JP7079831B2 - Liquid lead-acid battery - Google Patents

Description

The present invention relates to a liquid lead-acid battery.

With the seriousness of environmental problems in recent years, emission regulations for automobiles and the like have become stricter worldwide. To comply with this regulation, automobile manufacturers have developed various environmental technologies. As the environmental technology, an idling stop system (Idling Stop System, hereinafter referred to as "ISS") that temporarily stops the engine when the vehicle is stopped is known. An internal combustion vehicle equipped with an ISS (hereinafter referred to as an "ISS vehicle") can suppress fuel consumption due to idling when the vehicle is stopped at a traffic light or the like, so that fuel efficiency can be improved and the amount of exhaust gas can be reduced.

Liquid lead-acid batteries for ISS vehicles are charged and discharged in a partially charged state (Partial State of Charge, also referred to as "PSOC"), which is not a fully charged state because the engine frequently stops and starts. Is repeated. Liquid lead-acid batteries for ISS vehicles are used in a partially charged state with a charge rate of 80% to 90% because if the charge rate is higher than 90%, the charge acceptance becomes low and the utilization efficiency of regenerative energy decreases. It is said that it is desirable.

Stratification of the electrolytic solution, which is one of the deterioration factors of the liquid lead-acid battery, is a phenomenon in which the concentration difference of the electrolytic solution occurs between the upper part and the lower part in the battery case, and the partially charged state of 80% to 90% is maintained. It tends to occur when using a lead-acid battery by controlling it so as to. In the upper part where the concentration of the electrolytic solution is low, dendritic crystals (dendrites) of metallic lead are deposited and grown on the surface of the negative electrode plate, and an internal short circuit is likely to occur. On the other hand, in the lower part where the concentration of the electrolytic solution is high, the high concentration electrolytic solution tends to cause sulfation in which the non-conductor lead sulfate is enlarged on the surface of the negative electrode plate.

When sulfation occurs, the release of sulfuric acid from the negative electrode active material is suppressed, so that the charge acceptability of the lower part of the negative electrode plate is lowered. When the charge acceptability of the lower part of the negative electrode plate is lowered, the charge / discharge reaction mainly proceeds in the upper part of the negative electrode plate. Corrosion of the substrate made of lead alloy progresses, and the lead-acid battery reaches the end of its life at an early stage.

As a technique for suppressing the stratification of the electrolytic solution, for example, the technique described in Patent Document 1 can be mentioned.
In Patent Document 1, in order to more effectively utilize the stirring action of the electrolytic solution by the gas generated during charging and suppress stratification, the upper part of the accommodation space and the accommodation space for accommodating the electrode plates are separately described. It is described that a communication flow path that communicates with the lower part is provided. As a result, during charging, an upward flow of the electrolytic solution due to the rise of the gas generated by the electrode plates is generated in the accommodation space, and a corresponding downward flow is generated in the communication flow path. Therefore, it is described that the effective convection of the electrolytic solution in the electric tank enhances the stirring action of the electrolytic solution and suppresses stratification.

On the other hand, the liquid lead-acid battery includes a positive electrode plate in which a positive electrode mixture is held in a positive electrode current collector and a negative electrode plate in which a negative electrode mixture is held in a negative electrode current collector. The positive electrode current collector and the negative electrode current collector have a rectangular grid-like substrate and continuous ears on the grid-like substrate, as shown in FIG. 1 of Patent Document 2, for example. The grid-like substrate has an upper bone along one side of a rectangle forming the grid-like substrate, and a plurality of middle bones connected to the upper bone and located below the upper bone. The ear protrudes upward from a position offset from the center of one side of the upper bone to one side.
However, Patent Documents 1 and 2 do not describe the relationship between the potential distribution of the electrode plate during charging and discharging and the stirring action of the electrolytic solution.

Japanese Unexamined Patent Publication No. 2015-176659 Japanese Patent No. 3452171

An object of the present invention is to provide a novel liquid lead-acid battery in which stratification of an electrolytic solution is suppressed by the stirring action of a gas generated during charging even when the battery is used in a partially charged state.

In order to solve the above problems, it is a gist that the liquid lead-acid battery of the first aspect of the present invention has the following configurations (1) to (4).
(1) A group of electrode plates in which a positive electrode plate having a positive electrode current collector and a positive electrode mixture and a negative electrode plate having a negative electrode current collector and a negative electrode mixture are alternately laminated via a separator, and an electrolytic solution. It is a liquid lead-acid battery equipped with dilute sulfuric acid. The positive electrode current collector has a rectangular grid-like substrate and a continuous ear on the grid-like substrate, and the positive electrode mixture is held on the grid-like substrate. The grid-like substrate has an upper bone along one side of a rectangle forming the grid-like substrate, and a plurality of middle bones connected to the upper bone and located below the upper bone. The ear protrudes upward from a position offset from the center of one side of the upper bone to one side.

(2) Of the divisions formed by cutting the positive current collector along the diagonal line passing through the corner on one side of the rectangle forming the grid-like substrate, the division in which the ear exists is the upper bone of the ear. It is divided into a first part and a second part by a reference line K passing through the center point P on the boundary line and perpendicular to the upper bone, and the first part has a larger area than the second part.

(3) In the coordinate plane where both the x-axis and the y-axis are linear scales, the y-coordinates are the resistance values Rn between each cut surface Cn of the plurality of central bones and the center point P in the first part. All plots made with each distance Xn between the center point of each cut plane Cn and the center point P as the x coordinate can be approximated to two straight lines having different slopes with x = H as the intersection, and x <H. When the ratio A / B by the average value A of each resistance value Rn at the distance Xn and the average value B of each resistance value Rn at each distance Xn where x ≧ H is 0.35 or more and 0.55 or less. be.
The above-mentioned "approximate to a straight line" means that the absolute value | ρ | of the correlation coefficient ρ when a plurality of plots are linearly regressed by the least squares method is 0.90 or more. Further, "two straight lines having different slopes" means that the ratio (a1 / a2) of the slopes a1 and a2 (a1> a2) of the two straight lines is 1.3 or more.

(4) The electrolytic solution contains aluminum ions, and the concentration of aluminum ions in the electrolytic solution is 0.01 mol / L or more and 0.30 mol / L or less. It should be noted that this value is a value measured by analyzing an electrolytic solution collected in a state where the charge rate of the liquid lead-acid battery is 100%.

According to the present invention, it is possible to provide a novel liquid lead-acid battery in which stratification of an electrolytic solution is suppressed by the stirring action of a gas generated during charging even when the battery is used in a partially charged state.

It is a front view which shows the positive electrode current collector which constitutes the positive electrode plate which the liquid type lead storage battery of 1st Embodiment has. FIG. 3 is a front view showing a split body having ears, which is formed by cutting a positive electrode current collector of FIG. 1 along a diagonal line passing through a corner on one side of a rectangle forming a grid-like substrate. It is a front view which shows the positive electrode current collector which constitutes the positive electrode plate which the liquid type lead storage battery of the 2nd Embodiment has. FIG. 3 is a front view showing a split body having ears, which is formed by cutting a positive electrode current collector of FIG. 3 along a diagonal line passing through a corner on one side of a rectangle forming a grid-like substrate. The resistance value Rn between each cut surface Cn of the plurality of middle bones and the center point P of the ear in the first part of the positive electrode current collector obtained for the sample No. 1 prepared in the example. , Is a graph showing the relationship between each distance Xn between the center point of each cut surface Cn and the center point P of the ear. The resistance value Rn between each cut surface Cn of the plurality of middle bones and the center point P of the ear in the first part of the positive electrode current collector obtained for the sample No. 2 prepared in the example. , Is a graph showing the relationship between each distance Xn between the center point of each cut surface Cn and the center point P of the ear. The resistance value Rn between each cut surface Cn of the plurality of middle bones and the center point P of the ear in the first part of the positive electrode current collector obtained for the sample No. 3 prepared in the example. , Is a graph showing the relationship between each distance Xn between the center point of each cut surface Cn and the center point P of the ear. The resistance value Rn between each cut surface Cn of the plurality of middle bones and the center point P of the ear in the first part of the positive current collector obtained for the sample No. 4 prepared in the example. , Is a graph showing the relationship between each distance Xn between the center point of each cut surface Cn and the center point P of the ear. The resistance value Rn between each cut surface Cn of the plurality of middle bones and the center point P of the ear in the first part of the positive electrode current collector obtained for the sample No. 5 prepared in the example. , Is a graph showing the relationship between each distance Xn between the center point of each cut surface Cn and the center point P of the ear. With respect to each resistance value Rn between each cut surface Cn of a plurality of middle bones and the center point P of the ear in the first part of the positive current collector obtained for sample No. 6 prepared in the example. , Is a graph showing the relationship between each distance Xn between the center point of each cut surface Cn and the center point P of the ear. With respect to each resistance value Rn between each cut surface Cn of a plurality of middle bones and the center point P of the ear in the first part of the positive current collector obtained for sample No. 7 prepared in the example. , Is a graph showing the relationship between each distance Xn between the center point of each cut surface Cn and the center point P of the ear. It is a graph which shows the charge / discharge pattern of one cycle of the life test performed in an Example. It is a graph which shows the relationship of the cycle number with respect to the concentration of the aluminum ion in the electrolytic solution about the life test of the sample No. 1 to No. 49 prepared in an Example.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the embodiments shown below. In the embodiments shown below, technically preferable limitations are made for carrying out the present invention, but these limitations are not essential requirements of the present invention.

[Structure of liquid lead-acid batteries of the first embodiment and the second embodiment]
The liquid lead-acid batteries of the first embodiment and the second embodiment have a monoblock type battery, a lid, and a group of six plates. The battery case is divided into six cell chambers by a partition wall. The six cell chambers are arranged along the longitudinal direction of the battery case. One electrode plate group is arranged in each cell chamber. An electrolytic solution is injected into each cell chamber.
Each electrode plate group has a laminate composed of a plurality of alternately arranged positive electrode plates and negative electrode plates, and separators arranged between the positive electrode plates and the negative electrode plates.

The positive electrode plate has a positive electrode current collector and a positive electrode mixture (a mixture containing a positive electrode active material). The positive electrode current collector has a rectangular grid-like substrate and a continuous ear on the grid-like substrate, and the positive electrode mixture is held on the grid-like substrate. The negative electrode plate has a negative electrode current collector and a negative electrode mixture (a mixture containing a negative electrode active material). The negative electrode current collector has a rectangular grid-like substrate and a continuous ear on the grid-like substrate, and the negative electrode mixture is held on the grid-like substrate. A plurality of positive electrode plates and negative electrode plates are alternately arranged via a separator. The number M _n of the negative electrode plates constituting the laminated body is one more than the number M _p of the positive electrode plates. The number of negative electrode plates Mn may be one less than the number of positive electrode plates Mp, or may be the same.

The negative electrode plate is housed in a bag-shaped separator. Then, by alternately stacking the bag-shaped separator containing the negative electrode plate and the positive electrode plate, the separator is arranged between the positive electrode plate and the negative electrode plate. The positive electrode plate may be stored in the bag-shaped separator and alternately overlapped with the negative electrode plate.
Further, each electrode plate group includes a positive electrode strap and a negative electrode strap that connect a plurality of positive electrode plates and negative electrode plates constituting the laminate at different positions in the width direction, and a positive electrode intermediate pole column that rises from the positive electrode strap and the negative electrode strap, respectively. It also has a negative electrode intermediate pole column, a positive electrode pole pillar and a negative electrode pole pillar as external terminals.

The positive electrode strap and the negative electrode strap connect and fix the ears of the plurality of positive electrode plates and the negative electrode plates, respectively. The positive electrode intermediate pole columns and the negative electrode intermediate pole columns of the adjacent cell chambers are resistance welded to each other, and the adjacent cells are electrically connected in series.
The positive electrode pole column and the negative electrode pole pillar are formed on the positive electrode strap and the negative electrode strap arranged in the cell chambers at both ends in the cell arrangement direction via a small piece portion.
As the electrolytic solution, dilute sulfuric acid having a predetermined specific gravity is used. Aluminum ions are contained in the electrolytic solution. The concentration of aluminum ions is 0.01 mol / L or more and 0.30 mol / L or less with respect to the electrolytic solution. This value is a value measured by analyzing an electrolytic solution collected in a state where the charge rate of the liquid lead-acid battery is 100%.

[Positive current collector of the first embodiment]
As shown in FIG. 1, the positive electrode current collector 1 of the first embodiment has a rectangular grid-like substrate 11 and ears 12 continuous to the grid-like substrate 11, and a positive electrode mixture is held on the grid-like substrate 11. Has been done. The grid-like substrate 11 has an upper bone 111 along one side of a rectangle forming the grid-like substrate 11, and a plurality of middle bones 112 connected to the upper bone 111 and located below the upper bone 111. The ear 12 projects upward from a position shifted to one side (right side in FIG. 1) from the center of one side of the upper bone 111.

FIG. 2 shows the divided bodies having ears among the divided bodies generated by cutting the positive electrode current collector 1 along the diagonal line D passing through the right (one side) corner of the rectangle forming the grid-like substrate 11. show. The divided body 2 is divided into a first portion 21 and a second portion 22 by a reference line K passing through the center point P on the boundary line L with the upper bone 111 of the ear 12 and perpendicular to the upper bone 111. The first portion 21 has a larger area than the second portion 22.

The first portion 21 has a cut surface of 13 middle bones 112. On the coordinate plane where both the x-axis and y-axis are linear scales, the resistance values R1 to R13 between the 13 cut planes C1 to C13 and the center point P are the y coordinates, and the center of each cut plane C1 to C13. When the distances X1 to X13 between the point and the center point P are plotted as x-coordinates, all the plots can be approximated to two straight lines having different slopes with x = H as the intersection. The ratio A / B by the average value A of each resistance value Rn at each distance Xn where x <H and the average value B of each resistance value Rn at each distance Xn where x ≧ H is 0.35. It is 0.55 or less.

For example, when the dimension S1 = 115.0 mm, the dimension S2 = 110.0 mm, the dimension S3 = 100.0 mm, and the dimension S4 = 45.0 mm, the thickness of the middle bone 112 (cross-sectional area perpendicular to the longitudinal direction) is as a whole. It is the same, and it is 0.85 mm ² or more and 1.00 mm ² or less.
The positive electrode current collector 1 can be obtained by a usual method such as a punching method, an expanding method, and a gravity casting method.

[Positive current collector of the second embodiment]
As shown in FIG. 3, the positive electrode current collector 1A of the second embodiment has a rectangular grid-like substrate 11A and an ear 12 continuous to the grid-like substrate 11A, and the positive electrode mixture is held by the grid-like substrate 11A. Has been done. The grid-like substrate 11A has an upper bone 111 along one side of a rectangle forming the grid-like substrate 11A, and a plurality of middle bones connected to the upper bone 111 and located below the upper bone 111. The thickness of the middle bone changes at the intermediate position in the vertical direction, and the middle bone 112a above the intermediate position (upper bone 111 side) is thinner than the thickness of the middle bone 112b below the intermediate position.
The ear 12 projects upward from a position shifted to one side (right side in FIG. 3) from the center of one side of the upper bone 111.

FIG. 4 shows the divided bodies having ears among the divided bodies generated by cutting the positive electrode current collector 1A along the diagonal line D passing through the right (one side) corner of the rectangle forming the grid substrate 11A. show. The divided body 2A is divided into a first portion 21A and a second portion 22A by a reference line K passing through the center point P on the boundary line L with the upper bone 111 of the ear 12 and perpendicular to the upper bone 111. The first portion 21A has a larger area than the second portion 22A.

The first portion 21A has 13 cut surfaces of the middle bone. The cut surfaces C1 to C5 are the cut surfaces of the middle bone 112a, and the cut surfaces C6 to C13 are the cut surfaces of the middle bone 112b. On the coordinate plane where both the x-axis and y-axis are linear scales, the resistance values R1 to R13 between the 13 cut planes C1 to C13 and the center point P are the y coordinates, and the center of each cut plane C1 to C13. When the distances X1 to X13 between the point and the center point P are plotted as x-coordinates, all the plots can be approximated to two straight lines having different slopes with x = H as the intersection. The ratio A / B by the average value A of each resistance value Rn at each distance Xn where x <H and the average value B of each resistance value Rn at each distance Xn where x ≧ H is 0.35. It is 0.55 or less.

For example, when the dimension S1 = 115.0 mm, the dimension S2 = 110.0 mm, the dimension S3 = 100.0 mm, and the dimension S4 = 45.0 mm, the thickness of the middle bone 112a (cross-sectional area perpendicular to the longitudinal direction) is 0. The thickness of the middle bone 112b is 1.15 mm ² or more and 1.25 mm ² or less, and is 75 mm ² or more and 0.85 mm ² or less.
The positive electrode current collector 1A can be obtained by a usual method such as a punching method, an expanding method, and a gravity casting method.

[Concentration of aluminum ions in electrolyte]
As described above, in the liquid lead-acid batteries of the first embodiment and the second embodiment, the electrolytic solution contains aluminum ions, and the concentration of aluminum ions in the electrolytic solution is 0.01 mol / L or more and 0.30 mol / L. It is as follows.
The concentration of aluminum ions in the electrolytic solution can be adjusted by, for example, the following method. When the electrolytic solution is adjusted to have a desired specific gravity and injected into a liquid lead-acid battery, aluminum sulfate powder is mixed and dissolved in the electrolytic solution in advance, and the concentration of aluminum ions in the electrolytic solution is 0. Adjust so that it is 01 mol / L or more and 0.30 mol / L or less.
Further, the concentration of aluminum ions in the electrolytic solution can be measured by, for example, a high frequency inductively coupled plasma (ICP) emission spectrometry method.

[Action, effect]
The smaller the ratio A / B of the positive electrode current collector of the liquid lead-acid battery, the easier it is for the lower part of the positive electrode plate to polarize than the upper part during charging. Even so, the stirring action of the electrolytic solution can be obtained. However, when the ratio A / B is less than 0.35, the resistance value of the path from the lower part to the ear of the positive electrode collector is significantly larger than the resistance value of the path from the upper part to the ear, so that the resistance value at the lower part of the positive electrode plate is significantly higher. The charge / discharge reaction is less likely to proceed. Therefore, the amount of gas generated from the lower part is insufficient to obtain the electrolytic solution stirring action in the partially charged state.
In a liquid lead-acid battery having a positive electrode current collector ratio A / B of more than 0.55, the charge / discharge reaction is less likely to proceed in the entire positive electrode plate, so that the amount of gas generated is the electrolytic solution stirring action in a partially charged state. Not enough to get.

When the ratio A / B of the positive electrode current collector 1 of the first embodiment and the positive electrode current collector 1A of the second embodiment is in the range of 0.35 or more and 0.55 or less, the first embodiment and the second embodiment In the liquid lead-acid battery of the form, since the charge / discharge reaction is uniformly performed in the entire positive electrode plate, the amount of gas generated from the lower part is sufficient to obtain the stirring action of the electrolytic solution in the partially charged state. .. Therefore, according to the liquid lead-acid batteries of the first embodiment and the second embodiment, the stratification of the electrolytic solution is suppressed when the lead-acid battery is used in a partially charged state, and the life can be extended.
Further, in the liquid lead-acid batteries of the first embodiment and the second embodiment, the concentration of aluminum ions in the electrolytic solution is 0.01 mol / L or more and 0.30 mol / L or less, so that the stratification of the electrolytic solution is suppressed. It is possible to further enhance the effect and obtain a higher life improving effect.

In a liquid lead-acid battery, water in the electrolytic solution is electrolyzed during charging to generate gas. In a liquid lead-acid battery in which the concentration of aluminum ions in the electrolytic solution is 0 even if the ratio A / B of the positive electrode current collector satisfies 0.35 ≦ A / B ≦ 0.55, it is 0.01 mol / L or more. Compared with the one having a concentration of 0.30 mol / L or less, the effect of improving the charge acceptability is smaller in the lower part of the positive electrode plate, so that the effect of suppressing the stratification of the electrolytic solution is reduced.
Further, in a liquid lead-acid battery in which the concentration of aluminum ions in the electrolytic solution is 0.40 mol / L even if the ratio A / B of the positive electrode current collector satisfies 0.35 ≦ A / B ≦ 0.55. Compared with those having a concentration of 0.01 mol / L or more and 0.30 mol / L or less, the viscosity of the electrolytic solution increases and the gas is less likely to be discharged from the electrode plate group to the outside. Along with this, the stratification suppressing effect is reduced, so that a higher life improving effect cannot be obtained.

[Method]
As a second aspect of the present invention, there is a method of designing a positive electrode current collector constituting a positive electrode plate (after chemical conversion) of a liquid lead-acid battery. This design method has the following configurations (a) to (c).
(a) The positive current collector has a rectangular grid-like substrate and continuous ears on the grid-like substrate, and the positive electrode mixture is held on the grid-like substrate, and the grid-like substrate has an upper bone along one side of the rectangle. And a plurality of middle bones connected to the upper bone and located below the upper bone, and the ear protrudes upward from a position deviated from the center of one side of the upper bone to one side.
(b) Of the divisions formed by cutting the positive current collector along the diagonal line passing through the corner on one side of the rectangle, the divisions in which the ears are present are the center points P on the boundary line with the upper bone of the ears. It is divided into the first part and the second part by the reference line perpendicular to the upper bone of the street.
(c) On a coordinate plane in which both the x-axis and the y-axis are linear scales, between each cut surface Cn of a plurality of middle bones and the center point P in the first portion having a larger area than the second portion. All plots made with each resistance value Rn of the y-coordinate and each distance Xn between the center point and the center point P of each cut surface Cn as the x-coordinate are two straight lines having different slopes with x = H as the intersection. The ratio A / B is calculated by the average value A of each resistance value Rn at each distance Xn where x <H and the average value B of each resistance value Rn at each distance Xn where x ≧ H. It should be 0.35 or more and 0.55 or less.

[Making test batteries]
Sample No. 1 to No. 49 liquid lead-acid batteries were produced as liquid lead-acid batteries having the same structure as the liquid lead-acid batteries of the embodiment.
The liquid lead-acid batteries of Samples No. 1 to No. 49 are D23 type liquid lead-acid batteries for ISS vehicles. Samples No. 1 to No. 7 differ in the shape of the grid-like substrate of the positive electrode current collector, but all other points have the same configuration.
Samples No. 8 to No. 13 have the same shape as the sample No. 1 in the shape of the grid-like substrate of the positive electrode current collector. Samples No. 1 and No. 8 to No. 13 have different concentrations of aluminum ions in the electrolytic solution, but all other points have the same configuration.

Samples No. 14 to No. 19 have the same shape as the sample No. 2 in the shape of the grid-like substrate of the positive electrode current collector. Samples No. 2 and No. 14 to No. 19 have different concentrations of aluminum ions in the electrolytic solution, but all other points have the same configuration.
Samples No. 20 to No. 25 have the same shape of the grid-like substrate of the positive electrode current collector as that of sample No. 3. Samples No. 3 and No. 20 to No. 25 have different concentrations of aluminum ions in the electrolytic solution, but all other points have the same configuration.
Samples No. 26 to No. 31 have the same shape of the grid-like substrate of the positive electrode current collector as sample No. 4. Samples No. 4 and No. 26 to No. 31 have different concentrations of aluminum ions in the electrolytic solution, but all other points have the same configuration.

Samples No. 32 to No. 37 have the same shape of the grid-like substrate of the positive electrode current collector as that of sample No. 5. Samples No. 5 and No. 32 to No. 37 have different concentrations of aluminum ions in the electrolytic solution, but all other points have the same configuration.
Samples No. 38 to No. 43 have the same shape of the grid-like substrate of the positive electrode current collector as that of sample No. 6. Samples No. 5 and No. 38 to No. 43 have different concentrations of aluminum ions in the electrolytic solution, but all other points have the same configuration.
Samples No. 44 to No. 49 have the same shape of the grid-like substrate of the positive electrode current collector as that of sample No. 7. Samples No. 7 and No. 44 to No. 49 have different concentrations of aluminum ions in the electrolytic solution, but all other points have the same configuration.

<Sample No.1 and Samples No.8 to No.13>
The liquid lead-acid batteries of Sample No. 1 and Samples No. 8 to No. 13 have a positive electrode current collector 1 having the shape shown in FIG. 1, and have dimensions S1 = 115.0 mm, dimensions S2 = 110.0 mm, and dimensions. S3 = 100.0 mm, dimension S4 = 45.0 mm, and the thickness of the middle bone 112 (cross-sectional area perpendicular to the longitudinal direction) is 1.05 mm ² .
First, a punching process for a strip-shaped lead alloy sheet (size corresponding to a plurality of positive electrode current collectors 1), a filling step for a positive electrode active material paste (a kneaded product containing a positive electrode mixture) on a lattice-shaped substrate 11. By performing the preheating drying step, the aging drying step, and the cutting step, a positive electrode plate before chemical conversion having the positive electrode current collector 1 of FIG. 1 was produced. Each step was carried out by a usual method.

The negative electrode plate has a negative electrode collector having the same shape as the positive electrode collector 1 shown in FIG. 1, but in the negative electrode collector, the size S1 = 114.0 mm, the size S2 = 108.0 mm, and the size S3 = 100. It is 0 mm, the dimension S4 = 45.0 mm, and the thickness of the middle bone 112 (cross-sectional area perpendicular to the longitudinal direction) is 0.75 mm ² . The negative electrode plate before chemical conversion was also produced by performing each step in the same manner as the positive electrode plate by a usual method.
Next, seven sheets of the obtained pre-chemical electrode plates put in a polyethylene bag-shaped separator and six sheets of the obtained pre-chemical positive electrode plates were alternately laminated to obtain a laminate. Next, a group of electrode plates was obtained by forming a strap, an intermediate electrode column, and a terminal electrode column on the positive electrode plate and the negative electrode plate of each laminate using a COS (cast-on-strap) type casting apparatus.

The electrolytic solution was prepared by a usual method in which water was added to dilute sulfuric acid to adjust the specific gravity. At that time, aluminum sulfate powder was added as an additive at a predetermined ratio to the electrolytic solution. As a result, the concentration of aluminum ions in the electrolytic solution was 0.10 mol / L for No. 1, 0 mol / L for No. 8, 0.01 mol / L for No. 9, and 0.05 mol / L for No. 10. No. 11 was 0.20 mol / L, No. 12 was 0.30 mol / L, and No. 13 was 0.40 mol / L.

Six of the electrode plates are prepared and placed in each cell chamber of the battery chamber, resistance welding of intermediate pole columns between adjacent cell chambers, heat welding of the battery tank and lid, and injection holes into each cell chamber. A liquid lead-acid battery for a D23 type ISS vehicle was assembled by performing normal steps such as injecting an electrolytic solution and closing the injection hole. Then, by carrying out the electric tank chemical formation by a usual method, the specific density after the electric tank chemical formation was set to 1.285 (20 ° C. conversion value). In this way, sample No. 1 and samples No. 8 to No. 13 liquid lead-acid batteries were obtained.

<Sample No. 2 and Samples No. 14 to No. 19>
The liquid lead-acid batteries of Sample No. 2 and Samples No. 14 to No. 19 have the positive electrode current collector 1 having the shape shown in FIG. 1, and the thickness of the middle bone 112 (cross-sectional area perpendicular to the longitudinal direction). Is 1.00 mm ² . Other than that, sample No. 2 is the same as sample No. 1, sample No. 14 is the same as sample No. 8, sample No. 15 is the same as sample No. 9, and the sample. No. 16 is the same as sample No. 10, sample No. 17 is the same as sample No. 11, sample No. 18 is the same as sample No. 12, and sample No. 19 is sample No. 13. Is the same as.
After assembling the D23 type liquid lead-acid battery for ISS vehicles by the same method as sample No. 1 and samples No. 8 to No. 13 except that the thickness of the central bone 112 of the positive electrode current collector used is different. Battery chemicals were carried out to obtain liquid lead-acid batteries of Sample No. 2 and Samples No. 14 to No. 19.

<Sample No.3 and Samples No.20 to No.25>
The liquid lead-acid batteries of Sample No. 3 and Samples No. 20 to No. 25 have the positive electrode current collector 1 having the shape shown in FIG. 1, and the thickness of the middle bone 112 (cross-sectional area perpendicular to the longitudinal direction). Is 0.95 mm ² . Other than that, sample No. 3 is the same as sample No. 1, sample No. 20 is the same as sample No. 8, sample No. 21 is the same as sample No. 9, and the sample. No.22 is the same as sample No.10, sample No.23 is the same as sample No.11, sample No.24 is the same as sample No.12, and sample No.25 is sample No.13. Is the same as.
After assembling the D23 type liquid lead-acid battery for ISS vehicles by the same method as sample No. 1 and samples No. 8 to No. 13 except that the thickness of the central bone 112 of the positive electrode current collector used is different. Battery chemicals were carried out to obtain liquid lead-acid batteries of Sample No. 3 and Samples No. 20 to No. 25.

<Sample No.4 and Samples No.26 to No.31>
The liquid lead-acid batteries of Sample No. 4 and Samples No. 26 to No. 31 have a positive electrode current collector 1 having the shape shown in FIG. 1 and have a thickness of the middle bone 112 (cross-sectional area perpendicular to the longitudinal direction). Is 0.90 mm ² . Other than that, sample No. 4 is the same as sample No. 1, sample No. 26 is the same as sample No. 8, sample No. 27 is the same as sample No. 9, and the sample. No. 28 is the same as sample No. 10, sample No. 29 is the same as sample No. 11, sample No. 30 is the same as sample No. 12, and sample No. 31 is sample No. 13. Is the same as.
After assembling the D23 type liquid lead-acid battery for ISS vehicles by the same method as sample No. 1 and samples No. 8 to No. 13 except that the thickness of the central bone 112 of the positive electrode current collector used is different. Battery chemicals were carried out to obtain liquid lead-acid batteries of Sample No. 4 and Samples No. 26 to No. 31.

<Sample No.5 and Samples No.32 to No.37>
The liquid lead-acid batteries of Sample No. 5 and Samples No. 32 to No. 37 have the positive electrode current collector 1 having the shape shown in FIG. 1, and the thickness of the middle bone 112 (cross-sectional area perpendicular to the longitudinal direction). Is 0.85 mm ² . Other than that, sample No. 5 is the same as sample No. 1, sample No. 32 is the same as sample No. 8, sample No. 33 is the same as sample No. 9, and the sample. No.34 is the same as sample No.10, sample No.35 is the same as sample No.11, sample No.36 is the same as sample No.12, and sample No.37 is sample No.13. Is the same as.
After assembling the D23 type liquid lead-acid battery for ISS vehicles by the same method as sample No. 1 and samples No. 8 to No. 13 except that the thickness of the central bone 112 of the positive electrode current collector used is different. Battery chemicals were carried out to obtain liquid lead-acid batteries of Sample No. 5 and Samples No. 32 to No. 37.

<Sample No. 6 and Samples No. 38 to No. 43>
The liquid lead-acid batteries of Sample No. 6 and Samples No. 38 to No. 43 have the positive electrode current collector 1 having the shape shown in FIG. 1, and the thickness of the middle bone 112 (cross-sectional area perpendicular to the longitudinal direction). Is 0.75 mm ² . Other than that, sample No. 6 is the same as sample No. 1, sample No. 38 is the same as sample No. 8, sample No. 39 is the same as sample No. 9, and the sample. No. 40 is the same as sample No. 10, sample No. 41 is the same as sample No. 11, sample No. 42 is the same as sample No. 12, and sample No. 43 is sample No. 13. Is the same as.
After assembling the D23 type liquid lead-acid battery for ISS vehicles by the same method as sample No. 1 and samples No. 8 to No. 13 except that the thickness of the central bone 112 of the positive electrode current collector used is different. Battery chemicals were carried out to obtain liquid lead-acid batteries of Sample No. 6 and Samples No. 38 to No. 43.

<Sample No.7 and Samples No.44 to No.49>
The liquid lead storage batteries of Sample No. 7 and Samples No. 44 to No. 49 have a positive electrode current collector 1A having the shape shown in FIG. 3, and have dimensions S1 = 115.0 mm, dimensions S2 = 110.0 mm, and dimensions. S3 = 100.0 mm, dimension S4 = 45.0 mm, thickness of the middle bone 112a (cross-sectional area perpendicular to the longitudinal direction) 0.80 mm ² , thickness of the middle bone 112b (cross-sectional area perpendicular to the longitudinal direction) It is 1.20 mm ² .

Other than that, sample No. 7 is the same as sample No. 1, sample No. 44 is the same as sample No. 8, sample No. 45 is the same as sample No. 9, and sample. No.46 is the same as sample No.10, sample No.47 is the same as sample No.11, sample No.48 is the same as sample No.12, and sample No.49 is sample No.13. Is the same as.
After assembling the D23 type liquid lead-acid battery for ISS vehicles by the same method as sample No. 1 and samples No. 8 to No. 13 except that the positive electrode current collector 1A in FIG. 3 was used, the battery tank was formed. The liquid lead-acid batteries of Sample No. 7 and Samples No. 44 to No. 49 were obtained.

[Measurement of each resistance value of the cut surface of the split body]
First, the obtained sample No. 1 to No. 7 liquid lead-acid batteries were disassembled, and the positive electrode active material was removed from the positive electrode plate (after chemical conversion) randomly selected for each sample and washed. The washed positive electrode current collectors 1 and 1A of the samples No. 1 to No. 7 are cut with scissors along the diagonal line D shown in FIGS. 1 and 3, respectively, and are shown in FIGS. 2 and 4. , A split body 2, 2A in which ears are present was obtained. In the split body 2 in which the ears are present, the first portion 21 separated by the reference line K has 13 cut surfaces of the middle bone 112. In the split body 2A in which the ears are present, the first portion 21A divided by the reference line K has a total of 13 cut surfaces of the middle bones 112a and 112b.

Next, each resistance value Rn (R1 to R13) between the center point P of the ear 12 and the cut surface C1 to C13 of each middle bone is measured three times using a resistance meter (3554 BATTERY HiTESTER manufactured by HIOKI). It was measured and the average value was calculated. Further, each distance Xn (X1 to X13) between the center point P and the center points of the cut surfaces C1 to C13 was measured with a ruler. The measurement results (each resistance value Rn is the average value of three measurements) are shown in Tables 1 to 7.

Next, the measurement results were plotted for each sample on a coordinate plane in which both the x-axis and the y-axis are linear scales, with the resistance value Rn (mean value of three measurements) as the y coordinate and the distance Xn as the x coordinate. As a result, the graphs shown in FIGS. 5 to 11 were obtained. FIG. 5 shows the result of No. 1, FIG. 6 shows the result of No. 2, FIG. 7 shows the result of No. 3, FIG. 8 shows the result of No. 4, and FIG. 9 shows the result of No. 5. FIG. 10 shows the result of No. 6, and FIG. 11 shows the result of No. 7.

As shown in FIG. 5, in sample No. 1, all plots could be approximated to two straight lines T1 and T2 having different slopes with x = H (value between X8 and X9) as an intersection. Next, the average value A of each resistance value (average value of three measurements) R1 to R8 at each distance X1 to X8 where x <H, and each resistance value at each distance X9 to X13 where x ≧ H. (Mean value of three measurements) The average value B of Rn was calculated, and the ratio A / B was calculated from these calculated values. The results are shown in Table 8.

As shown in Table 8, the ratio A / B of sample No. 1 was 0.31.
Further, as shown in FIGS. 6 to 10, in Samples No. 2 to No. 6, all the plots have two different slopes with x = H (value between X9 and X10) as an intersection. It was possible to approximate the straight lines T1 and T2. Next, the average value A of each resistance value (average value of three measurements) R1 to R9 at each distance X1 to X9 where x <H, and each resistance value at each distance X10 to X13 where x ≧ H. (Average value of three measurements) The average value B of Rn was calculated, and the ratio A / B was calculated from these calculated values. The results are shown in Tables 9 to 13.

As shown in Tables 9 to 13, the ratio A / B of sample No. 2 is 0.35, the ratio A / B of sample No. 3 is 0.45, and the ratio A / B of sample No. 4 is 0. 50, the ratio A / B of sample No. 5 was 0.55, and the ratio A / B of sample No. 6 was 0.65.
Further, as shown in FIG. 11, in sample No. 7, all plots could be approximated to two straight lines T1 and T2 having different slopes with x = H (value of X10) as an intersection. Next, the average value A of each resistance value (average value of three measurements) R1 to R9 at each distance X1 to X9 where x <H, and each resistance value at each distance X10 to X13 where x ≧ H. (Mean value of three measurements) The average value B of Rn was calculated, and the ratio A / B was calculated from these calculated values. The results are shown in Table 14.

As shown in Table 14, the ratio A / B of sample No. 7 was 0.55.

[Measurement of aluminum ion concentration in electrolyte]
The obtained electrolytes of the liquid lead-acid batteries of Samples No. 1 to No. 49 were collected, and the sample solution and the calibration curve solution were adjusted by a known method, and a high-frequency inductively coupled plasma emission spectrometer (ICP: Shimadzu ICPS) was prepared. Quantitative analysis was performed by -7500). These results are shown in Tables 15 and 16.

[Test and evaluation]
The obtained sample No. 1 to No. 49 liquid lead-acid batteries were subjected to a life test using the EUCAR power assist profile. The charge / discharge pattern of one cycle of this test is shown in FIG. C ₂ is a 2-hour rate capacity. In this charge / discharge pattern, there is a deep discharge in the partially charged state.
Further, after performing this life test for 100 cycles, the specific gravity of the electrolytic solution was measured at the upper part and the lower part of the electric tank using an optical hydrometer, and the difference in the upper and lower specific densities was calculated from these measured values.

The results of these tests are shown in Tables 15 and 16 along with the configuration of the grid-like substrate for each sample. Table 15 shows the difference in vertical specific gravity and the life test for samples No. 1 to No. 7 having the same concentration of aluminum ions in the electrolytic solution of 0.10 mol / L but different resistance values A / B of the positive electrode current collector. It is a summary of the results of. Table 16 summarizes all the test results of Samples No. 1 to No. 49 so that the difference can be seen when the resistance ratio A / B is the same and the concentration of aluminum ions in the electrolytic solution is different. ..

As can be seen from Table 15, the No. 1 and No. 6 liquid lead-acid batteries that do not satisfy 0.35 ≤ A / B ≤ 0.55 have a difference in the vertical specific gravity of the electrolytic solution between 0.070 and 0.040. In contrast, the liquid lead-acid batteries No. 2 to No. 5 and No. 7 satisfying 0.35 ≤ A / B ≤ 0.55 had a difference in the vertical specific gravity of the electrolytic solution of 0.005 to 0. It was as small as 015. Further, the life of the No. 1 and No. 6 liquid lead-acid batteries that do not satisfy 0.35 ≦ A / B ≦ 0.55 was 8000 to 8500 cycles, whereas the life was 0.35 ≦ A / B. The life of the liquid lead-acid batteries No. 2 to No. 5 and No. 7 satisfying ≤0.55 was as long as 17,000 to 22,000 cycles.
From the results in Table 15, a liquid lead-acid battery having a positive electrode current collector satisfying 0.35 ≦ A / B ≦ 0.55 and having an aluminum ion concentration of 0.10 mol / L in the electrolytic solution is partially charged. It was confirmed that when used in a state, the stratification of the electrolytic solution is suppressed and the life can be extended.

Furthermore, the following can be seen from Table 16.
Samples No. 2 to No. 5 and No. 7 satisfying 0.35 ≦ A / B ≦ 0.55 and having an aluminum concentration in the electrolytic solution of 0.01 mol / L or more and 0.30 mol / L or less. , No.15-No.18, No.21-No.24, No.27-No.30, No.33-No.36 and No.45-No.48 liquid lead-acid batteries are electrolytic solutions. The difference in specific gravity between the top and bottom was as small as 0.004 to 0.019, and the life was as long as 15100 to 24000 cycles.
On the other hand, the liquid lead-acid batteries of Samples No. 1 and No. 8 to No. 13 and No. 6 and No. 38 to No. 43 that do not satisfy 0.35 ≦ A / B ≦ 0.55 are The difference in the vertical specific gravity of the electrolytic solution was as large as 0.035 to 0.081, and the life was as short as 7000 to 9100 cycles.

Further, samples No.14, No.20, No.26, No.32, No. The 44 liquid lead-acid batteries had a small difference in the vertical specific gravity of the electrolytic solution of 0.007 to 0.022, but had a life of 11000 to 14200 cycles, which was less than 15000 cycles. When these samples were disassembled after the test and investigated, it was observed that a large number of bubbles were retained between the positive electrode plate and the negative electrode plate with the separator interposed therebetween. In addition, grayish white lead sulfate crystals were observed on the surface of the negative electrode plate, indicating that sulfation was progressing.

Further, Samples No. 19, No. 25, No. 31, and No. 37, which satisfy 0.35 ≦ A / B ≦ 0.55 but have a concentration of aluminum ions in the electrolytic solution of 0.40 mol / L, In the No. 49 liquid lead-acid battery, the difference in the vertical specific gravity of the electrolytic solution was as large as 0.031 to 0.043, and the life was 10600 to 14000 cycles, which was less than 15,000 cycles. When these samples were disassembled and investigated after the test, traces of osmotic short circuit were found on the surface of the separator.

The reason for this result can be estimated as follows.
First, in a liquid lead-acid battery in which the concentration of aluminum ions in the electrolytic solution is 0 mol / L even if 0.35 ≦ A / B ≦ 0.55 is satisfied, the charge-acceptable electrolytic solution is improved by adding aluminum ions. It is probable that since the effect could not be obtained, the enlargement of lead sulfate, which is inactive in the partially charged state, progressed, so that sulfation occurred and the effect of improving the life was not so much obtained.

Next, in a liquid lead-acid battery in which the concentration of aluminum ions in the electrolytic solution is 0.40 mol / L even if 0.35 ≦ A / B ≦ 0.55 is satisfied, the charge acceptability becomes excessive and the negative electrode It is considered that the dendrite growth of metallic lead on the plate could not be suppressed, and the effect of improving the life was not so much obtained as compared with the sample in which the concentration of aluminum ions in the electrolytic solution was 0.001 mol / L or more.

As described above, from the results in Table 16, the positive electrode current collector satisfying 0.35 ≦ A / B ≦ 0.55 is provided, and the concentration of aluminum ions in the electrolytic solution is 0.10 mol / L or more and 0.30 mol / L. It was confirmed that the following liquid lead-acid batteries can have a long life by suppressing stratification of the electrolytic solution when used in a partially charged state.

1 Positive current collector 1A Positive current collector 11 Lattice substrate 11A Lattice substrate 12 Ear 111 Upper bone 112 Middle bone 112a Middle bone 112b Middle bone 2 Split body with ears 2A Split body with ears 21 First Part 21A First part 22 Second part 22A Second part

Claims (1)

A group of electrode plates in which a positive electrode plate having a positive electrode current collector and a positive electrode mixture and a negative electrode plate having a negative electrode current collector and a negative electrode mixture are alternately laminated via a separator, and dilute sulfuric acid as an electrolytic solution are used. It is a liquid lead-acid battery equipped with
The positive electrode current collector has a rectangular grid-like substrate and ears continuous to the grid-like substrate.
The positive electrode mixture is held on the grid-like substrate, and the positive electrode mixture is held.
The grid-like substrate has an upper bone along one side of the rectangle and a plurality of middle bones connected to the upper bone and located below the upper bone.
The ear protrudes upward from a position offset unilaterally from the center of the one side of the upper bone.
Of the splits formed by cutting the positive current collector along the diagonal line passing through the corner on one side of the rectangle, the split in which the ear is present is the center of the ear on the boundary line with the upper bone. It is divided into a first part and a second part by a reference line passing through the point P and perpendicular to the upper bone, and the first part has a larger area than the second part.
On a coordinate plane in which both the x-axis and the y-axis are linear scales, the resistance value Rn between each cut surface Cn of the plurality of central bones and the center point P in the first portion is set in the y coordinate. All plots made with each distance Xn between the center point of each cut surface Cn and the center point P as the x-coordinate can be approximated to two straight lines having different slopes with x = H as the intersection.
The ratio A / B by the average value A of each resistance value Rn at each distance Xn where x <H and the average value B of each resistance value Rn at each distance Xn where x ≧ H is 0.35. More than 0.55 or less,
The electrolytic solution contains aluminum ions, and the concentration of aluminum ions in the electrolytic solution is 0.01 mol / L or more and 0.30 mol / L or less.

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