22b are parallel to each other, the first reference plane and the second reference plane are also parallel to each other. If some irregularities are formed on the first surface 22a and the second surface 22b due to manufacturing errors or the like, the surfaces excluding the irregularities are designated as the first reference plane and the second reference plane. Then, the opening of the through hole 22c on the first reference surface and the second reference surface is the opening of the through hole 22c on the first surface 22a and the second surface 22b, and this opening area is defined as the first surface 22a and the second surface 22b. The opening area in.

As described above, in the lattice body 21 according to the present embodiment, when used for the electrode plate of the lead storage battery 1, the active material is retained in the first surface 22a, the second surface 22b, and the plurality of through holes 22c. However, since the first surface 22a and the second surface 22b are parallel to each other, the active material easily falls off from the first surface 22a and the second surface 22b. However, in at least one of the plurality of through holes 22c penetrating the first surface 22a and the second surface 22b, the opening area in the first surface 22a and the opening area in the second surface 22b are different, so that the active material is a through hole. It becomes difficult to drop out from 22c. Thereby, the dropout of the active material can be suppressed.

Further, in the lead-acid battery 1 according to the present embodiment, since the lattice body 21 is used as the positive electrode lattice body 12 and the negative electrode lattice body 14, it is possible to prevent the positive electrode active material 13 and the negative electrode active material 15 from falling off.

The present invention is not limited to the above embodiment, and can be appropriately modified as long as it does not deviate from the gist of the present invention.

For example, in all of the plurality of through holes 22c, the opening area on the first surface 22a and the opening area on the second surface 22b may be different. In this case, the lattice portion 22 is not formed with a through hole 22c in which the opening area on the first surface 22a and the opening area on the second surface 22b are the same. Further, as in the lattice portion 22B of the lattice body 21A of the modified example shown in FIG. 7, the through hole 22c in which the opening area on the first surface 22a is larger than the opening area on the second surface 22b and the first surface 22a The through hole 22c in which the opening area in the second surface 22b is smaller than the opening area in the second surface 22b may be mixed. As described above, by setting the opening area on the first surface 22a and the opening area on the second surface 22b to be different in all of the plurality of through holes 22c, it is possible to further suppress the dropping of the active material.

Further, in all of the plurality of through holes 22c, the opening area on the first surface 22a may be larger than the opening area on the second surface 22b. In this case, the lattice portion 22 is not formed with a through hole 22c in which the opening area on the first surface 22a is smaller than the opening area on the second surface 22b. As described above, by setting the opening area on the first surface 22a to be larger than the opening area on the second surface 22b in all of the plurality of through holes 22c, the lattice body 21 can be easily formed and the lattice body 21 can be formed. By filling the active material from the side of the first surface 22a, the filling property of the active material with respect to the lattice body 21 is improved.

Further, the total opening area of the plurality of through holes 22c on the first surface 22a may be larger than the total opening area of the plurality of through holes 22c on the second surface 22b. The total opening area of the plurality of through holes 22c on the first surface 22a is the total opening area of the first surface 22a of each through hole 22c, and the total opening area of the plurality of through holes 22c on the second surface 22b is , The sum of the opening areas of the second surface 22b of each through hole 22c. In this case, as in the lattice portion 22A of the lattice body 21A shown in FIG. 7, the through hole 22c in which the opening area on the first surface 22a is larger than the opening area on the second surface 22b and the opening on the first surface 22a. Through holes 22c whose area is smaller than the opening area on the second surface 22b may be mixed. As described above, by setting the total opening area of the plurality of through holes 22c on the first surface 22a to be larger than the total opening area of the plurality of through holes 22c on the second surface 22b, the active material as a whole becomes the through holes 22c. It becomes difficult to drop out from.

Further, in the cross section in the direction orthogonal to the first surface 22a and the second surface 22b, the inner wall surface of each of the plurality of through holes 22c may be formed in a straight line, but the lattice of the modified example shown in FIG. Like the lattice portion 22B of the body 21B, a recess 22d into which the active material enters may be formed on at least one inner wall surface of the plurality of through holes 22c. In this case, recesses 22d may be formed on all inner wall surfaces of the plurality of through holes 22c. Further, not only the concave portion 22d but also the convex portion may be formed so that the convex portion may be formed as a whole. The number, shape, size, etc. of the recesses 22d are not particularly limited, and can be appropriately set as long as the active material can enter. As described above, by assuming that the recesses 22d are formed on at least one inner wall surface of the plurality of through holes 22c, further, the recesses 22d are formed on all the inner wall surfaces of the plurality of through holes 22c. By assuming that, the active material enters the recess 22d. As a result, it is possible to further suppress the active material from falling off.

Further, in the cross section in the direction orthogonal to the first surface 22a and the second surface 22b, the inner wall surface of each of the plurality of through holes 22c may be formed in a straight line, but the lattice of the modified example shown in FIG. Like the lattice portion 22C of the body 21C, at least one of the plurality of through holes 22c includes a first tapered portion 22e that expands to reach the first surface 22a and a second tapered portion 22f that expands to reach the second surface 22b. , And may have. The opening area of the first surface 22a and the opening area of the second surface 22b are such that the inclination angle θ1 of the first tapered portion 22e and the inclination angle θ2 of the second tapered portion 22f are increased, or the first tapered portion 22e. And the larger the second tapered portion 22f, the larger the size.

In this case, each of the plurality of through holes 22c, that is, all of the plurality of through holes 22c may have the first tapered portion 22e and the second tapered portion 22f. In the first tapered portion 22e, the through hole 22c is inclined in a direction extending with respect to the first surface 22a in a cross section orthogonal to the first surface 22a to reach the first surface 22a. Similarly, in the second tapered portion 22f, the through hole 22c is inclined in a direction extending with respect to the second surface 22b in a cross section orthogonal to the second surface 22b to reach the second surface 22b. Further, in the cross section in the direction orthogonal to the first surface 22a and the second surface 22b, the first tapered portion 22e and the second tapered portion 22f do not necessarily have to be linear as long as they have a tapered shape as a whole. , It may be curved or uneven. As described above, by assuming that at least one of the plurality of through holes 22c has the first tapered portion 22e and the second tapered portion 22f, the active material filled in the through holes 22c becomes the first surface 22a and the second. It has a shape that spreads on both sides of the surface 22b. That is, the active material has a shape in which the lattice portion 22C of the lattice body 21C is sandwiched from both sides of the first surface 22a and the second surface 22b. Therefore, it is possible to further suppress the active material from falling off.

By the way, in the positive electrode lattice body, mudification (softening phenomenon) in which the bonds between the active materials are weakened progresses by repeating charging and discharging, but in the negative electrode lattice body 14, such mudification occurs. Does not occur. Therefore, the lattice body 21 may be used only as the positive electrode lattice body 12. As a result, it is possible to efficiently prevent the active material from falling off.

1 ... Lead storage battery, 2 ... Electrode tank, 3 ... Lid, 4 ... Positive terminal, 5 ... Negative terminal, 6 ... Liquid spout, 7 ... Electrode group, 8 ... Positive column, 9 ... Positive plate, 10 ... Negative plate, 11 ... Separator, 12 ... Positive electrode lattice, 12a ... Lattice part, 12b ... Ear part, 13 ... Positive electrode active material, 14 ... Negative electrode lattice body, 14a ... Lattice part, 14b ... Ear part, 15 ... Negative electrode active material, 16 ... Positive electrode side strap, 17 ... Negative electrode side strap, 21,21A, 21B, 21C ... Lattice body, 22, 22A, 22B, 22C ... Lattice portion, 22a ... First surface, 22b ... Second surface, 22c ... Through hole, 22d ... concave, 22e ... first tapered portion, 22f ... second tapered portion, 23 ... ear portion, θ1 ... tilt angle of the first tapered portion, θ2 ... tilt angle of the second tapered portion.

Claims (10)

A grid body containing lead used for the electrode plate of lead-acid batteries.
With the first and second surfaces parallel to each other,
The first surface and a plurality of through holes penetrating the second surface are provided.
In at least one of the plurality of through holes, the opening area on the first surface and the opening area on the second surface are different.
Lattice body. In all of the plurality of through holes, the opening area on the first surface and the opening area on the second surface are different.
The lattice body according to claim 1. In all of the plurality of through holes, the opening area on the first surface is larger than the opening area on the second surface.
The lattice body according to claim 1 or 2. The total opening area of the plurality of through holes on the first surface is larger than the total opening area of the plurality of through holes on the second surface.
The lattice body according to any one of claims 1 to 3. A recess is formed in at least one inner wall surface of the plurality of through holes.
The lattice body according to any one of claims 1 to 4. Recesses are formed on all inner wall surfaces of the plurality of through holes.
The lattice body according to any one of claims 1 to 4. At least one of the plurality of through holes has a first tapered portion that extends to the first surface and a second tapered portion that expands to reach the second surface.
The lattice body according to any one of claims 1 to 6. Each of the plurality of through holes has a first tapered portion that extends to reach the first surface and a second tapered portion that expands to reach the second surface.
The lattice body according to any one of claims 1 to 6. The lattice body according to any one of claims 1 to 8 is used as at least one lattice body of the positive electrode plate and the negative electrode plate.
Lead-acid battery. The lattice body is a positive electrode lattice body used for a positive electrode plate.
The lead storage battery according to claim 9.

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