TWI545831B - Control valve type leaded battery - Google Patents

Description

Control valve type lead storage battery

The present invention relates to a control valve type lead storage battery for use in a partially charged state.

A lead-acid battery used for power storage such as wind power or solar power generation and leveling of system power is generally used as a control valve type lead storage battery. The control valve type lead storage battery is always kept in a state of insufficient charge in a so-called partial state of charge (PSOC), and is subjected to pulse charging and discharging of a large current, and is required to be used under severe use conditions. However, if the charge and discharge are reversed in the PSOC state, the crystal of lead sulfate, which is a discharge material in the negative electrode, grows and coarsens, and the problem of loss of reversibility (sulfation) occurs. In the above-mentioned Patent Document 1 (JP-A-2003-123760), a technique is disclosed in which a negative electrode for a lead storage battery obtained by adding carbon black (acetylene black) to a negative electrode active material is used as the PSOC. The negative electrode of the lead battery used in the state.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-123760

However, the lead storage battery described in Patent Document 1 is biased toward automobile use. As a result of research by the team of the present invention, it has been found that the cycle characteristics are not sufficient in the case of a lead storage battery used for the storage of natural energy and the leveling of system power. .

The present invention has been made in view of the above circumstances, and aims to provide a control valve type lead storage battery excellent in cycle characteristics for a control valve type lead storage battery that is used in a partially charged state.

The control valve type lead storage battery to be improved according to the present invention is a control valve type lead storage battery including a negative electrode plate containing carbon black in a negative electrode active material. The negative electrode active material contains graphite in addition to carbon black. The graphite used in the present invention is graphite having an average particle diameter of 90 μm or less and a DBP oil absorption of 55 ml/100 g or more.

Here, the "average particle diameter" means a particle diameter (D50) in which the cumulative distribution of the volume basis measured by the laser diffraction/scattering method is 50%. In addition, the "IDBP oil absorption amount" is an oil absorption amount obtained by the oil absorption amount B method (squeegee mixing method) described in JIS K-6221 (1982). Further, graphite has a high DBP oil absorption, and generally indicates that graphite has high crystallinity.

If graphite and carbon have such average particle size and DBP oil absorption When black is added to the negative electrode active material, even in the case of a lead storage battery used in the PSOC state, the initial capacitance is maintained and the cycle characteristics are improved. In other words, a negative electrode plate using a negative electrode active material is provided, and the negative electrode active material contains graphite having a small average particle diameter and high crystallinity (the layered structure is not destroyed), and carbon black, thereby obtaining appearance. A control valve type lead storage battery with higher cycle characteristics than ever before.

Further, in the case of graphite having a small average particle diameter and high crystallinity, the upper limit of the average particle diameter of graphite and the upper limit of the DBP oil absorption amount are not limited. However, considering the availability of the graphite material, it is expected that the lower limit of the average particle diameter of graphite is about 1 μm, and the upper limit of the DBP oil absorption of graphite is about 300 ml/100 g.

The graphite to be added to the negative electrode active material is preferably graphite having an average particle diameter of 1 μm to 60 μm and a DBP oil absorption of 65 ml/100 g or more. When graphite having an average particle diameter and DBP oil absorption in such a numerical range is used, not only the cycle characteristics are improved, but also the initial capacitance can be improved.

Further, it is more preferable that the graphite has an average particle diameter of from 1 μm to 20 μm and a DBP oil absorption of 85 ml/100 g or more. If graphite having an average particle diameter and DBP oil absorption in such a numerical range is used, the initial capacitance is maintained or increased, and the cycle characteristics are remarkably improved.

Further, the content of graphite is preferably 0.5 to 3.0% by mass based on 100% by mass of the negative electrode active material. When the content of graphite is adjusted to such a numerical range, a control valve type lead storage battery in which initial capacitance and cycle characteristics are improved can be surely obtained.

More preferably, the content of graphite is relative to the negative electrode active material 100. The amount % is 1.0 to 3.0% by mass. When the content of graphite is adjusted to such a numerical range, it is possible to surely obtain a control valve type lead storage battery in which the initial capacitance is maintained or increased while the cycle characteristics are remarkably improved.

On the other hand, the content of the carbon black is preferably adjusted to be 0.3 to 3.0% by mass based on 100% by mass of the negative electrode active material. When the content of carbon black is adjusted to such a numerical range, even if the content of graphite is relatively small, a control valve type lead storage battery in which both initial capacitance and cycle characteristics are improved can be obtained.

More preferably, the content of the carbon black is adjusted to be 1.5 to 3.0% by mass based on 100% by mass of the negative electrode active material. When the content of the carbon black is adjusted to such a numerical range, even if the content of the graphite is relatively small, a control valve type lead storage battery in which the initial capacitance is maintained or increased and the cycle characteristics are remarkably improved can be obtained.

Further, examples of the carbon black added to the negative electrode active material include acetylene black, furnace black, channel black, thermal black, and Ketjen black. Further, in the case where acetylene black is used, the cycle characteristics can be improved as compared with the case of carbon black other than acetylene black.

Hereinafter, embodiments of the present invention will be described in detail. The control valve type lead storage battery of this example can be produced, for example, in the following manner.

(negative plate)

First, the negative electrode active material is a graphite powder containing at least carbon black (acetylene black) and a graphite powder having an average particle diameter of 90 μm or less and a DBP oil absorption of 55 ml/100 g or more. In addition, a mixture of barium sulfate, reinforcing short fibers (acrylic fiber, polypropylene fiber, polyethylene terephthalate (PET) fiber, etc.) and the like may be added as needed. The mixture was added to water and sodium ligninsulfonate and mixed, and dilute sulfuric acid was further added to prepare a negative electrode active material paste.

The content of the acetylene black to be added as the carbon black is preferably from 0.1 to 5.0% by mass based on 100% by mass of the negative electrode active material from the viewpoint of maintaining at least the initial capacitance and improving the cycle characteristics. Further, in consideration of not only improving the cycle characteristics but also increasing the initial capacitance, it is preferably 0.1 to 3.0% by mass based on 100% by mass of the negative electrode active material. Moreover, in order to improve the initial capacitance and obtain high cycle characteristics, it is preferably 1.5 to 3.0% by mass based on 100% by mass of the negative electrode active material.

The content of the graphite may be 0.5 to 5% by mass based on 100% by mass of the negative electrode active material, in consideration of at least maintaining the initial capacitance and improving the cycle characteristics. Further, in consideration of not only improving the cycle characteristics but also increasing the initial capacitance, it is preferably 0.5 to 3.0% by mass based on 100% by mass of the negative electrode active material. Moreover, in order to improve the initial capacitance and obtain high cycle characteristics, it is more preferably 1.0 to 3.0% by mass based on 100% by mass of the negative electrode active material.

Further, the DBP oil absorption of graphite can be obtained by the above-described spatula mixing method.

The average particle size of graphite, which is maintained by at least maintaining the initial capacitance From the viewpoint of characteristics, it can be set to 90 μm or less as described above. Further, from the viewpoint of not only improving the cycle characteristics but also increasing the initial capacitance, it is preferably from 1 μm to 60 μm, and more preferably from 1 μm to 20 μm from the viewpoint of improving the initial capacitance while further improving the cycle characteristics. Further, the average particle diameter is determined by the above particle diameter (D50).

Further, the DBP oil absorption of graphite can be set to 55 ml/100 g or more as described above from the viewpoint of maintaining at least the initial capacitance while improving the cycle characteristics. Further, from the viewpoint of not only improving the cycle characteristics but also increasing the initial capacitance, it is preferably 65 ml/100 g or more, and more preferably 85 ml/100 g or more from the viewpoint of improving the initial capacitance while further improving the cycle characteristics. In addition, the upper limit of the DBP oil absorption is not limited, but it is considered to be 500 ml/100 g or less from the viewpoint of practicality, and it is only required to be 300 ml/100 g or less in practice.

In addition, in order to further improve the discharge characteristics, sodium lignosulfonate may also be added. When sodium lignosulfonate is contained, the content thereof is preferably 0.05 to 1% by mass, more preferably 0.1 to 0.8% by mass, more preferably 0.2 to 0.6% by mass, based on 100% by mass of the negative electrode active material.

In addition, when the reinforcing short fibers are contained, the content thereof is preferably 0.01 to 0.3% by mass, more preferably 0.02 to 0.1% by mass, based on 100% by mass of the negative electrode active material.

In the case of using barium sulfate, the content thereof is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.5% by mass, based on 100% by mass of the negative electrode active material.

Next, the negative electrode active material paste prepared as described above is filled in The current collector grid is dried and dried to produce a negative electrode plate that has not yet been formed.

As the current collector lattice, a lead-calcium-tin alloy, a lead-calcium alloy, which is a lead-calcium-tin alloy, a lead-calcium alloy, or a trace amount of arsenic, selenium, silver, or antimony added thereto may be used. Etc.

The ripening condition is preferably 40 to 60 hours in an environment of a temperature of 35 to 85 ° C and a humidity of 50 to 90%. The drying condition is preferably set at 15 to 30 hours at a temperature of 50 to 80 °C.

(positive plate)

The positive electrode plate can be obtained, for example, by the following method. First, for the lead powder containing lead oxide as a main component, after adding short fibers for reinforcement, water and dilute sulfuric acid are added. This was kneaded to prepare a positive electrode active material paste. When preparing a positive active material paste, lead dan (Pb ₃ O ₄ ) may also be added. This positive electrode active material paste is filled in a current collector (such as a current collector lattice), and then matured and dried to obtain a positive electrode that has not yet been formed. In the positive electrode active material paste, the content of the reinforcing short fibers is preferably 0.005 to 0.3% by mass based on the total mass of the positive electrode active material. The type, ripening conditions, and drying conditions of the current collector lattice are almost the same as those of the negative electrode.

(Assembly of control valve type lead storage battery)

In the assembly process, for example, the negative electrode and the positive electrode produced as described above are laminated via a support plate or a separator, and the plates of the same polarity are connected to each other by a strap to obtain a plate. group. will The electrode group is placed in an electrolytic cell to produce a battery that has not yet been formed. Next, the dilute sulfuric acid is poured into a battery that has not yet been turned into a chemical conversion treatment. Then, the dilute sulfuric acid is drained and then poured into an electrolytic solution (dilute sulfuric acid) to obtain a lead storage battery. The specific gravity (in terms of 20 ° C) of dilute sulfuric acid is preferably 1.25 to 1.35. The material of the electrolytic cell is not particularly limited, and specifically, polypropylene, ABS, denatured PPE (polyphenylene ether), or the like can be used.

The lid body is not particularly limited as long as it is an opening that closes the opening of the electrolytic cell, and the material may be the same as the electrolytic cell or may be different. However, in order to prevent the cover from falling off due to deformation during heating, it is preferable to use the same degree of thermal expansion coefficient.

The control valve is used to discharge the remaining gas which is not absorbed by the gas absorption reaction of the negative electrode among the oxygen generated during charging to the outside of the electrolytic cell. The material is a material excellent in chemical resistance (acid resistance, silicone oil resistance), abrasion resistance, and heat resistance, and specifically, a fluorine rubber is preferably used.

The material of the support plate (separator) may be glass fiber or the like. Further, the chemical conversion conditions and the specific gravity of the dilute sulfuric acid can be adjusted in accordance with the electrode size. Further, the chemical conversion treatment is not limited to being carried out in an assembly process, and may be carried out in an electrode manufacturing process.

[Examples]

Hereinafter, the embodiment used in this example will be specifically described.

(Example 1) <Production of negative electrode plate>

For the lead powder, 100% by mass, 1.5% by mass of acetylene black (trade name: DENKA BLACK, manufactured by Denki Kagaku Kogyo Co., Ltd.) and graphite (trade name: UP-5, manufactured by Nippon Graphite Co., Ltd., average particle size: 5 μm, DBP) Oil absorption: 220 ml/100 g) 2% by mass, barium sulfate 1% by mass, polyethylene terephthalate fiber (PET fiber) 0.03 mass%, sodium lignosulfonate (trade name: VANILLEX N, manufactured by Nippon Paper Co., Ltd. After 0.5% by mass, it was dry-mixed. Next, while adding dilute sulfuric acid (specific gravity: 1.26/20 ° C conversion) and water, the negative electrode active material paste was prepared. On the other hand, a lead-calcium-tin alloy was melted and cast to prepare a current collector lattice having a length of 131.0 mm, a width of 116.0 mm, and a thickness of 2.5 mm. After the prepared negative electrode active material paste was filled in the current collector grid, a negative electrode plate was produced under the following aging and drying conditions.

Ripening conditions... Temperature: 40 ° C, humidity: 98%, time: 40 hours

Drying conditions... Temperature: 60 ° C, Time: 24 hours

The oil absorption of graphite is obtained by dropping a small amount of dibutyl phthalate (DBP) to graphite by a spatula mixing method, and measuring the amount of DBP dripping when the graphite sample is agglomerated. Further, the average particle diameter (D50) of graphite was measured by the method described in JIS R1629.

<Production of positive electrode plate>

On the basis of the total mass of the lead powder, a cut fiber composed of 0.15 mass% of polyethylene fibers and a lead mass of 6 mass% were added to the lead powder, followed by dry mixing. Next, dilute sulfuric acid (specific gravity: 1.26/20 ° C conversion) and water were added and kneaded to prepare a positive electrode active material paste. Lead - The calcium-tin alloy was melted and cast to produce a current collector lattice having a length of 130.0 mm, a width of 115.0 mm, and a thickness of 4.05 mm. After the positive electrode active material paste was filled in the current collector grid, the positive electrode plate was produced under the following aging and drying conditions.

Ripening conditions 1... Temperature: 80 ° C, humidity: 98%, time: 10 hours

Ripening condition 2... Temperature: 65 ° C, humidity: 75%, time: 11 hours

Drying conditions... Temperature: 60 ° C, Time: 24 hours

<Battery assembly>

A laminated plate made of glass fiber (a separator for a control valve type lead storage battery) is laminated on a support plate (a separator for a control valve type lead storage battery) which is not yet formed, and has not been formed into a negative electrode plate and two pieces have not yet been formed. After the positive electrode plate, the ear portions of the same polarity plate were connected to each other by a connecting piece to form an electrode group. The electrode group was inserted into an electrolytic cell, and a dilute sulfuric acid electrolyte having a specific gravity of 1.050 (20 ° C) was injected, and was formed under the conditions of a power supply amount of 250% of the theoretical capacity, a formation time of 40 hours, and an ambient temperature of 40 °C. After the chemical conversion, the electrolyte is discharged, and one sheet of the negative electrode plate and two sheets of the positive electrode plate are laminated through a support plate made of glass fiber, and then a predetermined amount of electrolyte solution (specific gravity: 1.275 dilute sulfuric acid) is injected, and a safety valve is attached and assembled. Into the control valve type lead storage battery.

(Example 2) - (Example 16) and (Comparative Example 1) - (Comparative Example 7)

A control valve type lead storage battery was obtained as in Example 1 except that the negative electrode plate was changed to the material and composition shown in Table 1.

<Evaluation of battery performance>

For the above-described control valve type lead storage battery, battery performance (initial capacitance and cycle characteristics) was measured in the following manner. The measurement results of the initial capacitance and the cycle characteristics of Comparative Example 1 were each set to 100, and the respective characteristics of the examples were evaluated. The results are shown in Table 1.

(initial capacitance)

For the above-mentioned control valve type lead storage battery, the initial capacitance test was carried out in accordance with the following procedures (a) to (d) to evaluate the battery performance. In addition, the test was carried out under the control of 25 ° C.

The battery's 10-hour capacity was set to 4 Ah, and the test was carried out according to the following procedures.

(a) Discharge at 0.4A, final voltage 1.80V

(b) Charging for 24 hours with 0.4A and control voltage of 2.42V

(c) rest for more than 24 hours

(d) Repeat the above procedures (a) to (c) twice.

The second discharge capacity of the lead storage battery is set as the initial capacitance. The initial capacitance is evaluated on the basis of the following criteria.

○: The initial capacitance is increased (in case the initial capacitance exceeds 100 and less than 120)

△: The initial capacitance remains unchanged (in case of initial capacitance of 95 or more and 100 or less)

×: The initial capacitance is reduced (in case the initial capacitance is less than 95)

(Circulation characteristics (PSOC cycle test of lead storage battery))

For the above-mentioned control valve type lead storage battery, the PSOC cycle test is carried out in accordance with the following procedures (e) to (h) for evaluation. In addition, the test was carried out under the control of 25 ° C.

The battery's 10-hour capacity was set to 4 Ah, and the test was carried out according to the following procedures.

(e) discharge at 0.4A for 9 hours

(f) charging at 2.0A for 1 hour

(g) charging 1.25 hours at 1.6A

(h) Repeat the above steps (e) to (g), and measure the discharge capacity at a rate of 10 hours every 100 cycles.

The number of cycles when the discharge capacity of the lead storage battery reaches 70% of the initial capacitance ratio is evaluated as the PSOC life cycle characteristic. The evaluation of the cycle characteristics was carried out on the basis of the following criteria.

◎: The cycle characteristics are significantly improved (when the cycle characteristics are 130 or more)

○: The cycle characteristics remain unchanged or increased (when the cycle characteristics are 100 or more and less than 130)

×: The cycle characteristics are reduced (when the cycle characteristics are less than 100)

From the initial capacitance and cycle characteristics thus evaluated, the battery performance of the control valve type lead storage battery was comprehensively evaluated. In addition, the comprehensive evaluation is based on the following criteria.

◎: The initial capacitance remains unchanged or increased, and the cycle characteristics are significantly improved (initial capacitance exceeds 100, and the cycle characteristics are above 130)

●: The initial capacitance and cycle characteristics are improved (initial capacitance exceeds 100, and the cycle characteristics exceed 100 and less than 130)

○: The initial capacitance is maintained and the cycle characteristics are improved (initial capacitance 95 or more and 100 or less, and the cycle characteristics exceed 100 and less than 130)

×: At least one of the initial capacitance and the cycle characteristic is lowered (in the case where the initial capacitance is less than 95 or the cycle characteristic is 100 or less)

In addition, the details of each material in Table 1 are as follows.

UP-5: graphite with a DBP oil absorption of 220 ml/100 g, an average particle diameter (D50) of 5 μm (manufactured by Nippon Graphite Co., Ltd.), UP-10: DBP oil absorption of 180 ml/100 g, and an average particle diameter (D50) of 10 μm of graphite (Japan) Graphite Industry Co., Ltd., SP-20: DBP oil absorption: 90ml/100g, average particle size (D50) 12μm graphite (manufactured by Nippon Graphite Co., Ltd.), ACB150: DBP oil absorption: 75ml/100g, average particle size (D50) 50μm Graphite (manufactured by Nippon Graphite Co., Ltd.), ACB100: DBP oil absorption 55 ml/100 g, average particle size (D50) 80 μm graphite (manufactured by Nippon Graphite Co., Ltd.), ACB100 (classification): DBP oil absorption 50 ml/100 g, average particle Graphite (D50) 100 μm graphite (inventors classified ACB100 to increase the average particle size of ACB100), ACB50: DBP oil absorption 40 ml/100 g, and average particle diameter (D50) 300 μm graphite (manufactured by Nippon Graphite Co., Ltd.) DENKA BLACK: acetylene black (manufactured by Electric Chemical Industry Co., Ltd.), VULCAN XC72: furnace black (manufactured by CABOT Co., Ltd.), PEARLLEX DP: high-purity modified sodium lignosulfonate (manufactured by Nippon Paper Industries Co., Ltd.), VANILLEX N: High-purity partial desulphation sodium lignosulfonate (manufactured by Nippon Paper Industries Co., Ltd.).

As can be seen from Table 1, in the examples 1 to 5 (average particle diameter: 5 to 80 μm, DBP oil absorption: 55 to 220 ml/100 g), the initial capacitance was maintained or increased and the cycle characteristics were obtained based on Comparative Example 1. Upgrade. Among them, in Examples 1 to 4 (average particle diameter: 5 to 50 μm, DBP oil absorption: 75 to 220 ml/100 g), it was found that not only the cycle characteristics were improved but also the initial capacitance was also improved. Further, in Examples 1 to 3 (average particle diameter: 5 to 12 μm, DBP oil absorption: 90 to 220 ml/100 g), it was found that the initial capacitance was improved and the characteristics were remarkably improved (any of the cycle characteristics were 130 or more). .

Further, in Comparative Example 2 (in the case where the average particle diameter and the DBP oil absorption amount were all less than the conditions of the present invention), the initial capacitance was lowered (the initial capacitance was less than 95). Further, in Comparative Example 3 (when the DBP oil absorption amount satisfies the conditions of the present invention, but the average particle diameter is less than the condition of the present invention), the initial capacitance is also lowered (the initial capacitance is less than 95).

Further, in Examples 6 to 10 (average particle diameter: 10 μm, DBP oil absorption: 180 ml/100 g, and addition amount: 0.5 to 5.0% by mass of graphite), it was found that the initial capacitance was maintained or increased, and the cycle characteristics were improved. Among them, in Examples 6 to 9 (average particle diameter: 10 μm, DBP oil absorption: 180 ml/100 g, and addition amount: 0.5 to 3.0% by mass of graphite), it was found that not only the cycle characteristics were improved but also the initial capacitance was also improved. Further, in Examples 7 to 9 (average particle diameter: 10 μm, DBP oil absorption: 180 ml/100 g, addition amount: 1.0 to 3.0% by mass of graphite), it was found that the cycle characteristics were remarkably improved while the initial capacitance was increased (the cycle characteristic was 130). the above). In addition, in the case of Comparative Example 4 (in the case where graphite was not added), there was almost no change in the cycle characteristics, and in the case of Comparative Example 5 (in the case where the amount of addition of graphite was 7 mass%), the initial capacitance and the cycle characteristics were all lowered. It is low.

In addition, in Examples 11 to 15 (the amount of acetylene black added: 0.1 to 5.0% by mass), it is understood that the amount of addition of graphite (average particle diameter: 10 μm, DBP oil absorption: 180 ml/100 g) is 1% by mass. In less cases, the initial capacitance remains the same or increases, while the cycle characteristics increase. Among them, in Examples 11 to 14 (the amount of acetylene black added was 0.1 to 3.0% by mass), it was found that not only the cycle characteristics were improved but also the initial capacitance was also improved. Further, in Examples 13 and 14 (the amount of acetylene black added was 1.5 to 3.0% by mass), it was found that the cycle characteristics were remarkably improved while the initial capacitance was increased (any of the cycle characteristics were 130 or more). Further, in Comparative Example 6 (in the case where acetylene black was not added), the cycle characteristics were lowered, and in Comparative Example 7 (when the amount of acetylene black added was 7% by mass), the initial capacitance and cycle characteristics were all lowered.

Further, in Example 16 (in the case where furnace black was used instead of acetylene black), it was found that the initial capacitance was also maintained and the cycle characteristics were improved. However, comparing Example 2 with Example 16, it is understood that in the case where acetylene black is used for the furnace black, not only the cycle characteristics are improved, but also the initial capacitance is improved.

As described above, by providing the negative electrode plate satisfying the conditions of the present invention, it is possible to obtain a control valve type lead storage battery which maintains or raises the initial capacitance and has excellent cycle characteristics.

The embodiments of the present invention have been specifically described above, but the present invention is not limited to the embodiments and examples. In other words, the conditions described in the above embodiments and examples can be changed in accordance with the technical idea of the present invention unless otherwise stated.

[Industry Utilization]

According to the present invention, the control valve type lead storage battery used in the partially charged state can contain graphite having an average particle diameter of 90 μm or less and DBP oil absorption of 55 ml/100 g or more in addition to carbon black in the negative electrode active material. A control valve type lead storage battery excellent in cycle characteristics is provided.

Claims (8)

A control valve type lead storage battery comprising a negative electrode plate containing carbon black in a negative electrode active material, wherein the negative electrode active material further contains an average particle diameter of 1 μm to 90 μm, and the DBP oil absorption amount is 55 ml/100 g or more. Graphite. The control valve type lead storage battery according to claim 1, wherein the graphite has an average particle diameter of 1 μm to 60 μm, and the DBP oil absorption amount is 65 ml/100 g or more. The control valve type lead storage battery according to claim 1, wherein the graphite has an average particle diameter of 1 μm to 20 μm, and the DBP oil absorption amount is 85 ml/100 g or more. The control valve type lead storage battery according to the first aspect of the invention, wherein the content of the graphite is 0.5 to 3.0% by mass based on 100% by mass of the negative electrode active material. The control valve type lead storage battery according to the first aspect of the invention, wherein the content of the graphite is 1.0 to 3.0% by mass based on 100% by mass of the negative electrode active material. The control valve type lead storage battery according to any one of claims 1 to 5, wherein the content of the carbon black is 0.1 to 3.0% by mass based on 100% by mass of the negative electrode active material. The control valve type lead storage battery according to any one of claims 1 to 5, wherein the content of the carbon black is 1.5 to 3.0% by mass based on 100% by mass of the negative electrode active material. A control valve according to any one of claims 1 to 5 A lead-acid battery, wherein the carbon black is acetylene black.