JP6326928B2 - Control valve type lead acid battery - Google Patents

Description

  The present invention relates to a control valve type lead storage battery.

  For example, a control valve type lead-acid battery used in an emergency power supply (UPS) such as a hospital or factory as described in Patent Document 1 always floats at a relatively low voltage (for example, about 2.23 V) during standby. The battery is charged and fully charged. Such a control valve lead-acid battery is required to have a life performance that can be used for a long period of time.

JP 2009-289595 A

  In general, when the float is used for a long period of time, the positive electrode current collector of the lead storage battery is always in a polarized state. Therefore, Pb is oxidized to PbO2, and the corrosion progresses gradually. It causes a decrease in conductivity and a decrease in the adhesion between the active material and the lattice due to the elongation of the current collector, and the lifetime is increased due to an increase in internal resistance and accumulation of lead sulfate. In particular, a stationary lead-acid battery using a cast current collector for the positive electrode has a problem in that the electrical conductivity of the current collector is remarkably lowered due to intergranular corrosion and the life performance is deteriorated.

  On the other hand, when the mass of the positive electrode current collector is increased in order to increase the lattice strength, there arises a problem that the volume energy density and the weight energy density are lowered. In addition, if only the current collector mass is increased without changing the mass of the positive electrode plate, the amount of the positive electrode active material filled in the positive electrode current collector is reduced, so that the utilization rate of the active material is increased, resulting in power outages and maintenance. When discharged during inspection or the like, the depth of discharge increases and the active material tends to deteriorate. As a result, an increase in internal resistance is caused, resulting in a problem that the life performance of the lead storage battery is lowered.

  The present invention was made for the purpose of solving the above problems, and by making the current distribution of the current collector uniform, the progress of corrosion of the current collector is made uniform, and the internal resistance associated with lattice corrosion. An object of the present invention is to provide a control valve type lead-acid battery that is excellent in life performance without decreasing the energy density and suppressing the increase in the amount of lead and the accumulation of lead sulfate.

  The control valve type lead storage battery of the present invention is a control valve type lead storage battery including a paste type positive electrode plate having a positive electrode current collector and a positive electrode active material, wherein the positive electrode current collector is provided with a current collecting ear portion. The first horizontal frame bone, the second horizontal frame bone arranged in parallel with the first horizontal frame bone, and a pair of vertical frame bones connecting both ends of the first horizontal frame bone and the second horizontal frame bone A plurality of longitudinal inner bones extending from the first lateral frame bone to one or both of the second lateral frame bone and the longitudinal frame bone, and a pair of the longitudinal frame bones A plurality of transverse inner bones arranged so as to connect each other, the sum (e) of the cross-sectional areas of the pair of longitudinal frame bones and all the longitudinal inner bones, and the transverse area (d) of the first transverse frame bone The ratio is 0.15 ≦ (e) / (d) ≦ 0.25.

Here, when the positive electrode current collector mass is constant, the positive electrode current collector mass is determined from the mass of the vertical frame bone, the horizontal frame bone, the vertical internal bone and the horizontal internal bone forming the current collector. When the cross-sectional area of the longitudinal inner bone increases and the mass increases, the mass of the lateral inner bone or lateral frame bone decreases, and conversely, the cross-sectional area of the lateral frame bone and lateral inner bone increases and the mass increases. Doing will result in a decrease in the mass of the longitudinal frame bone or longitudinal inner bone.
In addition, when the thickness of the frame bone and the inner bone is constant, the decrease in mass means that the number decreases, whereas when the number of the frame bone and inner bone is constant, the mass decreases, The thickness of the frame bone and inner bone will be thin.

  When the ratio of the sum (e) of the cross-sectional areas of the pair of longitudinal frame bones and all longitudinal internal bones to the cross-sectional area (d) of the first lateral frame bone is (e) / (d) <0.15, The number of longitudinal inner bones arranged between the frame bones is reduced, or the thickness of the longitudinal frame bones and longitudinal inner bones is reduced, the lattice strength is lowered, the active material holding performance is lowered, and the current distribution is reduced. It becomes non-uniform. However, in the control valve type lead storage battery of the present invention, the positive electrode current collector is configured to satisfy 0.15 ≦ (e) / (d), more preferably 0.018 ≦ (e) / (d). Therefore, it is possible to prevent a decrease in the number of the longitudinal inner bones, a decrease in the active material holding performance due to a decrease in the thickness of the longitudinal frame bone and the longitudinal inner bone, and an uneven current distribution.

  Further, when (e) / (d)> 0.25, the number of lateral inner bones decreases, or the lateral frame bones and lateral inner bones become thin and the strength decreases, resulting in a decrease in active material holding performance and current distribution. Although the problem of non-uniformity arises, in the control valve type lead storage battery of the present invention, the positive electrode current collector is configured so that (e) / (d) ≦ 0.25, so the number of lateral inner bones is reduced, Or the fall of the active material holding | maintenance performance by the reduction | decrease of the thickness of a horizontal frame bone and a horizontal inner bone, and the nonuniformity of electric current distribution can be prevented.

  Furthermore, the control valve-type lead-acid battery of the present invention has a ratio of an average value (c) of the cross-sectional areas of the pair of vertical frame bones and all the longitudinal inner bones to a cross-sectional area (d) of the first horizontal frame bones. 0.015 ≦ (c) / (d) ≦ 0.025.

  When the ratio of the average value (c) of the cross-sectional areas of a pair of longitudinal frame bones and all longitudinal internal bones to the cross-sectional area (d) of the first lateral frame bone is (c) / (d) <0.015, Although the lattice strength of the vertical frame bone or the vertical inner bone is reduced, it becomes susceptible to corrosion, and the life performance deteriorates due to the increase in internal resistance and accumulation of lead sulfate. Since the positive electrode current collector is configured so that .015 ≦ (c) / (d), more preferably 0.020 ≦ (c) / (d), the internal resistance due to lattice corrosion of the longitudinal inner bone Increase and accumulation of lead sulfate can be prevented.

  Further, when (c) / (d)> 0.025, the number of longitudinal inner bones arranged between the longitudinal frame bones is reduced, and the active material holding performance is deteriorated or the current distribution is not uniform. However, in the control valve type lead storage battery of the present invention, the positive electrode current collector is configured so as to satisfy (c) / (d) ≦ 0.025, so that the active material holding performance is deteriorated and the current distribution is not uniform. Can be prevented.

  Furthermore, in the control valve type lead storage battery of the present invention, it is preferable that the positive electrode current collector is punched from a cold rolled sheet of lead alloy.

  Examples of the method for producing the positive electrode current collector include a casting method and a punching method, but by manufacturing the positive electrode current collector by a punching method from a cold rolled sheet of a lead alloy, the intergranular corrosion is prevented and a layered structure is produced. Since the corrosion progresses uniformly, it is possible to prevent a decrease in conductivity and improve the life performance.

  In addition, in the control valve type lead storage battery of the present invention, the ratio of the mass (a) of the positive electrode current collector and the active material mass (b) of the positive electrode plate is 0.85 ≦ (a) / (b) ≦. It is 1.15.

  When the ratio of the mass (a) of the positive electrode current collector to the active material mass (b) of the positive electrode plate is (a) / (b) <0.85, since the mass of the positive electrode current collector is small, lattice corrosion Although the life performance deteriorates due to the increase in internal resistance and accumulation of lead sulfate, the control valve type lead storage battery of the present invention has 0.85 ≦ (a) / (b), preferably 0.9 ≦ (a). Since the positive electrode plate is configured to be / (b), it is possible to prevent an increase in internal resistance and accumulation of lead sulfate due to lattice corrosion.

Further, in the case of (a) / (b)> 1.15, if only the current collector mass is increased, the amount of the positive electrode active material filled in the positive electrode current collector is decreased, so that the active material utilization rate is increased. However, the active material deterioration due to deep discharge during power outage or maintenance / inspection tends to proceed, but the control valve type lead storage battery of the present invention has (a) / (b) ≦ 1.15, preferably (a) Since the positive electrode plate is configured so that /(b)≦1.1, deterioration of the active material can be prevented and life performance can be improved.
In the present specification, the active material is obtained by removing the current collector from the electrode plate, and includes materials other than the main components such as additives, conductive agents, and reinforcing materials.

  According to the present invention, by uniforming the current distribution of the current collector, the progress of corrosion of the current collector can be made uniform, and the increase in internal resistance and accumulation of lead sulfate accompanying lattice corrosion can be suppressed. . Therefore, it is possible to provide a control valve type lead storage battery having excellent life performance without lowering the energy density.

The schematic diagram which shows one Embodiment of the positive electrode grid in this invention. The schematic diagram which shows other embodiment of the positive electrode grid in this invention. In the control valve type lead acid battery of the present invention and the control valve type lead acid battery for comparison, the life when the ratio of the mass (a) of the positive electrode grid body and the active material mass (b) of the positive electrode plate is changed. A graph showing the number of years. The graph which contrasted the elongation of the positive electrode grid of the control valve type lead acid battery of this invention, and the control valve type lead acid battery for a comparison. The graph which contrasted the positive lead sulfate accumulation degree of the control valve type lead acid battery of this invention, and the control valve type lead acid battery for a comparison. In the control valve type lead acid battery of the present invention and the control valve type lead acid battery for comparison, the average value (c) of the cross-sectional areas of the pair of vertical frame bones and all the vertical inner bones and the crossing of the first horizontal frame bones The graph which shows the life years when changing ratio with an area (d). The graph which contrasted the elongation of the positive electrode grid of the control valve type lead acid battery of this invention, and the control valve type lead acid battery for a comparison. The graph which contrasted the positive lead sulfate accumulation degree of the control valve type lead acid battery of this invention, and the control valve type lead acid battery for a comparison. In the control valve type lead acid battery of the present invention and the control valve type lead acid battery for comparison, the sum (e) of the cross sectional areas of the pair of vertical frame bones and all the vertical inner bones and the cross sectional area of the first horizontal frame bone The graph which shows the lifetime years when changing the ratio of (d). The graph which contrasted the elongation of the positive electrode grid of the control valve type lead acid battery of this invention, and the control valve type lead acid battery for a comparison. The graph which contrasted the positive lead sulfate accumulation degree of the control valve type lead acid battery of this invention, and the control valve type lead acid battery for a comparison.

  Hereinafter, an embodiment of a control valve type lead storage battery in the present invention will be described.

  The control valve type lead-acid battery in this embodiment is disposed between a paste-type positive electrode plate, a paste-type negative electrode plate, a positive electrode plate and a negative electrode plate, and a separator that holds an electrolyte, a positive electrode plate, and a negative electrode plate And a battery case containing the separator. In this embodiment, for example, a grid-like current collector is used, and in this case, this current collector is hereinafter referred to as a grid body.

  The negative electrode plate is formed, for example, by filling a negative electrode grid made of a lead alloy such as a Pb—Ca alloy or a Pb—Ca—Sn alloy and filling the negative electrode grid with a negative electrode active material paste. is there. In addition, this negative electrode lattice body and negative electrode active material paste are not specifically limited, According to the objective and use, it can select from a well-known thing suitably and can be used.

  The separator is obtained by impregnating dilute sulfuric acid, which is an electrolytic solution, into a paper separator made of, for example, hydrophilic polyethylene fiber and silica powder. In addition, the structure of this separator is not specifically limited, According to the objective and use, it can select from a well-known thing suitably and can be used.

  The battery case is composed of, for example, a battery case body having a rectangular parallelepiped shape with an opening on one side and a lid for closing the opening. For example, the battery case is mainly formed by injection molding of thermoplastic plastic. In addition, the structure of this battery case is not specifically limited, According to the objective and the use, it can select from a well-known thing suitably and can be used.

  In the following, for the sake of convenience, the direction extending toward the opening of the battery case is defined as the vertical direction, and the width direction of the battery case is defined as the horizontal direction.

  The positive electrode plate is formed, for example, by filling a positive electrode grid made of a lead alloy such as a Pb-Ca alloy or a Pb-Ca-Sn alloy, and a positive electrode active material paste into the positive electrode grid. is there. The positive electrode grid and the positive electrode active material paste are not particularly limited, and can be appropriately selected from known materials according to the purpose and application.

  As shown in FIG. 1, the positive electrode grid body 1 includes a frame body 2 and an inner bone 3 disposed in the frame of the frame body 2.

  The frame 2 forms an outer frame of the positive electrode grid 1, and is separated from the first horizontal frame bone 2a provided with the current collecting ear portion 4 and the first horizontal frame bone 2a and the first horizontal frame. A pair of longitudinal frames that are arranged so as to be parallel to the bone 2a and that connect the two ends of the first lateral frame bone 2b and the second lateral frame bone 2b with the second lateral frame bone 2b provided with a pair of feet 5. It consists of a frame bone 2c. In addition, the positive electrode lattice body has a rectangular shape in a plan view in the present embodiment, but may be a square shape, and the size is appropriately selected according to the internal shape of the battery case.

  The inner bone 3 extends from the first lateral frame bone 2a toward the second lateral frame bone 2b, and a plurality of longitudinal inner bones 3a arranged at equal intervals in the lateral direction of the first lateral frame bone 2a, and a pair of longitudinal frames A plurality of lateral inner bones 3b arranged at equal intervals in the longitudinal direction of the longitudinal frame bone 2c so as to connect the frame bones 2c.

  In the present embodiment, the positive grid 1 has a standard grid shape in which the intersecting portions of the longitudinal inner bone 3a and the lateral inner bone 3b intersect at a right angle. However, as shown in FIG. A radial lattice in which the longitudinal inner bone 3a extends from the first lateral frame bone 2a toward either the second lateral frame bone 2b or the longitudinal frame bone 2c and is randomly arranged in the lateral direction of the first lateral frame bone 2a. It may be a shape.

  The positive grid 1 is manufactured by punching a cold rolled sheet of lead alloy, for example. Note that a casting method in which a lead alloy or the like is poured into a mold to produce an arbitrary shape may be used.

The positive electrode plate has a ratio of the mass (a) of the positive electrode lattice body and the active material mass (b) of the positive electrode plate is 0.85 ≦ (a) / (b) ≦ 1.15,
The ratio of the average value (c) of the cross-sectional areas of the pair of vertical frame bones and all the longitudinal inner bones to the cross-sectional area (d) of the first horizontal frame bone is 0.015 ≦ (c) / (d) ≦ 0. 025,
The ratio of the sum (e) of the cross-sectional areas of the pair of longitudinal frame bones and all longitudinal internal bones to the cross-sectional area (d) of the first lateral frame bone is 0.15 ≦ (e) / (d) ≦ 0.25 The configuration is as follows.

  Here, the average value (c) of the cross-sectional areas of the pair of vertical frame bones and all the longitudinal internal bones and the sum (e) of the cross-sectional areas of the pair of vertical frame bones and all the longitudinal internal bones are one For vertical frame bones or longitudinal inner bones, measure the cross-sectional area at any three points in the vertical direction and calculate the average value. This average value is the value of the cross-sectional area of the single vertical frame bone or vertical inner bone. The value calculated as is used.

  According to the invention, the ratio of the mass (a) of the positive grid to the active material mass (b) of the positive plate is 0.85 ≦ (a) / (b) ≦ 1.15, preferably 0.9. Since the positive electrode plate is configured so that ≦ (a) / (b) ≦ 1.1, an increase in internal resistance and accumulation of lead sulfate accompanying corrosion of the positive electrode lattice body can be prevented, and a decrease in energy density and positive electrode The active material utilization rate becomes high, and deterioration of the active material due to deep discharge during power outages and maintenance inspections can be prevented, thereby improving the battery life performance.

  Here, the mass of the positive electrode lattice body is determined from the vertical frame bone, the horizontal frame bone, the vertical internal bone, and the horizontal internal bone.

  Therefore, the ratio of the average value (c) of the cross-sectional areas of the pair of vertical frame bones and all the longitudinal inner bones to the cross-sectional area (d) of the first horizontal frame bone is 0.015 ≦ (c) / (d) ≦ The positive electrode grid is configured to be 0.025. Thereby, it is possible to prevent an increase in internal resistance and accumulation of lead sulfate due to lattice corrosion of the longitudinal frame bone and the longitudinal inner bone, and it is possible to prevent a decrease in active material holding performance and a non-uniform current distribution.

  In addition, the ratio of the sum (e) of the cross-sectional areas of the pair of longitudinal frame bones and all longitudinal internal bones to the cross-sectional area (d) of the first lateral frame bone is 0.15 ≦ (e) / (d) ≦ The positive electrode grid is configured to be 0.25. As a result, the mass of the lateral frame bone and the transverse inner bone decreases with the increase in the mass of the longitudinal frame bone and the longitudinal inner bone, that is, the decrease in the number of transverse inner bones and the active material retention performance due to the strength reduction of the lateral frame bone and lateral inner bone. It is possible to prevent a decrease and a non-uniform current distribution.

  Moreover, if the positive grid is manufactured from a cold rolled sheet of lead alloy by punching, the positive grid is prevented from intergranular corrosion and the positive grid is uniformly corroded in layers, thus preventing a decrease in conductivity. Thus, the life performance can be improved.

  The present invention can be variously modified without departing from the spirit of the present invention.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited only to these examples.

<Test Example 1>
About the control valve type lead acid battery (Examples 1 to 15) according to the present invention and the control valve type lead acid battery (Comparative Examples 1 to 6) for comparison, high temperature accelerated float life test, grid elongation Evaluation and positive lead sulfate accumulation degree were evaluated.

<Test preparation>
In Examples 1 to 5, the value of positive electrode lattice mass (a) / active material mass (b) of the positive electrode plate is set to 0.85, 0.9, 1, as the number of the examples increases. 1.1, 1.15, and the average value of the cross-sectional area (c) of the pair of longitudinal frame bones and all the longitudinal inner bones / the cross-sectional area (d) of the first lateral frame bone is The positive electrode grid is configured so that the value of 0.02 is the sum of the cross-sectional areas of a pair of vertical frame bones and all vertical internal bones (e) / the cross-sectional area (d) of the first horizontal frame bone is 0.2 It is what.

  In Examples 6 to 10, the positive electrode lattice was configured so that the value of (c) / (d) was 0.015 and the value of (e) / (d) was 0.15, Others are the same as in the first to fifth embodiments.

  In Examples 11 to 15, the positive electrode grids are configured so that the value of (c) / (d) is 0.025 and the value of (e) / (d) is 0.25. Others are the same as those in the first to fifth embodiments.

  In Comparative Example 1 and Comparative Example 2, the value of (a) / (b) was changed to 0.8 and 1.2, respectively, and the value of (c) / (d) was 0.02 , (E) / (d) is configured so that the positive electrode lattice body has a value of 0.2.

  In Comparative Example 3 and Comparative Example 4, the positive electrode lattice was configured so that the value of (c) / (d) was 0.015 and the value of (e) / (d) was 0.15, Others are the same as Comparative Example 1 and Comparative Example 2.

  Comparative Example 5 and Comparative Example 6 are obtained by configuring the positive electrode grid so that the value of (c) / (d) is 0.025, and the value of (e) / (d) is 0.25. Others are the same as Comparative Example 1 and Comparative Example 2.

<High temperature accelerated float life test>
Battery capacity when float charging is performed under a constant voltage condition of 2.23 V / cell in an environment of a temperature of 60 ° C. and discharged every month at a temperature of 25 ° C. and 0.2 CA until reaching 1.75 V / cell. Measure. Then, after measuring the battery capacity, a charge recovery of 120% of the electric capacity is performed with respect to the discharge capacity, and the time when the battery capacity becomes 80% or less of the nominal capacity is measured as the lifetime. The value converted to ° C. was calculated as the life years.

<Evaluation of lattice elongation>
The battery that had undergone the high-temperature accelerated float life test was disassembled, and the length and width of the positive electrode plate were measured at both ends and the central portion, respectively, and the elongation percentage relative to the initial dimension was calculated. And the place where elongation rate is the highest among this measurement location was evaluated in the following five steps.
That is, 1 when the elongation is 2% or less compared to the positive electrode plate before performing the life test, 2 when the elongation is more than 2% to less than 3%, and the elongation is 3% or more. It was evaluated as 3 when it was less than 4%, 4 when the elongation was 4% or more and less than 5%, and 5 when the elongation was 5% or more.

<Evaluation of accumulation of positive lead sulfate>
After disassembling the battery after the high-temperature accelerated float life test, washing and drying the positive electrode plate, the positive electrode active material was sampled from the upper, middle and lower portions of the positive electrode plate in the vertical direction. The amount of sulfur contained was analyzed and converted to the amount of lead sulfate. And the average value of the analysis result of the amount of lead sulfate contained in the sample obtained from each location was evaluated in the following five stages.
That is, 1 when the average value is 5% or less, 2 when the average value is more than 5% and less than 10%, 3 when the average value is 10% or more and less than 15%, and the average value is When the average value was 15% to less than 20%, it was evaluated as 4, and when the average value was 20% or more, it was evaluated as 5.

<Test results>
These test results are shown in Table 1, Table 2, Table 3, and FIG. 3, FIG. 4, and FIG.

FIG. 3 shows the values of (a) / (b) on the vertical axis and the life years on the horizontal axis based on the results of Tables 1, 2, and 3. As shown in FIG. 3, Examples 1 to 15 which are the control valve type lead storage batteries of the present invention exceed the lifetime of 15 years, which is a target value represented by a dotted line, and particularly 0.9 ≦ (a). When /(b)≦1.11, a good result exceeding the lifetime of 20 years was obtained.
On the other hand, in Comparative Example 1 to Comparative Example 6, it can be seen that the life years that are target values are not exceeded.

  Here, based on the results of Table 1, Table 2, and Table 3, as shown in FIG. 4 in which the elongation of the positive electrode lattices of Comparative Examples 1 to 6 and Examples 1 to 15 was evaluated in five stages, a comparative example was obtained. 1, 3, and 5 show that the positive electrode lattice has a larger elongation than Examples 1 to 15 and Comparative Examples 2, 4, and 6.

  Moreover, as shown in FIG. 5 which evaluated the sulfuric acid accumulation | storage degree of the positive electrode grid body of Comparative Examples 1-6 and Examples 1-15 in five steps based on the result of Table 1, Table 2, Table 3. In Comparative Examples 1-6, it turns out that the accumulation | storage degree of lead sulfate is high compared with Examples 1-15.

  From the above, in Comparative Example 1, Comparative Example 3, and Comparative Example 5, since the value of (a) / (b) is small, the lattice strength of the positive electrode lattice body is reduced, and due to lattice elongation caused by lattice corrosion. It is considered that the lifetime has not exceeded the target value due to an increase in internal resistance due to a decrease in the adhesion between the active material and the grid, and accumulation of lead sulfate accompanying a decrease in the conductivity of the grid.

  In Comparative Example 2, Comparative Example 4, and Comparative Example 6, since the value of (a) / (b) is large, if the mass of the positive electrode plate is constant, the mass of the positive electrode active material filled in the positive electrode grid is The active material utilization rate decreased and the active material deterioration progressed by repeating the discharge in the capacity confirmation test. Therefore, it is considered that the life years did not exceed the target value.

  On the other hand, the control valve type lead acid batteries of the present invention of Examples 1 to 15 were 0.015 ≦ (c) / (d) ≦ 0.025, 0.15 ≦ (e) / (d) ≦ 0. 25, 0.85 ≦ (a) / (b) ≦ 1.15, more preferably 0.9 ≦ (a) / (b) ≦ 1.11, so that the elongation of the lattice and sulfuric acid It is thought that the target lifespan was achieved by suppressing lead accumulation.

<Test Example 2>
About the control valve type lead acid battery (Examples 16 to 24) according to the present invention and the control valve type lead acid battery for comparison (Comparative Examples 7 to 12), high temperature accelerated float life test, lattice elongation Evaluation and positive lead sulfate accumulation degree were evaluated.

<Test preparation>
In Examples 16 to 18, the value of (c) / (d) was changed to 0.015, 0.02, and 0.025 as the number of the examples increased. ) / (B) has a value of 1 and (e) / (d) has a value of 0.2 so that the positive electrode grid is configured.

  In Examples 19 to 21, the positive electrode lattice was configured so that the value of (a) / (b) was 0.85 and the value of (e) / (d) was 0.15. Others are the same as those in Examples 16 to 18.

  In Examples 22 to 24, the positive electrode lattice was configured so that the value of (a) / (b) was 1.15 and the value of (e) / (d) was 0.25. Others are the same as those in Examples 16 to 18.

  In Comparative Example 7 and Comparative Example 8, the value of (c) / (d) was changed to 0.01 and 0.03, respectively, and the value of (a) / (b) was 1, ) / (D) is configured so that the positive electrode lattice body has a value of 0.2.

  In Comparative Examples 9 and 10, the positive electrode grids are configured so that the value of (a) / (b) is 0.85 and the value of (e) / (d) is 0.15. Others are the same as Comparative Example 7 and Comparative Example 8.

  In Comparative Examples 11 and 12, the positive electrode lattice is configured such that the value of (a) / (b) is 1.15 and the value of (e) / (d) is 0.25. Others are the same as Comparative Example 7 and Comparative Example 8.

<Test results>
These test results are shown in Table 4, Table 5, Table 6, and FIG. 6, FIG. 7, and FIG.

FIG. 6 shows the values of (c) / (d) on the vertical axis and the life years on the horizontal axis based on the results of Tables 4, 5 and 6. As shown in FIG. 6, Examples 16 to 24, which are control valve type lead-acid batteries of the present invention, exceed the target life value of 15 years represented by a dotted line, and in particular, 0.02 ≦ (c) When /(d)≦0.025, a good result exceeding the lifetime of 20 years was obtained.
On the other hand, in Comparative Example 7 to Comparative Example 12, it can be seen that the life years that are target values are not exceeded.

  Here, based on the results of Tables 4, 5, and 6, as shown in FIG. 7 in which the elongation of the positive electrode lattices of Comparative Examples 7 to 12 and Examples 16 to 24 was evaluated in five stages, Comparative Example 7, 9 and 11, it can be seen that the elongation of the positive electrode lattice is larger than those of Examples 16 to 24 and Comparative Examples 8, 10, and 12.

  Moreover, as shown in FIG. 8 which evaluated the lead sulfate accumulation | storage degree of Comparative Examples 7-12 and Examples 16-24 based on the result of Table 4, 5 and 6 in five steps, Comparative Examples 7-12 Then, it turns out that lead sulfate accumulation degree is large compared with Examples 16-24.

  That is, in the comparative example 7, the comparative example 9, and the comparative example 11, since the value of (c) / (d) is small, the lattice strength of the longitudinal frame bone and the longitudinal inner bone is lowered and the lattice is easily affected by corrosion. It is thought that the life years decreased due to the increase in internal resistance accompanying the growth of lead and the accumulation of lead sulfate due to the decrease in conductivity.

  In Comparative Example 8, Comparative Example 10, and Comparative Example 12, since the value of (c) / (d) is large, when (a) / (b) and (e) / (d) are constant, a vertical frame Since the number of longitudinal inner bones arranged between the bones and the longitudinal frame bones is reduced and the current distribution is not uniform, the accumulation degree of lead sulfate is increased as compared with Examples 16 to 24, and the lifespan is increased. The number of years is thought to have declined.

  On the other hand, the control valve type lead acid batteries of Examples 16 to 24 of the present invention satisfy 0.85 ≦ (a) / (b) ≦ 1.15, 0.15 ≦ (e) / (d) ≦ 0.25. Originally, by setting 0.015 ≦ (c) / (d) ≦ 0.025, more preferably 0.02 ≦ (c) / (d) ≦ 0.025, the longitudinal inner bone and the vertical frame The increase in internal resistance due to the growth of the bone lattice, the decrease in conductivity, and the accumulation of lead sulfate due to non-uniform current distribution were suppressed, so it is considered that the target lifespan was exceeded. .

<Test Example 3>
About the control valve type lead acid battery (Examples 25 to 33) according to the present invention and the control valve type lead acid battery for comparison (Comparative Examples 13 to 18), high temperature accelerated float life test, evaluation of lattice elongation, And the positive electrode lead sulfate accumulation degree was evaluated.

<Test preparation>
In Examples 25 to 27, the value of (e) / (d) was changed to 0.15, 0.2, and 0.25 as the number of the examples increased, and (a ) / (B) is set to 1 and (c) / (d) is set to 0.02.

  In Examples 28 to 30, the positive electrode lattices were configured so that the value of (a) / (b) was 0.85 and the value of (c) / (d) was 0.015. Others are the same as those of Example 25 to Example 27.

  In Examples 31 to 33, the positive electrode grids are configured so that the value of (a) / (b) is 1.15 and the value of (c) / (d) is 0.025. Others are the same as those of Example 25 to Example 27.

  In Comparative Example 13 and Comparative Example 14, the value of (e) / (d) was changed to 0.1 and 0.3, respectively, and the value of (a) / (b) was 1, ) / (D) is configured so that the positive electrode lattice body has a value of 0.02.

  In Comparative Examples 15 and 16, the positive electrode lattice was configured such that the value of (a) / (b) was 0.85 and the value of (c) / (d) was 0.015. Others are the same as Comparative Example 13 and Comparative Example 14.

  In Comparative Examples 17 and 18, the positive electrode lattice was configured so that the value of (a) / (b) was 1.15 and the value of (c) / (d) was 0.025. Others are the same as Comparative Example 13 and Comparative Example 14.

<Test results>
These test results are shown in Table 7, Table 8, Table 9, and FIG. 9, FIG. 10, and FIG.

FIG. 9 shows the values of (e) / (d) on the vertical axis and the life years on the horizontal axis based on the results of Tables 7, 8, and 9. As shown in FIG. 9, Example 25-Example 33 which is a control valve type lead acid battery of the present invention exceeds the target life value of 15 years represented by a dotted line, and particularly 0.18 ≦ (e) / In (d) ≦ 0.25, good results exceeding the life of 20 years were obtained.
On the other hand, in Comparative Example 13 to Comparative Example 18, it can be seen that the life years that are target values are not exceeded.

  Here, based on the results of Tables 7, 8, and 9, as shown in FIG. 10 in which the elongation of the positive electrode lattices of Comparative Examples 13 to 18 and Examples 25 to 33 was evaluated in five stages, Comparative Examples 13 to 18 shows that the elongation of the positive electrode lattice is larger than those of Examples 16 to 24.

  Moreover, as shown in FIG. 11 which evaluated the lead sulfate accumulation | storage degree of Comparative Examples 13-18 and Examples 25-33 in five steps based on the result of Table 7, 8, and 9, Comparative Examples 13-18 Then, it turns out that lead sulfate accumulation degree is large compared with Examples 25-33.

  That is, in Comparative Example 13, Comparative Example 15, and Comparative Example 17, since the value of (e) / (d) is small, when (a) / (b) and (c) / (d) are constant, It is considered that the number of bones is reduced and the current distribution becomes non-uniform, leading to an increase in lead sulfate accumulation and a decrease in the lifespan compared to Examples 25-33.

  In Comparative Example 14, Comparative Example 16, and Comparative Example 18, since the value of (e) / (d) is large, when (a) / (b) and (c) / (d) are constant, the horizontal frame The strength of the bones and transverse inner bones is reduced, the number of transverse inner bones is reduced, the active material retention performance is reduced, and the current distribution is uneven. Compared with Examples 25 to 33, lattice corrosion is caused as described above. It is thought that the number of years of life decreased due to an increase in the growth caused by the accumulation of lead sulfate and lead sulfate.

  On the other hand, the control valve type lead acid batteries of Examples 25 to 33 of the present invention have 0.85 ≦ (a) / (b) ≦ 1.15, 0.015 ≦ (c) / (d) ≦ 0. 025, 0.15 ≦ (e) / (d) ≦ 0.25, more preferably 0.18 ≦ (e) / (d) ≦ 0.25. It is considered that the life years, which is the target value, could be exceeded because the lattice elongation due to the non-uniform distribution and the strength reduction of the transverse bone could be suppressed.

From the above, in the control valve type lead storage battery of the present invention,
0.015 ≦ (c) / (d) ≦ 0.025,
By configuring the positive electrode current collector so as to be, it is possible to prevent a decrease in the lattice strength of the longitudinal frame bone or the longitudinal inner bone and a decrease in the active material holding performance due to a decrease in the number of longitudinal inner bones. Current distribution can be made uniform. For this reason, the control valve type lead-acid battery with excellent life performance can be obtained without making the progress of corrosion of the current collector uniform, suppressing the increase of internal resistance and lead sulfate accumulation due to lattice corrosion, and reducing the energy density. Can be configured.

Moreover, in the control valve type lead acid battery of the present invention,
0.015 ≦ (c) / (d) ≦ 0.025,
0.15 ≦ (e) / (d) ≦ 0.25,
By configuring the positive electrode current collector so as to prevent the decrease in the lattice strength of the longitudinal frame bone or the longitudinal inner bone and the decrease in the active material holding performance due to the decrease in the number of longitudinal inner bones, The current distribution of the current collector can be made more uniform by preventing the decrease in the active material holding performance due to the decrease or the decrease in the thickness of the lateral frame bone and the lateral inner bone. Therefore, the progress of corrosion of the current collector is made more uniform, increase in internal resistance due to lattice corrosion and accumulation of lead sulfate are suppressed, and control valve type lead-acid battery with excellent life performance without reducing energy density Can be configured.

Furthermore, in the control valve type lead acid battery of the present invention,
0.85 ≦ (a) / (b) ≦ 1.15,
0.015 ≦ (c) / (d) ≦ 0.025,
0.15 ≦ (e) / (d) ≦ 0.25,
By configuring the positive electrode current collector such that the mass ratio of the positive electrode current collector to the active material mass can be optimized. For this reason, control valve-type lead-acid batteries that have excellent life performance and prevent deterioration of active materials due to deep discharge during power outages and maintenance inspections are suppressed by suppressing internal resistance increase and lead sulfate accumulation due to lattice corrosion. can do.

DESCRIPTION OF SYMBOLS 1 ... Positive electrode grid body 2 ... Frame 2a ... First horizontal frame bone 2b ... Second horizontal frame bone 2c ... Vertical frame bone 3 ... Inner bone 3a ... Longitudinal inner bone 3b ... Horizontal inner bone 4 ... Current collecting ear 5 ... Foot

Claims (2)

A control valve type lead acid battery comprising a paste type positive electrode plate having a positive electrode current collector and a positive electrode active material,
The positive electrode current collector is
A first horizontal frame bone provided with a current collecting ear, a second horizontal frame bone arranged in parallel with the first horizontal frame bone, and both ends of the first horizontal frame bone and the second horizontal frame bone A frame consisting of a pair of vertical frame bones connecting
A plurality of longitudinal inner bones extending from the first lateral frame bone toward one or both of the second lateral frame bone and the longitudinal frame bone;
And a plurality of transverse profile bone arranged to connect between the pair of vertical frames bone,
The ratio of the sum (e) of the cross-sectional areas of the pair of longitudinal frame bones and all the longitudinal inner bones to the transverse area (d) of the first lateral frame bone is 0.15 ≦ (e) / (d) ≦ 0.25,
A ratio of an average value (c) of the cross-sectional areas of the pair of longitudinal frame bones and all longitudinal internal bones to a cross-sectional area (d) of the first lateral frame bone is 0.015 ≦ (c) / (d ) ≦ 0.025,
The ratio of the mass (a) of the positive electrode current collector to the active material mass (b) of the positive electrode plate satisfies 0.85 ≦ (a) / (b) ≦ 1.15. Lead acid battery.   The control valve type lead-acid battery according to claim 1, wherein the positive electrode current collector is stamped from a cold rolled sheet of a lead alloy.