WO2016114316A1

WO2016114316A1 - Lead-acid battery, micro-hybrid vehicle, and vehicle having idling stop system

Info

Publication number: WO2016114316A1
Application number: PCT/JP2016/050870
Authority: WO
Inventors: 康平島田; 柴原　敏夫; 隆之木村; 近藤　隆文; 和也丸山
Original assignee: 日立化成株式会社
Priority date: 2015-01-14
Filing date: 2016-01-13
Publication date: 2016-07-21
Also published as: JPWO2016114316A1; JP6432609B2

Abstract

The purpose of the present invention is to provide a lead-acid battery that can achieve excellent charge acceptance. The present invention pertains to a lead-acid battery provided with a positive electrode, a negative electrode, and an electrolyte, wherein: the positive electrode has a current collector and a positive-electrode material held by the current collector; the negative electrode has a current collector and a negative-electrode material held by the current collector; the positive-electrode material has a specific surface area of 11 m²/g or more; the negative-electrode material contains a negative-electrode active material and Ketjenblack; and the electrolyte contains aluminum ions.

Description

Lead acid battery, micro hybrid vehicle and idling stop system vehicle

The present invention relates to a lead storage battery, a micro hybrid vehicle, and an idling stop system vehicle.

In recent years, various measures for improving fuel efficiency have been studied for automobiles in order to prevent air pollution or global warming. Examples of automobiles with measures to improve fuel efficiency include micro-hybrids such as idling stop system cars (hereinafter referred to as “ISS cars”) that reduce engine operating time and power generation control cars that reduce alternator power generation by engine power. Cars are being considered.

In ISS cars, the number of engine starts increases, so the large current discharge of the lead storage battery is repeated. Further, in the ISS car and the power generation control car, the amount of power generated by the alternator is reduced, and the lead storage battery is charged intermittently, so that the charge is insufficient.

The lead storage battery that is used as described above is used in a partially charged state called PSOC (Partial State Of Charge). Lead acid batteries have a shorter life when used under PSOC than when used in a fully charged state.

In recent years, in Europe, the chargeability of lead-acid batteries during charge / discharge cycles in accordance with the control of micro-hybrid vehicles has been emphasized, and DCA (Dynamic Charge Acceptance) evaluation in this form is being standardized. is there. In other words, the use of lead-acid batteries as described above has been regarded as important.

On the other hand, in Patent Document 1 below, in order to improve the charging efficiency and life performance of the battery when used under PSOC, the ratio of the active material in the positive electrode plate is changed by changing the conditions of battery case formation. A technique for adjusting the surface area to 5.5 m ² / g or more is disclosed.

International Publication No. 2012/042917

By the way, when a lead-acid battery is used in a state where charging is not complete and charging is insufficient, the concentration of dilute sulfuric acid, which is an electrolyte, between the upper part and the lower part of the electrode (electrode plate, etc.) in the battery A stratification phenomenon occurs where a difference occurs. This is because the electrolyte solution is not sufficiently stirred because complete charging is not performed. In this case, the concentration of dilute sulfuric acid in the lower part of the electrode becomes high and sulfation occurs. Sulfation is a phenomenon in which lead sulfate, which is a discharge product, is difficult to return to a charged state. Therefore, when sulfation occurs, only the upper part of the electrode reacts intensively. As a result, deterioration such as weakening of the connection between the active materials progresses at the upper part of the electrode, and the active material peels from the current collector, leading to a decrease in battery performance and an early life.

Therefore, in recent lead-acid batteries, in order to improve the battery life performance when used under PSOC, it is extremely important to improve the charge acceptability compared to the conventional technology such as Patent Document 1 above. It has become a challenge.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a lead storage battery capable of obtaining excellent charge acceptability. An object of the present invention is to provide a micro hybrid vehicle and an ISS vehicle including the lead storage battery.

On the other hand, the present inventors have found that the above problem can be solved by using a positive electrode material having a specific specific surface area, a negative electrode material containing a specific component, and an electrolytic solution.

That is, the lead storage battery according to the present invention is a lead storage battery including a positive electrode, a negative electrode, and an electrolyte solution, and the positive electrode includes a current collector (positive electrode current collector) and a positive electrode material held by the current collector. The negative electrode has a current collector (negative electrode current collector) and a negative electrode material held by the current collector, and the specific surface area of the positive electrode material is 11 m ² / g or more. The negative electrode material contains a negative electrode active material and ketjen black (registered trademark, hereinafter the same), and the electrolytic solution contains aluminum ions.

According to the lead storage battery of the present invention, excellent charge acceptability can be obtained. Moreover, according to the lead acid battery which concerns on this invention, it can suppress that the lifetime of the lead acid battery used under PSOC becomes short. According to the lead acid battery of the present invention, especially after the charge and discharge are repeated to some extent from the initial state and the active material is sufficiently activated, the SOC (State Of) which tends to be low in the ISS car and the micro hybrid car. Charge) can be maintained at an appropriate level. Furthermore, when the sulfation described above occurs, other battery performance (discharge characteristics, cycle characteristics, etc.) may be reduced, but according to the lead storage battery according to the present invention, excellent charge acceptance and other excellent Both battery performance (discharge characteristics, cycle characteristics, etc.) can be achieved. Such a lead storage battery is particularly excellent as an application for an ISS vehicle, a micro hybrid vehicle, or the like.

Regarding the reason why the life of lead-acid batteries used under PSOC is shortened, if charging and discharging are repeated in a state where charging is insufficient, lead sulfate produced on the negative electrode (negative electrode plate, etc.) becomes coarse during discharge. This is thought to be because lead sulfate is difficult to return to the lead metal as the charge product. On the other hand, in the lead storage battery according to the present invention, it is presumed that the charge acceptability is improved and the life of the lead storage battery can be suppressed from shortening for the following reasons (1) to (3). The
(1) The current density is reduced by increasing the specific surface area of the positive electrode material, and charging is likely to occur because the charging overvoltage is reduced.
(2) Since ketjen black is excellent in the formation of an effective conductive network, a reaction (charging) from insulating lead sulfate to metallic lead tends to occur.
(3) By improving the diffusibility of sulfate ions by aluminum ions, lead sulfate is easily dissolved in the electrolytic solution, and charging is promoted.

The negative electrode material preferably further contains a bisphenol-based resin having at least one selected from the group consisting of a sulfone group and a sulfonate group. In this case, further excellent charge acceptability can be obtained.

The negative electrode material preferably further contains at least one selected from the group consisting of lignin sulfonic acid and lignin sulfonate. Thereby, the discharge characteristics can be further improved.

The specific gravity of the electrolytic solution is preferably 1.24 to 1.33 (20 ° C. conversion). In this case, charge acceptability, discharge characteristics, and cycle characteristics can be further improved in a balanced manner.

The content of the ketjen black is preferably 0.01 to 2% by mass based on the total mass of the negative electrode material. Thereby, cycle characteristics, discharge characteristics, and charge acceptability can be further improved in a balanced manner.

The specific surface area of the negative electrode material is preferably 0.5 to 1.2 m ² / g. Thereby, it is possible to achieve both excellent charge acceptability and other excellent battery performances (discharge characteristics, cycle characteristics, etc.) even better.

The concentration of the aluminum ions in the electrolytic solution is preferably 0.01 to 0.2 mol / L. Thereby, charge acceptability and cycle characteristics can be further improved.

The micro hybrid vehicle and the ISS vehicle according to the present invention include the lead storage battery.

According to the present invention, excellent charge acceptability can be obtained. In addition, according to the present invention, it is possible to achieve both excellent charge acceptance and other excellent battery performance (discharge characteristics, cycle characteristics, etc.). The lead storage battery according to the present invention can be suitably used in an ISS vehicle, a micro hybrid vehicle, or the like as a liquid lead storage battery in which charging is performed intermittently and high rate discharge is performed under PSOC.

According to the present invention, an application of a lead storage battery to a micro hybrid vehicle can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application of the lead storage battery to an ISS vehicle can be provided.

Hereinafter, embodiments of the present invention will be described in detail. In addition, since specific gravity changes with temperature, in this specification, it defines as specific gravity converted at 20 degreeC.

<Lead battery, micro hybrid vehicle and ISS vehicle>
The lead storage battery according to the present embodiment includes, for example, an electrode (electrode plate or the like), an electrolytic solution (dilute sulfuric acid or the like), and a separator. The electrode has a positive electrode (positive electrode plate or the like) and a negative electrode (negative electrode plate or the like). Examples of the lead storage battery according to this embodiment include a liquid lead storage battery, a control valve type lead storage battery, a sealed lead storage battery, and the like, and a liquid lead storage battery is preferable. The positive electrode has a current collector (positive electrode current collector) and a positive electrode material held by the current collector. The negative electrode has a current collector (negative electrode current collector) and a negative electrode material held by the current collector. In the present embodiment, the positive electrode material and the negative electrode material are, for example, electrode materials after chemical conversion (for example, in a fully charged state). When the electrode material is unformed, the electrode material (unformed positive electrode material and unformed negative electrode material) contains a raw material of an electrode active material (positive electrode active material and negative electrode active material). The current collector constitutes a conductive path for current from the electrode material. As a basic configuration of the lead storage battery, the same configuration as that of a conventional lead storage battery can be used. The micro hybrid vehicle and the ISS vehicle according to the present embodiment include the lead storage battery according to the present embodiment.

In the present embodiment, the specific surface area of the positive electrode material is 11 m ² / g or more. The negative electrode material contains at least (A) a negative electrode active material and (B) ketjen black, and may further contain an additive as necessary. The electrolytic solution contains aluminum ions.

(Positive electrode material)
[Positive electrode active material]
The positive electrode material contains a positive electrode active material. The positive electrode active material can be obtained by aging and drying a positive electrode material paste containing a raw material for the positive electrode active material to obtain an unformed positive electrode active material and then forming an unformed positive electrode active material. The positive electrode active material after chemical conversion preferably contains β-lead dioxide (β-PbO ₂ ), and may further contain α-lead dioxide (α-PbO ₂ ). There is no restriction | limiting in particular as a raw material of a positive electrode active material, For example, lead powder is mentioned. As the lead powder, for example, lead powder manufactured by a ball mill type lead powder manufacturing machine or a barton pot type lead powder manufacturing machine (in the ball mill type lead powder manufacturing machine, a mixture of powder of main component PbO and scale-like metal lead) ). Red lead as a raw material of the positive electrode active material _(Pb 3 _{O 4)} may be used. The unformed positive electrode material preferably contains an unformed positive electrode active material containing tribasic lead sulfate as a main component.

The average particle diameter of the positive electrode active material is preferably 0.3 μm or more, more preferably 0.5 μm or more, and even more preferably 0.7 μm or more, from the viewpoint of further improving charge acceptance and cycle characteristics. The average particle diameter of the positive electrode active material is preferably 2.5 μm or less, more preferably 2 μm or less, and even more preferably 1.5 μm or less from the viewpoint of further improving the cycle characteristics. The average particle diameter of the positive electrode active material is an average particle diameter of the positive electrode active material in the positive electrode material after chemical conversion. The average particle diameter of the positive electrode active material is, for example, the long side of all active material particles in the image of a scanning electron micrograph (1000 times) in the range of 10 μm in length × 10 μm in the positive electrode material at the center of the positive electrode after chemical conversion It can be obtained as a numerical value obtained by arithmetically averaging the length (maximum particle size) value.

The content of the positive electrode active material is preferably 95% by mass or more based on the total mass of the positive electrode material from the viewpoint of further excellent battery characteristics (capacity, low-temperature high-rate discharge performance, charge acceptance, cycle characteristics, etc.), 97 The mass% or more is more preferable, and 99 mass% or more is still more preferable. The upper limit of the content of the positive electrode active material may be 100% by mass or less. The content of the positive electrode active material is the content of the positive electrode active material in the positive electrode material after chemical conversion.

[Positive electrode additive]
The positive electrode material may further contain an additive. Examples of the additive include carbon materials (carbonaceous conductive material, excluding carbon fibers), reinforcing short fibers, and the like. Examples of the carbon material include carbon black and graphite. Examples of carbon black include furnace black (Ketjen black, etc.), channel black, acetylene black, thermal black, and the like. Examples of the reinforcing short fibers include acrylic fibers, polyethylene fibers, polypropylene fibers, polyethylene terephthalate fibers, and carbon fibers.

[Physical properties of positive electrode material]
The lower limit of the specific surface area of the positive electrode material is 11 m ² / g or more from the viewpoint of obtaining excellent charge acceptability. The specific surface area of the positive electrode material is preferably 11.5 m ² / g or more, more preferably 12 m ² / g or more, from the viewpoint of obtaining further excellent charge acceptance. Although there is no limit to the upper limit of the specific surface area of the cathode material, from the viewpoint of excellent practical point of view and utilization, preferably ^{20 m} 2 / g or less, more preferably ^{15 m} 2 / g or less, more preferably ^13m 2 / g or less . From these viewpoints, the specific surface area of the cathode material is preferably 11 ~ ^20m 2 / g, more preferably from 11.5 ~ ^15m 2 / g, more preferably 12 ~ ^13m 2 / g. The specific surface area of the positive electrode material is the specific surface area of the positive electrode material after chemical conversion. The specific surface area of the positive electrode material is, for example, a method of adjusting the amount of dilute sulfuric acid and water added when preparing the positive electrode material paste described below, a method of refining the active material at the stage of the unformed positive electrode active material, and chemical conversion conditions It can be adjusted by a method of changing.

The specific surface area of the positive electrode material can be measured by, for example, the BET method. The BET method is a method in which an inert gas (for example, nitrogen gas) having a known molecular size is adsorbed on the surface of a measurement sample, and the surface area is obtained from the adsorption amount and the area occupied by the inert gas. This is a general method for measuring the surface area. Specifically, it is measured based on the following BET equation.

Relationship of the following formula (1), _P / P _o is satisfied be in the range of 0.05-0.35. In addition, in Formula (1), the detail of each code | symbol is as follows.
P: Adsorption equilibrium pressure when in an adsorption equilibrium state at a constant temperature P _o : Saturated vapor pressure at the adsorption temperature V: Adsorption amount at the adsorption equilibrium pressure P V _m : Monomolecular layer adsorption amount (a gas molecule is a single molecule on a solid surface) Adsorption amount when layer is formed)
C: BET constant (parameter relating to the interaction between the solid surface and the adsorbent)

By transforming equation (1) (dividing the numerator denominator on the left side by P), the following equation (2) is obtained. In the specific surface area meter used for the measurement, gas molecules having a known adsorption occupation area are adsorbed on the sample, and the relationship between the adsorption amount (V) and the relative pressure (P / P _o ) is measured. From the measured V and P / _Po , the left side of Equation (2) and P / _Po are plotted. Here, assuming that the gradient is s, the following formula (3) is derived from the formula (2). Assuming that the intercept is i, the intercept i and the gradient s are as shown in the following formula (4) and the following formula (5), respectively.

When Expression (4) and Expression (5) are modified, the following Expression (6) and Expression (7) are obtained, respectively, and the following Expression (8) for obtaining the monomolecular layer adsorption amount V _m is obtained. That is, when the adsorption amount V at a certain relative pressure P / _Po is measured at several points and the slope and intercept of the plot are obtained, the monomolecular layer adsorption amount V _m is obtained.

The total surface area S _total (m ² ) of the sample is obtained by the following formula (9), and the specific surface area S (m ² / g) is obtained by the following formula (10) from the total surface area S _total . In the formula (9), N denotes the Avogadro's _{number, A CS} shows the adsorption cross sectional area ^{(m 2),} M indicates the molecular weight. Moreover, in Formula (10), w shows a sample amount (g).

The porosity of the positive electrode material is preferably 50% by volume or more, and more preferably 55% by volume or more from the viewpoint of increasing the capacity of the dilute sulfuric acid in the pores (holes) in the positive electrode material and increasing the capacity. Although there is no restriction | limiting in particular in the upper limit of the porosity of a positive electrode material, 70 volume% or less from the viewpoint which the amount of impregnation of the dilute sulfuric acid to the void | hole part in a positive electrode material is moderate, and can maintain the bonding force of active materials favorably. Is preferred. The upper limit of the porosity is more preferably 60% by volume or less from a practical viewpoint. The porosity of the positive electrode material is the porosity of the positive electrode material after chemical conversion. The porosity of the positive electrode material is, for example, a value (ratio based on volume) obtained from mercury porosimeter measurement. The porosity of the positive electrode material can be adjusted by, for example, the amount of dilute sulfuric acid added when producing the positive electrode material paste.

(Negative electrode material)
[(A) component: negative electrode active material]
The negative electrode active material can be obtained by chemical conversion of an unformed negative electrode active material after obtaining an unformed negative electrode active material by aging and drying a negative electrode material paste containing a raw material of the negative electrode active material. Examples of the negative electrode active material after chemical conversion include spongy lead. The spongy lead tends to react with dilute sulfuric acid in the electrolyte and gradually change to lead sulfate (PbSO ₄ ). Examples of the raw material for the negative electrode active material include lead powder. As the lead powder, for example, lead powder manufactured by a ball mill type lead powder manufacturing machine or a barton pot type lead powder manufacturing machine (in the ball mill type lead powder manufacturing machine, a mixture of powder of main component PbO and scale-like metal lead) ). The unformed negative electrode active material is composed of, for example, basic lead sulfate, metallic lead, and a lower oxide.

The average particle diameter of the negative electrode active material is preferably 0.3 μm or more, more preferably 0.5 μm or more, and even more preferably 0.6 μm or more, from the viewpoint of further improving charge acceptance and cycle characteristics. The average particle diameter of the negative electrode active material is preferably 2 μm or less, more preferably 1.8 μm or less, and even more preferably 1.5 μm or less from the viewpoint of further improving cycle characteristics. The average particle diameter of the negative electrode active material is an average particle diameter of the negative electrode active material in the negative electrode material after chemical conversion. The average particle diameter of the negative electrode active material is, for example, the long side of all the active material particles in the scanning electron micrograph (1000 times) image of the negative electrode material in the central part of the negative electrode after chemical conversion in the range of 10 μm in length × 10 μm in width. It can be obtained as a numerical value obtained by arithmetically averaging the length (maximum particle size) value.

The content of the negative electrode active material is preferably 93% by mass or more based on the total mass of the negative electrode material, from the viewpoint of further excellent battery characteristics (capacity, low-temperature high-rate discharge performance, charge acceptance, cycle characteristics, etc.), 95 More preferably, it is more preferably 98% by mass or more. The upper limit of the content of the negative electrode active material may be less than 100% by mass. The said content of a negative electrode active material is content of the negative electrode active material in the negative electrode material after chemical conversion.

[(B) component: Ketjen black]
Ketjen black has a hollow shell-like structure, a large number of primary particles per unit mass, and a large specific surface area. Examples of the ketjen black include “Carbon ECP600JD” manufactured by Lion Specialty Chemicals Co., Ltd.

Ketjen Black DBP oil absorption is preferably 100 to 600 mL / 100 g, more preferably 300 to 600 mL / 100 g. The DBP oil absorption of ketjen black may be 400 to 600 mL / 100 g. Ketjen Black having a DBP oil absorption in such a range is excellent in conductivity and easily forms a conductive network in the negative electrode material, and can further improve charge acceptance. The DBP oil absorption can be measured according to ASTM D2414.

The upper limit of the average particle diameter of ketjen black is preferably 100 μm or less, and preferably 50 μm or less from the viewpoint of excellent ease of incorporation into lead sulfate generated during discharge and the improvement of affinity with lead sulfate. Is more preferably 20 μm or less, and particularly preferably 10 μm or less. The lower limit of the average particle diameter of ketjen black is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.3 μm or more, and further preferably 0.5 μm or more from a practical viewpoint. Generally, commercially available ketjen black is in a state in which primary particles are aggregated (secondary particles). When primary particles of ketjen black are in an aggregated state, from the viewpoint of further improving cycle characteristics, discharge characteristics and charge acceptance, pulverize until the average particle size is 10 μm or less before preparing the negative electrode material paste. Alternatively, it is preferable to add ketjen black to the paste after stirring with a small amount of water. Such treatment increases the affinity for lead sulfate and facilitates the effect of ketjen black.

The average particle diameter of ketjen black can be determined in accordance with, for example, the laser diffraction / scattering method described in JISM8511 (2014). Specifically, a commercially available surfactant polyoxyethylene octylphenyl ether (for example, Roche Diagnostics) is used as a dispersant using a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd .: Microtrack 9220FRA). An appropriate amount of ketjen black is put into an aqueous solution containing 0.5% by volume of Triton X-100 manufactured by Co., Ltd., followed by irradiation with 40 W ultrasonic waves for 180 seconds while stirring. The calculated median diameter (D50) is taken as the average particle diameter of Ketjen Black. The average particle diameter of ketjen black may be an average particle diameter obtained before chemical conversion or may be an average particle diameter obtained after chemical conversion.

The content of ketjen black is preferably 0.01% by mass or more, preferably 0.03% by mass or more, based on the total mass of the negative electrode material, from the viewpoint of further improving the cycle characteristics, discharge characteristics and charge acceptance. Is more preferable, and 0.05 mass% or more is still more preferable. The content of ketjen black may be 0.1% by mass or more. The content of ketjen black is preferably 2% by mass or less, more preferably 1.5% by mass or less, based on the total mass of the negative electrode material, from the viewpoint of further improving the cycle characteristics, discharge characteristics and charge acceptance. 0.5% by mass or less is more preferable. The content of ketjen black may be 0.3% by mass or less. The content of ketjen black is preferably 0.01 to 2% by mass, preferably 0.03 to 1%, based on the total mass of the negative electrode material, from the viewpoint of further improving the cycle characteristics, discharge characteristics and charge acceptance. 0.5% by mass is more preferable, 0.03 to 0.5% by mass is still more preferable, and 0.05 to 0.5% by mass is particularly preferable. The content of ketjen black may be 0.1 to 0.3% by mass. The content of ketjen black is the content of ketjen black in the negative electrode material after chemical conversion.

[(C) component: resin having sulfone group and / or sulfonate group]
The negative electrode material is a resin having at least one selected from the group consisting of sulfone groups (sulfonic acid groups, sulfo groups) and sulfonic acid groups, from the viewpoint of further improving charge acceptability, discharge characteristics, and cycle characteristics. It is preferable to further contain (a resin having a sulfone group and / or a sulfonate group).

As the component (C), a bisphenol resin having at least one selected from the group consisting of a sulfone group and a sulfonate group (a bisphenol resin having a sulfone group and / or a sulfonate group. Hereinafter, simply referred to as “bisphenol resin”) ), Lignin sulfonic acid, lignin sulfonate, and the like. Among these, from the viewpoint of further improving the charge acceptability, bisphenol-based resins are preferable, (c1) bisphenol-based compounds, (c2) aminoalkyl sulfonic acids, aminoalkyl sulfonic acid derivatives, aminoaryl sulfonic acids, and aminoaryl sulfones. A bisphenol-based resin that is a condensate of at least one selected from the group consisting of acid derivatives and at least one selected from the group consisting of (c3) formaldehyde and formaldehyde derivatives is more preferable. Hereinafter, the bisphenol resin that is the condensate of (c1) to (c3) will be described in detail.

((C1) component: bisphenol compound)
A bisphenol-based compound is a compound having two hydroxyphenyl groups. Component (c1) includes 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “bisphenol A”), bis (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl) ethane. 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) butane, bis (4- Hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) sulfone (hereinafter, "Bisphenol S"). (C1) A component can be used individually by 1 type or in combination of 2 or more types. As the component (c1), bisphenol A is preferable from the viewpoint of further excellent charge acceptance, and bisphenol S is preferable from the viewpoint of further excellent discharge characteristics.

As the component (c1), it is preferable to use bisphenol A and bisphenol S in combination from the viewpoint that the cycle characteristics, the discharge characteristics, and the charge acceptability are easily improved in a balanced manner. In this case, the blending amount of bisphenol A for obtaining a bisphenol-based resin is 70 mol% or more based on the total amount of bisphenol A and bisphenol S from the viewpoint of easily improving the cycle characteristics, discharge characteristics and charge acceptability in a balanced manner. Is more preferable, 75 mol% or more is more preferable, and 80 mol% or more is still more preferable. The blending amount of bisphenol A is preferably 99 mol% or less, more preferably 98 mol% or less, based on the total amount of bisphenol A and bisphenol S, from the viewpoint that the cycle characteristics, discharge characteristics and charge acceptance are easily improved in a balanced manner. More preferably, it is 97 mol% or less.

((C2) component: aminoalkylsulfonic acid, aminoalkylsulfonic acid derivative, aminoarylsulfonic acid and aminoarylsulfonic acid derivative)
Examples of the aminoalkylsulfonic acid include aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 3-aminopropanesulfonic acid, 2-methylaminoethanesulfonic acid and the like.

Examples of aminoalkyl sulfonic acid derivatives include compounds in which a hydrogen atom of aminoalkyl sulfonic acid is substituted with an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms) or the like, and a sulfone group (—SO ₃ H) of aminoalkyl sulfonic acid. Examples thereof include alkali metal salts in which hydrogen atoms are substituted with alkali metals (for example, sodium and potassium).

Examples of aminoarylsulfonic acid include aminobenzenesulfonic acid and aminonaphthalenesulfonic acid. Examples of aminoarylsulfonic acid derivatives include aminobenzenesulfonic acid derivatives and aminonaphthalenesulfonic acid derivatives.

Examples of aminobenzene sulfonic acid include 2-aminobenzene sulfonic acid (also known as alternilic acid), 3-aminobenzene sulfonic acid (also known as metanylic acid), 4-aminobenzene sulfonic acid (also known as sulfanilic acid), and the like.

As the aminobenzenesulfonic acid derivative, a compound in which a part of hydrogen atoms of aminobenzenesulfonic acid is substituted with an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms) or the like, a sulfone group of aminobenzenesulfonic acid (—SO ₃ And an alkali metal salt (sodium salt, potassium salt, etc.) in which the hydrogen atom of H) is substituted with an alkali metal (for example, sodium and potassium). Examples of the compounds in which some hydrogen atoms of aminobenzenesulfonic acid are substituted with alkyl groups include 4- (methylamino) benzenesulfonic acid, 3-methyl-4-aminobenzenesulfonic acid, and 3-amino-4-methylbenzene. Examples include sulfonic acid, 4- (ethylamino) benzenesulfonic acid, and 3- (ethylamino) -4-methylbenzenesulfonic acid. Examples of the compound in which the hydrogen atom of the sulfone group of aminobenzenesulfonic acid is replaced with an alkali metal include sodium 2-aminobenzenesulfonate, sodium 3-aminobenzenesulfonate, sodium 4-aminobenzenesulfonate, 2-aminobenzenesulfone. Examples include potassium acid, potassium 3-aminobenzenesulfonate, and potassium 4-aminobenzenesulfonate.

Examples of aminonaphthalenesulfonic acid include 4-amino-1-naphthalenesulfonic acid (p-form), 5-amino-1-naphthalenesulfonic acid (ana-form), 1-amino-6-naphthalenesulfonic acid (ε-form) 5-amino-2-naphthalenesulfonic acid), 6-amino-1-naphthalenesulfonic acid (ε-form), 6-amino-2-naphthalenesulfonic acid (amphi-form), 7-amino-2-naphthalenesulfone Acid, aminonaphthalene monosulfonic acid such as 8-amino-1-naphthalenesulfonic acid (peri-form), 1-amino-7-naphthalenesulfonic acid (kata-form, 8-amino-2-naphthalenesulfonic acid); 1 -Amino-3,8-naphthalenedisulfonic acid, 3-amino-2,7-naphthalenedisulfonic acid, 7-amino-1,5-naphthalenedisulfonic acid Aminonaphthalenedisulfonic acid such as sulfonic acid, 6-amino-1,3-naphthalenedisulfonic acid, 7-amino-1,3-naphthalenedisulfonic acid; 7-amino-1,3,6-naphthalenetrisulfonic acid, 8- And aminonaphthalene trisulfonic acid such as amino-1,3,6-naphthalene trisulfonic acid.

Examples of the aminonaphthalenesulfonic acid derivative include compounds in which a part of hydrogen atoms of aminonaphthalenesulfonic acid is substituted with an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms) or the like, a sulfone group of aminonaphthalenesulfonic acid (—SO ₃ And an alkali metal salt (sodium salt, potassium salt, etc.) in which the hydrogen atom of H) is substituted with an alkali metal (for example, sodium and potassium).

(C2) A component can be used individually by 1 type or in combination of 2 or more types. As the component (c2), 4-aminobenzenesulfonic acid is preferable from the viewpoint of further improving cycle characteristics and charge acceptability.

From the viewpoint of further improving the discharge characteristics, the amount of the component (c2) for obtaining the bisphenol-based resin is preferably 0.5 mol or more, more preferably 0.6 mol or more, with respect to 1 mol of the component (c1). 0.8 mol or more is more preferable, and 0.9 mol or more is particularly preferable. Component (c2) is blended in an amount of preferably 1.3 mol or less, more preferably 1.2 mol or less, and 1.1 mol or less with respect to 1 mol of component (c1), from the viewpoint that the cycle characteristics and discharge characteristics can be further improved. Is more preferable.

((C3) component: formaldehyde and formaldehyde derivatives)
As formaldehyde, formaldehyde in formalin (for example, an aqueous solution of 37% by mass of formaldehyde) may be used. Examples of formaldehyde derivatives include paraformaldehyde, hexamethylenetetramine, and trioxane. (C3) A component can be used individually by 1 type or in combination of 2 or more types. You may use formaldehyde and a formaldehyde derivative together.

As the component (c3), a formaldehyde derivative is preferable and paraformaldehyde is more preferable from the viewpoint that excellent cycle characteristics are easily obtained. Paraformaldehyde has, for example, a structure represented by the following general formula (I).
HO (CH ₂ O) _n1 H (I)
[In the formula (I), n1 represents an integer of 2 to 100. ]

From the viewpoint of improving the reactivity of the component (c2), the amount of the component (c3) in terms of formaldehyde to obtain the bisphenol-based resin is preferably 2 mol or more, and 2.2 mol or more with respect to 1 mol of the component (c1). Is more preferable, and 2.4 mol or more is still more preferable. From the viewpoint of excellent solubility of the obtained bisphenol-based resin in a solvent, the amount of the (c3) component in terms of formaldehyde is preferably 3.5 mol or less and more preferably 3.2 mol or less with respect to 1 mol of the component (c1). 3 mol or less is more preferable.

For example, the bisphenol-based resin preferably has at least one of a structural unit represented by the following general formula (II) and a structural unit represented by the following general formula (III).

[In the formula (II), X ² represents a divalent group, A ² represents an alkylene group having 1 to 4 carbon atoms or an arylene group, and R ²¹ , R ²³ and R ²⁴ are each independently Represents an alkali metal or hydrogen atom, R ²² represents a methylol group (—CH ₂ OH), n21 represents an integer of 1 to 150, n22 represents an integer of 1 to 3, and n23 represents 0 Or 1 is shown. Further, the hydrogen atom directly bonded to the carbon atom constituting the benzene ring may be substituted with an alkyl group having 1 to 5 carbon atoms. ]

[In Formula (III), X ³ represents a divalent group, A ³ represents an alkylene group having 1 to 4 carbon atoms or an arylene group, and R ³¹ , R ³³ and R ³⁴ are each independently selected. Represents an alkali metal or a hydrogen atom, R ³² represents a methylol group (—CH ₂ OH), n31 represents an integer of 1 to 150, n32 represents an integer of 1 to 3, and n33 represents 0 Or 1 is shown. Further, the hydrogen atom directly bonded to the carbon atom constituting the benzene ring may be substituted with an alkyl group having 1 to 5 carbon atoms. ]

The ratio of the structural unit represented by the formula (II) and the structural unit represented by the formula (III) is not particularly limited, and may vary depending on synthesis conditions and the like. As the bisphenol-based resin, a resin having only one of the structural unit represented by the formula (II) and the structural unit represented by the formula (III) may be used.

Examples of X ² and X ³ include alkylidene groups (methylidene group, ethylidene group, isopropylidene group, sec-butylidene group, etc.), cycloalkylidene groups (cyclohexylidene group, etc.), phenylalkylidene groups (diphenylmethylidene group). , A phenylsulfonyl group, and the like; a sulfonyl group, and the isopropylidene group (—C (CH ₃ ) ₂ —) is preferable from the viewpoint of further excellent charge acceptance, and from the viewpoint of further excellent discharge characteristics. A sulfonyl group (—SO ₂ —) is preferred. X ² and X ³ may be substituted with a halogen atom such as a fluorine atom. When X ² and X ³ are cycloalkylidene groups, the hydrocarbon ring may be substituted with an alkyl group or the like.

Examples of A ² and A ³ include alkylene groups having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, and a butylene group; and divalent arylene groups such as a phenylene group and a naphthylene group. The arylene group may be substituted with an alkyl group or the like.

^Examples of the alkali metal for R ²¹ , R ²³ , R ²⁴ , R ³¹ , R ³³ and R ³⁴ include sodium and potassium. n21 and n31 are preferably 1 to 150, more preferably 10 to 150, from the viewpoint of further excellent cycle characteristics and solubility in a solvent. n22 and n32 are preferably 1 or 2, and more preferably 1, from the viewpoint that the cycle characteristics, the discharge characteristics, and the charge acceptability are easily improved in a balanced manner. Although n23 and n33 change with manufacturing conditions, 0 is preferable from a viewpoint which is further excellent in cycling characteristics and the storage stability of bisphenol-type resin.

The method for producing a bisphenol-based resin includes a resin production step of obtaining a bisphenol-based resin by reacting the component (c1), the component (c2) and the component (c3).

The bisphenol-based resin can be obtained, for example, by reacting the component (c1), the component (c2) and the component (c3) in a reaction solvent. The reaction solvent is preferably water (for example, ion exchange water). In order to promote the reaction, an organic solvent, a catalyst, an additive, or the like may be used.

In the resin production process, from the viewpoint of further improving the cycle characteristics, the blending amount of the component (c2) is 0.5 to 1.3 mol with respect to 1 mol of the component (c1), and the blending amount of the component (c3) is (C1) An embodiment in which the amount is 2 to 3.5 mol in terms of formaldehyde with respect to 1 mol of the component is preferable. Preferred blending amounts of the component (c2) and the component (c3) are the ranges described above for the blending amounts of the component (c2) and the component (c3).

The bisphenol-based resin is preferably obtained by reacting the component (c1), the component (c2) and the component (c3) under basic conditions (alkaline conditions) from the viewpoint that a sufficient amount of bisphenol-based resin can be easily obtained. In order to adjust to basic conditions, you may use a basic compound. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate and the like. A basic compound can be used individually by 1 type or in combination of 2 or more types. Among the basic compounds, sodium hydroxide and potassium hydroxide are preferable from the viewpoint of excellent reactivity.

When the reaction solution containing the component (c1), the component (c2) and the component (c3) is neutral (pH = 7) at the start of the reaction, the formation reaction of the bisphenol-based resin may not easily proceed. If the solution is acidic (pH <7), side reactions may proceed. Therefore, the pH of the reaction solution at the start of the reaction is preferably alkaline (exceeding 7) from the viewpoint of suppressing the side reaction from proceeding while the bisphenol-based resin formation reaction proceeds, and is 7.1 or more Is more preferable, and 7.2 or more is still more preferable. The pH of the reaction solution is preferably 12 or less, more preferably 10 or less, and even more preferably 9 or less from the viewpoint of suppressing the hydrolysis of the group derived from the component (c2) of the bisphenol resin. The pH of the reaction solution can be measured, for example, with a twin pH meter AS-212 manufactured by Horiba, Ltd. The pH is defined as the pH at 25 ° C.

Since it is easy to adjust the pH as described above, the blending amount of the strongly basic compound is preferably 1.01 mol or more, more preferably 1.02 mol or more with respect to 1 mol of the sulfone group contained in the component (c2). 1.03 mol or more is still more preferable. From the same viewpoint, the compounding amount of the strongly basic compound is preferably 1.1 mol or less, more preferably 1.08 mol or less, still more preferably 1.07 mol or less with respect to 1 mol of the sulfone group contained in the component (c2). . Examples of the strongly basic compound include sodium hydroxide and potassium hydroxide.

The synthesis reaction of the bisphenol-based resin is sufficient if the (c1) component, the (c2) component, and the (c3) component are reacted to obtain a bisphenol-based resin. For example, the (c1) component, the (c2) component, and the (c3) The components may be reacted simultaneously, or the remaining one component may be reacted after reacting two of the components (c1), (c2) and (c3).

The synthesis reaction of the bisphenol-based resin is preferably performed in two steps as follows. In the first-stage reaction, for example, aminoalkyl sulfonic acid and / or aminoaryl sulfonic acid, a solvent (such as water), and a basic compound are charged and stirred, and then aminoalkyl sulfonic acid and / or aminoaryl sulfonic acid are mixed. The hydrogen atom of the sulfone group in the acid is substituted with an alkali metal or the like to obtain an alkali metal salt of aminoalkyl sulfonic acid and / or aminoaryl sulfonic acid (aminoalkyl sulfonic acid derivative and / or aminoaryl sulfonic acid derivative). Thereby, it becomes easy to suppress a side reaction in the below-mentioned condensation reaction. The temperature of the reaction system is preferably 0 ° C. or higher, more preferably 25 ° C. or higher, from the viewpoint of excellent solubility of aminoalkylsulfonic acid and / or aminoarylsulfonic acid in a solvent (such as water). The temperature of the reaction system is preferably 80 ° C. or less, more preferably 70 ° C. or less, and still more preferably 65 ° C. or less from the viewpoint of suppressing side reactions. The reaction time is, for example, 5 to 30 minutes.

In the second stage reaction, for example, the components (c1) and (c3) are added to the reaction product obtained in the first stage and subjected to a condensation reaction to obtain a bisphenol-based resin. The temperature of the reaction system is preferably 75 ° C. or higher, more preferably 85 ° C. or higher, and still more preferably 87 ° C. or higher, from the viewpoint of excellent reactivity of the components (c1), (c2) and (c3). The temperature of the reaction system is preferably 100 ° C. or lower, more preferably 95 ° C. or lower, and still more preferably 93 ° C. or lower, from the viewpoint of suppressing side reactions. The reaction time is, for example, 5 to 20 hours.

A bisphenol-based resin is obtained in a reaction product (for example, a reaction solution) obtained by reacting the component (c1), the component (c2) and the component (c3), and the reaction product is dried to obtain a solvent (water, etc.) The component (c3) of the reaction may be removed. In this embodiment, the reaction product obtained by the method for producing a bisphenol-based resin may be used as it is for the production of an electrode to be described later, or the bisphenol-based resin obtained by drying the reaction product is dissolved in a solvent (water or the like). It may be used for the manufacture of an electrode to be described later.

Among the components (C), at least one selected from the group consisting of lignin sulfonic acid and lignin sulfonate is preferable, and lignin sulfonate is more preferable from the viewpoint of further improving discharge characteristics. Examples of the lignin sulfonate that is the component (C) include alkali metal salts in which the hydrogen atom of the sulfone group (—SO ₃ H) of lignin sulfonic acid is substituted with an alkali metal. Examples of the alkali metal salt include sodium salt and potassium salt.

The weight average molecular weight of the component (C) is preferably 15000 or more and more preferably 30000 or more from the viewpoint that the cycle characteristics are easily improved by suppressing the elution of the component (C) from the electrode to the electrolyte in the lead storage battery. Preferably, 40000 or more is further preferable, and 50000 or more is particularly preferable. The weight average molecular weight of the component (C) is preferably 70000 or less, more preferably 65000 or less, from the viewpoint that the cycle characteristics are easily improved by suppressing the decrease in the adsorptivity to the electrode active material and the dispersibility. Preferably, it is 62000 or less.

The weight average molecular weight of the component (C) can be measured, for example, by gel permeation chromatography (hereinafter referred to as “GPC”) under the following conditions.
(GPC conditions)
Apparatus: High performance liquid chromatograph LC-2200 Plus (manufactured by JASCO Corporation)
Pump: PU-2080
Differential refractometer: RI-2031
Detector: UV-visible spectrophotometer UV-2075 (λ: 254 nm)
Column oven: CO-2065
Column: TSKgel SuperAW (4000), TSKgel SuperAW (3000), TSKgel SuperAW (2500) (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Eluent: methanol solution containing LiBr (10 mM) and triethylamine (200 mM) Flow rate: 0.6 mL / min Molecular weight standard sample: Polyethylene glycol (molecular weight: 1.10 × 10 ⁶ , 5.80 × 10 ⁵ , 2.55 × 10 ⁵ , 1.46 × 10 ⁵ , 1.01 × 10 ⁵ , 4.49 × 10 ⁴ , 2.70 × 10 ⁴ , 2.10 × 10 ⁴ ; manufactured by Tosoh Corporation), diethylene glycol (molecular weight: 1 .06 × 10 ² ; manufactured by Kishida Chemical Co., Ltd.), dibutylhydroxytoluene (molecular weight: 2.20 × 10 ² ; manufactured by Kishida Chemical Co., Ltd.)

When the component (C) is used, the content of the component (C) is preferably 0.01% by mass or more in terms of resin solid content, based on the total mass of the negative electrode material, from the viewpoint of further improving discharge characteristics. 05 mass% or more is more preferable, and 0.1 mass% or more is still more preferable. The content of the component (C) is preferably 2% by mass or less, more preferably 1% by mass or less, in terms of resin solid content, based on the total mass of the negative electrode material, from the viewpoint of further excellent charge acceptance. A mass% or less is more preferable.

In producing the electrode, a resin composition containing the component (C) (for example, a liquid resin solution at 25 ° C.) may be used. The resin composition may further contain a solvent. The resin composition may be a reaction product obtained in the resin production process, and is a composition obtained by mixing the component (C) and other components after the resin production process (for example, using the component (C) as a solvent. A resin solution obtained by dissolution, and a composition obtained by mixing the component (C) with the component (A) and the component (B) may be used. Examples of the solvent include water (for example, ion exchange water) and an organic solvent. The solvent contained in the resin composition may be a reaction solvent used to obtain the component (C) (such as a bisphenol-based resin).

The pH of the resin composition (for example, a resin solution that is liquid at 25 ° C.) is alkaline (greater than 7) from the viewpoint of excellent solubility of the component (C) (bisphenol resin, etc.) in a solvent (water, etc.). Is preferably 7.1 or more. The pH of the resin composition is preferably 14 or less from the viewpoint of excellent workability during electrode paste preparation. In particular, when the resin composition obtained in the resin production process is used, the pH of the resin composition is preferably in the above range. The pH of the resin composition can be measured, for example, with a twin pH meter AS-212 manufactured by Horiba, Ltd. The pH is defined as the pH at 25 ° C.

[Negative electrode additive]
The negative electrode material may further contain an additive. Examples of the additive include barium sulfate, carbon materials (carbonaceous conductive material, excluding carbon fibers), reinforcing short fibers, and the like. Examples of the carbon material include carbon black and graphite. Examples of carbon black include furnace black (excluding components corresponding to ketjen black), channel black, acetylene black, thermal black, and the like. Examples of the reinforcing short fibers include acrylic fibers, polyethylene fibers, polypropylene fibers, polyethylene terephthalate fibers, and carbon fibers.

[Physical properties of negative electrode material]
The specific surface area of the negative electrode material is preferably 0.5 m ² / g or more from the viewpoint of achieving both excellent charge acceptance and other excellent battery performance (discharge characteristics, cycle characteristics, etc.), 55 m ² / g or more is more preferable, and 0.6 m ² / g or more is still more preferable. The specific surface area of the negative electrode material is preferably 1.2 m ² / g or less from the viewpoint of achieving both excellent charge acceptability and other excellent battery performances (discharge characteristics, cycle characteristics, etc.). 0m more preferably ² / g or less, 0.8 m ² / g or less is more preferable. The specific surface area of the negative electrode material may be 0.7 m ² / g or less. The specific surface area of the negative electrode material is 0.5 to 1.2 m ² / g from the viewpoint of further achieving both excellent charge acceptance and other excellent battery performance (discharge characteristics, cycle characteristics, etc.). it is preferable, more preferably 0.55 to 1.2 more preferably 0.6 ~ 1.0m ² / g, particularly preferably 0.6 ~ 0.8m ² / g. The specific surface area of the negative electrode material may be 0.6 to 0.7 m ² / g. The specific surface area of the negative electrode material is the specific surface area of the negative electrode material after chemical conversion. The specific surface area of the negative electrode material changes, for example, the method of adjusting the amount of dilute sulfuric acid and water added when preparing the negative electrode material paste, the method of refining the active material at the stage of the unformed negative electrode active material, and the chemical conversion conditions It can adjust by the method of making it. The specific surface area of the negative electrode material can be measured by, for example, the BET method.

(Current collector)
Examples of the method for producing the current collector include a casting method and an expanding method. Examples of the material of the current collector include a lead-calcium-tin alloy and a lead-antimony alloy. A small amount of selenium, silver, bismuth or the like can be added to these. The manufacturing method or material of the current collector for the positive electrode and the negative electrode may be the same or different from each other.

<Method for producing lead-acid battery>
The method for manufacturing a lead storage battery according to the present embodiment includes, for example, an electrode manufacturing process for obtaining electrodes (positive electrode and negative electrode) and an assembly process for obtaining a lead storage battery by assembling constituent members including the electrodes.

In the electrode manufacturing process, for example, after filling an electrode material paste (a positive electrode material paste and a negative electrode material paste) into a current collector (for example, a cast lattice body and an expanded lattice body), aging and drying are performed to thereby form an unformed electrode. Get. The positive electrode material paste contains, for example, a raw material (lead powder or the like) of the positive electrode active material, and may further contain other additives. The negative electrode material paste contains a raw material for the negative electrode active material (lead powder, etc.) and ketjen black, and preferably contains a component (C) (bisphenol resin, etc.) as a dispersant. An agent may be further contained.

A positive electrode material paste for obtaining a positive electrode material having a specific surface area of 11 m ² / g or more can be obtained by, for example, the following method. In producing the positive electrode material paste, lead (Pb ₃ O ₄ ) may be used as a raw material for the positive electrode active material from the viewpoint of shortening the chemical formation time.

(1) Method of using lead powder as a raw material for the positive electrode active material A reinforcing short fiber is added to the lead powder and dry mixed. Next, 5-10% by mass of water and 28-40% by mass of dilute sulfuric acid (specific gravity 1.28) are added to the mixture containing the lead powder and kneaded to prepare a positive electrode material paste. Here, the said compounding quantity of water and dilute sulfuric acid is a compounding quantity on the basis of the total mass of lead powder and the reinforcing short fiber. The dilute sulfuric acid (specific gravity 1.28) is preferably added gradually in several steps in order to reduce heat generation. In the production of the positive electrode material paste, rapid heat generation forms a sparse positive electrode material, and the bonding force between the active materials in the lifetime decreases. Therefore, it is desirable to suppress heat generation as much as possible.

(2) Method of using lead powder and red lead (Pb ₃ O ₄ ) as a raw material for the positive electrode active material First, a reinforcing short fiber is added to the lead powder and dry mixed. Next, 5-8 mass% of water is added to the mixture containing the lead powder and kneaded to prepare paste A. The said compounding quantity of water is a compounding quantity on the basis of the total mass of the lead powder used when producing lead powder and the reinforcing short fiber, and the below-mentioned paste B.

Next, lead tan (Pb ₃ O ₄ ) and first dilute sulfuric acid (specific gravity 1.3 to 1.4) 20 to 25 mass% are mixed and then kneaded. Subsequently, 7 to 17% by mass of second dilute sulfuric acid (specific gravity 1.45 to 1.6) is added and then kneaded to prepare paste B. Here, lead dioxide (PbO ₂ ) and lead sulfate (PbSO ₄ ), which are reaction products of red lead and dilute sulfuric acid, are generated. The blending amounts of the first and second dilute sulfuric acids are based on the total mass of lead powder and reinforcing short fibers used when preparing the paste A and the red lead used when preparing the paste B. It is the compounding quantity which was made.

Then, the paste B is added to the paste A and kneaded for 1 hour to prepare a positive electrode material paste. In this positive electrode material paste, the ratio of the lead powder contained in paste A and the lead powder contained in paste B (lead powder / lead powder) is 90/10 to 80/20 in mass ratio. It is preferable to adjust to. The total amount of water is preferably 4.5 to 7.0% by mass based on the total mass of lead powder, reinforcing short fibers and red lead. However, “water” here does not include water in dilute sulfuric acid.

An unformed positive electrode can be obtained by filling the positive electrode material paste into the current collector and then aging and drying.

When reinforcing short fibers are used in the positive electrode material paste, the blending amount 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 (lead powder, etc.) 0.05 to 0.3% by mass is more preferable.

As aging conditions for obtaining an unformed positive electrode, 15 to 60 hours are preferable in an atmosphere of a temperature of 35 to 85 ° C. and a humidity of 50 to 98 RH%. The drying conditions are preferably 45 to 80 ° C. and 15 to 30 hours.

The negative electrode material paste can be obtained, for example, by the following method. First, the mixture is obtained by adding the component (B) and additives (reinforcing short fibers, barium sulfate, etc.) to the raw material of the negative electrode active material (component (A)) and dry-mixing them. Next, a solvent (water such as ion-exchanged water or an organic solvent) is added to the mixture and kneaded. At this time, the component (C) may be further added together with the component (B). And a negative electrode material paste is obtained by adding dilute sulfuric acid and kneading. An unformed negative electrode can be obtained by filling the negative electrode material paste into the current collector and then aging and drying. In addition, although (A) component, (B) component, and (C) component may be added and mixed sequentially, (B) component, (C) component, and a small amount of water are mixed, and the secondary of Ketjen Black After the state of the aggregate is melted, the mixture of the component (B) and the component (C) and the component (A) may be mixed. Thereby, the effect of (B) component can fully be acquired.

In the negative electrode material paste, when the component (C) (bisphenol resin or the like), carbon material, reinforcing short fiber, or barium sulfate is used, the blending amount of each component is preferably in the following range. The blending amount of component (C) is preferably 0.01 to 2.0% by mass in terms of resin solids, based on the total mass of the negative electrode active material (lead powder, etc.). 0 mass% is more preferred, 0.1 to 0.5 mass% is still more preferred, and 0.1 to 0.3 mass% is particularly preferred. The blending amount of the carbon material is preferably 0.1 to 3% by mass, and more preferably 0.2 to 1.4% by mass, based on the total mass of the negative electrode active material (such as lead powder). The blending amount of the reinforcing short fibers is preferably 0.05 to 0.3% by mass, more preferably 0.05 to 0.2% by mass based on the total mass of the raw material of the negative electrode active material (lead powder or the like). The compounding amount of barium sulfate is preferably 0.01 to 2.0% by mass, more preferably 0.3 to 2.0% by mass, based on the total mass of the raw material of the negative electrode active material (lead powder or the like).

The amount of ketjen black is 0.01% by mass or more based on the total mass of the negative electrode active material (lead powder, etc.) from the viewpoint of improving the balance of cycle characteristics, discharge characteristics and charge acceptance. Preferably, 0.03 mass% or more is more preferable, and 0.05 mass% or more is still more preferable. 0.1 mass% or more may be sufficient as the said compounding quantity of ketjen black. The amount of ketjen black is preferably 2% by mass or less, based on the total mass of the negative electrode active material (lead powder, etc.), from the viewpoint of further improving the cycle characteristics, discharge characteristics, and charge acceptance. 1.5 mass% or less is more preferable, and 0.5 mass% or less is still more preferable. 0.3 mass% or less may be sufficient as the said compounding quantity of ketjen black. The amount of ketjen black is 0.01 to 2% by mass, based on the total mass of the negative electrode active material (lead powder, etc.), from the viewpoint of further improving the cycle characteristics, discharge characteristics and charge acceptance. Is preferable, 0.03 to 1.5% by mass is more preferable, 0.03 to 0.5% by mass is further preferable, and 0.05 to 0.5% by mass is particularly preferable. The amount of ketjen black may be 0.1 to 0.3% by mass.

As the aging conditions for obtaining the unformed negative electrode, it is preferable that the temperature is 45 to 65 ° C. and the humidity is 70 to 98 RH% for 15 to 30 hours. The drying conditions are preferably 45 to 60 ° C. and 15 to 30 hours.

In the assembling process, for example, the unformed negative electrode and the unformed positive electrode produced as described above are alternately stacked via separators, and the current collectors of the same polarity electrodes are connected (welded, etc.) with a strap. An electrode group is obtained. This electrode group is arranged in a battery case to produce an unformed battery. Next, after injecting an electrolytic solution (dilute sulfuric acid) into an unformed battery, a direct current is applied to form a battery case. The lead acid battery can be obtained by adjusting the specific gravity of the electrolyte after the formation to an appropriate specific gravity.

The electrolytic solution contains, for example, dilute sulfuric acid and aluminum ions, and can be obtained by mixing dilute sulfuric acid and aluminum sulfate powder. Aluminum sulfate to be dissolved in the electrolytic solution can be added as an anhydride or a hydrate.

The specific gravity after chemical conversion of the electrolytic solution (electrolytic solution containing aluminum ions) is preferably in the following range. The specific gravity of the electrolytic solution is preferably 1.24 or more, more preferably 1.25 or more, and even more preferably 1.255 or more from the viewpoint of suppressing osmotic short-circuiting or freezing and further improving discharge characteristics. The specific gravity of the electrolytic solution is preferably 1.33 or less, more preferably 1.30 or less, and even more preferably 1.29 or less, from the viewpoint of further improving charge acceptability and cycle characteristics. In addition, when the specific gravity of the electrolytic solution is 1.27 or less, lead sulfate generated by discharge is easily dissolved in the electrolytic solution, and charge acceptability can be further improved. From these viewpoints, the specific gravity of the electrolytic solution is preferably 1.24 to 1.33, more preferably 1.24 to 1.30, still more preferably 1.25 to 1.30, and 1.255 to 1.29. Is particularly preferable, and 1.255 to 1.27 is very preferable. The value of the specific gravity of the electrolytic solution can be measured by, for example, a floating hydrometer or a digital hydrometer manufactured by Kyoto Electronics Industry Co., Ltd.

The concentration of aluminum ions in the electrolytic solution (concentration of aluminum ions in the electrolytic solution) is preferably 0.01 mol / L or more, based on the total amount of the electrolytic solution, from the viewpoint of further improving charge acceptability and cycle characteristics, and 0.02 mol. / L or more is more preferable, and 0.03 mol / L or more is more preferable. The aluminum ion concentration may be 0.04 mol / L or more, 0.05 mol / L or more, or 0.06 mol / L or more. The aluminum ion concentration of the electrolytic solution is preferably 0.2 mol / L or less, more preferably 0.15 mol / L or less, based on the total amount of the electrolytic solution, from the viewpoint of further improving charge acceptance and cycle characteristics. More preferably, it is 13 mol / L or less. The aluminum ion concentration may be 0.1 mol / L or less. From these viewpoints, the aluminum ion concentration of the electrolytic solution is preferably from 0.01 to 0.2 mol / L, more preferably from 0.02 to 0.15 mol / L, based on the total amount of the electrolytic solution, from 0.03 to 0.13 mol / L is more preferable. The aluminum ion concentration may be 0.04 to 0.1 mol / L, 0.05 to 0.1 mol / L, or 0.06 to 0.1 mol / L. . The aluminum ion concentration of the electrolytic solution can be measured by, for example, ICP emission spectroscopy (high frequency inductively coupled plasma emission spectroscopy).

Although the details of the mechanism by which the charge acceptability is improved when the aluminum ion concentration of the electrolytic solution is within the predetermined range are not clear, it is estimated as follows. That is, when the aluminum ion concentration is within the predetermined range, the solubility of the crystalline lead sulfate, which is a discharge product, in the electrolytic solution increases under any low SOC, or due to the high ion conductivity of aluminum ions. This is presumably because the diffusibility of the electrolytic solution into the electrode active material is improved.

The details of the mechanism by which the cycle characteristics are improved when the aluminum ion concentration of the electrolytic solution is within the predetermined range are not clear, but are estimated as follows. First, when a normal electrolyte solution that does not contain aluminum ions is used, sulfate ions (for example, sulfate ions generated from lead sulfate) supplied to the electrolyte solution at the time of charging travel downward along the surface of the electrode (electrode plate, etc.). Move to. Under PSOC, the battery will not be fully charged, so the electrolyte is not agitated by gas generation. As a result, the electrolyte solution concentration at the lower part of the battery becomes higher, whereas the specific gravity of the electrolyte solution at the upper part of the battery becomes lower, resulting in non-uniform electrolyte concentration called “stratification”. When such a phenomenon occurs, crystalline lead sulfate that does not easily return to the original state even when charged is generated, and the reaction area of the active material decreases. Thereby, performance deterioration occurs in a life test in which charge and discharge are repeated. On the other hand, when the aluminum ion concentration of the electrolytic solution is in the predetermined range, sulfate ions are strongly attracted by the electrostatic attraction of aluminum ions, so that it is presumed that stratification is less likely to occur.

The battery case can accommodate electrodes (electrode plates, etc.) inside. The battery case preferably has a box body whose upper surface is opened and a lid body that covers the upper surface of the box body from the viewpoint of easily accommodating the electrode. Note that an adhesive, heat welding, laser welding, ultrasonic welding, or the like can be appropriately used for bonding the box and the lid. The shape of the battery case is not particularly limited, but a rectangular shape is preferable so that an ineffective space is reduced when an electrode (a plate plate or the like) is accommodated.

The material of the battery case is not particularly limited, but it needs to be resistant to an electrolytic solution (such as dilute sulfuric acid). Specific examples of the battery case material include PP (polypropylene), PE (polyethylene), and ABS resin. PP is advantageous in terms of acid resistance, workability and cost. PP is advantageous in terms of workability as compared with ABS resin, which is difficult to thermally weld the battery case and the lid.

When the battery case is composed of a box and a lid, the box and the lid may be made of the same material or different materials. As the material for the box and the lid, materials having the same thermal expansion coefficient are preferable from the viewpoint of not generating excessive stress.

Examples of the separator include a microporous polyethylene sheet; a nonwoven fabric made of glass fiber and synthetic resin.

Chemical conversion conditions and specific gravity of dilute sulfuric acid can be adjusted according to the properties of the electrode active material. Also, the chemical conversion treatment is not limited to being performed after the assembly process, and may be performed by immersing a large number of electrodes after aging and drying in the electrode manufacturing process together in a chemical conversion tank (tank chemical conversion).

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples.

<Synthesis of bisphenol resin>
The following components were charged into a reaction vessel equipped with a stirrer, a reflux device and a temperature controller to obtain a first mixed solution.
Sodium hydroxide: 1.05 mol [42.0 parts by mass]
Ion exchange water: 44.00 mol [792.6 parts by mass]
4-aminobenzenesulfonic acid: 1.00 mol [173.2 parts by mass]

The first mixture was mixed and stirred at 25 ° C. for 30 minutes. Subsequently, the following components were charged into the first mixed liquid to obtain a second mixed liquid.
Bisphenol A: 0.96 mol [219.2 parts by mass]
Bisphenol S: 0.04 mol [10.4 parts by mass]
Paraformaldehyde (manufactured by Mitsui Chemicals): 3.00 mol [90.9 parts by mass] (formaldehyde conversion)

A resin solution was obtained by reacting the second mixed solution (pH = 8.6) at 90 ° C. for 10 hours.

The bisphenol-based resin contained in the resin solution was isolated by low temperature drying (60 ° C., 6 hours), and the weight average molecular weight was measured by GPC under the following conditions. The weight average molecular weight of the bisphenol-based resin was 53900.

{GPC condition}
Apparatus: High performance liquid chromatograph LC-2200 Plus (manufactured by JASCO Corporation)
Pump: PU-2080
Differential refractometer: RI-2031
Detector: UV-visible spectrophotometer UV-2075 (λ: 254 nm)
Column oven: CO-2065
Column: TSKgel SuperAW (4000), TSKgel SuperAW (3000), TSKgel SuperAW (2500) (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Eluent: methanol solution containing LiBr (10 mM) and triethylamine (200 mM) Flow rate: 0.6 mL / min Molecular weight standard sample: Polyethylene glycol (molecular weight: 1.10 × 10 ⁶ , 5.80 × 10 ⁵ , 2.55 × 10 ⁵ , 1.46 × 10 ⁵ , 1.01 × 10 ⁵ , 4.49 × 10 ⁴ , 2.70 × 10 ⁴ , 2.10 × 10 ⁴ ; manufactured by Tosoh Corporation), diethylene glycol (molecular weight: 1 .06 × 10 ² ; manufactured by Kishida Chemical Co., Ltd.), dibutylhydroxytoluene (molecular weight: 2.20 × 10 ² ; manufactured by Kishida Chemical Co., Ltd.)

<Production of lead acid battery>
(Example 1)
[Production of positive electrode plate]
First, 0.25 mass% of acrylic fibers (based on the total mass of the lead powder) were added to the lead powder as a reinforcing short fiber and dry mixed. Next, 8% by mass of water is added to the mixture containing the lead powder (standard: lead powder, reinforcing short fibers, and the total mass of the red lead used when preparing the paste B described later). A paste A was prepared by kneading.

Next, the red lead (Pb ₃ O ₄ ) and 17% by mass of the first dilute sulfuric acid (specific gravity 1.35) were mixed and then kneaded. Subsequently, 6% by mass of second dilute sulfuric acid (specific gravity 1.50) was added and then kneaded to prepare paste B. In addition, the said compounding quantity of said 1st and 2nd dilute sulfuric acid is the lead powder and the short fiber for reinforcement which were used when producing the above-mentioned paste A, and the red lead used when producing the paste B. The amount is based on the total mass.

The paste B was added to the paste A and kneaded for 1 hour to prepare a positive electrode material paste. In this positive electrode material paste, the ratio (mass ratio) of the lead powder contained in the paste A and the lead powder contained in the paste B was adjusted to be lead powder / lead powder = 85/15. The total amount of water was 6.9% by mass based on the total mass of lead powder, reinforcing short fibers and red lead. In producing the positive electrode material paste, the paste B was added stepwise in order to avoid a rapid temperature rise.

The positive electrode material paste was filled in an expanded lattice produced by subjecting a rolled sheet made of a lead alloy to an expanding process. Next, the grid body (current collector) filled with the positive electrode material paste was aged in an atmosphere of a temperature of 50 ° C. and a humidity of 98% for 24 hours. Then, it dried at the temperature of 50 degreeC for 16 hours, and produced the unchemically formed positive electrode plate.

[Production of negative electrode plate]
Lead powder was used as a raw material for the negative electrode active material. 0.1% by mass of reinforcing short fibers (acrylic fibers), 1.0% by mass of barium sulfate, Ketjen Black (manufactured by Lion Specialty Chemicals, Inc., trade name: Carbon ECP600JD, DBP oil absorption: 489 mL / 100 g ) Was added to the lead powder and then dry mixed (the blending amount is based on the total mass of the negative electrode active material). Next, the resin solution containing the bisphenol-based resin obtained above is 0.2% by mass (standard: total mass of raw materials for the negative electrode active material) and 10% by mass of water (standard: negative electrode active material). And the raw material, reinforcing short fibers, barium sulfate, ketjen black and bisphenol-based resin) were added and kneaded. Subsequently, dilute sulfuric acid (specific gravity 1.280) 9.5% by mass (standard: raw material of negative electrode active material, reinforcing short fiber, barium sulfate, ketjen black and bisphenol-based resin) was added little by little. The negative electrode material paste was produced by kneading. The negative electrode material paste was filled in an expanded lattice produced by subjecting a rolled sheet made of a lead alloy to an expanding process. Next, the grid body (current collector) filled with the negative electrode material paste was aged in an atmosphere of a temperature of 50 ° C. and a humidity of 98% for 20 hours. Then, it dried and produced the unchemically formed negative electrode plate.

The ketjen black was pulverized before dry mixing to adjust the average particle size to 5 μm. The average particle diameter of ketjen black was calculated by the following method. The average particle diameter of ketjen black was determined according to the laser diffraction / scattering method described in JIS M8511 (2014). Specifically, a commercially available surfactant polyoxyethylene octylphenyl ether (Roche Diagnostics Co., Ltd.) is used as a dispersant, using a laser diffraction / scattering particle size distribution measuring device (manufactured by Nikkiso Co., Ltd .: Microtrack 9220FRA). A suitable amount of ketjen black was put into an aqueous solution containing 0.5% by volume of Triton X-100), and 40 W ultrasonic waves were irradiated for 180 seconds while stirring, and measurement was performed. The calculated median diameter (D50) was taken as the average particle diameter of Ketjen Black.

[Battery assembly]
An unformed negative electrode plate was inserted into a polyethylene separator processed into a bag shape. Next, five unchemically formed positive electrode plates and six unchemically formed negative electrode plates inserted in the bag-like separator were alternately laminated. Then, the electrode plate group was prepared by welding the ears of the same polarity electrode plates by a cast on strap (COS) method. The electrode plate group was inserted into a battery case to assemble a 2V single cell battery (corresponding to a B19 size single cell defined in JIS D 5301, a K42 size ISS car lead acid battery). Dilute sulfuric acid having a specific gravity of 1.200 in which aluminum sulfate anhydride was dissolved so that the aluminum ion concentration was 0.06 mol / L was injected into this battery. After standing for 1 hour, a lead storage battery was produced by chemical conversion in a water bath at 40 ° C. with an energizing current of 6 A for 20 hours. The specific gravity of the electrolytic solution after chemical conversion (after finishing) was adjusted as shown in Table 1. The content of ketjen black based on the total mass of the negative electrode material after chemical conversion was 0.2% by mass.

[Specific surface area measurement]
A sample for measuring the specific surface area was prepared by the following procedure. First, the formed battery was disassembled, the electrode plates (positive electrode plate and negative electrode plate) were taken out, washed with water, and dried at 50 ° C. for 24 hours. Next, 2 g of an electrode material (a positive electrode material and a negative electrode material) was collected from the center of the electrode plate and dried at 130 ° C. for 30 minutes to prepare a measurement sample.

The specific surface areas of the positive electrode material and the negative electrode material after chemical conversion were calculated according to the BET method by measuring the nitrogen gas adsorption amount at a liquid nitrogen temperature by a multipoint method while cooling the measurement sample prepared above with liquid nitrogen. The measurement conditions are as follows. As a result of measurement in this manner, the specific surface area of the positive electrode material was 11.5 m ² / g. Moreover, the specific surface area of the negative electrode material was 0.61 m ² / g.

{Measurement conditions for specific surface area}
Apparatus: Macsorb1201 (manufactured by Mountec Co., Ltd.)
Degassing time: 10 minutes at 130 ° C. Cooling: 5 minutes with liquid nitrogen Adsorbed gas flow rate: 25 mL / min

[Measurement of porosity]
The measurement sample was produced by the following procedure. First, the formed battery was disassembled, the positive electrode plate was taken out, washed with water, and dried at 50 ° C. for 24 hours. Next, 3 g of a positive electrode material lump was collected from the center of the positive electrode plate. The mass was crushed into small pieces having a maximum diameter of about 5 mm, and a total of 3 g of the small pieces was put into a measuring cell. And based on the following conditions, the porosity of the positive electrode material after chemical conversion was measured using the mercury porosimeter. The porosity of the positive electrode material was 53.5% by volume.

{Porosity measurement conditions}
Device: Autopore IV9500 (manufactured by Shimadzu Corporation)
Mercury intrusion pressure: 0 to 354 kPa (low pressure), atmospheric pressure to 414 MPa (high pressure)
Pressure holding time at each measurement pressure: 900 seconds (low pressure), 1200 seconds (high pressure)
Contact angle between sample and mercury: 130 °
Mercury surface tension: 480-490 mN / m
Mercury density: 13.5335 g / mL

(Example 2)
A lead-acid battery was produced in the same manner as in Example 1 except that the positive electrode plate was produced as follows.

[Preparation of Positive Electrode of Example 2]
First, 0.25 mass% of acrylic fibers (based on the total mass of the lead powder) were added to the lead powder as a reinforcing short fiber and dry mixed. Next, with respect to the mixture containing the lead powder, 6.2% by mass of water (standard: the total mass of the lead powder used when preparing the lead powder and reinforcing short fibers and the paste B described later) In addition, paste A was prepared by kneading.

Next, the red lead (Pb ₃ O ₄ ) and 19% by mass of the first dilute sulfuric acid (specific gravity 1.35) were mixed and then kneaded. Subsequently, 9.7% by mass of second dilute sulfuric acid (specific gravity 1.50) was added and then kneaded to prepare paste B. In addition, the said compounding quantity of said 1st and 2nd dilute sulfuric acid is the lead powder and the short fiber for reinforcement which were used when producing the above-mentioned paste A, and the red lead used when producing the paste B. The amount is based on the total mass.

The paste B was added to the paste A and kneaded for 1 hour to prepare a positive electrode material paste. In this positive electrode material paste, the ratio (mass ratio) of the lead powder contained in the paste A and the lead powder contained in the paste B was adjusted to be lead powder / lead powder = 85/15. The total amount of water was 5.3% by mass based on the total mass of lead powder, reinforcing short fibers, and red lead. In producing the positive electrode material paste, the paste B was added stepwise in order to avoid a rapid temperature rise.

The positive electrode material paste was filled into an expanded lattice produced by subjecting a rolled sheet made of a lead alloy to an expanding process, and then aged for 24 hours in an atmosphere at a temperature of 50 ° C. and a humidity of 98%. Then, it dried at the temperature of 50 degreeC for 16 hours, and produced the unchemically formed positive electrode plate. The specific surface area and porosity of the positive electrode material were measured in the same manner as in Example 1.

(Example 3)
A lead-acid battery was produced in the same manner as in Example 1 except that the positive electrode plate was produced as follows.

[Preparation of Positive Electrode of Example 3]
First, 0.25 mass% of acrylic fibers (based on the total mass of the lead powder) were added to the lead powder as a reinforcing short fiber and dry mixed. Next, 5.4% by mass of water with respect to the mixture containing the lead powder (standard: the total mass of the lead powder used when producing the lead powder and reinforcing short fibers, and paste B described later) In addition, paste A was prepared by kneading.

Next, the red lead (Pb ₃ O ₄ ) and the first dilute sulfuric acid (specific gravity 1.35) 21.5 mass% were mixed and then kneaded. Subsequently, 15% by mass of second dilute sulfuric acid (specific gravity 1.50) was added and then kneaded to prepare paste B. In addition, the said compounding quantity of said 1st and 2nd dilute sulfuric acid is the lead powder and the short fiber for reinforcement which were used when producing the above-mentioned paste A, and the red lead used when producing the paste B. The amount is based on the total mass.

The paste B was added to the paste A and kneaded for 1 hour to prepare a positive electrode material paste. In this positive electrode material paste, the ratio (mass ratio) of the lead powder contained in the paste A and the lead powder contained in the paste B was adjusted to be lead powder / lead powder = 85/15. The total amount of water was 4.6% by mass based on the total mass of lead powder, reinforcing short fibers and red lead. In producing the positive electrode material paste, the paste B was added stepwise in order to avoid a rapid temperature rise.

After the positive electrode material paste was filled in an expandable current collector produced by subjecting a rolled sheet made of a lead alloy to an expanding process, it was aged in an atmosphere of a temperature of 50 ° C. and a humidity of 98% for 24 hours. Then, it dried at the temperature of 50 degreeC for 16 hours, and produced the unchemically formed positive electrode plate. The specific surface area and porosity of the positive electrode material were measured in the same manner as in Example 1.

Example 4
A lead storage battery was produced in the same manner as in Example 1 except that the addition amount of aluminum sulfate anhydride was changed as follows when the battery was assembled.

[Assembly of Battery of Example 4]
A 2V single cell battery (corresponding to a B19 size single cell defined in JIS D 5301 and a K42 size lead acid battery for ISS vehicles) was assembled in the same manner as in Example 1. Dilute sulfuric acid having a specific gravity of 1.200 in which aluminum sulfate anhydride was dissolved so that the aluminum ion concentration was 0.04 mol / L was poured into this battery. After standing for 1 hour, a lead storage battery was produced by chemical conversion in a water bath at 40 ° C. with an energizing current of 6 A for 20 hours. The specific gravity of the electrolytic solution after chemical conversion (after finishing) was adjusted as shown in Table 1.

(Example 5)
A lead storage battery was produced in the same manner as in Example 1 except that the addition amount of aluminum sulfate anhydride was changed as follows when the battery was assembled.

[Assembly of the battery of Example 5]
A 2V single cell battery (corresponding to a B19 size single cell defined in JIS D 5301 and a K42 size lead acid battery for ISS vehicles) was assembled in the same manner as in Example 1. Dilute sulfuric acid having a specific gravity of 1.200 in which aluminum sulfate anhydride was dissolved so that the aluminum ion concentration was 0.1 mol / L was poured into this battery. After standing for 1 hour, a lead storage battery was produced by chemical conversion in a water bath at 40 ° C. with an energizing current of 6 A for 20 hours. The specific gravity of the electrolytic solution after chemical conversion (after finishing) was adjusted as shown in Table 1.

(Example 6)
A lead storage battery was produced in the same manner as in Example 1 except that the specific gravity of the electrolytic solution (dilute sulfuric acid) was changed as follows when the battery was assembled.

[Assembly of Battery of Example 6]
A 2V single cell battery (corresponding to a B19 size single cell defined in JIS D 5301 and a K42 size lead acid battery for ISS vehicles) was assembled in the same manner as in Example 1. Dilute sulfuric acid having a specific gravity of 1.180 in which aluminum sulfate anhydride was dissolved so that the aluminum ion concentration was 0.06 mol / L was poured into this battery. After standing for 1 hour, a lead storage battery was produced by chemical conversion in a water bath at 40 ° C. with an energizing current of 6 A for 20 hours. The specific gravity of the electrolytic solution after chemical conversion (after finishing) was adjusted as shown in Table 1.

(Example 7)
A lead storage battery was produced in the same manner as in Example 1 except that the specific gravity of the electrolytic solution (dilute sulfuric acid) was changed as follows when the battery was assembled.

[Assembly of the battery of Example 7]
A 2V single cell battery (corresponding to a B19 size single cell defined in JIS D 5301 and a K42 size lead acid battery for ISS vehicles) was assembled in the same manner as in Example 1. Dilute sulfuric acid having a specific gravity of 1.220 in which aluminum sulfate anhydride was dissolved so that the aluminum ion concentration was 0.06 mol / L was poured into this battery. After standing for 1 hour, a lead storage battery was produced by chemical conversion in a water bath at 40 ° C. with an energizing current of 6 A for 20 hours. The specific gravity of the electrolytic solution after chemical conversion (after finishing) was adjusted as shown in Table 1.

(Example 8)
A lead-acid battery was produced in the same manner as in Example 1 except that the negative electrode plate was produced as follows.

[Production of Negative Electrode Plate of Example 8]
Lead powder was used as a raw material for the negative electrode active material. 0.2% by mass of the above-obtained bisphenol-based resin, 0.1% by mass of reinforcing short fibers (acrylic fibers), 1.0% by mass of barium sulfate, Ketjen Black (Lion Specialty)・ Chemicals Co., Ltd., trade name: Carbon ECP600JD) containing 0.2% by mass was added to the lead powder and then dry-mixed (the compounding amount is based on the total mass of the negative electrode active material) Amount). Next, 8% by mass of water (reference: raw material of negative electrode active material, bisphenol resin, reinforcing short fiber, barium sulfate and ketjen black) was added and then kneaded. Subsequently, 15.5% by mass of dilute sulfuric acid (specific gravity 1.28) (reference: total mass of raw material of negative electrode active material, bisphenol resin, reinforcing short fiber, barium sulfate and ketjen black) was added little by little. The negative electrode material paste was produced by kneading. After this negative electrode material paste was filled in an expanded lattice produced by subjecting a rolled sheet made of a lead alloy to an expanding process, it was aged in an atmosphere of a temperature of 50 ° C. and a humidity of 98% for 20 hours. Then, it dried and produced the unchemically formed negative electrode plate. The specific surface area of the negative electrode material was measured in the same manner as in Example 1.

Example 9
A lead-acid battery was prepared in the same manner as in Example 1 except that sodium lignin sulfonate (manufactured by Nippon Paper Industries Co., Ltd., trade name “Vanilex N”) was used in place of the bisphenol-based resin during the production of the negative electrode plate. .

(Comparative Example 1)
A lead-acid battery was produced in the same manner as in Example 1 except that the positive electrode plate was produced as follows.

[Production of Positive Electrode Plate of Comparative Example 1]
First, 90 parts by weight of lead powder, 3.9 parts by weight of lead (Pb ₃ O ₄ ), 0.25 parts by weight of acrylic fiber as a reinforcing short fiber, and a crystal of tribasic lead sulfate by raising the pH of the paste 0.02 part by mass of sodium sulfate for promoting growth was blended. Next, after adding water, it knead | mixed and the paste A was produced. The amount of the water blended is 9.7 mass based on the total mass of the lead powder, the red lead, the reinforcing short fiber, the sodium sulfate, and the red lead used in preparing the paste B described later. %.

Next, 14.6% by weight of dilute sulfuric acid (specific gravity 1.35) was added to 6.1 parts by weight of red lead (Pb ₃ O ₄ ) and kneaded to prepare paste B. In addition, the compounding quantity of the said dilute sulfuric acid is a compounding quantity on the basis of the total mass of the lead powder used when producing the above-mentioned paste A and paste B, a red lead, a reinforcing short fiber, and sodium sulfate.

The paste B was added to the paste A and kneaded for 1 hour to prepare a positive electrode material paste. In this positive electrode material paste, the ratio (mass ratio) of the lead powder contained in the paste A and the lead powder contained in the paste B was adjusted to be lead powder / lead powder = 85/15. The total amount of water was 9.2% by mass based on the total mass of lead powder, red lead, reinforcing short fibers, and sodium sulfate. In producing the positive electrode material paste, the paste B was added stepwise in order to avoid a rapid temperature rise.

(Comparative Example 2)
A lead storage battery was produced in the same manner as in Example 1 except that the positive electrode plate was produced in the same manner as in Comparative Example 1 and the negative electrode plate was produced in the same manner as in Example 8. The specific surface area and porosity of the positive electrode material and the specific surface area of the negative electrode material were measured in the same manner as in Example 1.

(Comparative Example 3)
A lead-acid battery was produced in the same manner as in Example 1 except that the positive electrode plate was produced as follows.

[Production of Positive Electrode Plate of Comparative Example 3]
First, 0.07% by mass of acrylic fiber and 0.01% by mass of sodium sulfate were added to the lead powder as a reinforcing short fiber and dry mixed. Each compounding quantity of an acrylic fiber and sodium sulfate is a compounding quantity on the basis of the total mass of lead powder. Next, with respect to the mixture containing the lead powder, 10% by mass of water (standard: total mass of lead powder, reinforcing short fibers and sodium sulfate) and 9% by mass of dilute sulfuric acid (specific gravity 1.28) (standard: Lead powder, reinforcing short fibers and sodium sulfate) were added and kneaded to prepare a positive electrode material paste. In preparing the positive electrode material paste, dilute sulfuric acid was added step by step in order to avoid a rapid temperature rise.

(Comparative Example 4)
A lead-acid battery was produced in the same manner as in Example 1 except that the negative electrode plate was produced as follows.

[Production of Negative Electrode Plate of Comparative Example 4]
Lead powder was used as a raw material for the negative electrode active material. 0.2% by mass of the bisphenol-based resin obtained above in terms of solid content, 0.1% by mass of reinforcing short fibers (acrylic fibers), 1.0% by mass of barium sulfate, furnace black (manufactured by Cabot Corporation, A mixture containing 0.2% by mass of trade name: Vulcan XC72) was added to the lead powder and then dry-mixed (the compounding amount is based on the total mass of the raw material of the negative electrode active material). Next, 8% by mass of water (standard: raw material of negative electrode active material, bisphenol-based resin, reinforcing short fiber, barium sulfate and furnace black) was added and then kneaded. Subsequently, 15.5% by mass of dilute sulfuric acid (specific gravity 1.28) (standard: total raw material of negative electrode active material, bisphenol resin, reinforcing short fiber, barium sulfate and furnace black) is added little by little and kneaded. Thus, a negative electrode material paste was produced. After this negative electrode material paste was filled in an expanded lattice produced by subjecting a rolled sheet made of a lead alloy to an expanding process, it was aged in an atmosphere of a temperature of 50 ° C. and a humidity of 98% for 20 hours. Then, it dried and produced the unchemically formed negative electrode plate. The specific surface area of the negative electrode material was measured in the same manner as in Example 1.

(Comparative Example 5)
A lead-acid battery was produced in the same manner as in Example 1 except that aluminum sulfate anhydride was not used at the time of assembling the battery as described below.

[Assembly of Battery of Comparative Example 5]
A 2V single cell battery (corresponding to a B19 size single cell defined in JIS D 5301 and a K42 size lead acid battery for ISS vehicles) was assembled in the same manner as in Example 1. Dilute sulfuric acid having a specific gravity of 1.220 was poured into this battery. After standing for 1 hour, a lead storage battery was produced by chemical conversion in a water bath at 40 ° C. with an energizing current of 6 A for 20 hours. The specific gravity of the electrolytic solution after chemical conversion (after finishing) was adjusted as shown in Table 1.

(Comparative Example 6)
A lead-acid battery was produced in the same manner as in Comparative Example 5 except that the negative electrode plate was produced in the same manner as in Comparative Example 4. The specific surface area of the negative electrode material was measured in the same manner as in Example 1. The specific gravity of the electrolytic solution after chemical conversion (after finishing) was adjusted as shown in Table 1.

<Evaluation of battery characteristics>
About the said 2V single cell battery, the charge acceptance property, the discharge characteristic, and the ISS cycle characteristic were measured as follows. The results are shown in Table 1.

(Charge acceptance)
The produced lead storage battery was left for about 12 hours after chemical conversion, and then subjected to constant current discharge at 25 ° C. and a current value of 5.6 A for 30 minutes. Then, after being left for 6 hours, constant voltage charging was performed for 60 seconds at 2.33 V and a limiting current of 100 A, and current values from the start to the 5th second were measured. Relative evaluation was made with the measurement result of Comparative Example 1 as 100.

(Discharge characteristics)
As discharge characteristics, a constant current discharge was performed at 150 A at −15 ° C., and the discharge duration until the battery voltage reached 1.0 V was measured. Relative evaluation was made with the measurement result of Comparative Example 1 as 100. The longer the discharge duration, the better the battery.

(ISS cycle characteristics)
The ISS cycle characteristics were measured as follows. The ambient temperature was adjusted so that the battery temperature was 25 ° C. 7200 cycles of a test in which a constant current / constant voltage charge of 100 A-2.33 V-60 seconds after a constant current discharge of 45 A-59 seconds and a constant current discharge of 300 A-1 seconds were performed as one cycle were performed. . This test is a cycle test that simulates the use of lead-acid batteries in ISS cars. In this cycle test, since the amount of charge is small with respect to the amount of discharge, if the charging is not performed completely, the charging gradually becomes insufficient. As a result, the first-second voltage when the discharge current is 300 A for 1 second is gradually reduced. That is, if the negative electrode is polarized during constant current / constant voltage charging and switched to constant voltage charging at an early stage, the charging current is attenuated, resulting in insufficient charging. In this cycle test, when the first-second voltage at 300 A discharge after 7200 cycles was 1.2 V or more, it was determined as “A”, and when it was below 1.2 V, “B” was determined.

Claims

A lead acid battery comprising a positive electrode, a negative electrode and an electrolyte solution,
The positive electrode has a current collector and a positive electrode material held by the current collector;
The negative electrode has a current collector and a negative electrode material held by the current collector;
The positive electrode material has a specific surface area of 11 m 2 / g or more,
The negative electrode material contains a negative electrode active material and ketjen black,
A lead acid battery in which the electrolyte contains aluminum ions.
The lead acid battery according to claim 1, wherein the negative electrode material further contains a bisphenol-based resin having at least one selected from the group consisting of a sulfone group and a sulfonate group.
The lead acid battery according to claim 1 or 2, wherein the negative electrode material further contains at least one selected from the group consisting of lignin sulfonic acid and lignin sulfonate.
The lead acid battery according to any one of claims 1 to 3, wherein the electrolyte has a specific gravity of 1.24 to 1.33.
The lead acid battery according to any one of claims 1 to 4, wherein a content of the ketjen black is 0.01 to 2% by mass based on a total mass of the negative electrode material.
The lead acid battery according to any one of claims 1 to 5, wherein the negative electrode material has a specific surface area of 0.5 to 1.2 m 2 / g.
The lead acid battery according to any one of claims 1 to 6, wherein the concentration of the aluminum ions in the electrolytic solution is 0.01 to 0.2 mol / L.
A micro hybrid vehicle comprising the lead storage battery according to any one of claims 1 to 7.
An idling stop system vehicle comprising the lead storage battery according to any one of claims 1 to 7.