JPH0676815A - Anode plate for lead acid battery and manufacturing method thereof - Google Patents

Abstract

PURPOSE:To obtain a positive electrode plate for lead-acid battery, which has a high formation efficiency, a high capacity and a long lifetime. CONSTITUTION:A current collecting element is coated with the active material paste, which is obtained by kneading tribasic lead sulfate and red lead and water, or the active material paste, which is obtained by kneading red lead and water and sulfuric acid, to form the inside active material paste layer. Next, the active material paste, which is obtained by kneading red lead and water, is fitted on this inside active material paste layer to form the outside active material paste layer to manufacture a non-dried plate. This non-dried plate is dried, and thereafter, formation is performed to this plate to manufacture a plate for lead-acid battery.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anode plate for a lead storage battery and a method for manufacturing the same.

[0002]

2. Description of the Related Art A conventional lead-acid battery anode plate is manufactured as follows. First, a lead monoxide powder, diluted sulfuric acid, and water are mixed to prepare an active material paste, and the active material paste is filled in a lead or lead alloy current collector to prepare an undried electrode plate. next,
The undried electrode plate is aged and dried to form tribasic lead sulfate in the active material, and then is chemically converted to produce a lead acid battery anode plate. Thus, when only lead monoxide powder is used as the raw material of the active material paste, there is a problem that it takes at least 3 to 4 days to complete the electrode plate through aging, drying and chemical conversion. Therefore, a kneaded product obtained by kneading lead oxide containing lead (trilead tetraoxide) as a main component and water or a mixture obtained by kneading lead oxide and dilute sulfuric acid having a main component of red lead as an active material paste. It was proposed to use. Reedan reacts with sulfuric acid at the time of chemical conversion without lead aging (lead dioxide (P
In addition to producing bO ₂ ), the theoretical amount of electricity required for chemical conversion is about 65% lower than that of the electrode plate using the lead monoxide powder as the raw material of the active material paste. Therefore, when such a kneaded material is used as an active material paste, an anode plate for a lead storage battery having high chemical conversion efficiency can be manufactured in a short time.

[0003]

However, the undried electrode plate in which the active material paste prepared by kneading lead tin with water is filled in the current collector has a surface portion which is easily contacted with the electrolytic solution (dilute sulfuric acid) during formation. Although the conversion efficiency is high, the conversion efficiency inside the electrode plate is low because it takes time for sulfuric acid to penetrate into the electrode plate. Fig. 7 shows the electrodes examined by discharging at 1 CA for a plurality of 2V-2Ah batteries made using electrode plates with different thicknesses that were formed under the same conditions (formed in a low specific gravity sulfuric acid solution at a charge amount of 250%). It is a figure which shows the relationship between the thickness of a board and discharge time. As shown in FIG. 7, it can be seen that the thicker the electrode plate, the more difficult it is to form the inside, and the shorter the discharge time (the lower the initial capacity). In addition, since the active material paste obtained by kneading lead tin with water in this way has a low viscosity, water is easily released. Therefore, when the active material paste is filled or dried, the active material contracts to reduce the porosity, resulting in a problem that the capacity decreases.

When an active material paste prepared by kneading lead tin with dilute sulfuric acid is used instead of kneading with water, the binding force between lead dioxide and lead sulfate formed by the reaction of dilute sulfuric acid and lead tin. However, there is a problem in that the binding force between the active materials does not become sufficiently large and the life of the battery is shortened because of weakness.

An object of the present invention is to provide an anode plate for a lead storage battery having a high capacity and a long life, and a method for producing the anode plate for a lead storage battery in a short time by increasing the conversion efficiency.

[0006]

According to a first aspect of the present invention, a current collector is filled with an active material paste to prepare a undried electrode plate, and the undried electrode plate is dried and then subjected to chemical conversion for use in a lead acid battery. Targeting a method for manufacturing an anode plate, a current collector is filled with an active material paste obtained by kneading tribasic lead sulfate, red lead and water.
An undried electrode plate is prepared by forming an active material paste layer.

According to the invention of claim 2, in the manufacturing method of the invention of claim 1, the weight ratio of the tribasic lead sulfate to the red lead is 20 to 40%.

The invention of claim 3 specifies the crystal structure of the anode plate manufactured by the method of claim 1, and is intended for a lead-acid battery anode plate in which an active material is held by a current collector. , A crystal structure in which the active material is connected to a spherical or tabular lead dioxide (made from tribasic lead sulfate) in the form of prismatic lead dioxide (made from lead tin) in which the size of each part is 1 μm or less And an active material layer having

According to the invention of claim 4, in the invention of claim 3, the active material layer has a specific surface area of 10 m ² / g or more.

According to the invention of claim 5, a method for producing a lead-acid battery electrode plate by filling a current collector with an active material paste to prepare an undried electrode plate, drying the undried electrode plate and then performing chemical conversion. The step of forming an inner active material paste layer by filling the current collector with an active material paste prepared by kneading tribasic lead sulfate, red lead and water, and an active material obtained by kneading lead and water. The undried electrode plate is manufactured by filling the inner active material paste layer with the material paste to form the outer active material paste layer.

The invention of claim 6 specifies the crystal structure of the anode plate produced by the method of claim 5, and is intended for a lead-acid battery anode plate in which an active material is held by a current collector. A crystal in which the active material is bonded to prismatic lead dioxide (made from lead tin) having a size of 1 μm or less in each part and spherical or tabular lead dioxide (made from tribasic lead sulfate). Inner active material layer with structure and the dimension of each part is 1μm
The outer active material layer has the following prismatic crystal structure of lead dioxide.

[0012]

In the conventional method for producing a lead-acid battery electrode plate, tribasic lead sulfate was produced in the aging step. However, as in the invention of claim 1, tribasic lead sulfate, red lead and water are combined. When the current collector is filled with the kneaded active material paste to form the active material paste layer, the anode plate can be manufactured without performing the aging step which is conventionally performed. In addition, since tribasic lead sulfate easily becomes lead dioxide (PbO ₂ ) during the formation, even if the electrolyte solution (dilute sulfuric acid) has not yet sufficiently penetrated into the active material paste layer, lead dioxide (PbO ₂ ) can be obtained early. ₂ ) can be generated. Therefore, the chemical conversion efficiency of the anode plate can be increased as compared with the conventional case, and the manufacturing time of the anode plate can be significantly shortened.
Further, since such an active material paste has a relatively high viscosity, the porosity does not decrease due to release of water unlike the conventional active material paste obtained by kneading lead tin oxide with water. Further, according to the present invention, when the undried electrode plate is dried, tribasic lead sulfate causes a dissolution precipitation reaction with lead sulfate and lead oxide, or lead tin is contained in lead oxide in the active material paste. Lead oxide (Pb (O
H) ₂ ) is generated, and this lead hydroxide causes a dissolution and precipitation reaction, so that the bonds between the active materials are strengthened.

Pb ₃ O ₄ + Pb + 4H ₂ O → 4Pb (OH) _{2 In} addition, the solution precipitation reaction of tribasic lead sulfate and the current collector (Pb) or the red lead and current collector ( By the reaction with Pb), the binding force between the current collector and the active material can be increased.

Pb ₃ O ₄ + Pb → 4PbO Therefore, according to the present invention, the binding force between the active materials and the binding force between the current collector and the active material can be enhanced to improve the life characteristics of the battery. In the conventional manufacturing method using an active material paste prepared by kneading lead tin oxide with dilute sulfuric acid, lead tin reacts with dilute sulfuric acid to form lead dioxide, so that the active material strength cannot be increased as in the present invention. .

When the weight ratio of tribasic lead sulfate to red lead is 20 to 40% as in the second aspect of the invention, it is possible to obtain an anode plate used for a battery having a high capacity and a long life. If the weight ratio is less than 20%, the viscosity of the active material paste is reduced, the porosity of the active material is reduced, the capacity is reduced, and the binding force between the active materials is reduced, and the cycle life characteristics are reduced.
If the weight ratio exceeds 40%, the content of lead tin decreases, the chemical conversion efficiency decreases and the capacity decreases, and the lower oxide (PbO _x ) due to poor chemical conversion increases and the cycle life characteristics decrease.

According to the invention of claim 3, the size of each part is 1
If the active material is composed of an active material layer having a crystal structure in which spherical or tabular lead dioxide is bonded to prismatic lead dioxide of μm or less, the specific surface area of the active material layer is increased and the bonding strength of the active material layer is increased. Therefore, a battery having a high capacity and a long life can be obtained. When the prismatic lead dioxide exceeds 1 μm, the pores become large, but the contact area (bonding area) between the crystals becomes small and the bonding strength of the active material layer decreases.

When the specific surface area of the active material layer is 10 m ² / g or more as in the fourth aspect of the invention, the reaction area between the active material and the electrolytic solution increases and the battery has a high capacity.

When the anode plate is manufactured by the method of the invention of claim 1, the conversion efficiency can be increased as compared with the conventional manufacturing method, but when the thickness of the active material layer is increased to increase the capacity, Chemical conversion efficiency decreases. This is because the lead oxide in the active material located on the surface side of the electrode plate is converted into lead sulfate and volume expansion occurs, and the pores on the surface part of the electrode plate become smaller at the time of chemical formation, and the diffusion of the electrolyte solution inside the active material occurs. This is because the rate decreases. Therefore, in the method of the invention of claim 5, an active material paste layer made of an active material paste obtained by kneading tribasic lead sulfate, red lead and water is used as an inner active material paste layer, and red lead and water are placed outside thereof. An outer active material paste layer made of the active material paste obtained by kneading was prepared. Since the outer active material paste layer does not significantly suppress the diffusion of the electrolytic solution into the electrode plate, according to the present invention, the capacity can be increased and the chemical conversion efficiency can be improved. The active material paste prepared by kneading lead oxide with water has a problem that when the surface is filled with a smooth surface like a current collector, the active material shrinks and the porosity decreases. When it is filled in the uneven portion, the active material paste enters the uneven portion, so that the active material does not shrink and the porosity does not decrease.

According to the invention of claim 6, the size of each part is 1
An inner active material layer having a crystal structure in which spherical or tabular lead dioxide is bonded to prismatic lead dioxide of μm or less, and an outer active material layer having a prismatic lead dioxide crystal structure of 1 μm or less in each part size When the active material is composed of the above, the inner active material layer has a high bonding strength, and the outer active material layer has a high permeability of the electrolytic solution, so that a battery having a long life and a high capacity can be obtained.

[0020]

EXAMPLES Examples of the present invention will be described in detail below.

[Example 1] In this example, an anode plate for a lead storage battery was manufactured as follows. First, lead monoxide powder 0.
20 kg of sulfuric acid having a specific gravity of 1.26 was added to 8 kg and kneaded to prepare tribasic lead sulfate. Next, this tribasic lead sulfate 0.
An active material paste is prepared by kneading 9 g, 2.1 kg of red lead and 320 ml of water, and the active material paste is filled in a current collector made of a lead alloy lattice to form an active material paste layer having a thickness of 2.5 mm. Formed. In addition, the preferable weight range of tribasic lead sulfate with respect to red lead is 20 to 40%, and in this example, 3
It was 0% by weight. When the undried electrode plate is dried and then subjected to chemical conversion at an applied amount of 300%, the active material paste layer is formed into a prismatic lead dioxide (made of lead tin) having a size of 1 μm or less in each part, in a spherical or flat plate shape. Lead dioxide (made of tribasic lead sulfate) becomes an active material layer having a crystal structure.

Next, in order to investigate the characteristics of the anode plate for a lead storage battery manufactured by the method of this embodiment, four kinds of anode plates a1 to d are used.
I made 1 and tested it. The anode plate a1 is the anode plate of this embodiment. Anode plate b1 has 3 kg of lead monoxide powder and a specific gravity of 1.26.
It is a conventional anode plate manufactured by using an active material paste prepared by mixing 373 ml of dilute sulfuric acid and 300 ml of water. Anode plate c1
Is 3.5 kg of lead and 1.5 kg of powder of lead monoxide and 865.
It is a conventional anode plate manufactured by using an active material paste prepared by kneading with 8 ml. The anode plate d1 is a conventional anode plate manufactured by using an active material paste prepared by kneading 2.1 kg of red lead, 0.8 kg of lead monoxide powder, 203.6 ml of dilute sulfuric acid having a specific gravity of 1.26 and 320 ml of water. The weight of the active material of each of the anode plates a1 to d1 is the same. Then, 4Ah-6V type batteries A1 to D1 were made using the respective anode plates a1 to d1, and the initial capacity and cycle life characteristics of the respective batteries A1 to D1 were examined. The initial capacity of each battery is 25 ± 1 ° C ambient temperature,
The discharge time was measured by discharging at 0.25 CA (cutoff voltage 1.7 V). The cycle life of each battery is 0.25.
The number of cycles leading to the life of the battery was examined by repeating charging / discharging in which the battery was discharged at CA (cutoff voltage 1.75V) for 1 hour and then charged at 2.45V (limit current 0.3CA) for 6 hours. Table 1 shows a battery B using a conventional anode plate b1.
The ratio of the characteristics of each battery when the performance of 1 is 100% is shown. In addition, Table 1 also shows the ratio of the manufacturing time of each battery.

[0023]

[Table 1] From this table, it can be seen that in the battery C1 using the conventional anode plate c1, since the active material paste easily releases water, the porosity of the active material layer is decreased and the initial capacity of the battery is decreased. Further, it can be seen that in the battery D1 using the conventional anode plate d1, the cycle life characteristics are deteriorated because the binding force between the active materials is weak. In contrast to these batteries, the battery A1 using the anode plate a of this embodiment has an initial capacity of 19%, cycle life characteristics improved by 90%, and a manufacturing time of 40% compared to the battery B1 using the conventional anode plate b1. You can see that it is decreasing.

Next, FIG. 1 shows the relationship between the weight ratio of tribasic lead sulfate to red lead and the initial capacity ratio of the battery made using the active material paste having the weight ratio. This test was conducted using a battery manufactured by changing only the weight ratio of tribasic lead sulfate to red lead in the manufacturing method of this example. In this figure, the initial stage of battery B1 using conventional anode plate b1 is shown. 100% capacity
And From this figure, if the weight ratio of tribasic lead sulfate to red lead exceeds 40%, the conversion efficiency decreases and the initial capacity ratio decreases, and if the weight ratio falls below 20%, the viscosity of the active material paste decreases. It can be seen that the porosity of the active material decreases and the capacity decreases.

Next, the battery used in the measurement of FIG. 1 was repeatedly charged and discharged to examine the relationship between the weight ratio of tribasic lead sulfate to lead tin and the cycle life frequency ratio of the battery. FIG. 2 shows the measurement result. Also in this figure, the cycle life of the battery B1 using the conventional anode plate b1 is 100%.
From this figure, the weight ratio of tribasic lead sulfate to red lead can be 20-
It can be seen that when it is 40%, the cycle life characteristics are improved by about 90% as compared with the battery B1 using the conventional anode plate b1. If the weight ratio is less than 20%, the binding force between the active materials decreases, and the cycle life characteristics decrease. If the weight ratio exceeds 40%, lower oxide (PbO _x ) due to poor chemical conversion increases and cycle life characteristics deteriorate.

Next, prismatic PbO ₂ which forms the active material layer is formed.
3 shows the relationship between the average length and the initial capacity ratio of the battery having the active material layer. In this figure, the cycle life characteristics of a battery having an average length of PbO ₂ of 1 μm is 100%,
Anode plates with different average lengths of prismatic PbO ₂ were made by changing the size of red lead and the conditions of formation. From this figure, it can be seen that when the average length of PbO ₂ exceeds 1 μm, the contact area (bonding area) between the crystals becomes small, the bonding strength of the active material layer decreases, and the cycle life characteristics decrease.

Next, FIG. 4 shows the relationship between the specific surface area of the active material layer and the initial capacity ratio of the battery having the active material layer having the specific surface area. In this figure, the initial capacity of a battery having an active material layer having a specific surface area of 5 m ² / g was set to 100%, and anode plates having different active material layer specific surface areas were made by changing the formation conditions. From this figure, it can be seen that when the specific surface area of the active material layer is less than 10 m ² / g, the reaction area between the active material and the electrolytic solution is reduced and the capacity of the battery is reduced.

[Example 2] In this example, an anode plate for a lead storage battery was manufactured as follows. First, the weight ratio 10:10:
An active material paste is prepared by kneading the tribasic lead sulfate of No. 3, lead oxide and water into an active material paste, and the active material paste is filled in a current collector made of a lead alloy lattice to have an inner active material with a thickness of 1.5 mm. A paste layer was formed. The tribasic lead sulfate used was prepared in advance by mixing lead oxide and sulfuric acid having a specific gravity of 1.260 at a weight ratio of 3: 1. Next, an active material paste was prepared by kneading lead oxide and water in a weight ratio of 20: 3 and filling the inner active material paste layer with the outer active material paste layer having a thickness of 0.75 mm. Forming a thickness of 3 mm
Of the undried electrode plate was manufactured. The preferable weight range of lead trisulfate active material paste with respect to red lead is 20 to.
40%. After drying this undried electrode plate, the amount of electricity applied is 3
When the chemical conversion is performed at 00%, the inner active material paste layer is formed into a prismatic lead dioxide (made of lead tin) having a size of 1 μm or less in each part, and spherical or tabular lead dioxide (from tribasic lead sulfate). The outer active material paste layer has a prismatic lead dioxide (those made from lead tin) crystal structure in which the size of each part is 1 μm or less. It becomes the outer active material layer. When the electrode plate is manufactured by the method of the present embodiment, the manufacturing time can be reduced by about 60% as compared with the case where the electrode plate is manufactured using the active material paste in which the lead monoxide powder, dilute sulfuric acid and water are mixed. .

Next, in order to investigate the characteristics of the lead-acid battery anode plate manufactured by the method of this embodiment, three kinds of anode plates a2 to d are used.
2 was made and tested. The anode plate a2 is the anode plate of this embodiment. The anode plate b2 is an anode plate of another embodiment in which the active material layer is entirely made of an inner active material paste layer (active material paste obtained by kneading tribasic lead sulfate, red lead and water). The anode plate b2 has the same structure as the anode plate of Example 1 except for the thickness of the electrode plate. The anode plate c2 is a conventional anode plate manufactured by using an active material paste obtained by mixing lead monoxide powder, dilute sulfuric acid and water. The anode plate d2 is a conventional anode plate manufactured by using an active material paste prepared by kneading only red lead and water. Each of the anode plates a2 to d2 is a 3 mm thick electrode plate in which the same amount of the active material paste is filled in the current collector, and each of the anode plates a2 to d2 has the same structure except for the active material paste. There is. Using the anode plates a2 to d2 and the cathode plate having the same structure, batteries A2 to D2 of 2V-2Ah were prepared.
.About.D2 were formed in a low specific gravity sulfuric acid solution at a charge amount of 300% to form a battery case, and then discharged at 1 CA to measure the discharge time of each battery A2 to D2. The measurement result shows that the battery A2 using the anode plate a2 of this example has a discharge time of 45 minutes, while the battery B2 using the anode plate b2 of the other examples has a discharge time of 4 minutes.
3 minutes and battery C using conventional anode plates c2 and d2
2 and D2 each had a discharge time of 40 minutes. From this measurement result, it can be seen that by using the anode plate a2 of this embodiment, a battery having a higher formation efficiency and a higher initial capacity than the conventional anode plates c2 and d2 can be obtained.

Next, formation was performed by changing the amount of electricity applied to the batteries A2 to D2, and this was discharged, and the relationship between the amount of electricity applied to each of the batteries A2 to D2 and the discharge time was measured. FIG. 5 shows the measurement result. From this figure, it can be seen that the anode plate a2 of this embodiment has a higher chemical conversion efficiency (the discharge time becomes longer with the same amount of applied electricity) than the anode plate b2 of the other embodiments and the conventional anode plates c2 and d2.

Next, the batteries A2 to D2 were charged at 0.25 CA to a final voltage of 1.75 V, left for 1 hour, and then charged at 2.45 V for 4 hours at a limiting current of 0.9 CA. The cycle life characteristics of A2 to D2 were investigated. FIG. 6 shows the measurement result. From this figure, the battery A2 using the anode plate a2 of this embodiment has a longer life than the battery B2 using the anode plate b2 of the other embodiments and the batteries C2 and D2 using the conventional anode plates c2 and d2. I understand. In particular, when compared with the battery D2 using the anode plate d2 of the comparative example using only lead oxide as the active material, the battery A has a 200% longer life.

[0032]

According to the first aspect of the present invention, the active material paste obtained by kneading tribasic lead sulfate, red lead and water is filled in the current collector to form the active material paste layer. As compared with the manufacturing method, the conversion efficiency of the anode plate can be increased, and the manufacturing time of the anode plate can be significantly shortened. Further, since such an active material paste has a relatively high viscosity, the capacity of the battery can be increased. Further, when such an active material paste is used, tribasic lead sulfate causes a dissolution and precipitation reaction with lead sulfate and lead oxide when the undried electrode plate is dried, or red lead is contained in the active material paste. It reacts with a small amount of contained lead to produce lead hydroxide (Pb (OH) ₂ ), and this lead hydroxide causes a dissolution and precipitation reaction, so it looks like a paste prepared by mixing red lead and water. The bond between the active materials is not weakened. In addition, the binding force between the current collector and the active material can be increased by the dissolution and precipitation reaction of tribasic lead sulfate and the current collector (Pb) or the reaction of red lead and the current collector (Pb). Therefore, a battery with a long life can be obtained.

According to the invention of claim 2, since the weight ratio of tribasic lead sulfate to red lead is 20 to 40%, it is possible to obtain an anode plate used for a battery having a high capacity and a long life.

According to the invention of claim 3, the size of each part is 1
Since the active material is composed of an active material layer having a crystal structure in which spherical or tabular lead dioxide is bonded to prismatic lead dioxide having a size of μm or less, the specific surface area of the active material layer is increased and the bonding of the active material layer is also performed. Since the strength is increased, a battery having a high capacity and a long life can be obtained.

According to the invention of claim 4, since the specific surface area of the active material layer is 10 m ² / g or more, the reaction area between the active material and the electrolytic solution is increased, and the battery has a high capacity.

According to the invention of claim 5, an active material paste layer made of an active material paste obtained by kneading tribasic lead sulfate, red lead and water is used as an inner active material paste layer and sulfuric acid is not contained outside thereof. Since the outer active material paste layer is provided, when the thickness of the electrode plate is increased, diffusion of the electrolytic solution into the electrode plate is not significantly suppressed, and the formation efficiency of the battery can be improved.

According to the invention of claim 6, the size of each part is 1
An inner active material layer having a crystal structure in which spherical or tabular lead dioxide is bonded to prismatic lead dioxide of μm or less, and an outer active material layer having a prismatic lead dioxide crystal structure of 1 μm or less in each part size Since the active material is composed of the above, the inner active material layer has a high bonding strength, and the outer active material layer has a high permeability of the electrolytic solution, so that a battery having a long life and a high capacity can be obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between the weight ratio of tribasic lead sulfate to red lead and the initial capacity ratio of a battery.

FIG. 2 is a diagram showing the relationship between the weight ratio of tribasic lead sulfate to red lead and the cycle life frequency ratio of the battery.

FIG. 3 is a diagram showing the relationship between the average length of prismatic PbO ₂ and the initial capacity ratio of the battery.

FIG. 4 is a diagram showing the relationship between the specific surface area of the active material layer and the initial capacity ratio of the battery.

FIG. 5 is a diagram showing a relationship between a charge amount and a discharge time of a battery used in a test.

FIG. 6 is a diagram showing cycle life characteristics of a battery used in a test.

FIG. 7 is a diagram showing the relationship between the thickness of the electrode plate of the conventional lead storage battery anode plate and the discharge time.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ichiro Mukitani 2-1-1, Nishishinjuku, Shinjuku-ku, Tokyo Shin-Kindo Electric Co., Ltd.

Claims (6)

[Claims] 1. A method of manufacturing a positive electrode plate for a lead storage battery by filling a current collector with an active material paste to prepare a undried electrode plate, drying the undried electrode plate, and then performing conversion to form a positive electrode plate for a lead storage battery. A positive electrode plate for a lead storage battery, characterized in that the undried electrode plate is manufactured by filling a current collector with an active material paste prepared by kneading lead sulfate, red lead and water, and forming an active material paste layer. Production method. 2. The weight ratio of the tribasic lead sulfate to the lead tin is 20 to 40%.
The method for manufacturing the positive electrode plate for lead acid battery according to. 3. A positive electrode plate for a lead storage battery, wherein a current collector holds an active material. In the active material, spherical or flat lead dioxide is bonded to prismatic lead dioxide having a size of each part of 1 μm or less. An anode plate for a lead storage battery, comprising an active material layer having the above crystal structure. 4. The positive electrode plate for a lead storage battery according to claim 3, wherein the specific surface area of the active material layer is 10 m ² / g or more. 5. A method for producing a positive electrode plate for a lead storage battery by filling a current collector with an active material paste to prepare a undried electrode plate, drying the undried electrode plate, and then performing conversion to form a positive electrode plate for a lead storage battery. The step of filling the current collector with an active material paste obtained by kneading lead sulfate, red lead, and water to form an inner active material paste layer; and the active material paste obtained by kneading lead and water as the inner active material paste. A method for manufacturing a positive electrode plate for a lead storage battery, characterized in that the undried electrode plate is manufactured by a step of filling on the layer to form an outer active material paste layer. 6. A lead storage battery positive electrode plate comprising a current collector holding an active material, wherein the active material is a prismatic lead dioxide having a size of each part of 1 μm or less and spherical or flat lead dioxide bonded thereto. 2. An anode plate for a lead storage battery, comprising an inner active material layer having the above crystal structure, and an outer active material layer having a prismatic lead dioxide crystal structure with a dimension of each part of 1 μm or less.