JP2016213050A - Control valve-type lead storage battery and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a control valve-type lead storage battery by which the degradation of a control valve-type lead storage battery operated in a standby use manner owing to ripple can be avoided well and inexpensively.SOLUTION: In a control valve-type lead storage battery, the ratio (N)/(P) of a negative electrode active material total superficial area (N) to a positive electrode active material total superficial area (P) is in a range of 0.010-0.020 in the battery in a state of full charge after chemical conversion; and the ratio (n)/(p) of a negative electrode active material total amount (n) to a positive electrode active material total amount (p) is in a range of 0.4-0.7 in the battery in the state of full charge after chemical conversion. The above numeric value ranges are determined by selecting an additive agent in a process for manufacturing each electrode plate, and adjusting various kinds of parameters including a blend volume of the additive agent in preparing an active material paste, addition amounts of water and diluted sulfuric acid, and maturation and dry conditions of the electrode plates. In addition, the numeric value ranges are adjusted by a grid form, quantities of charged active materials, a chemical conversion condition, and the numbers of positive and negative electrode plates in a battery case.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a control valve type lead storage battery, and more particularly to a control valve type lead storage battery operated for standby use and a method for manufacturing the same.

  The control valve type lead acid battery is a secondary battery excellent in cost, safety and reliability, and is used for various applications.

  Conventionally, the power of a storage battery used for power storage, in particular, a DC power source of a telephone switch for a general line, is converted from 0.3 to 3.4 kHz voice to current intensity using a switch and transmitted to a fixed telephone line. Therefore, it is necessary to supply a rectified noise-free DC power supply.

  In recent years, the method of transmitting voice data as part of IP conversion and data communication has increased, and existing facilities due to digitization, data center installation, backbone facilities, etc. are often concentrated on a large scale. There is an increasing demand for lead-acid batteries as UPS power sources that can handle power consumption. Since the UPS is charged by being connected in parallel with a power supply device that converts commercial power into direct current, the power supplied to charge the UPS is rectified during the harmonics of the commercial power or during AC-DC conversion. A ripple (a pulsation component included in a direct current) such as a fluctuation part that could not be applied is applied.

  When a control valve type lead-acid battery is charged at a constant voltage with a power source having such ripples, the charging voltage fluctuates due to the ripple, so strictly speaking, it is not charged at a constant voltage. It will fluctuate according to the ripple, and it is considered that the deterioration of the positive electrode plate is promoted.

In particular, when a control valve type lead-acid battery is charged using a power source including ripples in a frequency band of 1 kHz or less, a Faraday reaction occurs in the positive electrode plate due to current fluctuations caused by voltage fluctuations caused by ripples. When the potential becomes unstable and the positive electrode potential decreases, the positive electrode active material PbO ₂ changes to PbO _x , PbSO ₄ , and the positive electrode corrosion reaction is accelerated. Further, when the positive electrode potential increases, electrolysis occurs, O ₂ is generated, and corrosion of the positive electrode plate is accelerated.

  However, the influence of the ripple on the positive electrode plate has not been clarified so far, and there are few countermeasures against this.

  Japanese Patent Application Laid-Open No. 9-247856 (Patent Document 1) discloses a vehicle power supply device using an electric double layer capacitor that satisfactorily supplies current to a large load, suppresses fluctuations in supply voltage, and effectively eliminates the influence of noise. It is disclosed.

  Japanese Patent Laid-Open No. 2001-037093 (Patent Document 2) describes a charging method in which an alternating high frequency voltage that is weaker than a direct current voltage is applied to a predetermined direct current voltage.

Japanese Patent Laid-Open No. 9-247856 JP 2001-037093 A

  However, in the invention described in Patent Document 1, since two devices are mounted, the cost of the uninterruptible power supply (UPS) is increased.

  Moreover, although patent document 2 is the content regarding the charging method which superimposes on a predetermined direct current voltage and applies a weak alternating current high frequency voltage compared with direct current voltage, the countermeasure by the side of a control valve type lead acid battery is not made.

  An object of the present invention is to provide a control valve type lead storage battery and a method for manufacturing the control valve type lead storage battery that can prevent deterioration of the positive electrode plate due to ripple of the control valve type lead storage battery operated in standby use in a good and inexpensive manner. There is to do.

  The present invention is directed to a control valve type lead-acid battery that is operated in a standby use including an electrode plate group including one or more negative electrode plates and one or more positive electrode plates. The control valve type lead-acid battery of the present invention comprises a total surface area (N) of negative electrode active materials of one or more negative plates and a total surface area of positive active materials of one or more positive plates in a fully charged electrode plate group after formation. The ratio of (P) is in the range of 0.010 <(N) / (P) <0.020, and the total mass (n) of the negative electrode active material of one or more negative plates and that of one or more positive plates The ratio of the positive electrode active material total mass (p) is in the range of 0.4 <(n) / (p) <0.7, and the negative electrode active material does not contain carbon. Here, the fully charged state is a state in which a substance that generates electrical energy by a chemical reaction when the storage battery discharges is sufficiently charged, that is, a charged state in which the rated capacity can be discharged. That is.

As in the present invention, the negative electrode active material does not contain carbon, and the above-mentioned numerical range allows the total surface area of the negative electrode active material to be very small relative to the total surface area of the positive electrode active material, and the charging voltage Even if the voltage fluctuates, the potential fluctuation of the positive electrode is suppressed because the potential fluctuation of the negative electrode first occurs. Moreover, the polarization of the negative electrode in the control valve type lead storage battery is increased, and the potential fluctuation of the positive electrode is suppressed. As a result, according to the present invention, the positive electrode potential becomes stable, the positive electrode potential decreases, and the positive electrode active material PbO ₂ is changed to PbO _x and PbSO ₄ , thereby suppressing the acceleration of the positive electrode corrosion reaction. it can. In addition, according to the present invention, it is possible to suppress the positive electrode potential from increasing, O ₂ being generated by electrolysis, and the corrosion of the positive electrode plate from being accelerated. Further, by not containing carbon, it is possible to reduce the charging current value during trickle charging, and it is possible to sufficiently ensure the life performance.

Within the above range, the ratio of the total surface area (N) of the negative electrode active material and the total surface area (P) of the positive electrode active material in the fully-charged control valve type lead storage battery, (N) / (P) is 0.010. The ratio of the total mass (n) of the negative electrode active material to the total mass (p) of the positive electrode active material (n) / (p) is preferably in the range of 0.4 to 0.6. . Within this range, even if the charging voltage largely fluctuates, the potential on the negative electrode side first fluctuates, and the fluctuation amount of this potential fluctuation increases, so that the potential fluctuation of the positive electrode is further suppressed and a stable state is achieved. Moreover, since the polarization of the negative electrode in the control valve type lead-acid battery becomes larger and the potential fluctuation of the positive electrode is further suppressed, the PbO _{2 of the} positive electrode active material is suppressed from being changed to PbO _x or PbSO _4, which is caused by electrolysis. O ₂ generation is suppressed and corrosion of the positive electrode plate can be suppressed.

  Further, within the above range, the ratio of the total surface area (N) of the negative electrode active material to the total surface area (P) of the positive electrode active material in the fully-charged control valve type lead storage battery, (N) / (P) is 0.010. The ratio of the total mass (n) of the negative electrode active material and the total mass (p) of the positive electrode active material (n) / (p) is in the range of 0.4 to 0.5. Further preferred.

  Within this range, the surface area of the negative electrode active material can be further reduced with respect to the surface area of the positive electrode active material, and even if the charging voltage varies, the potential fluctuation of the negative electrode occurs before the potential fluctuation of the positive electrode. Therefore, the potential fluctuation of the positive electrode is further suppressed. Moreover, the polarization of the negative electrode in the control valve type lead-acid battery becomes larger, and the potential fluctuation of the positive electrode is further suppressed.

  The negative electrode plate before chemical conversion is composed of a lead alloy negative electrode current collector made of lead monoxide as a main component, acid fiber for reinforcement, lead sulfate crystal growth inhibiting additive, and anti-shrink additive. A mixture obtained by aging and drying an active material-filled negative electrode plate filled with a paste-like negative electrode active material prepared by adding water and dilute sulfuric acid to a mixture that has been added and kneaded is preferable. By using the acid-resistant fiber for reinforcement, when the active material is filled into the negative electrode current collector, the active material can be prevented from coming off or falling off. By using the lead sulfate crystal growth inhibiting additive, the additive becomes a crystal nucleus of lead sulfate generated during charging, and fine lead sulfate can be formed. When the anti-shrink agent is added, it is possible to prevent the negative electrode active material from being changed in shape during charge / discharge and to agglomerate, and to maintain the surface area of the active material.

  Moreover, the positive electrode plate before chemical conversion is kneaded by adding water and dilute sulfuric acid to a mixture obtained by adding lead powder mainly composed of lead monoxide, red lead and an additive containing acid-resistant fiber for reinforcement. A material obtained by aging and drying an active material-filled positive electrode plate obtained by filling a paste-like positive electrode active material prepared in this manner into a positive electrode current collector made of a lead alloy is preferable. When the positive electrode current collector is filled with the active material by using the reinforcing acid-resistant fiber, the active material can be prevented from coming off and falling off. In addition, red lead can improve the chemical conversion during battery case formation and increase the utilization rate of the positive electrode active material.

  It is preferable that the reinforcing acid-resistant fiber added to the paste-like negative electrode active material is polyethylene terephthalate fiber, the lead sulfate crystal growth inhibiting additive is barium sulfate, and the antishrink agent is lignin sulfonate. The lead alloy for forming the positive electrode current collector is preferably made of a lead-calcium-tin alloy. Furthermore, it is preferable that the acid-resistant fiber for reinforcement added to the paste-like positive electrode active material is polyethylene terephthalate fiber. By setting the calcium content to 0.07 to 0.09 mass% and the tin content to 1.5 to 1.75 mass%, the alloy composition becomes dense and a positive electrode current collector excellent in corrosion resistance is formed. It becomes possible. The lead alloy for forming the negative electrode current collector is not particularly limited, but pure lead, calcium-tin alloy, and antimony alloy are generally used. It is desirable to use a calcium-tin alloy. Moreover, it is preferable to add 5-25 mass% of the red lead added to a paste-form positive electrode active material with respect to lead powder. When the amount of lead is less than 5%, the effect of the lead is not sufficiently exhibited, and when it is 25% or more, the durability of the active material is remarkably lowered.

  In a specific control valve type lead acid battery manufacturing method of the present invention, an acid-resistant fiber for reinforcement, a lead sulfate crystal growth inhibiting additive and a shrinkage-preventing agent are added to lead powder mainly composed of lead monoxide. Aged and dried active material-filled negative electrode plate formed by filling a negative electrode current collector made of a lead alloy with a paste-like negative electrode active material prepared by adding water and dilute sulfuric acid to a mixed mixture and kneading them Thus, the negative electrode plate before chemical conversion is manufactured. Moreover, water and dilute sulfuric acid are added to a mixture obtained by adding a lead powder mainly composed of lead monoxide, a lead powder, and an additive containing acid-resistant fibers for reinforcement to a positive electrode current collector made of a lead alloy. In addition, an active material-filled positive electrode plate formed by filling a paste-like positive electrode active material prepared by kneading is aged and dried to produce a positive electrode plate before chemical conversion. Then, after forming an electrode plate group including one or more pre-formation negative electrode plates and one or more pre-formation positive electrode plates, a fully charged state is obtained. In the present invention, the ratio of the total negative electrode active material surface area (N) of one or more negative electrode plates in the fully charged electrode plate group after formation to the total positive electrode active material surface area (P) of one or more positive electrode plates. Is in the range of 0.010 <(N) / (P) <0.020, the surface area of the negative electrode plate before chemical conversion and the surface area of the positive electrode plate before chemical conversion are determined by adding the additive and the amount of water. It is determined by adjusting at least one of the amount of dilute sulfuric acid, aging conditions and drying conditions. And the ratio of the negative electrode active material total mass (n) of one or more negative plates fully charged after the formation to the total positive electrode active material mass (p) of one or more positive plates is 0.4 <(n) The filling amount of the paste-type negative electrode active material into the negative electrode current collector and the filling amount of the paste-type positive electrode active material into the positive electrode current collector are determined so as to satisfy the range of /(p)<0.7. According to the manufacturing method of the present invention, the control valve type lead-acid battery of the present invention can be easily manufactured.

It is a perspective view which shows the member structure of an example of a control valve type lead acid battery. In some examples and comparative examples, the relationship between the ratio of the total surface area of the negative electrode active material and the total surface area of the positive electrode active material in the control valve battery in the fully charged state, the capacity ratio of the lead storage battery to the rated capacity, and the number of charge / discharge cycles is shown FIG. FIG. 3 is a curve diagram similar to FIG. 2 in the remaining examples and comparative examples.

  Hereinafter, embodiments of the present invention will be described in detail.

  In the control valve type lead storage battery of the present invention, the ratio of the negative electrode active material total surface area (N) and the positive electrode active material total surface area (P) in the fully charged control valve type lead storage battery is 0.010 < (N) / (P) <0.020, and the ratio of the negative electrode active material total mass (n) to the positive electrode active material total mass (p) is 0.4 <(n) / (p) <0. In the range of .7. The positive electrode plate used in the present invention includes, for example, selection of additives in the manufacturing process of the positive electrode plate, blending amount of the additive when preparing the positive electrode active material paste, addition amount of water and dilute sulfuric acid, aging / drying of the electrode plate Adjusting various parameters such as conditions, selection of additives in the manufacturing process of the negative electrode plate, compounding amount of additives when preparing the negative electrode active material paste, addition amount of water and dilute sulfuric acid, aging of the electrode plate and It can be manufactured by adjusting various parameters such as drying conditions. Further, the shape of the current collector filled with the active material, the amount of active material filling, chemical conversion conditions, and the number of positive and negative electrode plates in the battery case can be adjusted. However, the manufacturing method is not limited to this. .

  In the following embodiments, the total surface area ratio of positive and negative electrode active materials in a fully charged state in a formed state and the total mass ratio of positive and negative electrode active materials in a fully charged state in a formed state are adjusted as follows. ing.

  In other words, the positive electrode active material is a lead alloy current collector made by mixing a lead powder containing lead monoxide as a main component, adding red lead, mixing it, adding a predetermined amount of water and dilute sulfuric acid, and kneading. The body is filled and aged and dried under predetermined conditions. Here, by changing the addition amount of water and dilute sulfuric acid and the aging / drying conditions, the surface area of the active material of the positive electrode plate in the fully charged state in the formed state can be adjusted within a certain target range.

  The negative electrode active material is a powder of lead alloy containing lead powder containing lead monoxide as a main component, mixed with an additive, and mixed with a predetermined amount of water and dilute sulfuric acid. After filling, aging and drying are performed under predetermined conditions. Here, it is possible to adjust the surface area of the active material of the negative electrode plate in a fully charged state within a certain range by changing the amount of additive, water and dilute sulfuric acid added, aging and drying conditions. it can.

  Furthermore, it is possible to adjust the surface area of the positive and negative electrode active materials by changing the chemical conversion conditions.

  Further, the total mass ratio of the positive and negative electrode active materials can be adjusted by changing the amount of the pasty active material filled in the lead alloy current collector.

  As the additive added to the paste-like negative electrode active material, an acid-resistant fiber for reinforcement, a lead sulfate crystal growth inhibiting additive, and a shrinkage preventing agent are used. As the acid-resistant fiber for reinforcement, acrylic fiber, polyester fiber, polyethylene terephthalate (PET) fiber or the like can be used, and it is desirable to use PET fiber from the viewpoint of price and acid resistance. By using the acid-resistant fiber for reinforcement, when the active material is filled into the negative electrode current collector, the active material can be prevented from coming off or falling off. It is common to use barium sulfate as a lead sulfate crystal growth inhibiting additive. By adding barium sulfate, the barium sulfate remains in the active material without dissolving in the electrolyte, and the sulfuric acid produced during charging It becomes lead crystal nucleus and can form fine lead sulfate. A lignin sulfonate can be used as the anti-shrinking agent. There are synthetic lignin and tree-derived natural lignin as lignin sulfonate, and it is desirable to use natural lignin that exists stably for a long period of time for standby use applications that are operated for a long period of time. By adding lignin, it is possible to prevent the negative electrode active material from being changed in shape during charge and discharge and to be aggregated, and to maintain the surface area of the active material. Further, by not containing carbon, it is possible to reduce the current value during trickle charging, and it is possible to sufficiently ensure the life performance.

  As an additive added to the paste-like positive electrode active material, acid-resistant fibers for reinforcement and red lead are used. As the acid-resistant fiber for reinforcement, acrylic fiber, polyester fiber, PET fiber or the like can be used, and it is desirable to use PET fiber from the viewpoint of price and acid resistance. When the positive electrode current collector is filled with the active material by using the reinforcing acid-resistant fiber, the active material can be prevented from coming off and falling off. Lead red can improve the chemical conversion during battery cell formation and increase the surface area of the positive electrode active material to increase the utilization rate of the positive electrode active material, thereby achieving both the conversion of the active material and the durability of the active material. Therefore, it is desirable to add 5 to 25% by mass with respect to the lead powder. When the amount of lead is less than 5%, the effect of the lead is not sufficiently exhibited, and when it is 25% or more, the durability of the active material is remarkably lowered.

  The lead alloy for forming the positive electrode current collector is made of a lead-calcium-tin alloy. By making the calcium content and the tin content as described above, the alloy composition becomes dense and a positive electrode current collector excellent in corrosion resistance can be formed.

The lead alloy for forming the negative electrode current collector is not particularly limited, but pure lead, calcium-tin alloy, and antimony alloy are generally used. -It is desirable to use a tin alloy.
<Surface area of active material in fully charged state>
A general permeation method or gas adsorption method can be used for measuring the surface area of the active material. In the present embodiment, the surface area of the active material is Quantachrome Instrument.
It measured using NOVA 4200e which is a specific surface area measuring instrument which employ | adopts the gas adsorption method made from ts. The cell for measuring the surface area of the fully charged negative electrode active material after the formation uses NOVA 9 mm Large VALVE LONG CELL, and the surface area of the fully charged positive electrode active material after the formation uses NOVA STD 9 mm TEL LONG CELL. It was. The active material mass charged into the cell was 0.7 g for the positive electrode active material and 7.0 g for the negative electrode active material, respectively. Nitrogen gas was used as the gas used for the measurement. Nitrogen gas having a purity of 99.9995% was used. Then, a 6φ filler rod was put in the cell, and the surface area in a fully charged state was measured after the formation of the active material from the amount of nitrogen gas adsorbed on the surface of the active material. The total surface area of the negative electrode active material and the total surface area of the positive electrode active material were calculated using the amount of the active material before chemical conversion used in the negative electrode plate and the positive electrode plate included in the electrode plate group and the above-described measurement results.

<Measurement of total active material mass in fully charged state>
Take out one positive electrode plate and negative electrode plate from the electrode plate group that has been fully charged after formation, measure the mass, and subtract the mass of the current collector to charge each positive electrode plate and negative electrode plate fully. The total mass of negative electrode active material (n) and the total mass of positive electrode active material (p) are calculated based on the number of positive electrode plates and the number of negative electrode plates to be used. Asked.

<Preparation of paste-like positive electrode active material>
The paste-like positive electrode active material was prepared by adding additives such as red lead and cut fiber to lead powder containing lead monoxide as a main component, and adding water and dilute sulfuric acid to the mixture and kneading. .

<Preparation of pasty negative electrode active material>
The paste-like negative electrode active material is mixed with lead powder containing lead monoxide as a main component by adding additives such as lignin sulfosan salt, barium sulfate, cut fiber, and water and dilute sulfuric acid are added to the mixture. It was prepared by kneading.

<Positive electrode plate>
The positive and negative electrode plates described in the present invention are obtained by filling each of the paste-like active materials described above into a current collector, aging and drying. The current collector can be produced by an expanding method, a casting method, or the like.

  As the material of the current collector, tin, calcium, antimony and the like can be added with lead as a main component, and it is preferable to add tin and calcium. The addition of calcium can maintain the strength of the current collector and reduce self-discharge. However, the corrosion of the current collector bone, which is a problem when calcium is added, can be reduced. It is because it can suppress by addition of tin.

<Controlled lead-acid battery>
In the control valve type lead storage battery of the present embodiment, for example, as shown in FIG. 1, the ears of the same polarity electrode plates in which the positive electrode plates 2 and the negative electrode plates 3 are alternately laminated via the separators 4 are connected with straps. An electrode plate group configured as described above is used. The electrode plate group was accommodated in the battery case 5 and closed by the lid 6 to assemble a lead storage battery, and a predetermined amount of electrolyte was injected to form a battery case.

  When a plurality of cell chambers are provided in the battery case, electrode plate groups are accommodated in each cell chamber, and a predetermined polarity is obtained by mutually connecting between the electrode plate groups accommodated in the adjacent cell chambers and the opposite polarity straps. A lead-acid battery having a rated voltage and a rated capacity is configured. In the case of a single-cell battery case, terminals of a plurality of lead storage batteries can be connected in parallel or in series using a conductive plate to constitute a battery having a predetermined voltage and capacity.

  The material of the battery case 5 is not particularly limited, and specifically, polypropylene, ABS, modified PPE (polyphenylene ether) or the like can be used.

  In the control valve type lead-acid battery, a control valve for discharging the excess gas that cannot be absorbed by the gas absorption reaction of the negative electrode out of the oxygen gas generated at the positive electrode at the time of charging is attached. The material of the control valve is preferably a material excellent in chemical resistance (acid resistance, silicon oil resistance), wear resistance, and heat resistance, specifically, fluororubber.

  Examples created based on the embodiments of the present invention will be described below.

  In the following Examples and Comparative Examples, the following pasty negative electrode active materials were used in common.

  A lead-calcium-tin alloy (calcium content: 0.1% by mass, tin content: 0.2% by mass) is melted and length: 144.0 mm, width: 147.0 mm, thickness: 2 depending on the casting method. A negative electrode current collector of 4 mm was produced.

  In this current collector, 0.03 parts by mass of PET fiber, 0.05 parts by mass of barium sulfate, and 0.2 parts of lignin sulfonate with respect to 100 parts by mass of lead powder mainly composed of lead monoxide. Next, 10 parts by mass of water and 10 parts by mass of dilute sulfuric acid were added, and then the paste-like active material prepared by kneading was filled to prepare a negative electrode plate.

Example 1
A lead-calcium-tin alloy (calcium content: 0.08 mass%, tin content: 1.6 mass%) is melted and length: 143.0 mm, width: 145.0 mm, thickness: 4 depending on the casting method. A 0.0 mm positive electrode current collector was produced.

  To this current collector, 17 parts by weight of red lead and 0.15 parts by weight of PET fiber are added to and mixed with 100 parts by weight of lead powder mainly composed of lead monoxide, and then 10 parts by weight of water. After adding 17 parts by mass of dilute sulfuric acid, a paste-like active material prepared by kneading was filled to prepare a positive electrode plate.

  The prepared negative electrode active material paste and positive electrode active material paste were each filled in a current collector so that the total mass of negative electrode active material (n) / total mass of positive electrode active material (p) = 0.4 after formation.

After filling the grid in which the paste-like active material is created, the electrode plate filled with the paste-like negative electrode active material is
Aging condition: temperature: 40 ° C., humidity: 98%, time: 40 hours Drying condition: temperature: 60 ° C., time: aging for 24 hours, a negative electrode plate was produced.

  The electrode plate filled with the paste-like positive electrode active material was manufactured through the following aging conditions 1 to 3 and drying conditions.

Aging condition 1: temperature: 80 ° C., humidity: 98%, time: 10 hours Aging condition 2: temperature: 65 ° C., humidity: 75%, time: 13 hours Aging condition 3: temperature: 40 ° C., humidity: 65% Time: 40 hours Drying conditions: Temperature: 60 ° C., Time: 24 hours The above-described three positive electrode plates and four negative electrode plates described above are alternately laminated via a separator (retainer) made of glass fiber in a mat shape. The electrode groups were produced by connecting the same poles.

  The produced electrode plate group is inserted into the battery case, and after the positive electrode terminal and the negative electrode terminal are welded to the electrode plate group, the battery case is sealed. Next, an electrolyte containing dilute sulfuric acid as a main component was injected from the exhaust plug port, and after forming a battery case, a control valve was attached to produce a control valve type lead storage battery.

  The chemical conversion conditions were as follows: water temperature: 40 ° C., electric charge: 250% of the theoretical chemical electric charge of the positive electrode active material, and time: 60 hours.

(Example 2)
A pasty active material was prepared in the same manner as in Example 1 except that the dilute sulfuric acid added to the positive electrode active material paste was 16 parts by mass with respect to 100 parts by mass of lead powder containing lead monoxide as a main component. The produced negative electrode active material paste and positive electrode active material paste were filled into current collectors so that the total mass of negative electrode active material (n) / total mass of positive electrode active material (p) = 0.5 after chemical conversion. After filling the pasty active material, a control valve type lead-acid battery was produced in the same manner as in Example 1.

Example 3
A pasty active material was prepared in the same manner as in Example 1 except that the dilute sulfuric acid added to the positive electrode active material paste was 15 parts by mass with respect to 100 parts by mass of lead powder containing lead monoxide as a main component. The produced negative electrode active material paste and positive electrode active material paste were filled into current collectors so that the total mass of negative electrode active material (n) / total mass of positive electrode active material (p) = 0.6 after chemical conversion. After filling the pasty active material, a control valve type lead-acid battery was produced in the same manner as in Example 1.

Example 4
A pasty active material was prepared in the same manner as in Example 1 except that the dilute sulfuric acid added to the positive electrode active material paste was 14 parts by mass with respect to 100 parts by mass of lead powder containing lead monoxide as a main component. The produced negative electrode active material paste and positive electrode active material paste were filled into current collectors so that the total mass of negative electrode active material (n) / total mass of positive electrode active material (p) = 0.6 after chemical conversion. After filling the pasty active material, a control valve type lead-acid battery was produced in the same manner as in Example 1.

(Comparative Example 1)
Same as Example 1 except that the negative electrode active material paste and the positive electrode active material paste are filled in the current collector so that the total mass of negative electrode active material (n) / total mass of positive electrode active material (p) = 0.3 after the formation. Thus, a control valve type lead acid battery was produced.

(Comparative Example 2)
Same as Example 4 except that the negative electrode active material paste and the positive electrode active material paste are filled in the current collector so that the total mass of the negative electrode active material (n) / the total mass of the positive electrode active material (p) = 0.7 after the formation. A control valve type lead-acid battery was prepared.

(Examples 5-7)
After the formation of the negative electrode active material paste prepared in Example 1 and the positive electrode active material paste prepared in Example 2, the total mass of negative electrode active material (n) / total mass of positive electrode active material (p) = 0.4 (Example 5) , (N) / (p) = 0.6 (Example 6), (n) / (p) = 0.7 (Example 7) A control valve type lead-acid battery was produced in the same manner as described above.

(Comparative Examples 3-4)
After the formation of the negative electrode active material paste prepared in Example 1 and the positive electrode active material paste prepared in Example 2, the total mass of negative electrode active material (n) / total mass of positive electrode active material (p) = 0.3 (Comparative Example 3) , (N) / (p) = 0.8 (Example 4) A control valve type lead-acid battery was produced in the same manner as in Example 1 except that the current collector was filled.

  Table 1 below shows the amount of addition of the dilute sulfuric acid, the surface area ratio, and the active material amount ratio of the above-described Examples and Comparative Examples.

次に、実施例１〜７及び比較例１〜４の条件で作製した個々の鉛蓄電池について、リプルを印加させたトリクル充電期間ごとに放電容量を確認するリプル印加トリクル寿命試験を行った。

Next, the ripple application trickle life test which confirms a discharge capacity for every trickle charge period to which the ripple was applied was performed about each lead acid battery produced on the conditions of Examples 1-7 and Comparative Examples 1-4.

<Test method>
The discharge capacity confirmation test was based on 0.25 CA. That is, the fully-charged control valve type lead-acid battery is allowed to stand for 24 hours at an ambient temperature of 25 ° C., and then discharged to a final voltage of 1.70 V at 0.25 CA, and the discharge capacity at that time is measured. Then, under the conditions described in JIS C 8702-1, that is, at an ambient temperature of 25 ° C., the battery was charged at a constant current of 0.1 CA until the charge amount reached 110%, and the battery was fully charged.

  In the ripple application trickle life test, a fully-charged control valve lead-acid battery is continuously charged at a constant voltage of 2.275V. Thereafter, the ambient temperature is set to 75 ° C., and the battery is continuously charged for 24 hours at a constant voltage of 2.275V. Thereafter, a ripple having a voltage amplitude of ± 50 mV and a frequency of 25 Hz is applied to the set voltage of 2.275V. A ripple application trickle charge test was conducted for 15 days, and the discharge capacity was measured every 15 days.

<Test results>
FIG. 2 and FIG. 3 show the results of conducting the above life test on the control valve type lead storage batteries of Examples 1 to 7 and Comparative Examples 1 to 4. This was compared with the initial discharge capacity when the discharge test was performed at 0.25 CA after the formation, and when the discharge capacity after the 0.25 CA discharge test after the ripple applied trickle charge was 70% of the initial capacity.

  FIG. 2 shows the test results regarding the control valve type lead storage batteries of Examples 1 to 4 and Comparative Examples 1 and 2. From this, the relationship between the ratio of the total surface area of the negative electrode active material and the total surface area of the positive electrode active material and the life performance can be seen.

  FIG. 3 is a test result relating to the control valve type lead storage batteries of Examples 2, 5 to 7 and Comparative Examples 3 and 4, and the relationship between the ratio of the total mass of the negative electrode active material and the total mass of the positive electrode active material and the life performance thereof. I understand.

  When the ratio of the total mass of the negative electrode active material to the total mass of the positive electrode active material is decreased, the life performance is improved. Comparative Example 1 in which the total surface area ratio is smaller than that in Example 1 and Comparative Example 3 in which the total mass ratio of the active material is smaller than that in Example 2 are too low due to the trickle life test. The life performance decreased due to the strong negative electrode deterioration.

  2 and 3, the ratio of the total surface area (N) of the negative electrode active material and the total surface area (P) of the positive electrode active material in the control valve type lead storage battery is 0.010 <(N) / (P) <0.020. The ratio of the negative electrode active material total mass (n) and the positive electrode active material total mass (p) in the control valve type lead storage battery is 0.4 <(n) / (p) <0.7. When it is in the range, it can be seen that the life is long.

  Preferably, the ratio of the negative electrode active material total surface area (N) and the positive electrode active material total surface area (P) in the control valve type lead-acid battery is in the range of 0.010 <(N) / (P) <0.018. The ratio of the negative electrode active material total mass (n) and the positive electrode active material total mass (p) in the control valve type lead storage battery is in the range of 0.4 <(n) / (p) <0.6. Examples 1, 2, 3, 5, and 6 have longer lifetimes.

  Furthermore, the ratio of the negative electrode active material total surface area (N) and the positive electrode active material total surface area (P) in the control valve type lead-acid battery is in the range of 0.010 <(N) / (P) <0.014, An embodiment in which the ratio of the total mass (n) of the negative electrode active material and the total mass (p) of the positive electrode active material in the control valve type lead-acid battery is in the range of 0.4 <(n) / (p) <0.5 1, 2, and 5 have a long life.

According to the control valve type lead storage battery of the present invention, the positive electrode potential becomes stable, the positive electrode potential decreases, and the positive electrode active material PbO ₂ changes to PbO _x , PbSO ₄ , and the positive electrode corrosion reaction is accelerated. Can be suppressed. Moreover, according to the control valve type lead-acid battery of the present invention, it is possible to suppress the positive electrode potential from rising and to suppress the generation of O ₂ by electrolysis and the acceleration of the positive electrode plate.

DESCRIPTION OF SYMBOLS 1 Control valve type lead acid battery 2 Positive electrode plate 3 Negative electrode plate 4 Separator 5 Battery case 6 Lid

Claims (6)

  A control valve-type lead-acid battery operated in a standby use having an electrode plate group including one or more negative electrode plates and one or more positive electrode plates, in the electrode plate group in a fully charged state after formation The ratio of the negative electrode active material total surface area (N) of the one or more negative plates to the positive electrode active material total surface area (P) of the one or more positive plates is 0.010 <(N) / (P) <0. The ratio of the negative electrode active material total mass (n) of the one or more negative plates to the positive electrode active material total mass (p) of the one or more positive plates is 0.4 <(n ) / (P) <0.7, and the negative electrode active material does not contain carbon.   A control valve-type lead-acid battery operated in a standby use having an electrode plate group including one or more negative electrode plates and one or more positive electrode plates, in the electrode plate group in a fully charged state after formation The ratio of the negative electrode active material total surface area (N) of the one or more negative plates to the positive electrode active material total surface area (P) of the one or more positive plates is 0.010 <(N) / (P) <0. The ratio of the total negative electrode active material mass (n) of the one or more negative plates to the total positive electrode active mass (p) of the one or more positive plates is 0.4 <(n ) / (P) <0.6 and the negative electrode active material does not contain carbon.   A control valve-type lead-acid battery operated in a standby use having an electrode plate group including one or more negative electrode plates and one or more positive electrode plates, wherein the electrode plate group in the fully charged state after formation The ratio of the total negative electrode active material surface area (N) of one or more negative plates to the total positive electrode active material surface area (P) of the one or more positive plates is 0.010 <(N) / (P) <0. The ratio of the total negative electrode active material mass (n) of the one or more negative electrode plates to the total positive electrode active material mass (p) of the one or more positive electrode plates is 0.4 <(n). /(P)<0.5, and the negative electrode active material does not contain carbon. The negative electrode plate before chemical conversion is made of a lead alloy-based negative electrode current collector with lead-resistant oxide fiber, lead sulfate crystal growth inhibitor additive, and anti-shrink agent added to lead powder mainly composed of lead monoxide. An active material-filled negative electrode plate filled with a paste-like negative electrode active material prepared by adding water and dilute sulfuric acid to a mixture added and mixed as an agent and kneading was dried and dried,
The positive electrode plate before chemical conversion is a mixture in which a positive electrode current collector made of a lead alloy is mixed with lead powder mainly composed of lead monoxide, red lead, and an additive containing acid-resistant fibers for reinforcement. The control valve system according to any one of claims 1 to 3, wherein an active material-filled positive electrode plate filled with a paste-like positive electrode active material prepared by adding water and dilute sulfuric acid to the mixture and aging is dried and aged. Lead acid battery. The reinforcing acid-resistant fiber added to the paste-like negative electrode active material is polyethylene terephthalate fiber, the lead sulfate crystal growth inhibiting additive is barium sulfate, and the shrinkage preventing agent is lignin sulfonate,
The lead alloy for forming the positive electrode current collector is made of a lead-calcium-tin alloy,
The control valve system according to claim 4, wherein the acid-resistant fiber for reinforcement added to the paste-like positive electrode active material is polyethylene terephthalate fiber, and 5 to 25% by mass of the red lead is added to lead powder. Lead acid battery. The negative electrode plate before chemical conversion is added to a negative electrode current collector made of a lead alloy, lead powder mainly composed of lead monoxide, acid fiber for reinforcement, lead sulfate crystal growth inhibitor additive and anti-shrink additive. In addition, the active material-filled negative electrode plate formed by filling and mixing the paste-like negative electrode active material prepared by adding water and dilute sulfuric acid to the mixed mixture was aged and dried to produce a negative electrode plate before conversion. ,
Water and dilute sulfuric acid are added to a mixture of a lead alloy consisting of lead alloy and lead powder containing lead monoxide as a main component, red lead and an additive containing acid-resistant fiber for reinforcement. An active material-filled positive electrode plate formed by filling a paste-like positive electrode active material prepared by kneading and aging is aged and dried to produce a positive electrode plate before conversion,
A method of manufacturing a control valve type lead-acid battery that is charged for the first time after forming an electrode plate group including one or more pre-formation negative electrode plates and one or more pre-formation positive electrode plates,
The ratio of the negative electrode active material total surface area (N) of one or more negative electrode plates in the fully charged electrode plate group after the formation to the positive electrode active material total surface area (P) of one or more positive electrode plates is 0. 0.010 <(N) / (P) <0.020, the specific surface area of the negative electrode plate before chemical conversion and the specific surface area of the positive electrode plate before chemical conversion are determined by adding the additive, By adjusting at least one of the amount of water, the amount of dilute sulfuric acid, the aging conditions and the drying conditions,
The ratio of the negative electrode active material total mass (n) of the one or more negative electrode plates in the fully charged electrode plate group after the formation to the total positive electrode active material mass (p) of the one or more positive electrode plates is , 0.4 <(n) / (p) <0.7, the amount of the paste-type negative electrode active material charged into the negative-electrode current collector and the paste-type positive electrode into the positive-electrode current collector A method for manufacturing a control valve type lead-acid battery, characterized in that the filling amount of an active material is determined.

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