JP2011249223A - Positive electrode current collector for lead-acid storage battery and lead-acid storage battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive electrode current collector for a lead-acid storage battery in which contact resistance between the current collector and an active material is reduced and a life performance is improved.SOLUTION: A positive electrode current collector 11 for a lead-acid storage battery comprises a titanium or titanium-alloy current collector substrate 12 with which a tin-dioxide membrane 13 is formed on a surface. On a surface of the tin-dioxide membrane 13, a β-type lead-dioxide membrane 14 containing β-type lead dioxide is formed. A half-value width of a maximum strength peak among peaks of tin dioxide in an X-ray diffraction pattern of the tin-dioxide membrane 13 is 1° or less, and a sum of the half-value width A and a half-value width B of a maximum-strength peak among peaks of β-type lead-dioxide in the X-ray diffraction pattern of the β-type lead-dioxide membrane 14 is 1.2° or more. Otherwise, the half-value width is more than 1°, and the sum of the half-value width A and the half-value width B is 1.2° or more and 2.2° or less.

Description

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

  Lead-acid batteries have long been used as secondary batteries with excellent cost, safety, and reliability. However, in recent years, the performance has been significantly improved and the energy density compared to the popular nickel-metal hydride batteries and lithium-ion batteries. Has the disadvantage of being low.

  One of the causes of the low energy density of lead-acid batteries is that lead or lead alloys used as positive electrode current collectors gradually corrode and deteriorate over the period of use, so in order to ensure sufficient life performance, lead Therefore, the thickness of the electrode plate is increased and the mass is increased.

  To solve this problem, the weight is reduced by using a current collector made of titanium or titanium alloy having a specific gravity smaller than that of lead. A passive layer is formed on the surface, and the resistance increases in a short period of time. Therefore, a material in which a tin dioxide film, which is a conductive ceramic, is formed on the surface of a current collector base material made of titanium or a titanium alloy (also referred to as “made of titanium (alloy)” has been proposed.

By covering the surface of the current collector base material made of titanium (alloy) with a conductive ceramic protective film such as a tin dioxide film, titanium as a base material is prevented from being passivated, and the tin dioxide film The low conductivity of the base material is supplemented by titanium as a base material. However, a lead-acid battery using a positive electrode current collector made of titanium (alloy) covered with a tin dioxide film has a problem that its life performance is not sufficient.
As a solution to the above problem, Patent Document 1 proposes a positive electrode current collector in which a current collector base material made of titanium (alloy) is covered with a highly crystalline tin dioxide film.

International Publication No. 07/37382 Pamphlet

  However, since the positive electrode current collector described in Patent Document 1 is coated with highly crystalline tin dioxide, the adhesion with the active material is poor, and the contact resistance between the positive electrode current collector and the active material is large. .

  Therefore, in the lead storage battery using the positive electrode current collector described in Patent Document 1, the high repulsive force obtained when the positive electrode plate and the negative electrode plate with the separators interposed therebetween are highly compressed in the plate thickness direction is used. The positive electrode current collector and the positive electrode active material are physically pressed with a high pressing force (100 to 400 kPa) to ensure adhesion between them (see paragraph [0067] of Patent Document 1).

However, in the lead storage battery that needs to press the positive electrode current collector and the positive electrode active material with a high pressure force like the one described in Patent Document 1, an outer body for compression is necessary, and the mass is accordingly. It becomes heavier and more expensive.
The present invention has been completed based on the above circumstances, and it is possible to reduce the contact resistance between the current collector and the active material without applying high-pressure force, and to improve the life performance. An object of the present invention is to provide a positive electrode current collector for a lead storage battery.

  To solve the above problems, a positive electrode current collector in which a β-type lead dioxide film is formed on the surface of a current collector base material on which a highly crystalline tin dioxide film as described in Patent Document 1 is formed As a result, in the positive electrode current collector of this configuration, when the β-type lead dioxide film has high crystallinity, the contact resistance between the current collector and the active material cannot be reduced. On the other hand, the positive electrode current collector in which the β-type lead dioxide film having low crystallinity is formed on the current collector base material on which the tin dioxide film having low crystallinity is formed has a problem that the life performance is lowered.

Therefore, in the positive electrode current collector formed by sequentially laminating a tin dioxide film and a β-type lead dioxide film on the current collector substrate, the peak having the maximum intensity among the tin dioxide peaks in the X-ray diffraction pattern of the tin dioxide film. Half-value width A (referred to as half-value width A of tin dioxide film) and the half-value width B (β-type lead dioxide film having the maximum intensity among the β-type lead dioxide peaks in the X-ray diffraction pattern of the β-type lead dioxide film) The following findings were obtained.
When the half-value width A of the tin dioxide film is 1 ° or less, the sum of the half-value width A of the tin dioxide film and the half-value width B of the β-type lead dioxide film is 1.2 ° or more. When A is greater than 1 °, the current collector is controlled so that the sum of the half-value width A of the tin dioxide film and the half-value width B of the β-type lead dioxide film is 1.2 ° or more and 2.2 ° or less. As the adhesion between the body and the active material is improved, the contact resistance can be reduced without applying a high pressing force, and the life performance of the titanium (alloy) current collector is prevented from being passivated. Can be improved (for details, see Examples). The present invention is based on such novel findings.

  That is, the present invention is a positive electrode current collector for a lead storage battery comprising a current collector base material made of titanium or a titanium alloy on which a tin dioxide film containing tin dioxide is formed, and is formed on the surface of the tin dioxide film. Is formed with a β-type lead dioxide film containing β-type lead dioxide, and the half-value width A of the peak with the highest intensity among the tin dioxide peaks in the X-ray diffraction pattern of the tin dioxide film is 1 ° or less, and The sum of the full width at half maximum and the full width at half maximum B of the peak of β-type lead dioxide in the X-ray diffraction pattern of the β-type lead dioxide film is 1.2 ° or more, or the half-value width A positive current collector for a lead storage battery, wherein A is greater than 1 °, and the sum of the half-value width A and the half-value width B is 1.2 ° or more and 2.2 ° or less, and the lead It is a lead acid battery provided with the positive electrode electrical power collector for storage batteries.

  According to the present invention, since the adhesion between the positive electrode current collector and the positive electrode active material is improved, the contact resistance between the positive electrode current collector and the positive electrode active material can be reduced without applying a high pressing force, and Further, it is possible to improve the life performance by preventing passivation of the positive electrode current collector.

  In the present invention, when the half-value width A of the tin dioxide film is 1 ° or less and the sum of the half-value width A of the tin dioxide film and the half-value width B of the β-type lead dioxide film is 1.2 ° or more, It is preferable because the life performance can be improved.

  The X-ray diffraction pattern in the present invention is an X-ray diffraction measurement in which an X-ray (CuKα ray) is irradiated on a sample while scanning an incident angle θ within a predetermined angle range, and the intensity of X-ray diffracted during this time This is obtained by counting and plotting the diffraction angle 2θ on the horizontal axis and the diffraction intensity on the vertical axis. Identifying the type of crystal plane corresponding to the diffraction angle 2θ at which the peak of the X-ray diffraction intensity appeared based on the crystal structure of the tin dioxide film and the lead dioxide film and the wavelength of the irradiated X-ray by the X-ray diffraction pattern Can do.

  The peak refers to a mountain-shaped portion in the X-ray diffraction pattern. Each peak corresponds to a crystal plane. The full width at half maximum represents the diffraction angle width of the peak curve at an X-ray diffraction intensity that is ½ of the peak intensity (X-ray diffraction intensity at the peak curve peak). A peak having a small half width has a steep mountain shape, and it can be said that the crystallinity of the crystal plane is high. On the other hand, a peak with a large half-value width has a gentle mountain shape with a wide skirt, and it can be said that the crystallinity of the crystal plane is low.

  According to the present invention, it is possible to provide a positive electrode current collector for a lead-acid battery capable of reducing the contact resistance between the current collector and the active material and improving the life performance without applying a high pressure force. it can.

Sectional drawing of the lead storage battery (unit cell) of Embodiment 1. The figure which shows the X-ray-diffraction pattern of the positive electrode electrical power collector base material which formed the tin dioxide film The figure which shows the X-ray-diffraction pattern of the positive electrode collector of an Example, and the positive electrode collector of a comparative example Sectional drawing of the lead acid battery (assembled battery) using the single battery of Embodiment 1. Sectional drawing of the lead acid battery of Conventional Example 1

<Embodiment 1>
The lead acid battery 1 of Embodiment 1 provided with the positive electrode current collector 11 of the present invention will be described with reference to FIG.
As shown in FIG. 1, the lead storage battery 1 of the present embodiment includes a battery case 2 that houses a positive electrode active material 15, a separator 3, and a negative electrode active material 25, and a positive electrode current collector 11 and a negative electrode that sandwich the battery case 2. Current collector 21. The positive electrode current collector 11 and the negative electrode current collector 21 are arranged so as to seal the upper and lower opening portions of the battery case 2.

  The battery case 2 is an insulating frame for hermetically housing the positive electrode active material 15, the separator 3, and the negative electrode active material 25, and includes an exhaust port 2a that communicates with the outside. A control valve 4 is attached to the opening of the exhaust port 2 a of the battery case 2. A valve retainer 5 is attached to the control valve 4 so as not to come off.

The positive electrode active material 15, the separator 3, and the negative electrode active material 25 housed in the battery case 2 are impregnated with an electrolytic solution (not shown) containing dilute sulfuric acid as a main component.
The positive electrode plate 10 of the lead storage battery 1 according to the present embodiment includes a tin dioxide film 13 containing tin dioxide and a β-type lead dioxide on one side 12A (the lower side in FIG. 1) of the positive electrode current collector base 12. A positive electrode current collector 11 formed by sequentially laminating a lead film 14 and a positive electrode active material 15 disposed in contact with the lower side of the positive electrode current collector 11 are provided.

  The positive electrode active material 15 is a plate-shaped material mainly composed of lead dioxide obtained by chemical conversion and charging of a positive electrode active material paste obtained by a normal method for producing a lead-acid battery. As a material for the positive electrode active material paste, lead powder, water, dilute sulfuric acid, or the like can be used.

The positive electrode current collector substrate 12 is made of titanium or a titanium alloy having a thickness of 0.1 mm. Of the surface of the positive electrode current collector substrate 12, the lower side surface 12A (positive electrode active material 15 is disposed in FIG. As described above, the tin dioxide film 13 containing tin dioxide (SnO ₂ ) and the β-type lead dioxide film 14 containing β-type lead dioxide (PbO ₂ ) are laminated on this side in this order.

In the present embodiment, the half-value width A (the half-value width A of the tin dioxide film 13) having the maximum intensity among the tin dioxide peaks in the X-ray diffraction pattern of the tin dioxide film 13 and the β-type lead dioxide film 14. Of the peaks of β-type lead dioxide in the X-ray diffraction pattern, the half-value width B (the half-value width B of the β-type lead dioxide film 14) of the peak having the maximum intensity is controlled as follows.
When the half width A of the tin dioxide film 13 is 1 ° or less, the sum of the half width A of the tin dioxide film 13 and the half width B of the β-type lead dioxide film 14 is 1.2 ° or more. When the half-value width A is larger than 1 °, the sum of the half-value width A of the tin dioxide film 13 and the half-value width B of the β-type lead dioxide film 14 is controlled to 1.2 ° or more and 2.2 ° or less. Since the adhesion between the positive electrode current collector 11 and the positive electrode active material 15 is improved by controlling the half-value width A and the half-value width B as described above, a high compression force as in the lead-acid battery described in Patent Document 1. Even if it does not apply, the contact resistance of the positive electrode collector 11 and the positive electrode active material 15 can be made small, and the lifetime performance of a positive electrode collector can be improved.

The reason why the above-described effects can be obtained by controlling the half-value width A of the tin dioxide film 13 and the half-value width B of the lead dioxide film 14 as described above is considered as follows.
When the half width B of the β-type lead dioxide film 14 is small (high crystallinity), the durability is good, but oxygen lattice defects that cause holes necessary for electronic conduction are reduced, and the carrier density is lowered. Resistance increases. Similarly to the β-type lead dioxide film 14, the tin dioxide film 13 also has a maximum half-value width A (half-value width A of the tin dioxide film 13) among the tin dioxide peaks in the X-ray diffraction pattern of the tin dioxide film 13. ) Is small (high crystallinity), the durability is good, but the carrier density decreases and the resistance increases.

Therefore, when the half-value width A of the tin dioxide film 13 is 1 ° or less, the half-value width A of the tin dioxide film 13 and the half-value width B of the β-type lead dioxide film 14 are both reduced (half-value width A and half-value width B). And the durability of the entire film composed of the tin dioxide film 13 and the β-type lead dioxide film 14 is good, but the carrier density is lowered and the electrical conductivity is deteriorated.
Therefore, when the half-value width A of the tin dioxide film 13 is 1 ° or less, if the half-value width B is set large, it is possible to prevent the carrier density of the lead dioxide film 14 from being lowered and the electrical conductivity from being deteriorated. The electrical conductivity of the entire film (the tin dioxide film 13 and the β-type lead dioxide film 14) becomes a level that can be used as the positive electrode current collector 11, and the contact resistance with the positive electrode active material 15 is also reduced. Specifically, when the half width A of the tin dioxide film 13 is 1 ° or less, the sum of the half width A of the tin dioxide film 13 and the half width B of the β-type lead dioxide film 14 is 1.2 ° or more. When controlled, the contact resistance between the positive electrode current collector 11 and the positive electrode active material 15 can be reduced, and passivation of the positive electrode current collector 11 can be prevented to improve the life performance.

  On the other hand, when the half width A of the tin dioxide film 13 is larger than 1 °, the durability of the tin dioxide film 13 is lower than when the half width A is 1 ° or less. Therefore, when the tin dioxide film 13 having a lower half-value width A than 1 ° is formed, the tin dioxide film 13 is covered by increasing the crystallinity of the β-type lead dioxide film 14 to some extent. Although the conductivity of the β-type lead dioxide film 14 is lowered, the durability is increased, and the deterioration of the life performance can be suppressed. Further, in the positive electrode current collector 11 having this configuration, the conductivity of the tin dioxide film 13 is higher than that in the case where the half-value width A is 1 ° or less. The resistance can be set to a level that can be used as the current collector 11. Specifically, when the half width A of the tin dioxide film 13 is larger than 1 °, the sum of the half width A of the tin dioxide film 13 and the half width B of the β-type lead dioxide film 14 is 1.2 ° or more 2 When controlled to 2 ° or less, the entire film (the tin dioxide film 13 and the β-type lead dioxide film 14) is excellent in durability, so that the passivation of the positive electrode current collector 11 can be prevented and the positive electrode current collector can be prevented. The contact resistance between the electric body 11 and the positive electrode active material 15 can be reduced.

  The half-value width A of the tin dioxide film 13 and the half-value width B of the β-type lead dioxide film 14 are equal to or less than 1 ° and the sum of the half-value width A and the half-value width B is 1.2 °. It is preferable to control as described above. This is because the lifetime performance can be remarkably improved by forming such a tin dioxide film 13 having a small half width (high crystallinity).

The thickness of the tin dioxide film 13 is preferably 20 nm to 500 nm or less. If the thickness is less than 20 nm, pinholes formed in the film increase and portions where the substrate is not covered are likely to occur. If the thickness exceeds 500 nm, the tin dioxide film referred to as a mud crack and the substrate This is because cracks that occur during cooling after film formation due to the difference in linear expansion coefficient are likely to occur.
Moreover, it is preferable that the tin dioxide film 13 includes antimony. By including antimony in the tin dioxide film 13, the conductivity is improved. As described above, when the conductivity of the tin dioxide film 13 is high, the internal resistance of the lead storage battery 1 is lowered, so that the life performance of the lead storage battery 1 is further improved. Of those containing antimony, those containing fluorine in addition to antimony are particularly preferred because of their high conductivity.

The thickness of the β-type lead dioxide film 14 (PbO ₂ film 14) is preferably 100 μm or less because it is difficult to peel off from the surface 13A of the tin dioxide film 13. When the thickness of the β-type lead dioxide film 14 exceeds 100 μm, carbon dioxide is accumulated due to misfit caused by the difference in lattice constant between PbO ₂ contained in the β-type lead dioxide film 14 and SnO ₂ contained in the tin dioxide film 13. This is because the β-type lead dioxide film 14 is easily peeled off from the surface of the tin film 13.

  The negative electrode plate 20 of the lead storage battery 1 according to the present embodiment is obtained by applying a lead plating with a thickness of 20 to 30 μm to the surface 22A (the upper surface in FIG. 1) of a copper negative electrode current collector base material 22 with a thickness of 0.1 mm. And a negative electrode active material 25 disposed in contact with the upper side of the negative electrode current collector 21.

  The negative electrode active material 25 is a plate-like active material 25 mainly composed of spongy metallic lead obtained by forming and charging a negative electrode active material paste obtained by a normal method for producing a lead-acid battery. As a material for the negative electrode active material paste, lead powder, water, dilute sulfuric acid, carbon, barium sulfate, lignin and the like can be used.

Next, an example of the manufacturing method of the lead storage battery 1 of this embodiment is demonstrated.
First, the positive electrode current collector 11 is produced by the following method. A tin dioxide film 13 is formed on the surface 12A of the positive electrode current collector base 12. As titanium used as the material of the positive electrode current collector base material 12, titanium (JIS type 1) or titanium (JIS type 2) is used. Ti-5Al-2.5V, Ti-3Al-2.5V, Ti-6Al-4V, etc. are used as a titanium alloy.

As a method of forming the tin dioxide film 13 on the surface 12A of the positive electrode current collector base material 12, the surface of the positive electrode current collector base material 12 made of titanium or a titanium alloy obtained by heating a raw material solution in which a tin compound is dissolved in a solvent. The method of spraying intermittently on 12A etc. is mention | raise | lifted. According to this method, the highly crystalline tin dioxide film 13 can be formed on the surface 12A of the positive electrode current collector substrate 12.
Examples of tin compounds used in this method include organic tin compounds such as dibutyltin diacetate and tributoxytin, which are organic tin compounds, and inorganic tin compounds such as tin tetrachloride. As the solvent, an organic solvent such as ethanol or butanol is used.

  In the case of forming the tin dioxide film 13 containing antimony, a raw material solution in which a tin compound containing antimony is dissolved in a solvent is used by a method of mixing a compound containing antimony atoms such as an antimony chloride. . When the tin dioxide film 13 containing fluorine is formed, a raw material solution in which a tin compound containing fluorine is dissolved in a solvent is used by a method of mixing a compound containing fluorine atoms.

  When forming the tin dioxide film 13 by the above method, the positive electrode current collector substrate 12 is heated so that the tin compound of the raw material liquid is thermally decomposed when sprayed on the positive electrode current collector substrate 12. There is a need to. The temperature suitable for heating depends on the type of tin compound. For example, when using a raw material liquid in which a dibutyltin diacetate solution (solvent: ethanol) is mixed with an antimony chloride solution (solvent: ethanol), the temperature is usually 400 ° C or higher, preferably 450 ° C or higher, Preferably it is 500 degreeC or more.

  In addition, the half value width A of the tin dioxide film 13 can be controlled by changing the heating temperature of the positive electrode current collector substrate 12. The lower the heating temperature of the positive electrode current collector substrate 12, the lower the crystallinity of tin dioxide (the half-value width A becomes larger), and the higher the heating temperature, the higher the crystallinity (the half-value width A becomes smaller).

  When spraying the raw material liquid onto the surface 12A of the positive electrode current collector base material 12, the spraying is repeated (intermittently) with a time interval so as not to lower the heating temperature. When forming the highly crystalline tin dioxide film 13, it is preferable that the thickness of the tin dioxide film 13 formed by one spray is 5 nm or less. This is because the tin dioxide film 13 having high crystallinity can be obtained by the method of laminating the tin dioxide film 13 having an extremely small film thickness. In order to form the tin dioxide film 13 having a very small thickness as described above, the spray amount per time is preferably 0.4 milliliter or less.

  The details of the reason why high crystallinity can be obtained by forming the tin dioxide film 13 having an extremely small film thickness as described above are not clear, but probably the surface 12A of the positive electrode current collector base material 12 It is considered that the titanium oxide present in the film and the oxide of titanium and tin formed in the initial stage of forming the tin dioxide film 13 serve as an underlayer, and tin dioxide constituting the tin dioxide film 13 is epitaxially grown.

  Next, a β-type lead dioxide film 14 is formed on the surface of the tin dioxide film 13 formed on the surface 12A of the positive electrode current collector substrate 12 by an electrolytic plating method. In the electrolytic plating method, in a state where the positive electrode current collector base material 12 on which the tin dioxide film 13 having a predetermined size is formed and a counterpart plate (for example, a carbon plate) having a predetermined size are separated by a predetermined distance, It is immersed in an aqueous 10-30% lead nitrate solution, and the solution is stirred with a stirrer and energized with the positive electrode current collector substrate 12 side as an anode. Electrodeposition is performed on the surface 13 A of the tin dioxide film 13 of the material 12. Thereby, the positive electrode current collector 11 of the present embodiment is obtained.

  The crystallinity of β-type lead dioxide contained in the β-type lead dioxide film 14 can be controlled by adjusting the concentration of the solution and the plating speed. If the plating speed is fast, many β-type lead dioxide crystal nuclei are deposited on the surface in a short period of time, so that each particle crystal becomes fine and crystallinity does not increase, but if the plating speed is slow, A crystal grows on the crystal nucleus formed first, and the lead dioxide film 14 having high crystallinity is formed.

The positive electrode plate 10 is obtained by arranging the positive electrode active material 15 mainly composed of lead dioxide on the surface of the positive electrode current collector 11 produced as described above on the β-type lead dioxide film 14 side.
The negative electrode plate 20 produces a negative electrode current collector 21 formed by performing lead plating with a thickness of 20 to 30 μm on the surface of a copper negative electrode current collector base material 22, and the lead-plated surface side of the negative electrode current collector 21 It is obtained by disposing the negative electrode active material 25 on the surface.

  The positive electrode plate 10 and the negative electrode plate 20 are accommodated in the battery case 2. At this time, between the positive electrode plate 10 and the negative electrode plate 20, the separator 3 which made the glass fiber the mat shape is arrange | positioned. When the positive electrode plate 10, the separator 3, and the negative electrode plate 20 are stored in the battery case 2, the opening of the battery case 2 is covered with the positive electrode current collector base material 12 and the negative electrode current collector base material 22. Next, when an electrolytic solution is injected from the exhaust port 2A of the battery case 2, the lead storage battery 1 (unit cell 1) of the first embodiment is obtained.

The unit cell 1 produced in this way can be used as an assembled battery 50 by stacking and connecting a plurality of unit cells in series. Specifically, as shown in FIG. 4, the negative electrode current collector 21 of the single cell 1 is placed on the positive electrode current collector 11 of another adjacent single cell 1 so that a plurality of ( Four unit cells 1 in FIG. 4 are stacked and connected in series. The unit cell group laminated in this manner is put in the auxiliary frame member 51, and a copper terminal plate 52 and an insulating plate 53 made of a lightweight insulating material are arranged on the upper and lower sides thereof, and the insulating plate 53 is screwed on the screw 54. As a result, the assembled battery 50 shown in FIG. 4 is obtained.
Since the unit cell 1 of the present embodiment includes the positive electrode current collector 11 having the above-described configuration, the adhesion between the positive electrode current collector 11 and the positive electrode active material 15 is improved. Therefore, when the assembled battery 50 is manufactured, it may be fixed by applying a pressure (20 to 40 kPa) of the same level as that of a normal lead storage battery. Therefore, as in the lead storage battery 100 shown in FIG. Fixing members such as 120, nuts 121 and bolts 122 are unnecessary, and the cost is low. Details of the lead-acid battery 100 of Conventional Example 1 in FIG. 5 will be described in the following examples.

<Example>
The following examples further illustrate the present invention.
1. Preparation of positive electrode current collector of Examples 1 to 4 and positive electrode current collector of Comparative Examples 1 to 3 (Preparation of positive electrode current collector of Example 1)
(1) Formation of tin dioxide film and X-ray diffraction measurement A dibutyltin diacetate solution (solvent: ethanol) and an antimony chloride solution (solvent: ethanol) were mixed to prepare a raw material solution. The amount of dibutyltin diacetate is adjusted so that the mass as tin dioxide is 2.5% with respect to the whole raw material liquid, and the amount of antimony chloride is the mass as antimony with respect to the tin dioxide. Was adjusted to 2.5%.

The raw material liquid was sprayed intermittently on the surface of the plate-shaped positive electrode current collector substrate heated to 320 ° C. During spraying, the spray interval was set so that the temperature of the positive electrode current collector substrate could be maintained at 320 ° C. By spraying the raw material liquid, thermal decomposition occurred on the surface of the current collector base material, and a current collector base material on which a tin dioxide film was formed was obtained. In addition, as a positive electrode electrical power collector base material, the square flat plate of a magnitude | size of 20 mm x 70 mm was used.
The positive electrode current collector base material on which the tin dioxide film was formed was subjected to X-ray diffraction measurement using an X-ray diffractometer (manufactured by Mac Science, MXP3), and the tin dioxide peak of the obtained X-ray diffraction pattern was measured. Among them, the half width of the peak with the maximum intensity (half width of tin dioxide film, described as “half width of SnO ₂ ” in Table 1) is shown in Table 1.

(2) Formation of β-type lead dioxide film and X-ray diffraction measurement State where cathode current collector base material on which tin dioxide film is formed and carbon plate (counter plate) having a size of 20 mm × 70 mm are separated by 50 mm Then, it was immersed in 30% strength lead nitrate aqueous solution, and the solution was stirred with a stirrer, and the positive electrode current collector substrate was energized as an anode, and the β-type lead dioxide film was electrodeposited on the surface of the tin dioxide film by anodic oxidation. Thus, the positive electrode current collector of Example 1 was obtained. The plating time for β-type lead dioxide was 20 minutes.
The β-type lead dioxide film-forming surface of the obtained positive electrode current collector was subjected to X-ray diffraction measurement using an X-ray diffractometer (manufactured by Rigaku, Ultimate IV), and the obtained X-ray diffraction pattern of the β-type lead dioxide Table 1 shows the half-width of the peak having the maximum intensity (half-width of the β-type lead dioxide film, described as “half-width of β-PbO ₂ ” in Table 1).
Table 1 also shows the sum of the half-value width of the tin dioxide film and the half-value width of the β-type lead dioxide film (described in Table 1 as “sum of the half-value widths of SnO ₂ and β-PbO ₂ ”). .

(Preparation of the positive electrode current collector of Example 2)
The positive electrode of Example 2 in the same manner as in Example 1, except that the heating temperature of the positive electrode current collector substrate was 410 ° C. and a tin dioxide film was formed, and the β-type lead dioxide plating time was 3 minutes. A current collector was obtained. In the same manner as in Example 1, X-ray diffraction measurement was performed on the positive electrode current collector base material on which the tin dioxide film was formed and the positive electrode current collector in Example 2, and the half width of the lead dioxide film and the β-type lead dioxide film Table 1 shows the sum of the half width, the half width of the lead dioxide film, and the half width of the β-type lead dioxide film.

(Preparation of the positive electrode current collector of Example 3)
The positive electrode of Example 3 in the same manner as in Example 1, except that the heating temperature of the positive electrode current collector base material was 440 ° C. and a tin dioxide film was formed and that the plating time of β-type lead dioxide was 2 minutes. A current collector was obtained. As in Example 1, X-ray diffraction measurement was performed on the positive electrode current collector base material on which the tin dioxide film was formed and the positive electrode current collector in Example 3, and the half width of the lead dioxide film and the β-type lead dioxide film Table 1 shows the sum of the half width, the half width of the lead dioxide film, and the half width of the β-type lead dioxide film.

(Preparation of the positive electrode current collector of Example 4)
The positive electrode of Example 4 in the same manner as in Example 1, except that the heating temperature of the positive electrode current collector base material was 430 ° C. and a tin dioxide film was formed, and the β-type lead dioxide plating time was 6 minutes. A current collector was obtained. In the same manner as in Example 1, X-ray diffraction measurement was performed on the positive electrode current collector substrate on which the tin dioxide film was formed and the positive electrode current collector in Example 4, and the half width of the lead dioxide film and the β-type lead dioxide film were measured. Table 1 shows the sum of the half width, the half width of the lead dioxide film, and the half width of the β-type lead dioxide film.

(Preparation of the positive electrode current collector of Comparative Example 1)
Comparative Example 1 positive electrode in the same manner as in Example 1 except that the heating temperature of the positive electrode current collector base material was 435 ° C. and a tin dioxide film was formed, and the β-type lead dioxide plating time was 6 minutes. A current collector was obtained. In the same manner as in Example 1, X-ray diffraction measurement was performed on the positive electrode current collector substrate on which the tin dioxide film was formed and the positive electrode current collector in Comparative Example 1, and the half width of the lead dioxide film and the β-type lead dioxide film were measured. Table 1 shows the sum of the half width, the half width of the lead dioxide film, and the half width of the β-type lead dioxide film.

(Preparation of the positive electrode current collector of Comparative Example 2)
The positive electrode of Comparative Example 2 in the same manner as in Example 1, except that the heating temperature of the positive electrode current collector base material was 440 ° C. and a tin dioxide film was formed and the β-type lead dioxide plating time was 9 minutes. A current collector was obtained. In the same manner as in Example 1, X-ray diffraction measurement was performed on the positive electrode current collector base material on which the tin dioxide film was formed and the positive electrode current collector in Comparative Example 2, and the half width of the lead dioxide film and the β-type lead dioxide film Table 1 shows the sum of the half width, the half width of the lead dioxide film, and the half width of the β-type lead dioxide film.

(Preparation of the positive electrode current collector of Comparative Example 3)
The positive electrode of Comparative Example 3 in the same manner as in Example 1 except that the heating temperature of the positive electrode current collector substrate was set to 320 ° C. and a tin dioxide film was formed and the β-type lead dioxide plating time was 2 minutes. A current collector was obtained. As in Example 1, X-ray diffraction measurement was performed on the positive electrode current collector substrate on which the tin dioxide film was formed and the positive electrode current collector in Comparative Example 3, and the half-value width of the lead dioxide film and the β-type lead dioxide film Table 1 shows the sum of the half width, the half width of the lead dioxide film, and the half width of the β-type lead dioxide film.

2. Results and Discussion of X-ray Diffraction Measurement (1) X-ray Diffraction Measurement of Positive Electrode Current Collector Base Material Formed with Tin Dioxide Film FIG. 2 shows each positive electrode current collector preparation of Comparative Example 2, Example 2, and Comparative Example 3. The X-ray diffraction pattern of the tin dioxide film obtained in the middle of the process was shown. The description “≈Example 3” in FIG. 2 indicates that the X-ray diffraction pattern of the tin dioxide film obtained in the positive electrode current collector preparation process of Example 3 is the same as that in the positive electrode current collector preparation process of Comparative Example 2. It means that the obtained tin dioxide film is approximate to the X-ray diffraction pattern, and the description “≈Example 1” indicates that the tin dioxide film obtained in the positive electrode current collector preparation step of Example 1 It means that the X-ray diffraction pattern approximates the X-ray diffraction pattern of the tin dioxide film obtained in the positive electrode current collector preparation step of Comparative Example 3. In FIG. 2, the peak with a black dot belongs to titanium.

In the X-ray diffraction pattern of the tin dioxide film obtained in the middle of the positive electrode current collector preparation process of Comparative Example 2, the peak curve of each crystal plane is steep, and the intensity is the maximum peak (200) plane. The full width at half maximum of the peak was 0.72 °, which was smaller than in Example 2 and Comparative Example 3. From this result, it is considered that the crystallinity is higher than that of Example 2 and Comparative Example 3.
In the X-ray diffraction pattern of the tin dioxide film obtained in the middle of the positive electrode current collector production process of Example 2, the peak curve of each crystal plane was obtained in the middle of the positive electrode current collector production process of Comparative Example 2. It was gentle compared to the tin dioxide film. In Example 2, the peak with the maximum intensity was the (200) plane peak, and its half-value width was 0.93 °.
In the X-ray diffraction pattern of the tin dioxide film obtained in the middle of the positive electrode current collector production process of Comparative Example 3, the peak curve of each crystal plane was obtained in the middle of the positive electrode current collector production process of Example 2. It was much gentler than the peak of the tin dioxide film. In Comparative Example 3, the peak with the maximum intensity was the (200) plane peak, and its half-value width was 1.88 °.

From these results, when the heating temperature of the positive electrode current collector base material when forming the tin dioxide film is increased, the peak curve becomes steeper and the half width of the tin dioxide film becomes smaller (the crystallinity becomes higher). I understood.
In Comparative Example 2 and Example 3, the heating temperature of the positive electrode current collector base material when forming the tin dioxide film was 440 ° C., and in Comparative Example 3 and Example 1, both of the tin dioxide films were formed. Since the heating temperature of the positive electrode current collector substrate at the time of formation is 320 ° C., it is considered that the X-ray diffraction pattern of the tin dioxide film was approximate.

(2) X-ray diffraction measurement of positive electrode current collector of Example and positive electrode current collector of Comparative Example FIG. 3 shows β-type lead dioxide films of the positive electrode current collectors of Example 3, Example 4, and Example 1. The X-ray diffraction pattern of was shown. The description “≈ Comparative Example 3” in FIG. 3 indicates that the X-ray diffraction pattern of the β-type lead dioxide film of the positive electrode current collector of Example 3 is the same as that of the positive electrode current collector of Comparative Example 3. It means that it approximates the X-ray diffraction pattern of the lead film. In FIG. 3, the peak with a black dot belongs to α-type lead dioxide.
In the order of Example 3, Example 4, and Example 1, the peak of each crystal plane of the β-type lead dioxide film was steep.

  In the X-ray diffraction pattern of the β-type lead dioxide film of the positive electrode current collector of Example 3, the peak intensity on the (301) plane was the maximum, and the half width was 0.70 °. In the X-ray diffraction pattern of the β-type lead dioxide film of the positive electrode current collector of Example 4, the peak intensity on the (200) plane was the maximum, and the half width was 0.40 °. In the X-ray diffraction pattern of the β-type lead dioxide film of the positive electrode current collector of Example 1, the peak intensity on the (110) plane was the maximum, and the half width was 0.21 °.

In addition, the plating time of the β-type lead dioxide film is 2 minutes in Example 3, 6 minutes in Example 4, and 20 minutes in Example 1. Therefore, when the plating time is set long, the half width of the lead dioxide film is small. It was found that the crystallinity becomes high.
Furthermore, in Example 3 and Comparative Example 3, since the plating time of the β-type lead dioxide film is 2 minutes, it is considered that the X-ray pattern of the β-type lead dioxide film was approximate.

3. Evaluation test 1 (contact resistance test, life test)
3-1. Contact Resistance The contact resistance between the positive electrode current collectors of Examples 1 to 4 and Comparative Examples 1 to 3 and the positive electrode active material was calculated and evaluated by the following method.
(1) Preparation of Sample (Positive Electrode Plate) A positive electrode active material paste was prepared by kneading lead powder, water, and sulfuric acid in accordance with an ordinary lead battery manufacturing method. By applying the positive electrode active material to a range of W20 × H20 mm on one side of the positive electrode current collectors of Examples 1 to 4 and Comparative Examples 1 to 3, and performing the aging and drying process in the same manner as the production method of a normal lead battery, An unchemically formed positive electrode plate was produced.
This unformed positive electrode plate was first charged in dilute sulfuric acid electrolyte using the negative electrode plate of a lead battery produced by a conventional method as the counter electrode, and then the positive electrode active material was formed. The specific gravity was adjusted to 1.270 (20 ° C.).

(2) Test method Using the positive electrode plate prepared in (1) and the negative electrode plate of a normal lead battery, a diluted sulfuric acid electrolyte with a specific gravity of 1.270 (20 ° C.) has a current density of 80 mA / g per positive electrode active material mass. Discharge was performed at a constant current. At this time, a reference electrode (Pb / PbSO ₄ ) was put in the electrolyte, and the potential drop of the positive electrode plate was measured.

(3) Calculation of contact resistance The positive electrode potential difference before discharge and 1 second after discharge was defined as the first second potential drop. Further, the discharge current value per unit area was calculated by dividing the absolute value of the discharged current by the area where the positive electrode active material was applied.
The contact resistance (Ωcm ² ) was calculated by dividing the first second potential drop by the discharge current value per unit area, and is shown in Table 1.
The contact resistance was determined according to the following criteria, and the determination results are shown in Table 1.
○: Less than ² Ωcm ² ×: 2 Ωcm ² or more

3-2. Life test A life test was conducted using the positive electrode current collectors of Examples 1 to 4 and the positive electrode current collectors of Comparative Examples 1 to 3. The method of the life test is as follows.
(1) Production of test cell A positive electrode active material paste was produced by kneading lead powder, water, and sulfuric acid in accordance with an ordinary method for producing a lead-acid battery. Thereafter, the positive electrode active material paste was filled in a frame having a diameter of 10 mm and a thickness of 8 mm and dried to obtain a positive electrode active material pellet. This was put in a dilute sulfuric acid solution having a concentration of 20% and energized at 50 mA to form and charge.

  The positive electrode active material pellets are flattened and brought into contact with the positive electrode current collectors of Examples 1 to 4 and the positive electrode current collectors of Comparative Examples 1 to 3, respectively. Was put in a dilute sulfuric acid solution with a concentration of 40% in a state of being pressure-contacted at a pressure of about 20 kPa, and this was used as a positive electrode plate. A lead plate was used as the negative electrode plate. A test cell was prepared using the positive electrode plate and the negative electrode plate thus prepared.

(2) Life test A constant voltage of 2.3 V was applied to the test cell, and a constant voltage overcharge test was conducted in a gas phase at 65 ° C.
The test cell was periodically removed from the test environment and left at room temperature for 24 hours. Then, the positive electrode capacity was measured by discharging at 150 mA. When the measured positive electrode capacity falls below 50% of the initial value, it is determined that the “life is exhausted” time, and the number of days until the end of the life is defined as “life performance (day)”. Table 1 shows the number of days up to the point when the time runs out.
The life performance was determined according to the following criteria, and the determination results are shown in Table 1.
A: 240 days or more (long-life product or more)
○: 100 days or more and less than 240 days (more than general lead storage battery)
×: Less than 100 days

3-3. Discussion As is apparent from the results shown in Table 1, the half width of the tin dioxide film is 1.0 ° or less, and the sum of the half width of the tin dioxide film and the half width of the β-type lead dioxide film is 1. In the positive electrode current collectors of Examples 2 to 4 controlled to 2 ° or more, the contact resistance was small and the life performance was excellent. In addition, the half width of the tin dioxide film was made larger than 1.0 °, and the sum of the half width of the tin dioxide film and the half width of the β-type lead dioxide film was 1.2 ° or more and 2.2 ° or less. The positive electrode current collector of Example 1 had low contact resistance and excellent life performance.

On the other hand, Comparative Examples 1 and 2 in which the half width of the tin dioxide film was 1.0 ° or less and the sum of the half width of the tin dioxide film and the half width of the β-type lead dioxide film was controlled to be less than 1.2 °. In the positive electrode current collector, the contact resistance was large and the life performance was poor.
Comparative example in which the half-value width of the tin dioxide film was made larger than 1.0 ° and the sum of the half-value width of the tin dioxide film and the half-value width of the β-type lead dioxide film was made larger than 2.2 ° In the positive electrode current collector of No. 3, the contact resistance was small, but the life performance was poor.

  From this result, in the positive electrode current collector formed by laminating a tin dioxide film and a β-type lead dioxide film on the surface of the positive electrode current collector base material, the half-value width of the tin dioxide film was 1.0 ° or less, and The sum of the half width of the tin film and the half width of the β-type lead dioxide film is 1.2 ° or more, or the half width of the tin dioxide film is made larger than 1.0 °, and It can be seen that if the sum of the half-value width and the half-value width of the β-type lead dioxide film is 1.2 ° or more and 2.2 ° or less, a lead-acid battery having low contact resistance and excellent life performance can be obtained. It was.

  In Examples 1 to 4, the half width of the tin dioxide film is 1.0 ° or less, and the sum of the half width of the tin dioxide film and the half width of the β-type lead dioxide film is 1.2 ° or more. The positive electrode current collectors of Examples 2 to 4 controlled to have particularly excellent life performance. From this result, in the present invention, the half width of the tin dioxide film is 1.0 ° or less, and the sum of the half width of the tin dioxide film and the half width of the β-type lead dioxide film is 1.2 ° or more. It was found that this is preferable.

4). Evaluation test 2 (energy density, cost)
The lead storage battery (lead storage battery 50 of Example 5) provided with the positive electrode current collector of the present invention and the lead storage battery 100 (lead storage battery 100 of conventional example 1) provided with the positive electrode current collector 111 of the conventional product were respectively produced. Density and cost were evaluated.
(1) Manufacture of single battery Using the positive electrode current collector 11 of Example 1 and the conventional positive electrode current collector 111, each of the single cell 1 of Embodiment 1 and the conventional single cell 110 is four. Produced.
As the positive electrode current collector 111 of the conventional product, one produced by the following method was used.
(1-1) Preparation of Conventional Positive Electrode Current Collector 111 A dibutyltin diacetate solution (solvent: ethanol) and an antimony chloride solution (solvent: ethanol) were mixed to prepare a raw material solution. The amount of dibutyltin diacetate is adjusted so that the mass as tin dioxide is 2.5% with respect to the whole raw material liquid, and the amount of antimony chloride is the mass as antimony with respect to the tin dioxide. Was adjusted to 2.5%.

The raw material liquid was sprayed intermittently on the surface of a flat plate current collector base material heated to 410 ° C. During spraying, the spray interval was set so that the temperature of the positive electrode current collector substrate could be maintained at 410 ° C. By spraying the raw material liquid, thermal decomposition occurred on the surface of the current collector base material, and a current collector base material on which a tin dioxide film was formed was obtained. This was used as a conventional positive electrode current collector 111. In addition, as a positive electrode electrical power collector base material, the square flat plate of a magnitude | size of 20 mm x 70 mm was used.
The X-ray diffraction measurement was performed on the conventional positive electrode current collector 111 by the X-ray diffractometer used in (1) of Example 1. Of the tin dioxide peaks in the obtained X-ray diffraction pattern, the half-width of the peak having the maximum intensity was 0.93 °.

(1-2) Manufacture of unit cell Four unit cells 1 having the structure shown in FIG. 1 were prepared using the positive electrode current collector 11 of Example 1, and the conventional positive electrode current collector 111 was used. Four unit cells 110 (conventional unit cells 110) shown in FIG.
The positive electrode current collector 111 of the cell 110 of the conventional example is different from the cell 1 of FIG. 1 in that it does not include a β-type lead dioxide layer, but the other configurations are generally the same as in FIG. Parts having the same configuration as the unit cell 1 are denoted by the same reference numerals.
In FIG. 5, 112 is a positive electrode active material, 113 is a positive electrode plate, 114 is a separator, 115 is a negative electrode active material, 116 is a negative electrode current collector, and 117 is a negative electrode plate.

The positive electrode plate 10 of the unit cell 1 and the positive electrode plate 113 of the unit cell 110 of the conventional example were produced by the following procedure. A positive electrode active material paste was prepared by kneading lead powder, water, and sulfuric acid, and a plate-like positive electrode active material mainly composed of PbO ₂ was prepared using this positive electrode active material paste according to a conventional method. A positive electrode plate was produced by arranging this positive electrode active material on each positive electrode current collector.
As the negative electrode current collector, a copper plate (thickness: 0.1 mm) plated with lead (thickness: 20 to 30 μm) was used. As the negative electrode active material, a negative electrode active material paste is prepared by kneading lead powder, water, dilute sulfuric acid, carbon, barium sulfate, lignin, etc., and using this negative electrode active material paste, spongy metallic lead A plate-like active material mainly composed of was used. This negative electrode active material was placed on a negative electrode current collector to produce a negative electrode plate.
As the separator, a glass fiber in a mat shape was used. The positive electrode plate and the negative electrode plate were laminated via a separator, housed in a battery case, and an electrolytic solution was injected to manufacture the unit cell 1 and the unit cell 100 of the conventional example.

(2) Production of lead acid battery (assembled battery) Next, the lead acid battery of Example 5 using four lead acid batteries 1 (unit cells 1) manufactured using the positive electrode current collector 11 of Example 1. 50 (assembled battery 50) was manufactured (see FIG. 4). Moreover, the lead storage battery 100 (assembled battery 100) of the prior art example 1 was manufactured using the four lead storage batteries 110 (unit cell 110) manufactured using the positive electrode collector 101 of the conventional product (FIG. 5). See).
First, four single cells were stacked in series so that the negative electrode current collector of each single cell was placed on the positive electrode current collector of another adjacent single cell.

  In the lead-acid battery 100 of Conventional Example 1, a copper terminal plate 118, an insulating plate 119 made of an insulating material, and a metal exterior body 120 are respectively disposed on and stacked on the upper and lower sides of the stacked unit cells 110, and the upper The bolts 122 were inserted through the nuts 121, and the nuts 121 were tightened below to fix the bolts. A pressure of about 100 to 400 kPa was applied as a gauge pressure to the lead storage battery 100 of Conventional Example 1 by tightening each nut 110 with a nut 121 sandwiched between metal outer bodies 120. In each unit cell 110 constituting the lead storage battery 100 of Conventional Example 1, the separator 114 is in a compressed state, and the positive electrode active material 112 is converted into a positive electrode current collector 111 at a gauge pressure of about 250 kPa by the repulsive force due to the compression. The negative electrode active material 115 is pressed against the negative electrode current collector 116.

  In the lead storage battery 50 of the fifth embodiment, the stacked unit cells 1 are placed in the auxiliary frame member 51, and the copper terminal plate 52 and the insulating plates 53 made of a lightweight insulating material are arranged on the upper and lower sides thereof to insulate. The plate 53 was fixed with screws 54. The pressure applied to the lead storage battery 50 was the same level as that of a normal lead storage battery (20 to 40 kPa).

(3) Energy density The mass energy density at the time of 0.5 A discharge was compared regarding the lead acid battery 50 of Example 5, and the lead acid battery 100 of the prior art example 1 (both nominal capacity is 2.3 Ah). Specifically, the ratio of the mass energy density at the time of 0.5 A discharge of the lead storage battery 50 of Example 5 when the mass energy density at the time of 0.5 A discharge of the lead storage battery 100 of Conventional Example 1 is set to 1. The results are shown in Table 2.

(4) Manufacturing Cost When the cost required for manufacturing the lead storage battery 50 of Example 5 and the cost required for manufacturing the lead storage battery 100 of Conventional Example 1 are estimated, the manufacturing cost of the lead storage battery 100 of Conventional Example 1 is set to 1. The cost ratio of the lead storage battery 50 of Example 5 was calculated and shown in Table 2.

(5) Discussion From the results shown in Table 2, the energy density of the lead storage battery 50 including the positive electrode current collector 10 of Example 1 is significantly higher than that of the lead storage battery 100 including the conventional positive electrode current collector 101. all right.
Moreover, in the lead storage battery 50 provided with the positive electrode collector 10 of Example 1, it turned out that cost can be remarkably made lower than the lead storage battery 100 of the prior art example 1. FIG. The reason is considered as follows.
In each single battery 110 constituting the lead storage battery 100 of Conventional Example 1, the separator 114 is in a compressed state. By this repulsive force, the positive electrode active material 112 is pressed against the positive electrode current collector 111 and the negative electrode active material 115 is pressed against the negative electrode current collector 116 at a gauge pressure of about 250 kPa. In this lead storage battery 100, in order to stabilize the charge / discharge performance, it is necessary to apply a pressure of about 100 to 400 kPa as a gauge pressure. In order to apply such a high pressing force, the metal exterior body 120 is Necessary.
On the other hand, in the lead acid battery provided with the positive electrode current collector of the present invention, the lead acid battery may be fixed by applying the same pressure (20 to 40 kPa) as that of a normal lead acid battery. Because there is no need to apply high pressure as in the case of, heavy metal exteriors, bolts, nuts, etc. necessary for high pressure are unnecessary, which can significantly reduce costs. It is thought.

1 ... Lead-acid battery (single cell)
DESCRIPTION OF SYMBOLS 10 ... Positive electrode plate 11 ... Positive electrode collector 12 ... Positive electrode collector base material 13 ... Tin dioxide film 14 ... β-type lead dioxide film 15 ... Positive electrode active material 20 ... Negative electrode plate 21 ... Negative electrode collector 22 ... Negative electrode collector Body base material 25 ... Negative electrode active material 50 ... Lead acid battery (assembled battery)

Claims (3)

A positive electrode current collector for a lead storage battery comprising a current collector base material made of titanium or a titanium alloy on which a tin dioxide film containing tin dioxide is formed,
A β-type lead dioxide film containing β-type lead dioxide is formed on the surface of the tin dioxide film,
Of the tin dioxide peaks in the X-ray diffraction pattern of the tin dioxide film, the half-value width A of the peak having the maximum intensity is 1 ° or less, and the half-value width A and the X-ray diffraction of the β-type lead dioxide film Of the β-type lead dioxide peaks in the pattern, the sum of the half-width B of the peak with the maximum intensity is 1.2 ° or more, or
The positive current collector for a lead storage battery, wherein the half-value width A is greater than 1 ° and the sum of the half-value width A and the half-value width B is 1.2 ° or more and 2.2 ° or less. 2. The positive electrode current collector for a lead storage battery according to claim 1, wherein the half-value width A is 1 ° or less, and the sum of the half-value width A and the half-value width B is 1.2 ° or more. body. A lead storage battery comprising the positive electrode current collector for a lead storage battery according to claim 1.

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