TW200408156A - Positive electrode plate for lead storage battery and lead storage battery - Google Patents

Abstract

This invention is to provide a positive electrode plate for a lead storage battery excellent in discharge characteristics and life characteristics which improves utilization rate of an active material and prevents degradation of life of a positive electrode plate, and to provide a lead storage battery using the same; which utilizes paste kneaded with lead powder containing red lead and minium as main ingredients to fill a positive electrode frame body made from a lead alloy containing tin by not less than 1.2 weight percent; and said above minium content in the above lead powder is 5 to 50 weight percent, and the priority of said positive active material porosity after chemical treatment is not less than 58%.

Description

200408156 A7 _ B7 V. Description of the invention (4) 1 Please read the notes on the back before filling in this invention. This invention relates to a method that can prevent the life performance of lead batteries from decreasing, and can improve the utilization of positive active materials, and improve the discharge characteristics of lead batteries. Invention. [Technical Field of the Invention] [Prior Art] So far, attempts have been made to increase the utilization rate of active materials for positive plates for lead storage batteries, which is indispensable for reducing the weight and size of batteries, especially to improve the utilization rate during high-efficiency discharge. Many research trials were conducted. The main research direction is to increase the porosity of the positive electrode active material. Although increasing the porosity of the positive electrode active material can bring great effects, it will also have an adverse effect on the life of the lead storage battery. Therefore, there is also a limit in improving the porosity. In the past, the upper limit has been 60% in practical use. For this reason, when the porosity is increased, the bonding between the active materials will be weakened, and the conductivity of the active materials will gradually decrease. Therefore, only the active materials near the grid body will be discharged during the discharge, which will cause The electrical conductivity around the grid body is extremely low, causing lead sulfate to accumulate. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In recent years, in order to improve the corrosion resistance of the grid body, more than 1% by weight of tin has been added to the lead alloy of the grid body. It will cause the adhesion between the active material and the grid body to deteriorate. This is because the surface of the grid body is coated with tin oxide during the maturation step in manufacturing the positive electrode plate, which hinders the combination of the active material and the grid body. Therefore, when the porosity of the active material is increased, the life performance of the positive electrode plate will be worsened than in the past, which will form a barrier that hinders the improvement of the performance of lead batteries. 5- 200408156 A7 B7 V. Explanation of the invention (2). The present invention is an invention proposed to solve the foregoing object, and its purpose is to improve the utilization rate of the positive electrode active material and prevent the deterioration of the life performance of the positive electrode plate, and provide a discharge performance of the lead storage battery which can be improved at the same time. And life performance of the positive electrode plate for lead batteries. [Contents of the Invention] To achieve the foregoing object, the present invention has the contents described in the following (1) to (8). (1) A positive electrode plate for a lead storage battery, which is a positive electrode grid body of a lead alloy containing more than 1.2% by weight of tin, and is filled with lead powder and red lead (minum) powder as a main component. The positive electrode plate for lead storage batteries produced by mixing the positive electrode active material raw materials with the lead paste obtained by dilute sulfuric acid is characterized in that the positive electrode active material printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs contains 5 weights or more and 50 weights. The positive electrode plate for lead storage batteries produced with red lead content of less than% and the lead paste obtained by using the positive electrode active material raw material has a porosity of 58% or more. (2) The positive electrode plate for lead storage battery as described in (1) above, wherein the raw material of the positive electrode active material is a lead paste containing more than 5% by weight and less than 30% by weight of red lead, and the positive electrode active material is obtained by using the same. The porosity of the prepared positive electrode plate for a lead storage battery after the formation of the positive electrode active material is 58% or more. (3) The positive electrode plate for lead-acid batteries as described in (1) above, in which the original paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -6-200408156 A7 B7 3 V. Description of the invention (Extremely active substances) The raw material is a red paste component of 12% by weight or more and 42% by weight or less. The ship powder contains a lead metal component of 31% by weight or more and 40% by weight or less. The resulting positive electrode plate for lead storage batteries has a porosity of 58% or more after the formation of the positive electrode active material. (4) The positive electrode plate for lead storage batteries as described in (3) above, wherein the positive electrode active material is The metal powder is added, and the metal lead component in the positive electrode active material raw material calculated from the metal lead component in the lead powder and the added metal lead powder is 19% by weight or more and 26% by weight or less, and this positive electrode active material raw material is used The porosity of the positive electrode active material after the formation of the obtained positive electrode positive electrode plate for lead storage battery is 58% or more. (5) The positive electrode plate for lead storage battery as described in (1) above, which The raw material of the positive electrode active material contains 10% by weight or more and 50% by weight or less of the red lead component, and the average particle size of the red lead powder is 2.2 times or less the average particle size of the lead powder. (6), as described above (1) A positive electrode plate for a lead storage battery, wherein the lead powder is a positive electrode plate produced from a lead alloy containing an antimony component of 0.005% by weight or more and 0.1% by weight or less. (7) One of the above (1) to (6) The positive electrode plate for a lead storage battery according to any one of the above items, characterized in that the positive electrode grid body used is a stretched grid body. (8) A lead storage battery characterized by using the above (1) to (7) The positive electrode plate for lead battery in any one of the above items. 047 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Please read the precautions on the back before writing on this page. 200200156 A7 ____B7_ V. Description of the invention (4) [Simplified description of the diagram] Figure 1 shows the initial capacity change with the change of the red lead composition. Figure 2 shows the discharge capacity of the fifth cycle with the change of the red lead composition. Variety Figure 3 shows the change of the capacity ratio (B / A) with the change of the red lead composition. Figure 4 shows the relationship between the tin content and the amount of active substances attached with the change of the red lead composition. Figure 5 shows the change with the red lead composition. The fifth cycle of the discharge capacity and metal lead composition. Figure 6 shows the relationship between the initial capacity and the metal lead composition with red lead composition. Figure 7 is the fifth cycle with the red lead composition. Figure 8 shows the relationship between the discharge capacity and the metal lead composition. Figure 8 is the relationship between the capacity ratio and the metal lead composition as the red lead composition changes. Figure 9 is the result of the cycle life test of the sealed lead-acid battery. Printed by the Bureau ’s Consumer Cooperatives. Figure 10 is the capacity movement display of a sealed lead-acid battery at a floating charge test at 60 ° C. FIG. 11 is a graph showing a particle size distribution of red lead. FIG. 12 is a diagram showing the movement of the self-discharge rate when the red lead composition changes. Figure 13 is a graph showing the change of the cycle life ratio when the weight% of antimony in a lead alloy is changed with respect to various red lead components. Μ; This paper size applies the Chinese National Standard (CNS) A4 specification (210x297 mm) -8-200408156 A7 B7 V. Description of the invention (5) [The best form of implementing the invention] The first embodiment The first embodiment, When a certain amount of red lead is mixed in the raw material of the positive electrode active material, when the porosity of the positive electrode active material is higher than 58% or more, the life performance of the positive electrode plate can be improved upward. This will be described in detail below. The grid body with a height of 72mm, a width of 45mm, and a thickness of 2.9mm is made of a bell alloy containing 0.05% of age and 1.5% of the tin grave%. The aforementioned grid body is filled with a thickness of 3.0mm. The positive electrode active material lead paste prepared according to the formula shown in Table 1 was given the names of samples Nos. 1 to 12, and several samples were prepared for each sample. Then, it was placed in an environment with a temperature of 50 ° C and a humidity of 90% for 72 hours, and then 3 pieces were randomly taken out from each sample, and the active material dropping test was repeated 20 times at a height of 90 cm. To determine the amount of active material attached to the surface of the grid body. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, each of the nine samples was taken from the previous sample and placed in 28% dilute sulfuric acid for 24 hours, including 1 discharge to anodize the total charge of 20 Ah. (Chemical conversion) as a positive electrode plate. The red lead used is more than 95% pure. Subsequently, 6 pieces were randomly selected from each positive electrode plate, and the porosity of the positive electrode active material of 3 of them was measured by mercury intrusion method. The weight of Pb02 after the formation of the other 3 pieces! Then use the iodine labeling method. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -9- 200408156 A7 B7 V. Description of the invention (6) In addition, the adhesion amount of the obtained active substance is measured, and the weight% and porosity of Pb02 after formation The results are shown in Table 1. In the embodiment, the lead powder used is a metal lead-containing component used in a conventionally manufactured positive electrode plate in an amount of 25% by weight or more and 30% by weight or less. In addition, dilute sulfuric acid is an amount when the raw material of the positive electrode active material reaches 1 kg. (Please read the precautions on the back before filling this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -10- 200408156 B7 V. Description of the invention ( 7) Printed in Table 1 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Sample No., Active Material Adhesion (mg) after the Active Material Shedding Test of the Positive Electrode before Lead Paste Formation (Red) (% By weight) Dilute sulfuric acid Specific gravity • Volume (〇 Porosity (%) Pb02 (Weight 〇 / 〇) 1 100 0 1.14-1.5 450 54 91.3 2 100 0 1.16-1.7 290 56 91.5 3 100 0 1.16-1.9 252 58 91.9 4 100 0 1.16-2.2 223 62 92.5 5 100 0 1.16-2.4 191 64 93.6 6 97.5 25 1.16-2.2 268 62 93.0 7 95 5 1.16-2.2 506 62 93.5 8 88 12 1.16-2.2 621 62 94.5 9 82 18 1.16 -2.2 653 63 94.8 10 76 24 1.16-2.2 640 63 95.6 11 70 30 1.16-2.2 643 63 95.8 12 64 36 1.16-2.2 638 64 96.1 (Please read the precautions on the back before filling out this page) The size of the paper is applicable China National Standard (CNS) A4 specification (210X297 mm -11-200408156 A7 B7 8 V. Description of the invention (Second, the other three positive plates were respectively formed into three groups in a 40% excess dilute sulfuric acid in a manner corresponding to the lead plate and discharged, and the initial capacity was measured. A and the discharge capacity of the fifth cycle. The measurement conditions are based on the discharge current being a constant current of 0.7A, and the end-of-discharge voltage is determined by using lead dioxide and lead immersed in dilute sulfuric acid with a concentration of 40%. -5 OOmV of lead paste type electrode obtained by alloy. Initial capacity A is the one showing the maximum capacity in 3 cycles of discharge after chemical conversion. The discharge capacity in the 5th cycle is the discharge showing the initial capacity as the 0th cycle. And the discharge capacity during the 5th cycle of discharge. In addition to the results shown in Table 2, the ratio of the discharge capacity B (capacity ratio b / a) of the 5th cycle to the initial capacity A is also loaded at once. Please read the precautionary page of the page printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives. This paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -12- 200408156

7 B V. Description of the invention (9) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 Sample No. Initial capacity A (Ah) Discharge capacity B (Ah) in the 5th cycle B / A 1 2.34 2.41 1.030 2 2.45 2.40 0.980 3 2.59 2.48 0.957 4 2.78 2.25 0.809 5 2.82 1.84 0.65 1 6 2.77 2.37 0.856 7 2.76 2.70 0.978 8 2.81 2.78 0.989 9 2.80 2.76 0.986 10 2.81 2.75 0.979 11 2.86 2.56 0.895 12 2.83 2.35 0.830 (Please read the back first Note: Please fill in this page again.) The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -13- 200408156 A7 B7 10 V. Description of the invention (Second, Table 2 for lead powder is 100% by weight) Samples Nos. 1, 2, and 3, when the red lead content in the raw material of the positive electrode active material was set to 12% by weight, and the positive electrode active material lead paste was prepared according to various formulas shown in Table 3, and then filled with the same In the above grid body, sample No. la, sample No. 2a, and sample No. 3a were used. When the red lead content in the raw material of the positive electrode active material was set to 18% by weight, it was as shown in Table 3. Show various recipes The positive electrode active material lead paste was similarly filled in the above-mentioned grid body as Sample No. 1 b, Sample No. 2b, and Sample No. 3b. In addition, red lead in the raw material of the positive electrode active material was used. When the composition was set to 24% by weight, positive electrode active material lead paste was prepared according to various formulas shown in Table 3, and then the same was filled into the grid of the above body as Sample No. 1c, Sample No. 2c, Sample No. 3c. When the red lead content in the raw material of the positive electrode active material was set to 27% by weight, the positive electrode active material lead paste was prepared according to various formulas shown in Table 3, and then the same was filled in the above net. In the grid, sample No. Id, sample No. 2d, and sample No. 3d were used. When the red lead content in the raw material of the positive electrode active material was set to 30% by weight, various formulas shown in Table 3 were used. A positive electrode active material lead paste was prepared, and the same was filled into the above-mentioned mesh grid in the same manner as Sample No. 1e, Sample N0.2e, and Sample No. 3e. In addition, the red in the raw material of the positive electrode active material was red. When the lead content was set to 36% by weight, a positive electrode was prepared according to various formulations shown in Table 3. The lead paste of the sexual substance is similarly filled in the grid body of the above, as the sample No. If, the size of the sample paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Please read the notes on the back first Refill this page Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 200408156 A7 B7 11 V. Description of the invention (Article N0.2f, Sample No. 3f. In addition, when the red lead content in the raw material of the positive electrode active material was set to 42% by weight, the positive electrode active material lead paste was prepared according to various formulas shown in Table 3, and then the same was filled in the grid of the above-mentioned grid, so that Sample No. 1 g, Sample N 0.2 g, and Sample No. 3 g. Subsequently, they were matured under the above conditions, anodized (formed) as the positive electrode plate, and the weight percentage and porosity of Pb02 after the formation were measured according to the method described above, and the other three positive electrode plates were taken to make the battery, and its initial capacity The changes in the ratio (B / A) of the discharge capacity at the fifth cycle to the fifth discharge capacity B at the initial capacity A are described in Table 3. In addition, the initial capacity change obtained with the change of red lead is shown in Fig. 1, and the change of the square capacity of the fifth cycle under the same method is shown in Fig. 2. The change of the ratio (B / A) under the same method is shown in Fig. 1. Contents shown in 3. In addition, the aforementioned ratio (B / A) is also the life performance index of the positive plate. Please read the notes on the back before filling in this page. The paper printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is compliant with China National Standard (CNS) A4 (210X297 mm) -15- 200408156 A7 B7 12 V. Description of the invention ( Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 3 Sample No. The initial capacity of the positive electrode plate after the formation of lead paste A (Ah) The discharge capacity of the fifth cycle B (Ah) The capacity ratio B / A lead powder (% by weight) Red lead (weight 0 / 〇) Dilute sulfuric acid Specific gravity • volume (liters) Porosity (%) Pb02 (weight 0 / 〇) la 88% 12% 1.14-1.5 55 91.8 2.39 2.46 1.029 2a 88% 12% 1.16-1.7 57 91.9 2.49 2.55 1.024 3a 88% 12% 1.16-1.9 58 92.5 2.61 2.66 1.019 lb 82% 18% 1.14-1.5 55 91.9 2.40 2.50 1.042 2b 82% 18% 1.16-1.7 57 92.9 2.52 2.55 1.012 3b 82% 18% 1.16- 1.9 59 92.3 2.62 2.72 1.038 lc 76% 24% 1.14-1.5 54 92.1 2.40 2.52 1.050 2c 76% 24% 1.16-1.7 57 92.8 2.63 2.60 1.028 3c 76% 24% 1.16-1.9 59 93.8 2.69 2.79 1.037 Id 73% 27% 1.14-1.5 54 92.1 2.41 2.52 1.046 2d 73% 27% 1.16-1.7 57 92. 9 2.54 2.61 1.028 3d 73% 27% 1.16-1.9 59 93.8 2.79 2.83 1.037 le 70% 30% 1.14-1.5 55 92.3 2.49 2.54 1.045 2e 70% 30% 1.16-1.7 56 92.9 2.54 2.62 1.031 3e 70% 30% 1.16- 1.9 59 94.0 2.77 2.83 1.022 If 64% 36% 1.14-1.5 55 92.8 2.42 2.51 1.037 2f 64% 36% 1.16-1.7 56 99.1 2.53 2.69 1.039 3f 64% 36% 1.16-1.9 59 94.2 2.82 2.81 0.996 is 58% 42% 1.14-1.5 55 93.2 2.44 2.46 1.088 2g 58% 42% 1.16-1.7 57 93.6 2.55 2.52 0.988 3g 58% 42% 1.16-1.9 59 94.2 2.83 2.75 0.972 Please read the precautions below to order

This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) -16- 200408156 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (13) Known from Figure 1 and Table 3, and Samples No. 1 to No. 1 in Table 1 with sample N0.1 having almost the same porosity (54 to 55%) are the same as those in Table 1.

Sample No. 2a to 2g of No. 2 having almost the same porosity (56 to 57%) and Sample No. 3a to 3g of almost the same porosity (58 to 59%) as in Sample No. 3 in Table 1 One, when compared with the initial capacity of Sample No. 1 shown in Table 2, the red lead content in the raw material of the positive electrode active material gradually increased from 12% to 42% by weight, that is, the initial capacity increased. In particular, especially for samples No. 3a to 3g (58 to 59%), the red lead content in the raw material of the positive electrode active material increased from 24% to 36% by weight, and it was found that the initial capacity increased significantly. In addition, according to FIG. 1 and Table 3, when the porosity is in the range of 54 to 5 7%, when the red lead content in the raw material of the positive electrode active material increases, the initial capacity itself also increases. The porosity and 58 In addition to the smaller ~ 59%, the proportion of increase is also lower. Similarly, when the porosity is in the range of 62 to 64%, when the red lead content in the raw material of the positive electrode active material increases, the initial capacity itself will also increase. When the porosity is compared with 58 to 59% Larger. Therefore, if the initial porosity is 58% or more, it can be expected to increase as the red lead content of the positive electrode active material increases. This point is presumably because when the red lead component is added to the raw material of the positive electrode active material, the weight percentage of Pb02 after formation can be increased, and as a result, the initial capacity will be increased. In addition, according to the contents shown in Figure 2 and Table 3, the paper size is the same as the sample No. 1 in Table 1. The Chinese National Standard (CNS) A4 specification (210X297 mm)

17- 200408156 A7 _____B7_ V. Description of the invention (14) Sample No.la ~ lg with almost the same porosity (54 ~ 55%), and sample No.2 with the same porosity (56 ~ 57%) in Table 1 Sample

Any of No. 2a to 2g and Sample No. 3a to 3g having the same porosity (58 to 59%) as that of Sample No. 3 in Table 1, is the same as No. 1 of Sample No. 1 in Table 2. When comparing the discharge capacity of 5 cycles, the red lead content in the raw material of the positive electrode active material was increased to 30% by weight, and it was found that the fifth discharge capacity was the increase. In particular, when sample No. 3a to 3g (porosity = 58 to 59%), the red lead content of the positive electrode active material raw material was increased to 30% by weight, and the discharge capacity at the fifth cycle was significantly increased. In addition, according to FIG. 2 and Table 3, when the porosity is in the range of 5 4 to 57%, when the red lead content in the raw material of the positive electrode active material increases, the discharge capacity in the fifth cycle also increases in the fifth cycle. The discharge capacity itself is smaller than the porosity of 5 8 ~ 59%, and its increase ratio is also lower. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Similarly, when the porosity is in the range of 62 to 64%, the red lead content of the positive electrode active material raw material is increased from 5% to 30% by weight. The discharge capacity of the cycle will be greatly increased, especially when the weight of the red lead component is in the range of 5% by weight or more and 24% by weight or less. Therefore, the discharge capacity of the fifth cycle, if the porosity is Above 58%, it can be expected to increase with the increase of red lead in the raw material of the positive electrode active material. In addition, according to the contents shown in FIG. 3 and Table 3, it is known that the sample No. la ~ lg having the same porosity (54 ~ 55%) as the sample No. 1 in Table 1, and the paper size of the table apply the Chinese national standard (CNS) A4 size (210X29 * 7mm) ~ " -18- 200408156 A7 B7 V. Description of the invention (15) Sample N0.2 in sample 1 has almost the same porosity (56 ~ 57%)

Any of No. 2a to 2g and Sample No. 3a to 3g having almost the same porosity (58 to 59%) as that of Sample No. 3 in Table 1, are not the same as those in Table 2.

When the capacity ratio (B / A) of No. 1 is compared, the capacity ratio (B / A) is increased when the red lead content in the raw material of the positive electrode active material is increased from 5% to 27% by weight. In addition, among Sample Nos. 11 and 12 of Table 1 and Samples No. le to 3e, If to 3f, and lg to 3g of Table 3, it was found that a positive electrode active material was accumulated in the battery in the fifth measurement cycle. It is presumed that due to excessive red lead content, the bonding force between the positive electrode active materials is reduced, and the conductive path between the positive electrode active material particles will also be broken during the charge and discharge cycle. For this reason, the raw material of the positive electrode active material is mixed with the red lead powder, and the porosity of the positive electrode active material is 58% or more, preferably 58% or more, and 62% by weight of the red lead component in an amount of 5% to 30% by weight. In the following cases, a positive electrode plate for a lead storage battery capable of increasing the initial capacity and the discharge capacity of the fifth cycle can be obtained. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. It is known from Sample Nos. 4 and 6 to 11 in Table 1 that if the red lead powder mixed with the positive electrode active material raw material is added, the amount of active material adhesion can be increased. It is caused by the problem of the adhesion between the mesh grid and the positive electrode active material caused by the coating of tin oxide produced on the surface of the mesh grid. When using a mesh grid made of a lead alloy containing 1.5% tin, The presence of the red lead component improves the adhesion between the grid body and the positive electrode active material. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) -19 200408156 A7 ___B7__ V. Description of the invention (16) In order to confirm the theory described in the sample, the samples No. 4, 6 ~ 11 according to Table 1 can be the same The positive electrode active material lead paste prepared by the formula was filled in a grid with a tin content of 1.2% by weight, 1.1% by weight, and 1.0% by weight, and the adhesion amount of the active material was similarly investigated. The results are shown in FIG. 4 Show. It can be known from the content of FIG. 4 that if the weight of the red lead powder mixed with the positive electrode active material is increased in the grid body with a tin content of io wt% and 1.1 wt%, the adhesion amount will decrease as the proportion increases. In a grid body having a tin content of 1.2% by weight and 1.5% by weight, if the red lead component mixed with the positive electrode active material raw material is 5% by weight or more, the amount of active material adhesion will increase significantly. As a result, it is estimated that the life performance will be improved. Based on the foregoing, if the lead active material lead paste prepared by using the lead content of the red lead component to be 5% by weight or more and 30% by weight or less of the raw material of the positive electrode active material, the tin content of the lead content is 1.2% by weight or more. When the grid body is used, a positive electrode plate for a lead storage battery which can increase the initial capacity and the discharge capacity of the fifth cycle, and can also improve the life performance can be obtained. The second embodiment is printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The second embodiment relates to the positive electrode plate of the first embodiment described above. The red lead component with insufficient life performance is 30% by weight or more. In order to obtain a positive electrode plate that is not inferior to the first embodiment even when the porosity is 5 8% or more. The lead powder in the first embodiment is based on the premise that the metal lead content is 25% by weight or more and 30% by weight or less. If the metal lead content is mixed with 30% by weight, the Chinese paper standard (CNS) A4 specification applies to this paper. (210X297 mm ^ ~ -20- 200408156 A7 ______B7_ V. When the content of the invention is more than (17)%, the effect that can be achieved in the first embodiment will be reduced. In the second embodiment, the quality is stable because of the desire to produce stability The lead powder often requires a great investment in equipment, so even for lead powders with a lead content of more than 30% by weight, the purpose is to effectively use the lead powder. That is, the second embodiment is based on the When the lead content exceeds 30% by weight, a positive electrode plate that is not inferior to the first embodiment can also be produced. The first embodiment described above is a method in which red lead is mixed with a positive electrode active raw material to make a positive electrode plate. The life performance is improved upwards, but when the red lead content exceeds 30% by weight, the adhesion between the active materials will be reduced, so there is a certain limit to the increase of the red lead content, even if red lead is mixed, The effect of improving the life performance of the positive electrode plate has not been fully exerted, and the second embodiment is to solve this problem by adjusting the content of gold and lead in the lead powder of the positive electrode active material. The second embodiment will be described in detail. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints a grid body with a height of 72mm, a width of 45mm, and a thickness of 2.9mm. It is a lead alloy containing 0.05% by weight of calcium and 1.5% by weight of tin. It is obtained by drawing. In the aforementioned grid body, the positive electrode active material lead paste prepared according to each formula shown in Table 4 was filled with a thickness of 3 mm, and the sample numbers shown in Table 4 were prepared separately. No. number of samples. After the aforementioned samples were aged under the same conditions as in the first embodiment, they were placed in dilute sulfuric acid at a concentration of 28% for 24 hours, including one discharge to make the anode a total charge of 20 Ah. Oxidation (formation) is used as the positive electrode. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -21-200408156 A7 ___B7______ 5. Description of the invention (4.) 18 〇 The red lead is one with a purity of 95% or more (Evaluation test 1) For each positive electrode plate prepared according to the formula shown in Table 4, the Pb02 (wt%) and porosity after chemical conversion under the same conditions as in the first embodiment are measured. The results are as shown in Table 4. (Please read the notes on the back before filling this page) —M, order the paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs to apply the Chinese National Standard (CNS) A4 specification ( 210X 297 mm) -22- 200408156 A7 B7 V. Description of the invention (19) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 4 Sample positive paste No. lead pink pink lead powder after dilute sulfate formation Later porosity (% by weight) (% by weight) Metal bell (% by weight) Specific gravity-volume (〇Pb02 (% by weight) (%) A-1 100 0 26 1.16-2.2 92.5 62 A-2 88 12 26 1.16 -2.2 94.5 62 A-3 82 18 26 1.16-2.2 94.8 63 A-4 76 24 26 1.16-2.2 95.6 63 A-5 73 27 26 1.16-2.2 95.6 63 A-6 70 30 26 1.16-2.2 95.8 63 A-7 64 36 26 1.16-2.2 96.1 64 A-8 58 42 26 1.16-2.2 96.8 64 A-2 · 88 12 35 1.16-2.2 94.5 62 A-3 '82 18 35 1.16-2.2 94.8 62 A-4, Ί6 24 35 1.16-2.2 95.6 63 A-5, 73 27 35 1.16-2.2 95.6 63 A-6, 70 30 35 1.16-2.2 95.8 63 A-7, 64 36 35 1.16 -2.2 96.1 63 A-8f 58 42 35 1.16-2.2 96.2 62 A-2 ”88 12 40 1.16-2.2 93.5 62 A-3” 82 18 40 1.16-2.2 94.0 62 Α-4Π 76 24 40 1.16-2.2 95.0 63 A-5H 73 27 40 1.16-2.2 95.4 62 A-6- 70 30 40 1.16-2.2 95.9 64 A-7, 64 36 40 1.16-2.2 95.7 63 A-8- 58 42 40 1.16-2.2 96.0 64 A- 6… 70 30 28 1.16-2.2 96.2 63 Ar 64 36 28 1.16-2.2 96.2 64 A-8… 58 42 28 1.16-2.2 96.5 64 A-6…, 70 30 31 1.16-2.2 95.8 62 A-7…, 64 36 31 1.16-2.2 96.1 63 A-8…, 58 42 31 1.16-2.2 96.3 63 Please read the following items and fill in this paper. The paper dimensions are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1 «-23- 200408156 A7 ______ B7_ V. Description of the invention (20) (Evaluation test 2) For the other three positive electrode plates different from the positive electrode plate used in evaluation test 1 and corresponding to each sample No, the measurement was the same as the first embodiment Conditional initial capacity A and 5th Discharge capacity of the ring B, which results are shown in Table 5 content, and, for the first five cycles of the discharge capacity A of the initial capacity ratio of the amount (volume ratio B / A) is also described in which a Merger. In addition, Fig. 5 shows the change in the discharge capacity in the fifth cycle when the red lead composition is changed, and it is marked according to each metal lead composition. Printed on the paper by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 24-200408156 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs on A7 B7. ) Table 5 Sample No. Initial capacity A (Ah) Discharge capacity B (Ah) in the 5th cycle B / A A-1 2.78 2.25 0.809 A-2 2.81 2.78 0.989 A-3 2.80 2.76 0.986 A-4 2.81 2.75 0.979 A-5 2.82 2.69 0.954 A-6 2.86 2.56 0.896 A-7 2.83 2.35 0.830 A-8 2.80 2.20 0.786 A-2 '2.79 2.77 0.993 A-3f 2.79 2.76 0.989 Α-4 · 2.79 2.76 0.989 Α · 5, 2.82 2.72 0.965 Α-6 · 2.85 2.69 0.944 Α-7 · 2.81 2.61 0.929 Α-8 '2.83 2.59 0.915 Α-2 ”2.77 2.77 1.000 Α-3Π 2.77 2.75 0.993 Α_4, 2.80 2.77 0.989 Α-5 丨 2.84 2.79 0.982 Α-6 "2.84 2.74 0.965 Α-7 " 2.80 2.69 0.957 Α-8, · 2.84 2.60 0.915 Α-6, Μ 2.83 2.59 0.916 Α-7, Μ 2.85 2.51 0.882 Α · 8 · 丨 丨 2.84 2.44 0.860 Α- 6, Μ, 2.86 2.68 0.936 A-7 ,, 2.86 2.62 0.914 A-8, 2.85 2.57 0.902 Please read the notes of the memorandum before filling in

The paper size of the edition applies to the Chinese National Standard (CNS) A4 specification (210X29 * 7 mm) -25- 200408156 A7 B7 22 V. Description of the invention (discharge capacity of the 5th cycle measured according to the above evaluation test 2 is based on lead The change of the red lead composition of each metal lead composition in the powder is shown in Figure 5. Please read the precautions on the back before filling in this page. From Figure 5 and Tables 4 and 5, it is known that the metal lead composition is 26% by weight. Sample A-1 without red lead powder mixed in the raw material of the positive electrode active material with lead powder as the main component, samples A-2 to A-8 with a red lead content of 30% by weight or more, and 12% by weight or more with red lead powder, When comparing samples A-2 to A-5 in the range of 27% by weight or less, the discharge capacity and capacity ratio (B / A) at the 5th cycle were significantly lower. However, the metal lead content was 35 weight. Red lead powder was mixed in the raw material of the positive electrode active material with a lead content of 12%. Samples A-2 '~ A-8' with a red lead content of 12% by weight or more and 42% by weight or less were respectively different from Sample A-2 ~ A-8 When comparing, especially in A-6 '~ A-8', the discharge capacity at the 5th cycle The amount and capacity ratio (B / A) showed an increase. This tendency is also seen in sample A-2 ', which also mixes red lead in the raw material of the positive electrode active material with a lead content of 40% by weight as a main component. '~ A-8 ,,. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, especially in A-6 ~ A-8, because there are too many red lead components in the raw material of the positive electrode active material, the active material after chemical conversion The weaker binding force between the particles, in A-6 '~ A-8', A-6 "~ A-8", the metal lead content in the lead powder of the main component of the positive electrode active material was increased to 35% by weight or 40% by weight, so the red bell component in the ripening can react with the metal to the component to strengthen the binding force of the particles. In addition, according to the content of Figure 5, the red lead component and the metal lead in the lead powder The composition of the paper is in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) -26- 200408156 A7 —_B7__ 5. Description of the invention (23) When the composition range is investigated, it is known that The composition uses a metal lead composition of 26 weight; Samples A-6 ~ A-8, samples A-6 obtained by using 28% by weight and 31% by weight of lead powder, A-6 ,, A-6, '', A-6 '' '' ~ A-8 ' The discharge capacity of '5' in the 5th cycle will increase, and the capacity ratio (B / A) will increase. The reason is that the capacity ratio between the metal lead component is 28% by weight and 26% by weight ( B / A), which is the turning point where the life performance has changed greatly. Generally, the lead powder used in the manufacture of electrode plates uses lead powder with a metal lead content of about 25% to 30% by weight. This second embodiment, in When using the lead powder to produce the positive electrode plate, the improvement of the life performance has not exerted sufficient effects, but the positive electrode plate prepared by using the foregoing positive electrode active material raw material mixed with red lead powder in the lead powder can overcome the red The disadvantage is that the lead component cannot reach 30% by weight or more, and the effect is exhibited. That is, in this second embodiment, even if a lead powder having a metal lead content of 31 wt./0 or more is used and the red lead content is set to 30 wt% or more, a capacity ratio (B / A) of 0.90 or more can be obtained. The positive electrode plate with good life can increase the yield of lead powder. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, especially when using lead powder with a metal lead content of 25% by weight or more and 30% by weight or less, if the metal lead content is in the range of 28% by weight or more and 30% by weight or less, such as samples A-6 '' 'shows the same result, which can produce a positive electrode plate with a higher capacity ratio (B / A). In the evaluation tests 1 and 2, the tests performed on the positive electrode plate with a porosity of about 62% can be known from the contents of FIG. 2 and FIG. 3. The foregoing positive electrode plate with a porosity is to suppress the red lead content to exceed 30% by weight. At the time of the 5th cycle, the paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -27- 200408156 A7 B7 V. Description of the invention (24) The reduction of discharge capacity and capacity ratio (B / A) Users, therefore, a positive electrode plate with a porosity less than 62% can also be said to produce a positive electrode plate with good life performance without using lead powder with such a high metal lead content. When the metal lead content in the lead powder is 31% by weight or more and 40% by weight or less, the same can be obtained when the red lead content is 30% by weight or less, preferably 12% by weight or more and 30% by weight or less. effect. In addition, when the metal lead content in the lead powder is 40% by weight or more, the particle size of the lead powder produced by the ball mill type lead powder machine of the main lead powder manufacturing equipment is too large, which will affect the performance of the positive electrode plate. Also, because of the rapid oxidation of metal lead, lead powder storage problems will occur, so it is not good. The above evaluation tests 1, 2 are based on the lead content of the metal in the lead powder, and the metal in the lead powder. When the lead component is too large, it is easy to cause raw material management difficulties in the manufacturing process, so the metal lead component in the lead powder is preferably smaller. Among them, when the metal lead content in the lead powder is too large, it is better to add a metal bell powder to the positive electrode active material raw material containing lead powder and red lead powder as main components. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs To confirm the effectiveness of the present invention, the following evaluation tests will be performed. (Evaluation test 3) In a lead powder having a metal lead content of 26% by weight, according to the formula shown in Table 6, the red lead powder and the positive electrode active material raw material mixed with the metal lead powder were used under the same conditions as in the second embodiment. The cathode active material lead paste was prepared in the same way, and the grid was filled with a thickness of 3.0mm in the same manner, and the paper size of the paper was prepared and applied to the Chinese National Standard (CNS) A4 specification (210X297 mm) -28- 200408156 A7 B7 V. Description of the invention (%)

Samples of sample number No. shown in ZO 6. After the aforementioned sample was aged under the same conditions as in the second embodiment, it was left for 24 hours in dilute sulfuric acid with a concentration of 2S%, which included a single discharge to anodic oxidation (formation) with a total charge of 20 Ah as a positive electrode plate. 〇The red lead powder used is more than 95% pure. The positive electrode plate used here was measured for Pb02 (wt%) and porosity after formation under the same conditions as in the first embodiment. The results are shown in Table 6. (Please read the precautions on the back before filling this page) 丨 ¾. Order the paper printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs to apply the Chinese National Standard (CNS) A4 specification (210 X297 mm) -29- 200408156 A7 B7 26 5. Description of the invention (Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Table 6 Sample No. Positive electrode lead material after the formation of positive electrode active material (wt.%) Red lead (wt.%) Metal lead powder (wt.%) Metal content (%) Pb〇2 (wt%) Porosity (%) A-1 100.0 0.0 0.0 26.0 92.5 62 A-2 88.0 12.0 0.0 22.3 94.5 62 A-3 82.0 18.0 0.0 21.3 94.8 63 A- 4 76.0 24.0 0.0 19.8 95.6 63 A-5 73.0 27.0 0.0 19.0 95.6 63 A-6 70.0 30.0 0.0 18.2 95.8 63 A-7 64.0 36.0 0.0 16.6 96.1 64 A-8 58.0 42.0 0.0 15.1 96.8 64 a-4, 75.5 24.0 0.5 20.1 95.5 63 a-5, 72.0 27.0 1.0 19.7 95.5 63 a-6, 68.0 30.0 2.0 19.7 95.3 62 a-7 · 60.0 36.0 4.0 19.6 94.1 62 a-8 '52.0 42.0 6.0 19.5 93.5 62 a-2 丨, 85.0 12.0 3.0 25.1 94.5 62 a-3 " 77.0 18.0 5.0 25.0 95.2 62 a-4 ”68.0 24.0 8.0 25.7 95.0 62 a-5” 64.5 27.0 8.5 25.3 93.6 61 a-6 " 60.5 30.0 9.5 25.2 92.8 62 a-7 ”52.5 36.0 11.5 25.2 89.8 61 a-8” 44.5 42.0 13.5 25.1 88.2 61 a-2M '78.0 12.0 10.0 30.5 85.3 61 a-3M, 70.0 18.0 12.0 30.2 83.0 60 a-4 ·, 62.0 24.0 14.0 30.1 80.5 59 a-9' 47.5 45.0 7.5 19.6 93.8 62 a-10 '43.2 48.0 8.8 20.0 93.7 62 ( (Please read the notes on the back before filling out this page) m

、 1T Γ This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 30- 200408156 A7 B7 27 V. Description of the invention ((Evaluation Test 4) For positive electrode plates different from those used in Evaluation Test 3, and For the other three positive plates corresponding to each sample No, the initial capacity A and the discharge capacity B of the fifth cycle under the same conditions as in the second embodiment were measured. The results are shown in Table 7 and the initial capacity A The ratio of the 5th cycle discharge capacity (capacity ratio B / A) is also described here. Fig. 6 shows the initial capacity when the metal lead composition mixed with the metal lead powder is changed and the red lead composition is changed. Fig. 7 shows the change in the discharge capacity in the fifth cycle under the same conditions, and Fig. 8 shows the change in capacity ratio (B / A) under the same conditions. In the above evaluation tests 3 and 4, 26 weights were selected to select the metal lead composition. %, The sample using this lead powder, in the previous evaluation test 2, showed that the discharge capacity at the 5th cycle will be significantly reduced when the red lead content is increased. Please read the precautions on the back before filling in this page. Economy Ministry of Wisdom Printed by the Consumer Cooperative of the Property Bureau This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) 200408156 A7

7 B V. Description of the invention (28) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 7 Sample No. Initial capacity A (Ah) Discharge capacity B (Ah) in the fifth cycle Capacity ratio B / A A-1 2.78 2.25 0.809 A-2 2.81 2.78 0.989 A-3 2.80 2.76 0.986 A-4 2.81 2.75 0.979 A-5 2.82 2.69 0.954 A-6 2.86 2.56 0.895 A-7 2.83 2.35 0.830 A-8 2.80 2.20 0.786 a-4 · 2.80 2.70 0.964 a-5 · 2.80 2.74 0.979 a-6 '2.81 2.67 0.950 a-7f 2.75 2.60 0.945 a-81 2.71 2.58 0.952 a-2 ”2.71 2.68 0.989 a-3 丨, 2.76 2.70 0.978 a-4M 2.76 2.73 0.989 a- 5n 2.72 2.64 0.971 a-6 ”2.65 2.60 0.981 a-7M 2.49 2.45 0.984 a-8 " 2.41 2.46 1.021 a-2, 丨, 2.39 • • a-3 ·, 2.11 exposure • a-4M, 1.99 • shop a -9 '2.61 2.50 0.958 a-10 * 2.52 2.25 0.893 (Please read the notes on the back before this page) The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm) -32- 200408156 A7 B7 5 Explanation of the invention (29) It is known from FIGS. 6-8, Tables 6 and 7 that the metal lead content is 26% by weight of lead powder as the main component, and it is mixed When metal lead powder is mixed with red lead powder, with the increase of the red lead content, the weight% of the metal lead powder in the raw material of the positive electrode active material will decrease. Increase the weight% of the metal lead component. As a result, the discharge capacity of the fifth cycle will increase. For example, in sample No. A-6 (the same as the sample No. · A-6 in Table 5) with a red bell component of 30.0% by weight, the metal bell component is 18.2% by weight, and in sample No.a-6 'It is a mixture of metal lead powder, and when the metal lead powder reaches 2.0% by weight, its metal lead content will be 19.7% by weight. In addition, Sample No.a-6 '' is a mixture of metal lead powders so that when the metal lead powder reaches 9.5% by weight, its metal lead content will be 25.2% by weight. Regardless of the metal lead content in any of the positive electrode active material raw materials, All weight% increase. As a result, the discharge capacity of the fifth cycle is increased as compared with the case where the metal lead powder is not mixed. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, however, sample A-7 with the same red lead content of 36.0% by weight (same as sample A-7 in Table 5) and sample A-8 with the red lead content of 42.0% (with The sample A-8 in Table 5 is the same), with 16.6 wt% and 15.1 wt% of the metal lead component, and sample No.a-7 'is mixed with the metal lead powder to make the metal lead powder to 4.0 wt%, Sample No.a-8 'is mixed with metal lead powder, and when the metal lead powder reaches 6.0% by weight, the metal lead components will be 19.6% and 19.5% by weight. In addition, sample No.a-7 '' is mixed with metal lead powder, so that the paper size of the metal lead powder is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -33- 200408156 A7 _B7_ V. Description of the invention (3 ()) When it reaches 11.5% by weight, sample No.a-8 "is mixed with metal lead powder. When the metal lead powder reaches 13.6% by weight, the metal lead content will be 25.2% by weight and 25.1% by weight. As a result, the weight percentage of the metal lead component in the raw material of the positive electrode active material can be increased, and the discharge capacity at the fifth cycle is increased as compared with the case where the metal lead powder is not mixed. The initial capacity was found to be reduced in samples No. a-7 ', a-8' ', or sample No. a-2' '' to a-4 '' '. The reason is that samples 1 ^ 〇. &Amp; -7 ’’, _. &Amp; -8 ’’ are formed after formation? 1) The weight of 02 is reduced compared to samples No.A-7 and No.A-8. This is because when the metal powder is mixed, if the metal powder exceeds 10% by weight, it will react with the red lead component. In addition to the effect of increasing the binding force between the particles of the positive electrode active material, the plutonium has the effect of reducing the formation efficiency of the positive electrode plate. Action 〇 This point can be confirmed by mixing the metal powder, the metal lead content exceeds 30 weight! ¾, the sample No. a-2 '' '~ a-4' '' in the initial capacity is reduced. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. From Figures 6 to 8, Tables 6 and 7, the main component is a lead powder with a metal lead content of 26% by weight. Sample mixed with red lead powder to make the red lead content 45.0% by weight and 48% by weight

No.a-9 '~ a-10', the significant decrease in the discharge capacity at the fifth cycle can also be confirmed. From the above description, when a lead powder having a metal lead content of 26% by weight is used as a positive electrode active material raw material, the red lead component is mixed with a metal lead powder in an amount of 30% by weight or more and 42% by weight or less, so that the metal lead content is 19 weight Above 26% and less than 26% by weight, the initial capacity and the fifth cycle of the paper size can be applied to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -34- 200408156 A7 B7 V. Description of the invention (31) The capacitance is increased. Especially when the metal powder is 10% by weight or less when mixed, as shown in the sample Nos. A-4 '~ a-8', a-2 '' ~~ a-6 '' of Table 7, the effect is extremely significant. . In addition, as a result of mixing the metal lead component in the lead powder with the metal lead powder, even when the metal lead component is 19% by weight or more and 26% by weight or less, it can be seen from FIG. 6 to FIG. 30% by weight or less, preferably 12% by weight or more and 30% by weight or less, have the same effect. According to the above-mentioned first and second embodiments and the results of evaluation tests 1 to 4, the effective range of the technology of the present invention, which mainly uses lead powder and red lead powder as the main ingredients of the positive electrode active material, is 1. The lead paste obtained by kneading the raw material of the positive electrode active material with red lead powder and dilute sulfuric acid is filled in the positive electrode plate for a lead battery obtained by filling the positive electrode grid body. The red lead component in the positive electrode active material is 5% by weight. Above, 30% by weight, preferably above 5% by weight, and below 24% by weight; printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs2, and the red lead component in the raw material of the positive electrode mentioned above is 1 2 More than 4% by weight and less than 42% by weight, and the metal lead component in the lead powder is more than 31% by weight and less than 40% by weight; The red lead content is more than 12% by weight and 42% by weight or less, and the metal lead content in the same raw material is more than 19% by weight and less than 26% by weight; This paper size applies to Chinese National Standards (CNS) A4 specification (210X297 mm) -35 200408156 A7 B7 V. Description of the invention (32) 4. Also, the metal lead powder in the same raw material is less than 10% by weight; preferably. Third Embodiment The third embodiment relates to the positive electrode plate for lead storage batteries in the first and second embodiments described above. Even when a large amount of red lead powder is added to the lead powder, based on the result of limiting the average particle size of the red lead powder, The shape that can improve its own discharge characteristics without impairing the life performance of lead storage batteries. When red lead powder is added to the lead powder produced by Shimadzu-type ball mill or Burton lead powder machine, the discharge characteristics of lead storage batteries can be improved, but when a large amount of red lead powder is added, it will react with the sulfuric acid of the electrolyte to generate sulfuric acid. Lead, if it has a larger growth than the pores of the positive plate, the result will destroy the bond structure of the active material, and reduce the life performance of the positive plate. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In the third embodiment, the red lead powder added to the lead powder of the main component of the positive electrode active material reacts with sulfuric acid to generate lead sulfate, and the particle diameter is set so that the average particle diameter of the lead powder does not become too large. The particle size distribution of the lead powder is in an appropriate range with respect to the particle size distribution of the lead powder. As a result of this setting, the bonding structure of the active material will not be damaged, the life performance of the lead storage battery will not be reduced, and the effect of improving its own performance can be exerted by adding red lead powder. Hereinafter, the third embodiment will be described in detail. The lead powder used in this embodiment is produced by a Shimadzu-type ball mill with an average particle size of about 2.3 // m and a metal lead content of 25 to 30 weight! ¾ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -36- 200408156 A7 ______B7_ V. Lead powder of invention description (33). It should be noted that the red powder is an average particle diameter of about 2.2 // m. This mixture of lead powder and red lead powder was mixed with dilute sulfuric acid to prepare a positive electrode active material lead paste. The prepared positive electrode active material lead paste was filled into the grid body and the cast grid body obtained by the stretching process, and then matured under the same conditions as in the first embodiment. In this embodiment, the average particle diameter is calculated by using a mixed solvent having a ratio of cyclohexanol 3 and methanol 1 to disperse the lead powder and the red lead powder, and measuring the sedimentation rate. Table 8 shows the lead paste external ratio (appearance specific gravity), the lead paste external ratio after maturation, etc., when the lead paste prepared by red lead with a content of 0 to 50% by weight of the positive electrode active material is kneaded. In addition, the meaning of the red lead component is 50 weight, and when it exceeds this ratio, the effect on the cycle life described later (please refer to Table 10) is also exhibited. In the mixture of lead powder and red lead powder whose red lead content is changed within 50% by weight, printed by the staff consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the positive electrode active material lead paste prepared by mixing dilute sulfuric acid is mixed with matured after mixing. The dried tincture is almost the same as the tin oxide of the positive electrode active material lead paste prepared without mixing red lead. This is because during the kneading step of the positive electrode active material lead paste, dilute sulfuric acid, and red lead powder, the reactivity of lead powder and red lead powder is almost the same for dilute sulfuric acid. The dilute sulfuric acid used therein is a weight of 10 kg of the active material of the positive electrode of lead powder and red lead powder having a specific gravity of 1.16, and the Chinese national standard (CNS) A4 specification (210X297) is applied to the paper size. Mm) -37 · 200408156

7 7 A B V. Description of the invention (μ) Ο ^ τ is obtained by mixing at a ratio of 2.0 (liters). Table 8 Remarks after the red lead composition is matured and dried [Weight%] Lead paste external ratio Lead paste external ratio [g / cm3] [g / cm3] 0 4.02 3.44 Comparative Example 10 4.03 3.43 Example 1 20 4.04 3.45 Example 2 30 4.02 3.47 Example 3 40 4.03 3.45 Example 4 50 4.02 3.45 Example 5 (Please read the precautions on the back before filling this page}

1T Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs, the anode plate after ripening as shown in Table 8 (using a cast grid body) is formed by the so-called trough formation of dilute sulfuric acid with a specific gravity of 1.10. Almost the same steps were used to convert the dried negative electrode plate into a sealed lead-acid battery with a tolerance equivalent to 7AH (20 hours rate) after using a fine glass mesh positioner to compactly arrange it at about 40kg / dm2. . At this time, the electrolysis injected into the sealed lead-acid battery was also dilute sulfuric acid with a specific gravity of 1.300. The sealed battery produced in this way was divided into Comparative Examples and Examples 1 to 5, respectively, and after recharged at a rate of about 150% for 10 hours, the battery was left at 40 ° C for 30 days to investigate its own discharge characteristics. Similarly, the dried positive electrode plate shown in Table 8 is used (the standard of this paper is drawn to apply Chinese National Standard (CNS) A4 specification (210X297 mm) -38-200408156 A7 B7 35) V. Description of the invention (net grid body ) And, the negative electrode plate that has been matured and dried after undergoing almost the same steps is combined with a fine glass mesh positioner and compactly arranged at about 40 kg / dm2, and then subjected to a so-called electric cell formation treatment to obtain the equivalent of A sealed lead-acid battery with a capacity of 7AH (2G hour rate). In addition, the electrolyte used at this time reaches a specific gravity of 1.3 00 at the end of the formation of the electric cell, so a dilute sulfuric acid with a specific gravity of 1.22 5 to 1.24 5 is used. In the sealed lead-acid battery prepared in this way, the comparative examples and Examples 1 to 5 prepared with various red lead components were placed at 40t for 30 days, respectively, and their discharge characteristics were similarly investigated. Self-discharge characteristics , Is the first discharge after 30 days and the charge is continuously carried out 3 times at a rate of 10 hours and charged at 8.4AH. The difference between the average discharge and its respective discharge is divided by 30 and then multiplied by 100. Discharge rate itself. The results are shown in Table 9. Please read the precautions on the back before printing the sheet printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The type of the positive plate itself is put at a rate of [% / day]. Comparative Example of Battery Prepared by Electric Cell Formation 2.5 2.1 Example 1 2.0 1.6 Example 2 1.4 1.0 Example 3 1.2 0.9 Example 4 1.2 0.8 Example 5 1.1 0.8 This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) 39- 200408156 A7 B7 V. Description of the invention (36) As shown in Table 9, even if it undergoes tank formation treatment or electric tank formation treatment, its own discharge rate tends to decrease as the red lead content increases. The reduction of the self-discharge rate gradually decreases when the red lead content exceeds 30% by weight. In addition, in the absolute limit of the self-discharge rate, the sealed lead-acid battery using the positive electrode plate produced by the formation of the electric cell is more than the closed cell. The sealed lead-acid battery produced by the chemical conversion treatment of the positive electrode plate is smaller. Secondly, the sealed lead-acid battery prepared by the chemical conversion treatment described above is performed under the conditions of JIS C 8702. Ring life test. The test temperature is 25 ° C ± 2 ° C. Discharge 0.25CA 2 hours charge 0.1CA 6 hours capacity confirmation, based on 25 cycles from each fully charged state to a discharge current equivalent to 0.25CA, termination The discharge is performed until the voltage reaches 1.7V / reservoir, and the cycle that reduces the capacity to less than 50% of the initial capacity is the cycle life. The results are printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and the results are shown in Figure 9. As shown in FIG. 9, the battery of Example 5 (the red lead content is 50% by weight) has the same cycle life performance as the battery of the comparative example. In addition, the capacity test results of the batteries using the float charge in Comparative Examples and Examples 1 to 5 are shown in FIG. 10, and the capacity of the battery of Example 3 (the red lead content was 30% by weight) was reduced. The rate is minimal. In addition, the floating charge test is based on the standard of this paper at 2.275 V / storage room at 60 ° C. The Chinese National Standard (CNS) A4 specification (210X297 mm) -40 200408156 A7 _____ Β7_ _ V. Description of the invention (37) The floating charge test was strengthened to check the capacity every month. The capacity confirmation is the same as the conditions of the above-mentioned cycle life test. When the capacity is reduced to less than 60% of the initial capacity, it is used as a criterion for determining the floating charge life. According to the average particle size of the red lead powder shown in Table 8, the same method (tank formation) is used to produce a peak 値 of about 2.2 // m (about 1.0 times the average particle size of the lead powder, which is called red lead A). ), About 5.0 // m (about 2.2 times the average particle diameter of lead powder, called red lead B), about 10.5 // m (about 4.6 times the average particle diameter of lead powder, called Red lead C), about 14.9 // m (about 6.5 times the average particle size of lead powder, called red lead D). The self-discharge test, cycle life test, and enhanced floating charge test at 60 ° C were performed in the same manner as in the third embodiment. The results are shown in Table 10. The particle size distribution of red lead A to D is as follows. Figure 11 shows. The average particle diameter of the lead powder was 2.3 / zm. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -41 200408156 A7 B7 V. Description of the invention () Particle size ratio of printed red lead 1.0 (red lead A) 2.2 (red lead B) 4.6 (red lead C) 6.5 (red lead D) 0 wt% 2.5 40% itself 1 0 wt% 2.0 2.5 2.7 2.9 Discharge rate 2 0 wt% 1.4 1.6 2.6 3.0 [% / day] 3 0 wt% 1.2 1.3 2.6 3.2 4 0 wt% 1.2 1.3 2.9 3.2 5 0 wt% 1.1 1.2 3.0 3.2 0 wt% 300 times 1 0 wt% 3 10 times 3 10 290 back to 280 back to cycle 2 0 wt% 320 back to 320 back to 280 back to 270 back to mouth layer 3 0 wt% 340 back to 3 3 0 back to 270 back to 260 back to 40 wt% 320 back to 3 10 back to 270 back to 250 back 5 0 wt% 3 10 rounds, 300 rounds, 270 rounds, 240 rounds 0 wt% 12 · May 1 0 wt% 13.2 March 13.2 March 12.5 March 1 1 · 〇 6 0 ° C 20wt% 14.2 March 14.2 November 11 August 10.2 Monthly floating charge 3 0 wt% 15.8 months 15.0 months 10 July July 9.8 months 4 0 wt% 14.3 months 14.4 months 10.2 months 9.7 months 5 0 wt% 14.4 months 14.4 months 9.9 months 9 · March (Please read the precautions on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -42- 200408156 A7 B7 39 V. Description of the invention (as shown in Table 10) It is shown that when the weight percentage of the components of the red Ming is the same, the lead storage battery produced by using the red bells c and D has a shorter cycle life than the lead storage battery produced by using the red lead a and B. This reason is presumed that the red lead When the average particle diameter of the powder exceeds about 2.2 times that of the lead powder, the crystal particle size of the lead sulfate obtained by decomposition with dilute sulfuric acid is coarsened, and the bonding structure of the positive electrode active material is destroyed.

In addition, when the generation of lead sulfate is too slow, the amount of red lead that reacts with sulfuric acid in the discharge test itself will increase. As a result, the floating current will be increased in the 60 ° C promotion test to promote the corrosion of the grid of the positive plate. Speed, and the floating charging life is also shortened. In addition, it is known from FIG. 12 that if the average discharge rate of 40t is 40 times the average particle size of the red lead powder, it will decrease with the increase of the red lead content. When it is more than 2.2 times of lead powder, it will rise with the increase of red lead content. The reason is that the effect of adding red lead powder in the process of tank formation or in the formation of electric tanks will cause its own discharge rate to decrease. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs from the above, it is known that in the discharge rate of 40t itself, the red lead content is 20% by weight to 50% by weight, and the average particle size of the red lead powder is 2.2 of the lead powder. It is better to be less than twice. It is more preferable that the red lead content is 30% by weight or more and 50% by weight or less, and the average particle size of the red lead powder is 1.0 times that of the lead powder. In the cycle life, the red lead component is preferably from 10% by weight to 50% by weight, and the average particle diameter of the red lead powder is preferably 2.2 times or less the lead powder. More preferably, the content of red lead is more than 20% by weight and less than 40% by weight. The size of this paper applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -43-200408156 A7 _____B7 5. Description of the invention (4〇) and It is more preferable that the average particle diameter of the red lead powder is 2.2 times or less of the lead powder. (Please read the precautions on the back before filling this page.) In the 60 ° C cycle life, the red bell component is 10% by weight to 50% by weight, and the average particle size of the red lead powder is the same as that of the lead powder. Preferably less than 2.2 times. It is more preferable that the red lead component is 20% by weight or more and 40% by weight or less, and the average particle diameter of the red lead powder is 2.2 times that of the lead powder. In the third embodiment, a description is given of a sealed lead-acid battery made using a fine glass mesh positioner. As a result of the foregoing lead-acid battery being pressed, the active material is made even when the red lead content is 50% by weight. Does not fall off, but can exert the effect of adding red lead powder. The fourth embodiment is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The fourth embodiment is a lead alloy made of lead powder containing a certain amount of antimony (Sb) in a lead battery positive electrode plate of the foregoing 1 to 3 embodiments. Producers, in the case of increasing the red lead content, in addition to suppressing the decrease in the early life performance of the positive electrode plate, can also suppress the decrease in discharge capacity due to the softening of the positive electrode active material, and provide a lead storage battery with excellent life performance. . When a positive electrode plate is produced by using a positive electrode active material containing red lead powder in a lead powder, the adhesion between the active material and the grid body can be improved, and when it is produced from a lead alloy obtained by a lead powder containing a certain amount of antimony, the lead powder is passed through The synergistic effect produced by the combination with red lead powder will improve the adhesion between active materials. Especially with respect to the positive electrode material, the weight percentage of the red lead component will be subject to the Chinese National Standard (CNS) A4 if the paper size is included. Specifications (210X297 mm) -44-200408156 A7 _ B7 V. Description of the invention (41) When the content is more than 5% by weight and less than 50% by weight, the adhesion between the active material and the grid can be improved. In addition, if antimony ( Sb) The lead powder produced from a lead alloy containing 0.005% by weight or more and 0.1% by weight or less based on the weight of lead can suppress the softening of the positive electrode active material and significantly improve the life performance of the positive electrode plate. Hereinafter, the fourth embodiment will be described in detail. Pb-Sb alloys with different amounts of antimony (Sb) were used to produce lead powder with a ball mill. The lead content of this lead powder is 25% by weight or more and 30% by weight or less, and the amount of antimony (Sb) relative to the weight of lead is 0.001% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight 7 kinds of alloys such as 0.5% by weight and 1% by weight. In addition, once produced lead powder produced from pure lead (the amount of antimony is 0% by weight / 0) ° Among the various lead powders described above, the red lead powder is 3% by weight and 5% by weight relative to the raw material of the positive electrode active material. , 10% by weight, 20% by weight, 30% by weight, 45% by weight, 50% by weight, and 75% by weight. The external ratio of the mixed lead paste printed by the employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is 3.85g / cm3 of positive electrode active material lead paste. Subsequently, the foregoing lead paste was filled in a stretched grid body obtained from Pb-0.08% by weight, Ca-1.5% by weight, and a Sn alloy, and it was aged and dried under the same conditions as in the i-th embodiment to produce An unformed positive electrode plate having a thickness of 1.6 mm was obtained. The external ratio of the lead paste formed in this position to the positive electrode is 4.02g / cm3, and the porosity is 59%. The paper size is suitable for Guancai County (CNS) A4 · (210X297 mm) -45- 200408156 A7 B7 V. Description of the invention () V 42 ； Among them, the positive electrode active material lead paste filled in the grid body is prepared under the same conditions as the molar amount of lead. In addition, the positive electrode grid body increases its corrosion resistance with an increase in the amount of tin added. When the amount of tin is 1.2% by weight or more, the reason why the adhesion between the unformed active material and the grid body decreases is as before. As described. Among them, according to the application scope of the implementation form of the present invention, it is known from the past experience that the amount of tin added causes a problem in the adhesion between the active material and the grid body, and the amount of tin added is 1.5% by weight of a lead alloy. These 6 positive electrode plates are made with the same method as the 7th negative electrode plate with a thickness of 1.3mm and 7 negative electrode plates. Polyethylene spacer plates are used to produce a nominal capacity of 36 Ah (5 time rate) and a voltage of 2 V. Lead battery. In addition, the positive active material lead paste was prepared by using lead powder produced from a lead alloy containing antimony (Sb) or lead powder produced from pure lead without mixing red lead powder, and using the same as a positive electrode plate. Make lead-acid batteries. In order to compare the capacity reduction caused by the peeling of the grid and the active material and the degree of capacity reduction caused by the softening of the active material, the results of the cycle life test performed on each lead storage battery are shown in FIG. 12. The Consumer Life Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed a cycle life test, which is a condition of charging at a constant current of 5A for 5 hours (125% of the discharge capacity) after a 1 hour discharge at an ambient temperature of 40 ° C and a current of 20A. Next. In order to confirm the discharge capacity at the 25th cycle, a discharge at an ambient temperature of 40 ° C and a current of 20 A was performed, and the discharge capacity was measured until the voltage reached 1.7V. In the cycle life test or capacity confirmation, the discharge capacity is lower than the nominal size of this paper. The Chinese national standard (CNS) A4 specification (21〇χ: 297 mm) is applied. 46- 200408156 A7 ____B7 V. Description of the capacity (43) 50% or less, and the life is confirmed in a way that the capacity does not increase at the next discharge. In addition, the cycle life ratio in Fig. 13 refers to the use of lead powder produced from pure lead not mixed with red lead to modulate the positive electrode active material, and the lead storage battery composed of the obtained positive electrode plate is used at the beginning of the cycle life test. Reached its service life. As a result of the disassembling investigation of this lead storage battery, it was found that the positive electrode active material and the grid body were peeled off, which resulted in a decrease in the positive electrode capacity and limited the battery capacity. In addition, red lead powder is obtained by mixing at 5% by weight or more. Regardless of whether it is produced using lead powder produced from pure lead or lead powder produced from lead alloy containing antimony (Sb), it is used as a positive electrode active material to prepare a positive electrode. The active material lead paste and the lead-acid battery obtained by using it as a positive electrode plate have not reached the end of their useful life in the early stage. Therefore, it has been confirmed that the addition of red lead powder can improve the life span. The aforementioned mixed red lead powder, whether produced using lead powder produced from pure lead, or lead powder produced from lead alloys, can be confirmed to have the effect of preventing capacity reduction at the beginning of the cycle life test and reaching service life. However, when the content of red lead exceeds 30% by weight, it can be confirmed that the lead storage battery produced by using lead powder produced from pure lead has the effect of preventing capacity reduction at the beginning of the cycle life test. However, it contains antimony (Sb) Among lead storage batteries made from lead powder produced from lead alloy production, the effects of lead storage batteries made from lead powder produced from lead alloy containing other antimony (Sb) have not been confirmed. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm). Please read the notes at the back first.

pi Page I Order Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-47- 200408156 A7 B7 V. Description of the Invention (44) For this reason, the fourth embodiment is a lead storage battery that has not been compacted. In the course of the discharge cycle, the positive electrode active material is liable to soften and fall off, but as described below, the combination of lead powder and red lead powder produced from a lead alloy containing antimony (Sb) has a synergistic effect. In addition, the red lead content is 3% by weight. When compared with the higher red lead content, its cycle life test expenditure will greatly reduce its capacity, and it is a lead storage battery produced by using lead powder produced from pure lead. Have the same tendency. This is because the weight percentage of the red lead component is too small, so the effect is limited. When comparing lead batteries produced from lead alloys containing lead powder containing antimony (Sb) and using them, compared with lead batteries using pure lead and using lead batteries made from them, the red lead content exceeds 3 In the area of 0% by weight, the effect of a smaller capacity reduction in the cycle life test was confirmed. However, when the lead powder produced by a lead alloy containing antimony was used in an area where the red lead content exceeded 50% by weight, it was almost impossible. Get any effect to increase life. Based on the above results, the range of the weight percentage of the red lead component is preferably 5% by weight or more and 50% by weight or less with respect to the positive electrode active material. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Next, the conditions under which lead powder containing antimony can be substantially exerted will be explained. As shown in FIG. 13, if the red lead content is 5% by weight or more and 50% by weight or less, the weight of antimony in the lead powder to the weight of lead is 0.05% by weight or more and 0.1% by weight or less. It is produced by lead alloy. Therefore, when comparing lead powder with those produced by pure lead, it is confirmed that the life performance of the produced lead-acid battery can be improved. This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 48- 200408156 A7 _B7_ V. Description of the invention (45) After confirming that the lead-acid battery has reached the end of its service life, its positive electrode capacity is regulated. Among them, when a lead alloy in which the weight of antimony (Sb) in the lead powder is 0.005 wt% or more is produced, the cycle life may decrease. As a result of disassembling investigation after reaching the end of its life, the negative electrode plate deteriorated earlier than the positive electrode plate, which should be the reason for the limited discharge capacity. Therefore, the red lead powder is produced by mixing a lead active material with a weight of 5 weight ° / 0 or more and 50 weight% or less, and the weight of antimony (Sb) to lead is 0.005 to 0.1 weight! , Has a substantial effect on improving life performance. In addition, the grid bodies used in the above embodiments are all produced by stretching. The aforementioned grid system is obtained by calendering a lead alloy into a sheet-like object, and then cut and expanded to obtain a mesh. The surface is smoother than the surface of the grid body obtained by casting. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Therefore, the adhesion between the positive electrode active material and the grid is much lower than that of the cast grid. In order to increase the porosity of the positive electrode active material, the adhesion needs to be further reduced. When red lead powder is mixed in the raw material of the positive electrode active material, the decrease in adhesion can be overcome, and a lead storage battery with excellent life performance can be obtained when a stretched grid body with excellent productivity is used. The foregoing content is also applicable to the case where the cast grid body is used in the present invention. [Industrial applicability] As shown above, according to the content of the present invention, if it contains 1.2% by weight, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)

£ · Q -49- 200408156 A7 _B7_ V. Description of the invention (46) A positive electrode grid body made of a lead alloy of tin or more will produce a tin oxide film on the surface during the ripening step of manufacturing a positive electrode plate, and It hinders the adhesion between the active material and the positive grid. By mixing a certain amount of red lead powder in the raw material of the positive active material, it can eliminate the adhesion between the positive grid and the active material. In addition, in the case of mixing red lead powder, the adhesion between the active materials is reduced. The maturation step can be accelerated by regulating the metal lead component in the lead powder of the positive electrode active material raw material or by mixing the metal lead component with the raw material. The redox reaction between red lead and metal lead in the subsequent formation step suppresses the decrease in adhesion at the end of the formation step, and a positive electrode plate capable of withstanding long-term use is obtained. Therefore, the present invention has great industrial applicability. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) -50-

Claims (1)

200408156 8 8 8 8 ABCD 々, patent application scope i 1. A positive electrode plate for lead storage battery, which is in a positive electrode grid body of a lead alloy containing more than 1.2% by weight of tin, and is filled with lead powder and red lead powder The positive electrode plate for a lead storage battery prepared by mixing a positive electrode active material raw material and a dilute sulfuric acid-based lead paste as a main component is characterized in that the positive electrode active material raw material contains a red lead component of 5 wt% or more and 50 wt% or less. In addition, the porosity of the positive electrode active material after the formation of the positive electrode plate for a lead battery prepared by using the lead paste obtained from the raw material of the positive electrode active material is 58% or more. 2. For example, the positive electrode plate for lead storage batteries in the scope of patent application, wherein the raw material of the positive electrode active material contains more than 5% by weight and less than 30% by weight of red lead, and the lead obtained by using the positive electrode active material material The porosity of the positive electrode active material after the formation of the positive electrode plate for a lead storage battery prepared by the paste is more than 58%. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 3. The positive electrode plate for lead storage batteries, such as item 1 of the scope of patent application, in which the raw material of the iE active material contains 12% by weight and 42% by weight of red lead. The powder is a positive electrode plate for lead storage batteries containing 31% by weight or more and 40% by weight or less of a metal lead component and a lead paste obtained by using the positive electrode active material raw material. More than 58%. 4. For example, the positive electrode plate for lead storage batteries in the scope of patent application No. 3, in which the metal lead powder is added to the raw material of the positive electrode active material, and it is calculated from the metal lead component in the lead powder and the added metal lead powder. The metal lead content in the raw material of the positive electrode active material is 19% by weight or more and 26% by weight or less, and the lead storage gS6 obtained by using the lead paste obtained from the positive electrode active material raw material is applicable to the Chinese National Standard (CNS). Input 4 specifications (21 × χ: 297 mm) -51-200408156 A8 B8 C8 __D8 々, patent application scope 2 Positive electrode plate for batteries, the porosity of the positive electrode active material after its formation is more than 58%. 5. For the positive electrode plate for lead storage battery as described in the first item of the patent application scope, wherein the raw material of the positive electrode active material contains more than 10% by weight and less than 50% by weight of red lead, and the average particle size of the red lead powder is lead The average particle size of the powder is 2.2 times or less. 6. The positive electrode plate for a lead storage battery as described in the first item of the patent application scope, wherein the lead powder is a positive electrode plate produced from a lead alloy containing an antimony component of 0.005% by weight or more and 0.1% by weight or less. 7. A positive electrode plate for lead storage batteries according to any one of claims 1 to 6, wherein the positive electrode grid body used is a stretched grid body. 8. A lead-acid battery characterized by using a positive electrode plate for a lead-acid battery according to any one of claims 1 to 7 of the scope of patent application. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ㈣7 paper sizes are applicable to Chinese National Standards (CNS) M specifications (21 × 297 mm) -52-