Clad type positive electrode plate for lead-acid battery and lead-acid battery

Abstract

To provide a clad type positive electrode plate for a lead acid battery that can increase a chemical conversion degree of a positive electrode material, and a lead acid battery including the same.SOLUTION: A clad type positive electrode plate for a lead acid battery includes at least one porous tube 31, a positive electrode material 32 filling the tube 31, and a positive electrode current collector 33. The positive electrode current collector 33 includes at least one core grid 35 with first and second end parts, and a current collector part 34 connecting to the first end part 35a. The core grid 35 is disposed in the tube 31, and is in contact with the positive electrode material 32. The core grid 35 includes an eccentric part 35d including a bent part 35c in which the second end part 32b bends to get close to the tube 31. When a length of the core grid 35 in a direction where the tube 31 extends is L0 and a length in the same direction from the first end part 35a to the eccentric part 35d is L1, a ratio L1 / L0 is 0.80 or more.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present invention relates to a clad type positive electrode plate for a lead-acid battery and a lead-acid battery. [Background technology]

[0002] In lead-acid batteries, a paste type positive plate, a clad type positive plate, etc. are used as the positive plate. The clad type positive plate includes, for example, a plurality of porous tubes, a metal core housed in the tube, and a positive electrode material filled in the tube. In the clad type positive plate, the characteristics of the battery change depending on the shape of the positive electrode current collector. Therefore, various positive electrode current collectors have been proposed.

[0003] Patent Document 1 (JP Patent Publication 8-203505) discloses a clad type anode plate characterized in that "multiple blades (1') are provided only on both side surfaces parallel to the plate surface of a cylindrical core (1), and the height c of the blades (1') is set to be equal to or greater than the value calculated by the formula [(tube inner diameter a - core outer diameter b) ÷ 2 × 0.74]."

[0004] Patent Document 2 (Japanese Utility Model Publication No. 62-064956) discloses "a fiber-clad anode plate having a core inserted into the center of a hollow cylindrical sleeve and an active material filled in the gap between the sleeve and the core, characterized in that the diameter of the lower 1 / 3 of the core is 20 to 30% larger than the diameter of the upper 2 / 3." [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 8-203505 [Patent Document 2] Japanese Utility Model Application Publication No. 62-064956 Summary of the Invention [Problem to be solved by the invention]

[0006] In the conventional clad type positive plate, the degree of chemical conversion of the positive electrode material may not be sufficiently increased in some cases. In such a situation, an object of the present invention is to provide a clad type positive plate for a lead-acid battery capable of increasing the degree of chemical conversion of the positive electrode material, and a lead-acid battery including the same. [Means for solving the problem]

[0007] One aspect of the present invention relates to a clad type positive plate for a lead acid battery, the positive plate including at least one porous tube, a positive electrode material filled in the tube, and a positive current collector, the positive electrode collector including at least one core having first and second ends and a current collector connected to the first end, the core being disposed in the tube and in contact with the positive electrode material, the core including an eccentric portion including a bent portion where the second end is bent so as to approach the tube, and a ratio L1 / L0 of 0.80 or more is obtained when L0 is a length of the core in a direction in which the tube extends and L1 is a length from the first end to the eccentric portion in the direction.

[0008] Another aspect of the present invention relates to a lead-acid battery comprising the clad-type positive electrode plate for a lead-acid battery of the present invention. Effect of the Invention

[0009] According to the present invention, there is provided a clad type positive electrode plate for a lead-acid battery capable of increasing the degree of chemical conversion of the positive electrode material, and a lead-acid battery including the same. [Brief description of the drawings]

[0010] [Figure 1] FIG. 2 is a top view showing a schematic diagram of a clad type positive electrode plate according to one embodiment of the present invention. [Diagram 2] FIG. 2 is a schematic cross-sectional view taken along line II-II in FIG. [Diagram 3] FIG. 3 is a schematic cross-sectional view taken along line III-III in FIG. 2. [Figure 4]4 is a diagram showing an example of the shape of a bent portion of the core bar shown in FIG. 2 and FIG. 3. FIG. [Diagram 5] FIG. 4 is a diagram showing a schematic example of the shape of the core bar shown in FIG. 2 and FIG. 3. [Figure 6] FIG. 1 is a perspective view showing a schematic example of a lead-acid battery according to an embodiment of the present invention with the lid removed. [Figure 7A] FIG. 7 is a front view of the lead-acid battery of FIG. 6. [Figure 7B] 7B is a schematic cross-sectional view taken along line VIIB-VIIB in FIG. 7A, seen from the direction of the arrows. [Figure 8] 1 is a graph showing some of the results of the examples. [Figure 9] FIG. 1 is a schematic cross-sectional view showing a structure of an example of a conventional clad type positive electrode plate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] In the following, the embodiment of the present invention will be described with examples, but the present invention is not limited to the examples described below. In the following description, specific numerical values ​​and materials may be exemplified, but other numerical values ​​and materials may be applied as long as the effects of the present invention can be obtained. In this specification, the range described as "numerical value A to numerical value B" includes numerical value A and numerical value B, and can be read as "A or more and B or less."

[0012] (Clad type positive electrode plate for lead-acid batteries) The clad type positive plate of this embodiment is used in a lead-acid battery. The clad type positive plate includes at least one porous tube, a positive electrode material filled in the tube, and a positive current collector. The porous tube may be referred to as a "tube (T)" below. The positive current collector includes at least one core having first and second ends, and a current collector connected to the first end. The core is disposed in the tube (T) and is in contact with the positive electrode material. The core includes an eccentric portion. The eccentric portion includes a bent portion that bends so that the second end approaches the tube (T). When the length of the core in the direction in which the tube (T) extends is L0, and the length from the first end to the eccentric portion in the same direction is L1, the ratio L1 / L0 is 0.80 or more.

[0013] The direction in which the tube (T) extends may be referred to below as the "direction DL." From another perspective, the direction DL is a direction parallel to the central axis of the tube (T) or the longitudinal direction of the tube (T).

[0014] The radius of curvature of the central axis of the core bar at the bent portion is 2700 mm or less (for example, 1900 mm or less, 1200 mm or less, 800 mm or less, or 600 mm or less). In other words, the portion having such a radius of curvature is defined as the bent portion. The radius of curvature of the central axis of the core bar at the bent portion may be 200 mm or less. The bent portion may be a bent portion where the core bar is bent sharply. The bent portion is a portion where the radius of curvature of the central axis of the core bar is 20 mm or less (for example, 10 mm or less, 5 mm or less, or 3 mm or less). As long as the core bar at the second end portion is not bent toward the first end portion from the direction perpendicular to the inner surface of the tube (T), there is no limitation on the lower limit of the radius of curvature of the central axis of the bent portion, but the radius of curvature may be 1 mm or more (for example, 2 mm or more, or 5 mm or more). These lower and upper limits can be combined arbitrarily as long as the lower limit is not lower than the upper limit. In the following, a bent portion where the radius of curvature of the central axis of the core bar is 20 mm or less may be referred to as a bent portion, and a bent portion where the radius of curvature of the central axis of the core bar is greater than 20 mm and less than 2700 mm (for example, less than 1900 mm, less than 1200 mm, less than 800 mm, or less than 600 mm) may be referred to as a curved portion.

[0015] It is possible to determine whether a bend exists in a specific part of the core bar without measuring the radius of curvature. For example, it is possible to determine whether a bend exists in a specific part of the core bar by selecting three arbitrary points from the central axis of the specific part of the core bar and based on the positions of the three points.

[0016] Length L1 is the length (length along direction DL) between the first end and a bent portion included in the eccentric portion (more specifically, the start point of the bent portion, which is closer to the current collector, out of the two start points of the bent portion). Specifically, L1 can be the length (length along direction DL) between the start point (the start point closer to the current collector) of the bent portion whose central axis of the core has a radius of curvature in the above range and the first end. When there are multiple bent portions (bends and / or curved portions), L1 is the length between the bent portion closest to the first end and the first end. The start point of the bent portion means the two ends of the portion whose central axis of the core has a radius of curvature in the above range.

[0017] When a component (such as a rod-shaped portion or a tube (T)) is cylindrical or hollow cylindrical, the central axis of the component at a certain position P1 is the center of the circular cross section of the component at that position P1 (a cross section perpendicular to the direction in which the component extends at position P1). When a component is neither cylindrical nor hollow cylindrical, the position of the central axis of the component at a certain position P1 can be the position of the center of gravity of the cross section of the component at that position P1 (a cross section perpendicular to the direction in which the component extends at position P1). That is, in this case, the line connecting the centers of gravity along the direction DL can be regarded as the central axis.

[0018] In a typical positive electrode current collector of a clad type positive electrode plate, the position of the core metal on the current collecting part side is fixed, but the positions of the other core metals are not fixed. Therefore, when such a typical positive electrode current collector is used, the position of the core metal tends to become eccentric the further away from the current collecting part (i.e., the more easily it is displaced from the central axis of the porous tube). A schematic cross-sectional view of an example of such a conventional clad type positive electrode plate is shown in FIG. 9.

[0019] The positive electrode plate shown in FIG. 9 includes a porous tube 1031, a positive electrode material 1032, and a positive current collector 1033. The positive current collector 1033 includes a current collector 1034 and a metal core 1035. The positive electrode material 1032 and the metal core 1035 are disposed in the tube 1031. The tip side of the metal core 1035 is not fixed. Therefore, when a general positive current collector 1033 is used, the metal core 1035 on the current collector 1034 side is located near the center of the tube 1031, but the metal core 1035 located away from the current collector 1034 may be eccentric enough to come into contact with the inner circumferential surface of the tube 1031. In FIG. 9, the part away from the tube 1031 may be referred to as a separated part 1035a, and the part of the metal core 1035 close to the tube 1031 may be referred to as a close part 1035b. In the example of FIG. 9, the core metal 1035 located closer to the current collecting portion 1034 is the distant portion 1035a, and the core metal 1035 located farther from the current collecting portion 1034 is the adjacent portion 1035b.

[0020] The positive electrode material contains a large amount of lead monoxide (PbO) with low electrical conductivity (hereinafter, may be referred to as "unformed active material"). In addition, ions involved in the formation reaction move through the pores of the positive electrode material. Therefore, in the positive electrode material around the adjacent portion 1035b, the resistance of the unformed active material and the resistance when the ions pass through the pores are relatively small. Therefore, around the adjacent portion 1035b, a larger formation current flows in the early stage of formation, and as a result, the PbO generated by the formation reaction is 2 The amount of PbO increases. 2 The positive electrode material around the adjacent portion 1035b has a higher electrical conductivity than the unconverted active material, so that the conversion reaction proceeds rapidly due to the originally low resistance and the electrical conductivity that increases as the conversion proceeds.

[0021] The chemical formation also proceeds simultaneously on the negative plate facing the positive plate. Therefore, even on the negative plate, chemical formation proceeds first from the negative electrode material in the portion facing the adjacent portion 1035b. When chemical formation of the active material is almost completed in the positive electrode material around the adjacent portion 1035b and in the negative electrode material in the portion facing the adjacent portion 1035b (for example, in the later stage of chemical formation), most of the chemical formation current flows into the separated portion 1035a. However, in addition to the current density increasing due to the chemical formation current concentrating in the separated portion 1035a, the resistance of the positive electrode material around the separated portion 1035a is originally high, so that in the separated portion 1035a, the PbO 2 The rate of increase (i.e., anodization efficiency) is significantly lower in the adjacent portion 1035b than in the adjacent portion 1035c.

[0022] Due to the mechanism described above, in conventional clad-type positive plate having an eccentric core, the variation in the degree of conversion of the positive electrode material throughout the positive plate tends to be greater than in positive plate having a core without eccentricity, and the degree of conversion of the positive electrode material throughout the positive plate tends to be lower.

[0023] The variation in the degree of anodization of the positive electrode material is relatively small when the anodization current applied during anodization is small. However, when the anodization current is large (for example, when high-speed anodization is performed), the difference between the anodization current density in the adjacent portion 1035b and the anodization current density in the separated portion 1035a becomes extremely large in the early stage of anodization. Furthermore, in the later stage of anodization when the anodization of the adjacent portion 1035b is almost completed, the anodization current is concentrated in the separated portion 1035a, which has a high resistance, and the anodization efficiency decreases. Therefore, when the anodization current is large, the variation in the degree of anodization of the positive electrode material becomes significant.

[0024] The core of the positive electrode current collector used in this embodiment has an eccentric portion including a bent portion where the second end bends toward the tube. In addition, the above ratio L1 / L0 is 0.80 or more. This configuration makes it easy to reduce the overall bias of the core. For example, it is easy to prevent the portion from the first end to the vicinity of the second end from contacting the tube (T). As a result, the bias of the chemical conversion degree in the entire positive electrode plate is reduced, and the chemical conversion degree of the entire positive electrode can be increased. Furthermore, by disposing most of the core near the central axis of the tube (T), the active material is evenly disposed around the core. As a result, it is possible to suppress corrosion of the core.

[0025] The core has a first and a second end. The core is a portion of the positive electrode current collector having a surface in contact with the positive electrode material. The current collector is not in contact with the positive electrode material. The first end is at the boundary between the core and the current collector. The second end is the end opposite the first end.

[0026] The ratio L1 / L0 is 0.80 or more, and may be 0.81 or more, 0.86 or more, or 0.91 or more. The ratio L1 / L0 may be 0.99 or less, 0.98 or less, 0.97 or less, 0.95 or less, or 0.91 or less. These lower and upper limits can be combined in any way as long as the lower limit is below the upper limit. For example, the ratio L1 / L0 may be in the range of 0.80 to 0.99, 0.81 to 0.99, 0.86 to 0.99, or 0.91 to 0.99. In these ranges, as long as the lower limit is below the upper limit, the upper limit may be 0.98, 0.97, 0.95, or 0.91.

[0027] The length L0 of the core bar in the extending direction of the tube (T) is not limited and may be in the range of 150 mm to 450 mm (for example, in the range of 200 mm to 400 mm). When the length L0 is 360 mm or less (for example, in the range of 200 mm to 360 mm), the effect of the present invention is enhanced.

[0028] The eccentric portion may include a bent portion where the second end is bent so as to approach the tube (T). The bent portion is a portion where the core bar is sharply bent. In a preferred example, the core bar includes only one bent portion as the bent portion.

[0029] When the bent portion includes a bent portion, the angle at which the core bar is bent at the bent portion may be 2° or more. For example, the angle may be 2° or more, 5° or more, 10° or more, 20° or more, 30° or more, or 40° or more. The angle may be 90° or less, 75° or less, 60° or less, or 45° or less. These lower and upper limits can be combined arbitrarily as long as the upper limit is not equal to or less than the lower limit. For example, the angle may be in the range of 2° to 90°, 5° to 90°, 10° to 90°, 20° to 90°, 30° to 90°, or 40° to 90°. In these ranges, the upper limit may be replaced with 75°, 60°, or 45°. For example, the angle may be in the range of 2° to 60°. The larger the angle, the longer the distance between the first end and the eccentric portion. As a result, the deviation of the degree of formation in the positive electrode can be suppressed, and therefore the degree of formation of the entire positive electrode can be easily increased. On the other hand, by reducing the angle, the variation in the packing density of the positive electrode material can be easily reduced. The angle may be in the range of 2° to 75° (for example, in the range of 2° to 60°, in the range of 5° to 60°, or in the range of 5° to 45°).

[0030] The direction in which the tube (T) extends may be referred to below as the "direction DL." Furthermore, the direction perpendicular to the direction DL may be referred to below as the "cross-sectional direction DR." Furthermore, the end of the eccentric portion that is on the first end side may be referred to as the "end K." The portion from the end K to the second end constitutes the eccentric portion.

[0031] Here, the distance in the cross-sectional direction DR between the central axis of the core at end K and the central axis of the core at the second end is distance E (mm). The inner diameter of the tube (T) is inner diameter Dt (mm). The diameter of the core is Dm (mm). Here, it is assumed that Dt and Dm are constant. Furthermore, it is assumed that the central axis of the core and the central axis of the tube (T) intersect at end K, and that the core is in contact with the tube at the second end. In that case, (E+0.5Dm) is approximately equal to 0.5Dt. The distance E, the inner diameter Dt, and the diameter Dm may satisfy -2.0≦(E+0.5Dm-0.5Dt)≦2.0, preferably -1.0≦(E+0.5Dm-0.5Dt)≦1.0, and more preferably -0.5≦(E+0.5Dm-0.5Dt)≦0.5 (for example, -0.25≦(E+0.5Dm-0.5Dt)≦0.25). By satisfying these conditions, it becomes easy to bring the region between the first end and the second end closer to the central axis of the tube (T). In these formulas, the right side may be set to half the absolute value of the left side. In these formulas, the right side may be set to 0. Any of the multiple ranges exemplified here for the value of (E+0.5Dm-0.5Dt) and any of the multiple ranges of L1 / L0 exemplified above can be arbitrarily combined. It should be noted that the values ​​of the inner diameter Dt and the diameter Dm can be those at the end K (this also applies to the following explanation).

[0032] The value of the distance E (mm) is preferably in the range of 0.4 to 1.6 times (0.5Dt-0.5Dm), more preferably in the range of 0.8 to 1.2 times, and particularly preferably in the range of 0.9 to 1.1 times. The upper limit of these ranges may be 1.0 times. Any of the ranges exemplified here for the distance E and any of the ranges exemplified above for L1 / L0 may be arbitrarily combined.

[0033] In the positive electrode plate of this embodiment, the second end is preferably close to the tube (T), more preferably in contact with the tube (T). For example, the shortest distance between the second end and the tube (T) may be in the range of 0 to 1 mm, preferably in the range of 0 to 0.5 mm. The second end may be in contact with the tube (T). By satisfying these conditions, it becomes easy to bring the region between the first end and the second end closer to the central axis of the tube (T).

[0034] The bent portion is a portion that is bent even when the core metal is not deformed by an external force. From one viewpoint, when the core metal is not deformed by an external force, there is no bent portion in the portion from the first end to the eccentric portion. When filling the tube (T) with a positive electrode material, the fewer the eccentric portion, the easier it is to fill the positive electrode material uniformly. In a typical example of this configuration, the core metal (typically a rod-shaped portion) between the first end and the bent portion extends in a straight line unless a force such as gravity is applied. The state in which the core metal is not deformed by an external force is, for example, a state in which the core metal that is not placed in the tube (T) is left stationary so as not to be deformed by gravity.

[0035] The core metal may include a rod-shaped portion. Here, the rod-shaped portion means a region whose diameter is generally constant, excluding protrusions that are partially added. For example, the rod-shaped portion may be a portion whose maximum and minimum diameters are within a range of ±15% (preferably ±5%) of their average values. The diameter of the rod-shaped portion is the diameter of a cross section perpendicular to the direction in which the rod-shaped portion extends (the direction of the central axis). When the cross section of the rod-shaped portion is not circular, the diameter of the rod-shaped portion is the diameter of a circle (equivalent circle) having the same area as the area of ​​the cross section.

[0036] The rod-shaped portion typically has a cylindrical shape. The diameter (e.g., diameter) of the rod-shaped portion is not particularly limited, and may be in the range of 0.25 to 0.45 times (e.g., 0.30 to 0.38 times) the inner diameter of the tube. The rod-shaped portion may have a shape other than a cylindrical shape (e.g., a prismatic shape).

[0037] In the positive electrode plate of this embodiment, the core metal may include a rod-shaped portion continuing from the first end to the eccentric portion, and it is preferable that the rod-shaped portion does not contact the tube (T). According to this configuration, it is possible to particularly increase the degree of conversion of the positive electrode material, and particularly suppress the corrosion of the positive electrode core metal. In addition, in the region from the first end to the eccentric portion, a part of the rod-shaped portion curved by gravity or the like during filling of the electrode material may come into contact with the tube (T). Even in such a case, according to the positive electrode plate of this embodiment, the length of the part of the core metal close to the central axis of the tube (T) can be made longer than that of a conventional positive electrode current collector. Therefore, even if a part of the rod-shaped portion is in contact with the tube (T) in the region from the first end to the eccentric portion, it is possible to obtain the effect of the present invention.

[0038] A typical rod-shaped portion is columnar (e.g., cylindrical), continues from the first end to the second end (or near the first and second ends), and has a bent portion on the second end side. There is no particular limitation on the diameter (e.g., diameter) of the rod-shaped portion, and it may be in the range of 2.0 mm to 4.0 mm (e.g., 2.5 mm to 3.5 mm). Note that the core bar may be tapered near the second end (e.g., within a distance of about 5 mm from the second end), but that portion can be considered as a rod-shaped portion. Note that when the cross-sectional shape of the rod-shaped portion is not circular, the diameter of the rod-shaped portion is the diameter of a circle (equivalent circle) having the same area as the cross-sectional area.

[0039] The core may be composed of only a rod-shaped portion, or may be composed of a rod-shaped portion and a tapered portion described later. The length of the rod-shaped portion (rod-shaped portion of the core) in the direction DL may be in the range of 0.93 to 1.0 times (for example, in the range of 0.96 to 1.0 times) the length of the core in the direction DL.

[0040] Typically, the positive electrode plate of this embodiment includes a plurality of tubes (T) arranged in a row, and the positive electrode current collector includes a plurality of cores whose first ends are connected by a current collecting portion. The number of tubes (T) is the same as the number of cores. There is no limitation on the number of tubes (T) and cores, and each may be in the range of 1 to 30 (for example, in the range of 3 to 20).

[0041] In the positive electrode plate of this embodiment, the multiple core metals may be eccentric in the same direction at their respective eccentric portions. From another perspective, the multiple core metals may be bent in the same direction at their respective bent portions. With these configurations, when filling the tube (T) with the positive electrode material, it becomes easy to bring the second end closer to the tube (T). There is no limitation on the direction in which the core metal is eccentric (the direction in which the core metal is bent), and the direction may be parallel to or perpendicular to the direction in which the multiple tubes (T) are arranged. By making the direction in which the core metal is eccentric parallel to the direction in which the multiple tubes (T) are arranged, it becomes easy to manufacture the core metal by casting.

[0042] The above-described multiple different configurations can be arbitrarily combined as long as there is no contradiction. The positive electrode plate of the present embodiment may satisfy at least one of the above-described multiple configurations.

[0043] (lead acid battery) The lead-acid battery of the present embodiment includes the clad type positive plate of the present embodiment. With this configuration, the chemical degree of the positive plate can be increased, and as a result, it is possible to suppress the initial self-discharge of the battery and improve the initial discharge capacity. There is no particular limitation on the configuration other than the positive plate, and a known configuration used in a clad type lead-acid battery may be applied.

[0044] Hereinafter, examples of the main components of the clad type positive plate of the present embodiment and the lead acid battery including the same will be described. However, the components of the present invention are not limited to the following examples. Hereinafter, an example in which the positive plate includes a plurality of porous tubes (T) will be described.

[0045] (Clad positive plate) The clad type positive plate includes a plurality of porous tubes (T), a positive electrode material filled in the tubes (T), and a positive current collector. The positive current collector has the above-mentioned characteristics. The clad type positive plate usually includes a linking member that connects the plurality of tubes (T). The positive current collector has the above-mentioned characteristics.

[0046] (Positive electrode current collector) The positive electrode current collector is made of, for example, a lead alloy. As the lead alloy, it is preferable to use a Pb-Sb alloy. The Pb-Sb alloy may contain at least one element selected from the group consisting of arsenic, selenium, bismuth, and tin, if necessary.

[0047] The core metal of the positive electrode current collector may include a tapered portion on the current collector side and a rod-shaped portion extending from the tapered portion. The tapered portion may have a diameter that decreases from the current collector side toward the rod-shaped portion side and may have a truncated cone shape (including a shape similar to a truncated cone shape). The core metal may include a columnar portion disposed between the tapered portion and the current collector. The columnar portion usually has a cylindrical shape (including a shape similar to a cylindrical shape). In the vicinity of the current collector, the tapered portion, or the tapered portion and the columnar portion are disposed so as to close the opening of the current collector side of the tube (T). A resin (e.g., polyolefin (polyethylene, polypropylene, etc.)) may be filled in the gap between a part of the tapered portion and the inner circumferential surface of the tube, or the gap between a part of the tapered portion and the columnar portion and the inner circumferential surface of the tube.

[0048] The manufacturing method of the positive electrode current collector is not particularly limited, and may be manufactured by a known method. For example, the positive electrode current collector may be manufactured by a casting method (including a die casting method). In this case, casting may be performed so that an eccentric part of the core metal is formed during casting. Alternatively, the bent part of the eccentric part of the core metal may be formed by bending a part of the core metal of the cast positive electrode current collector.

[0049] (Porous tube) The porous tube (tube (T)) accommodates a core metal and a positive electrode material therein. The tube (T) has a hollow cylindrical shape as a whole. The tube (T) is porous and allows an electrolyte to pass through. The tube (T) is usually a tubular fiber assembly. The tubular fiber assembly may be an assembly formed by weaving fibers into a tube shape. The tubular fiber assembly may be a tubular nonwoven fabric or woven fabric. Examples of fibers include inorganic fibers (such as glass fibers), resin fibers, and the like. The tube (T) may be heat-treated as necessary. The tube (T) may be formed by impregnating a tubular fiber assembly with a resin.

[0050] The length of the tube (T) may be selected according to the length of the core. For example, the length of the tube (T) may be longer than the length L0 of the core in the direction DL to some extent. The inner diameter and thickness of the tube (T) may be selected according to the shape of the core and / or the use of the lead-acid battery.

[0051] The inner diameter of the tube (T) is not particularly limited, and may be in the range of 8.5 mm to 11 mm (for example, in the range of 9.0 mm to 10.5 mm or in the range of 9.3 mm to 10.3 mm). The inner diameter of the tube (T) is the diameter in a cross section perpendicular to the longitudinal direction of the tube (T). The cross section of the tube (T) has a shape that is a perfect circle or close to a perfect circle. Therefore, the cross-sectional shape of the tube (T) can be considered to be a perfect circle.

[0052] There is no particular limitation on the thickness of the tube (T) as long as it functions as a tube for a clad type positive electrode plate. The thickness of the tube (T) may be in the range of 0.1 mm to 0.8 mm (for example, in the range of 0.3 mm to 0.6 mm).

[0053] The positive electrode material contains a positive electrode active material (specifically, at least one of lead dioxide and lead sulfate) that exhibits capacity through an oxidation-reduction reaction. The positive electrode material may contain other additives as necessary.

[0054] There is no limitation on the manufacturing method of the clad type positive electrode plate, and for example, the positive electrode plate may be manufactured by the following method. First, each of the multiple core metals is housed in a multiple tube (T). Next, an unformed positive electrode material (a material that will become the positive electrode material) is filled into the tube (T) to form an unformed positive electrode plate. The unformed positive electrode plate is formed into a positive electrode plate.

[0055] When filling the tube (T) with the unformed positive electrode material, it is preferable to fill the tube (T) with the second end of the core metal in contact with the tube (T). For example, the filling may be performed with the positive electrode collector and the tube (T) tilted so that the second end is located at the lowest position in a cross section including the second end (a cross section perpendicular to the central axis of the tube (T)). This makes it possible to reduce the distance between the second end and the tube (T). For example, filling can be completed with the second end in contact with the tube (T).

[0056] The unformed positive plate may be manufactured by the following procedure. First, each of the multiple core metals is housed in a tube (T). Next, one end of each of the multiple tubes (T) is fixed to the current collector with an upper connecting member. Next, the unformed positive electrode material is filled into the tube (T) from the opening at the other end of each of the multiple tubes (T). Next, the opening at the other end of each of the multiple tubes (T) is sealed with a lower connecting member. In this manner, an unformed positive plate is obtained.

[0057] The unformed positive electrode material may be a known material used in lead-acid batteries. The unformed positive electrode material includes a powder containing lead. The powder includes at least lead monoxide. The powder may further include at least one selected from the group consisting of metallic lead, red lead, and lead sulfate. The unformed positive electrode material may include an additive as necessary.

[0058] The filling of the unformed positive electrode material may be either dry filling or wet filling. For example, in the case of dry filling, the material in a dry state is filled directly into the tube (T). In the case of wet filling, the material in a slurry state is filled into the tube (T). The material in a slurry state may be prepared by mixing a powder containing lead, water, sulfuric acid, and, if necessary, an additive.

[0059] In the conventional clad type positive electrode plate, it is difficult to fix the core metal on the central axis of the tube in the case of wet filling compared to dry filling, and the core metal is easily eccentric. Therefore, when wet filling is performed, the degree of formation is easily varied. With the positive electrode plate of this embodiment, it is possible to suppress the variation in the degree of formation even in the case of wet filling.

[0060] The unformed positive plate is formed. The formation produces lead dioxide. The formation may be performed by charging the plate assembly, which includes the unformed plates, while immersing the plate assembly in an electrolyte in a lead-acid battery container. Alternatively, the formation of the positive plate may be performed before the assembly of the plate assembly.

[0061] (lead acid battery) The lead-acid battery of this embodiment usually includes a positive plate, a negative plate, a separator, an electrolyte, a battery case, and a lid. The positive plate is a clad type positive plate of this embodiment. There is no particular limitation on the components other than the clad type positive plate, and known components used in lead-acid batteries may be used.

[0062] The battery case contains a positive electrode plate, a negative electrode plate, a separator, and an electrolyte. The separator is disposed between the positive electrode plate and the negative electrode plate. The positive electrode plate, the separator, and the negative electrode plate are stacked to form an electrode plate group. The electrode plate group may include a plurality of positive electrode plates and a plurality of negative electrode plates. The lid seals the opening of the battery case.

[0063] (Negative plate) The negative electrode plate includes a negative current collector and a negative electrode material. The negative electrode material is the portion of the negative electrode plate excluding the negative current collector. Note that a member such as a mat or pasting paper may be attached to the negative electrode plate. Such a member (attaching member) is used integrally with the negative electrode plate, and is therefore included in the negative electrode plate. In addition, when the negative electrode plate includes such a member, the negative electrode material is the portion excluding the negative electrode collector and the attaching member.

[0064] The negative electrode current collector may be formed by casting lead or a lead alloy, or may be formed by processing a lead or lead alloy sheet. Examples of the processing method include expanding and punching. It is preferable to use a lattice-shaped current collector (negative electrode lattice) as the negative electrode current collector, since it is easy to support the negative electrode material.

[0065] The lead alloy constituting the negative electrode current collector may be any of Pb-Sb alloy, Pb-Ca alloy, and Pb-Ca-Sn alloy. The lead or lead alloy constituting the negative electrode current collector may contain at least one element selected from the group consisting of Ba, Ag, Al, Bi, As, and Se as an additive element.

[0066] The negative electrode material contains, as an essential component, a negative electrode active material (lead or lead sulfate) that develops capacity through an oxidation-reduction reaction. The negative electrode material may contain additives such as an organic shrinkage inhibitor, a carbonaceous material, and barium sulfate. The negative electrode active material in a charged state is sponge-like lead, but an unformed negative plate is usually made using a powder containing lead. The lead-containing powder preferably contains lead monoxide, and may further contain metallic lead.

[0067] The organic shrink-proofing agent may be at least one of lignins and synthetic organic shrink-proofing agents. Examples of lignins include lignin derivatives such as lignin, lignin sulfonic acid or its salt (such as alkali metal salt such as sodium salt). The synthetic organic shrink-proofing agent is an organic polymer containing a sulfur element. Examples of the synthetic organic shrink-proofing agent include, but are not limited to, a condensation product of a compound having a sulfur-containing group and an aromatic ring with an aldehyde compound (aldehyde or its condensation product).

[0068] (fully charged) In this specification, the fully charged state of a lead-acid battery refers to a state in which the battery is charged in a water tank at 25°C at a constant current (A) of 0.2 times the value given as the rated capacity (unit: Ah) until the battery reaches 2.8 V / cell, and then further charged at a constant current of 0.2 times the value given as the rated capacity for 2 hours.

[0069] A fully charged lead-acid battery refers to a lead-acid battery that has already been chemically prepared and is fully charged. A lead-acid battery may be fully charged immediately after chemical preparation, or after a certain amount of time has passed since chemical preparation (for example, a lead-acid battery that is in use (preferably in the early stages of use) after chemical preparation may be fully charged). An early stage battery refers to a battery that has not been in use for very long and has hardly deteriorated at all.

[0070] Examples of the carbonaceous material contained in the negative electrode material include carbon black, graphite, etc. Examples of the carbon black include acetylene black, furnace black, lamp black, etc. The graphite may be any carbon material containing a graphite-type crystal structure, and may be either artificial graphite or natural graphite.

[0071] The method for producing the negative electrode plate is not limited, and the negative electrode plate may be produced by the following method. First, a negative electrode paste is prepared by adding water and sulfuric acid to a powder containing lead and various additives and kneading them. Next, the negative electrode paste is applied or filled onto a negative electrode collector, and the obtained electrode plate is aged and dried to obtain an unformed negative electrode plate. After that, the unformed negative electrode plate is formed to obtain a negative electrode plate.

[0072] The formation of the unformed negative plates may be performed by charging the plate group including the unformed negative plates while the plate group is immersed in an electrolyte in a lead-acid battery container, or may be performed prior to assembly of the lead-acid battery or plate group.

[0073] (Separator) The separator disposed between the negative and positive electrode plates may be made of a nonwoven fabric or a microporous membrane. The thickness and number of separators to be disposed between the negative and positive electrode plates may be selected according to the distance between the electrodes. The fibers constituting the separator (e.g., nonwoven fabric) may be glass fiber, polymer fiber (polyolefin fiber, acrylic fiber, polyester fiber such as polyethylene terephthalate fiber, etc.), pulp fiber, etc. The nonwoven fabric may contain components other than fibers (inorganic powder, polymer as a binder, etc.).

[0074] The separator may be in a sheet shape or in another shape (for example, a bag shape), or may be a separator obtained by folding a sheet-shaped separator into an accordion shape.

[0075] (electrolyte) The electrolyte is an aqueous solution containing sulfuric acid. The specific gravity of the electrolyte in a fully charged lead-acid battery at 20°C is, for example, 1.20 or more, and may be 1.23 or more. The specific gravity of the electrolyte in a fully charged lead-acid battery at 20°C is, for example, 1.32 or less, and may be 1.30 or less. The specific gravity of the electrolyte in a fully charged lead-acid battery at 20°C may be 1.20 or more (or 1.23 or more) and 1.32 or less, or 1.20 or more (or 1.23 or more) and 1.30 or less.

[0076] An example of an embodiment of the present invention will be described below with reference to the drawings. The above-mentioned components can be applied to the components of the example described below. The example described below can be modified based on the above description. The matters described below may be applied to the above-mentioned embodiment. In the embodiment described below, components that are not essential for the positive electrode plate and lead-acid battery of the present invention may be omitted.

[0077] Fig. 1 is a top view showing a clad type positive electrode plate 30 according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view of the cross section taken along line II-II in Fig. 1 as viewed from the direction of the arrows. Fig. 3 is a schematic cross-sectional view of the cross section taken along line III-III in Fig. 2 as viewed from the direction of the arrows. Note that Fig. 3 omits the illustration of the upper link seat.

[0078] The clad type positive electrode plate 30 includes a number of porous tubes 31 (tubes (T)) arranged in a row, a positive electrode material 32, and a positive current collector 33. The positive current collector 33 includes a current collecting portion 34 and a number of core metals 35. The core metals 35 are also arranged in a row in the same direction as the tubes 31. Each tube 31 contains one core metal 35. The tube 31 is filled with a positive electrode material 32. The tubes 31 and core metals 35 not shown in FIGS. 2 and 3 also have the same structure as those shown in FIGS. 2 and 3.

[0079] 2 and 3, the metal core 35 is a portion of the positive electrode current collector 33 that is housed in the tube 31 and has a surface in contact with the positive electrode material 32. The metal core 35 has a first end 35a and a second end 35b. One end (first end 35a) of each of the multiple metal cores 35 is connected by the current collecting portion 34.

[0080] One end and the other end of the multiple tubes 31 arranged in a row are fixed by an upper linking seat 38 and a lower linking seat 39, respectively. The opening of the tube 31 on the current collecting section 34 side is sealed by the core metal 35 and the upper linking seat 38. The other opening of each tube 31 is sealed by the lower linking seat 39. An ear 34a for collecting current from the clad type positive electrode plate 30 is formed at one longitudinal end of the current collecting section 34. The ear 34a protrudes outward from the upper linking seat 38. The upper linking seat 38 and the lower linking seat 39 are formed of resin or the like.

[0081] The core metal 35 includes a tapered portion 351 on the current collecting portion 34 side and a rod-shaped portion 352 extending from the tapered portion 351. The core metal 35 has a bent portion 35c that is bent so that the second end portion 35b approaches the tube 31. The bent portion 35c is formed in the rod-shaped portion 352. The core metal 35 from the start point of the bent portion 35c (the start point on the first end portion 35a side of the two start points) to the second end portion 35b is the eccentric portion 35d. The end portion K is the end portion on the first end portion 35a side of the two ends of the eccentric portion 35d. Note that when the radius of curvature of the bent portion 35c is sufficiently small, the length of the bent portion 35c (the length along the direction DL) is negligibly short. Therefore, in FIG. 2 and FIG. 3, the position of the bent portion 35c is regarded as the end portion K, ignoring the length of the bent portion 35c. The diameter of the tapered portion 351 decreases from the current collecting portion 34 side toward the rod-shaped portion 352 side.

[0082] The length of the core 35 in the direction DL in which the tube 31 extends is designated as L0, and the length from the first end 35a to the bent portion 35c in the direction DL is designated as L1. The ratio L1 / L0 is within the above-mentioned range. With this configuration, the degree of formation of the positive electrode plate can be increased.

[0083] In the example shown in the figure, the second end 35b is in contact with the tube 31, and the rod-shaped portion 352 is not in contact with the tube 31 in the region from the first end 35a to the bent portion 35c. Furthermore, the core bar 35 is bent only at the bent portion 35c.

[0084] An enlarged cross-section of bent portion 35c is shown typically in Fig. 4. As shown in Fig. 4, core bar 35 is bent at angle α. Angle α is the angle (an angle of 90° or less) formed by central axes 35t of two adjacent portions (e.g., portions having a length of about 20 to 30 mm) of core bar 35 sandwiching bent portion 35c therebetween. As described above, in a preferred example, all core bar 35 is bent in the same direction at bent portion 35c.

[0085] FIG. 5 is a diagram showing a schematic arrangement of the core metal 35 shown in FIG. 2 and FIG. 3. FIG. 5 shows the arrangement of the core metal 35 (more specifically, the rod-shaped portion 352) from the second end portion 35b to the bent portion 35c. The distance between the central axis 35t of the core metal 35 at the bent portion 35c and the central axis 35t of the core metal 35 at the second end portion 35b in the cross-sectional direction DR (the direction perpendicular to the longitudinal direction DL of the tube 31, i.e., the direction parallel to the paper surface of FIG. 5) is defined as the distance E (mm). The inner diameter of the tube 31 is defined as the inner diameter Dt (mm). The diameter of the core metal 35 is defined as Dm (mm). Here, it is assumed that Dt and Dm are substantially constant. Furthermore, it is assumed that the position of the central axis 35t of the core metal 35 and the position of the central axis 31t of the tube (T) are the same at the bent portion 35c, and that the core metal 35 is in contact with the tube at the second end portion 35b. In that case, (E+0.5Dm) is approximately equal to 0.5Dt.

[0086] Fig. 6 is a perspective view showing an example of a lead-acid battery 1 according to one embodiment of the present invention with the cover removed. Fig. 7A is a front view of the lead-acid battery of Fig. 6, and Fig. 7B is a schematic cross-sectional view of the cross section taken along line VIIB-VIIB of Fig. 7A as viewed from the direction of the arrows.

[0087] The lead-acid battery 1 includes a battery case 10 that contains an electrode plate group 11 and an electrolyte 12. The electrode plate group 11 is formed by stacking a plurality of negative electrode plates 2 and a plurality of positive electrode plates 30 with a separator 4 interposed therebetween. The positive electrode plate 30 is the above-mentioned clad type positive electrode plate. In this embodiment, a state in which a sheet-like separator 4 is sandwiched between the negative electrode plate 2 and the clad type positive electrode plate 30 is shown, but the shape of the separator is not particularly limited.

[0088] The upper portion of each of the plurality of negative electrode plates 2 is provided with an upwardly protruding current collecting lug (not shown). The upper portion of each of the plurality of clad type positive electrode plates 30 is also provided with an upwardly protruding current collecting lug (not shown). The lugs of the negative electrode plates 2 are connected and integrated with each other by a negative electrode strap 5a. Similarly, the lugs of the clad type positive electrode plates 30 are connected and integrated with each other by a positive electrode strap 5b. The lower end of the negative electrode pole 6a is fixed to the upper portion of the negative electrode strap 5a. The lower end of the positive electrode pole 6b is fixed to the upper portion of the positive electrode strap 5b.

[0089] (Evaluation of chemical conversion degree) The degree of formation of the positive electrode material is evaluated by dismantling a lead-acid battery after formation and using the clad positive electrode plate taken out according to the following procedure.

[0090] First, the portion of the removed positive electrode plate where the core metal exists is divided into three equal parts, the upper, middle, and lower, from the current collector side along the direction DL in which the tube (T) extends. Then, the positive electrode material of each of the upper, middle, and lower parts is taken out separately. Below, the analysis of the upper positive electrode material is explained, but the positive electrode material of the middle and lower parts is also analyzed in the same way. Approximately 1.5 g is taken from the removed upper positive electrode material, and its mass W (g) is measured.

[0091] Next, about 1.5 g of the collected positive electrode material was placed in a beaker, and 50 cm of acetic acid solution (concentration: 5% by mass) was added. 3 Next, the acetic acid aqueous solution in the beaker is heated and boiled for 10 minutes. This process dissolves the lead monoxide in the positive electrode material. Next, the heated solution is cooled, and then filtered through filter paper (JIS3801-1995 type 6), and the residue on the filter paper is washed with distilled water. In this way, the dissolved material (including dissolved lead monoxide) is removed. Next, the above residue (including lead dioxide) is poured into another beaker with distilled water. Furthermore, the residue remaining on the filter paper is washed with 10 cm of 30% nitric acid solution. 3 and 1cm of hydrogen peroxide 3The lead dioxide is dissolved in a mixture of the above and distilled water and placed in a beaker. The liquid in the beaker is then heated to 80°C for 10 minutes and then cooled. The liquid in the beaker is then filtered and the filtrate (containing dissolved lead dioxide) is placed in a measuring flask. The filter paper is then washed with distilled water and the washings are placed in the measuring flask, and the liquid in the measuring flask is then poured over 250cm. 3 The filtrate is diluted to 50 cm 3 Add 1 g of tartaric acid and 20 cm of 28% ammonia water. 3 Add a few drops of BT indicator to the resulting liquid, then titrate with a 0.1 mol / L EDTA (ethylenediaminetetraacetic acid) aqueous solution. The end point of the titration is when the color of the solution changes from reddish purple to blue, and the amount of EDTA solution at that point is recorded. Calculate the lead dioxide content (mass%) using the following formula. FA is the titer of the 0.1 mol / L EDTA aqueous solution. PbO 2 Content (mass%) = 100 × (amount of EDTA solution dropped (cm 3 )) × 23.92 × 5 × FA / (mass of sample W(g))

[0092] PbO calculated by the above method 2 The content (mass%) of reflects the degree of conversion, and therefore the content (mass%) is used as the value of the conversion degree (%), which is a relative evaluation value of the conversion degree.

[0093] The clad type positive electrode plate and the lead-acid battery according to one aspect of the present invention will be described below.

[0094] (1) A clad type positive plate for a lead-acid battery, comprising: at least one porous tube; a positive electrode material filled in the tube; and a positive current collector, wherein the positive electrode current collector includes at least one core having first and second ends, and a current collecting portion connected to the first end, the core is disposed within the tube and is in contact with the positive electrode material, the core includes an eccentric portion including a bent portion where the second end is bent toward the tube, wherein the length of the core in the extension direction of the tube is L0 and the length from the first end to the eccentric portion in the extension direction is L1, and a ratio L1 / L0 is 0.80 or more.

[0095] (2) In the clad type positive electrode plate for a lead-acid battery described above in (1), the radius of curvature of the central axis of the core metal at the bent portion may be 2700 mm or less.

[0096] (3) In the clad positive electrode plate for a lead-acid battery of (1) or (2) above, when a direction perpendicular to the direction in which the tube extends is defined as a cross-sectional direction DR and an end of the eccentric portion on the side of the first end is defined as an end K, a distance E (mm) in the cross-sectional direction DR between a central axis of the core at the end K and a central axis of the core at the second end, an inner diameter Dt (mm) of the tube, and a diameter Dm (mm) of the core may satisfy -2.0≦(E+0.5Dm-0.5Dt)≦2.0.

[0097] (4) In the clad type positive electrode plate for a lead-acid battery according to any one of the above (1) to (3), the second end may be in contact with the tube.

[0098] (5) In the clad type positive electrode plate for a lead-acid battery according to any one of (1) to (4) above, the core metal may include a rod-shaped portion continuing from the first end to the eccentric portion, and the rod-shaped portion may not be in contact with the tube.

[0099] (6) The clad type positive electrode plate for a lead-acid battery according to any one of (1) to (5) above may include a plurality of the tubes arranged in a row, and the positive electrode current collector may include a plurality of the core metals, each of which has the first end connected by the current collecting portion.

[0100] (7) In the clad type positive electrode plate for a lead acid battery according to (6) above, the plurality of core metals may be eccentric in the same direction at the eccentric portions.

[0101] (8) A lead-acid battery including the clad type positive electrode plate for a lead-acid battery according to any one of (1) to (7) above.

[0102] [Example] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. Note that all lead-acid batteries in the following examples are single-cell batteries with a rated voltage of 2V.

[0103] Example 1 In Example 1, lead-acid batteries A1 to A4 and CA1 to CA4 are produced and evaluated.

[0104] 《Lead acid batteries A1~A4, CA1~CA4》 (1) Fabrication of clad positive electrode plate A clad type positive electrode plate having a core metal as shown in Figures 2 and 3 is fabricated by the following procedure. The fabricated positive electrode plate has a configuration generally similar to that shown in Figure 1, except for the number of tubes and core metals.

[0105] First, a positive electrode current collector is manufactured by casting. At this time, a plurality of positive electrode current collectors are manufactured by changing the above-mentioned ratio L1 / L0 as shown in Table 1. For the core of the positive electrode current collector, a core having a bent portion at a position where the length from the first end is L1 is used. No bend is formed in the core except for the bent portion. Assuming that the position of the central axis of the core and the position of the central axis of the tube (T) are the same at the bent portion, the angle of the bent portion of the core is changed so that the core contacts the tube at the second end. In other words, the angle of the bent portion of the core is changed so that the above-mentioned (E+0.5Dm-0.5Dt) becomes 0 mm. The diameter of the rod-shaped portion of the core is 3.0 mm.

[0106] In addition, in the manufacture of the battery CA4, a positive electrode collector that does not form a bent portion is used. The number of core metals included in one positive electrode collector is 15. The 15 core metals of the manufactured positive electrode collector are housed in 15 tubes. Next, the collector part and one end of the tube are covered with resin to form a resin upper link. The material of the positive electrode collector is a Pb-Sb alloy. The length L0 of each core metal is 295 mm. A porous tube made of glass fiber is used for the tube. The length of the tube is 310 mm, the outer diameter is 9.5 mm, and the inner diameter is 9.0 mm.

[0107] Next, the positive electrode slurry is filled from the opening of the tube (the opening on the opposite side to the current collector). At this time, the integrated positive electrode current collector and the tube are tilted, and the positive electrode slurry is filled in a state where the second end of the core metal is in contact with the tube. The positive electrode slurry is prepared by kneading lead powder (containing 80 mass % lead oxide and 20 mass % metallic lead), red lead, water, and dilute sulfuric acid. The mass ratio of the lead powder to red lead is 9:1. Next, the opening of the tube is sealed with a lower connecting member. In this way, an unformed clad type positive electrode plate is produced. The amount of positive electrode slurry filled is determined by the amount of the positive electrode active material after formation is converted into PbO 2 This is adjusted to contain 841±8g per sheet.

[0108] (2) Preparation of the negative electrode A negative electrode paste is prepared by mixing lead powder (containing 80% by mass of lead oxide and 20% by mass of metallic lead), 0.15% by mass of an organic shrinkage preventer (sodium lignin sulfonate), and 1.2% by mass of barium sulfate with water and dilute sulfuric acid. The negative electrode paste is filled into a cast grid made of an Sb-based alloy as a negative electrode current collector, and the resulting mixture is dried to prepare an unformed negative electrode plate. At this time, a 2.7 mm thick negative plate (negative plate A) is produced using a 2.6 mm thick grid collector, and a 4.5 mm thick negative plate (negative plate B) is produced using a 4.4 mm thick grid collector. The same number of negative plates A and B are produced. The amount of negative paste filled is adjusted so that the amount of negative active material contained in one negative plate A is 420±6 g, converted into Pb, and the amount of negative active material contained in one negative plate B is 750±6 g, converted into Pb. The length of the negative plate is the same as the length of the positive plate tube, and the width of the negative plate is the same as the width of the positive plate.

[0109] (3) Preparation of lead-acid battery Four unformed negative plates and three unformed clad-type positive plates are stacked alternately with a separator (a microporous polypropylene film) between them to form an electrode assembly as shown in Figure 7B. Negative plate A is used as the two outer negative plates of the electrode assembly, and negative plate B is used as the two inner negative plates.

[0110] Next, the electrode plate group is placed in a polypropylene battery case, and a lid is attached to the opening of the battery case. Next, dilute sulfuric acid (concentration: 14% by mass) is poured into the battery case. Next, formation is performed while the battery case is held in a water tank at 30°C. The formation is performed by high-speed formation. The high-speed formation is performed by passing a constant formation current of 31.5 A for a formation time of 40 hours. In this manner, lead-acid batteries A1 to A4 and CA1 to CA4 are obtained.

[0111] (4) Evaluation of chemical conversion degree The degree of formation of the positive electrode material of the above-mentioned lead-acid battery is evaluated by the procedure described below.

[0112] The ratio L1 / L0 and the degree of formation of the positive electrode material in the above batteries are shown in Table 1. Table 1 shows the degree of formation of each part of the positive electrode material and the degree of formation of the entire positive electrode material. The degree of formation of the entire positive electrode material is the average value of the degrees of formation of the positive electrode material in each part. The degree of formation shown in Table 1 is the average value of the evaluation results of three batteries produced for each battery.

[0113] [Table 1]

[0114] The metal core of the positive electrode current collector of battery CA4 is a conventional metal core that does not have a bent portion, and is curved with its tip in contact with the tube as shown in Fig. 9. For example, the metal core of the positive electrode current collector of battery CA4 is in contact with the tube at a distance from the first end in the range of 0.60L0 to L0. The metal core of battery CA4 does not include a portion with a radius of curvature of 2700 mm or less.

[0115] FIG. 8 shows the relationship between the ratio L1 / L0 and the degree of formation of the entire positive electrode material for batteries A1 to A4 and CA1 to CA3 shown in Table 1. As shown in Table 1 and FIG. 8, by setting the ratio L1 / L0 to 0.80 or more, the degree of formation of the entire positive electrode material can be made higher than that of batteries CA1 to CA3 (comparative examples) and battery CA4 (conventional example). In batteries CA1 to CA3 and battery CA4, the degree of formation is high in the lower part but low in the upper part, and there is a large bias in the degree of formation. As a result, the overall degree of formation is low. On the other hand, in batteries A1 to A4, the bias in the degree of formation is small and the overall degree of formation is high.

[0116] (Cycle life evaluation) The cycle life of the above-mentioned batteries A1, A4, CA1, CA2, and CA4 is evaluated. Specifically, first, a cycle test is performed on each battery by the following method. The cycle test is performed by repeating a charge / discharge process in which a discharge process and a charge process constitute one cycle. The discharge process is performed by discharging at a constant current (50A) for 3 hours so that 75% (150Ah) of the nominal capacity (200Ah) of each battery is discharged in 3 hours. The charge process is performed by charging at 45A for 3 hours, and then charging at 20A for 2 hours. In the first charge, charging is performed to 90% of the discharge amount (150Ah), and in the entire charging process, charging is performed to 117% of the discharge amount (150Ah). These conditions are close to the usage conditions of a battery for a forklift.

[0117] The discharge capacity of the battery is measured every 100 cycles of the cycle test. First, the battery is charged at 40A for 5 hours to thoroughly stir the electrolyte. Then, at the end of the charge, the specific gravity of the electrolyte is adjusted to 1.280 (20°C conversion). Next, the battery is stored in a water tank at 30°C for 12 hours, and the discharge capacity is measured in the water tank under the conditions of a discharge current of 40A and a final voltage of 1.70V.

[0118] The number of cycles when the measured discharge capacity falls below 135A is X2, and the discharge capacity at that time is C2. Furthermore, the discharge capacity at the time of the previous discharge capacity measurement is C1. The number of life cycles X is calculated by the following formula. X=X2-100+100×(C1-135) / (C1-C2) Table 2 shows the evaluation results of the battery ratio L1 / L0 and the number of life cycles.

[0119] [Table 2]

[0120] As shown in Table 2, the number of life cycles of batteries A1 and A4, which have an L1 / L0 ratio of 0.80 or more, is significantly longer than the number of life cycles of other batteries. The reason for this is not clear at present, but one possible reason is that the deterioration of the positive electrode current collectors of batteries A1 and A4 is small.

[0121] Example 2 In Example 2, a number of batteries (batteries B2 to B4, and batteries CB1 and CB2) were fabricated under the same conditions as those for battery A2 in Example 1, except that the angle of the bent portion was changed so that the value of (E+0.5Dm-0.5Dt) was the value shown in Table 2. The positive electrode material of the fabricated batteries was then evaluated in the same manner as in Example 1. The values ​​of (E+0.5Dm-0.5Dt) and the evaluation results are shown in Table 3. Since battery B1 is the same as battery A2, the results for battery B1 are shown in Table 3 for battery A2.

[0122] [Table 3]

[0123] As shown in Table 3, by setting the value of (E+0.5Dm-0.5Dt) to -2.0 mm or more, the bias in the degree of formation can be reduced and the degree of formation of the entire positive electrode material can be increased. When the value is in the range of -1.0 to 0 mm (for example, in the range of -0.5 to 0 mm), a particularly high effect can be obtained. In addition, considering the structure of the core metal, if the absolute value of (E+0.5Dm-0.5Dt) is in a predetermined range (for example, the same range of fluctuation from 0 mm), a certain degree of effect can be expected. [Industrial Applicability]

[0124] The present invention is used in a clad-type positive electrode plate and a lead-acid battery including the same. The use of the lead-acid battery is not limited, and it can be used for various purposes. The lead-acid battery of the present invention is preferably used as an industrial long-life storage battery and a storage battery for electric vehicles (forklifts, etc.). The lead-acid battery of the present invention may also be used as a storage battery for vehicles such as automobiles and motorcycles. [Explanation of symbols]

[0125] 1:Lead acid battery 30: Clad type positive electrode plate 31: Tube 32: Positive electrode material 33: Positive electrode current collector 34: Current collector 35: Core 35a: First end 35b: second end 35c: Bent section (curved section) 35d: Eccentric part 352: Rod-shaped part DL :Direction K: End α :Angle

Claims

1. at least one porous tube; A positive electrode material filled in the tube; A positive electrode current collector, the positive electrode current collector includes at least one core having first and second ends and a current collecting portion connected to the first end, the mandrel is disposed within the tube and in contact with the positive electrode material; the core bar includes an eccentric portion including a bent portion that bends so that the second end approaches the tube, A clad positive electrode plate for a lead-acid battery, wherein a ratio L1 / L0 is 0.80 or more, where L0 is the length of the core bar in the direction in which the tube extends, and L1 is the length from the first end to the eccentric portion in the same direction.

2. 2. The clad type positive electrode plate for a lead-acid battery according to claim 1, wherein a radius of curvature of a central axis of said core metal at said bent portion is 2700 mm or less.

3. When a direction perpendicular to the direction in which the tube extends is defined as a cross-sectional direction DR, and an end portion of the eccentric portion on the side of the first end portion is defined as an end portion K, 3. The clad positive electrode plate for a lead-acid battery according to claim 1, wherein a distance E (mm) between the central axis of the core metal at the end K and the central axis of the core metal at the second end in the cross-sectional direction DR, an inner diameter Dt (mm) of the tube, and a diameter Dm (mm) of the core metal satisfy -2.0≦(E+0.5Dm-0.5Dt)≦2.

0.

4. The clad type positive electrode plate for a lead acid battery according to any one of claims 1 to 3, wherein the second end is in contact with the tube.

5. the core bar includes a rod-shaped portion extending from the first end to the eccentric portion, The clad type positive electrode plate for a lead acid battery according to any one of claims 1 to 4, wherein the rod-shaped portion is not in contact with the tube.

6. A plurality of the tubes arranged in a row, The positive electrode collector includes a plurality of the core metals, each of the first ends of which is connected by the current collecting portion. The clad type positive electrode plate for a lead-acid battery according to any one of claims 1 to 5.

7. 7. The clad type positive electrode plate for a lead-acid battery according to claim 6, wherein the plurality of core metals are eccentric in the same direction at the eccentric portion.

8. A lead-acid battery comprising the clad type positive electrode plate for lead-acid batteries according to any one of claims 1 to 7.

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