JP6958685B2 - Lead-acid batteries, idling stop system vehicles and micro-hybrid vehicles - Google Patents

Description

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

In recent years, various fuel efficiency improvement measures have been studied for automobiles in order to prevent air pollution or global warming. Vehicles that have taken measures to improve fuel efficiency include, for example, micro-hybrid vehicles such as idling stop vehicles that reduce engine operating time (hereinafter referred to as "ISS vehicles") and power generation control vehicles that use engine rotation for power without waste. Is being considered.

In the ISS vehicle, the number of times the engine is started increases, so that the large current discharge of the lead storage battery is repeated. Further, in the ISS vehicle and the power generation control vehicle, the amount of power generated by the alternator is reduced, and the lead storage battery is charged intermittently, resulting in insufficient charging.

The lead-acid battery 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.

Furthermore, when intermittent charging and large current discharge are repeated under PSOC as in ISS vehicle applications, the selvage portion of the negative electrode current collector tends to become lead sulfate, and the selvage portion becomes thin and suddenly reaches the end of its life due to ear breakage. It is known to reach.

On the other hand, Patent Document 1 below describes a long-life lead-acid battery that does not suddenly reach the end of its life, which delays the deterioration of the negative electrode of the battery when used in ISS vehicles and further delays the fracture of the ear. To provide, a technique using a negative electrode current collector containing a specific concentration of Sn and an electrolytic solution containing a specific concentration of aluminum ions is disclosed.

Patent No. 4515902

Patent Document 1 discloses that the life of a lead-acid battery can be extended by delaying the deterioration of the negative electrode and further delaying the life of the lead storage battery due to the breakage of the ear. However, lead-acid batteries for ISS vehicles are required to have a longer life.

By the way, when a lead-acid battery is used in a state where it is not fully charged and is insufficiently charged, the difference in density of dilute sulfuric acid, which is an electrolytic solution, between the upper part and the lower part of the electrodes (electrode plates, etc.) in the battery. The stratification phenomenon occurs. In this case, the concentration of dilute sulfuric acid in the lower part of the electrode becomes high and sulfation occurs. Therefore, the reactivity of the lower part of the electrode is lowered, and only the upper part of the electrode reacts intensively. As a result, deterioration such as weakening of the bond between the active materials progresses, and the active material is peeled off from the lattice at the upper part of the electrode, leading to deterioration of battery performance and early life.

Therefore, in recent lead-acid batteries for automobiles, it is an extremely important issue to improve charge acceptability in order to improve the life performance of the battery when used under PSOC.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a lead storage battery having excellent charge acceptability and excellent ISS cycle characteristics.

In response to the above problems, in a lead-acid battery including a positive electrode, a negative electrode, and an electrolytic solution, the negative electrode has a negative electrode material and a negative electrode current collector, and the negative electrode material is a bisphenol resin and a negative electrode active material. It has been found that the negative electrode current collector has an ear portion, and the ear portion has a Sn or Sn alloy surface layer formed therein, whereby the above-mentioned problem can be solved.

That is, in the lead-acid battery according to the present invention, in a lead-acid battery including a positive electrode, a negative electrode, and an electrolytic solution, the negative electrode has a negative electrode material and a negative electrode current collector, and the negative electrode material is a bisphenol resin and a negative electrode active material. , The negative electrode current collector has an ear portion, and the ear portion is a lead-acid battery in which a surface layer of Sn or a Sn alloy is formed.

According to the lead storage battery according to the present invention, it is possible to obtain excellent charge acceptability. Therefore, in particular, the SOC, which tends to be low in ISS vehicles, micro-hybrid vehicles, etc., can be maintained at an appropriate level after the active material is sufficiently activated by repeating charging and discharging to some extent from the initial state. .. Further, according to the lead storage battery according to the present invention, it is possible to obtain excellent charge acceptability and excellent ISS cycle characteristics under PSOC.

Further, according to the lead storage battery according to the present invention, since the electrolytic solution contains aluminum ions, further excellent charge acceptability and excellent ISS cycle characteristics under PSOC can be obtained.

According to the lead storage battery according to the present invention, it is possible to obtain excellent charge acceptability. Further, according to the lead storage battery according to the present invention, it has excellent ISS cycle characteristics under PSOC. The lead-acid battery according to the present invention can be suitably used in ISS vehicles, micro-hybrid vehicles, etc. as a liquid lead-acid battery in which charging is intermittently performed and high-rate discharge to a load is performed under PSOC.

According to the present invention, it is possible to provide an application of a lead storage battery to a micro-hybrid vehicle. According to the present invention, it is possible to provide an application of a lead storage battery to an ISS vehicle.

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

<Lead-acid battery>
The lead-acid battery according to the present embodiment includes, for example, an electrode (electrode plate or the like), an electrolytic solution (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-acid battery according to the present embodiment include a liquid-type lead-acid battery, a control valve type lead-acid battery, a closed-type lead-acid battery, and the like, and a liquid-type lead-acid 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 unchemical, the electrode material (unmodified positive electrode material and unmodified negative electrode material) contains raw materials for the electrode active material (positive electrode active material and negative electrode active material) and the like. The current collector constitutes a conductive path for the current from the electrode material.

(Positive 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 unchemicald active material and then chemicalizing the paste. 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). The raw material for the positive electrode active material is not particularly limited, and examples thereof include lead powder. As the lead powder, for example, lead powder produced by a ball mill type lead powder manufacturing machine or a barton pot type lead powder manufacturing machine (in a ball mill type lead powder manufacturing machine, a mixture of a powder of the main component PbO and scaly metal lead). Can be mentioned. _{Lead tan (Pb 3} O ₄ ) may be used as a raw material for the positive electrode active material. The unchemicald positive electrode material preferably contains an unchemicald positive electrode active material containing tribasic lead sulfate as a main component.

[Positive electrode additive]
The positive electrode material may further contain an additive. Examples of the additive include a carbon material (carbon conductive material), short reinforcing fibers and the like. Examples of the carbon material include carbon black and graphite. Examples of carbon black include furnace black (Ketjen black and the like), 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, carbon fibers and the like.

(Negative electrode material)
[Negative electrode active material]
The negative electrode active material can be obtained by aging and drying a negative electrode material paste containing a raw material for the negative electrode active material to obtain an unchemicald active material and then chemicalizing the paste. Examples of the negative electrode active material after chemical conversion include spongy lead and the like. The spongy lead reacts with sulfuric acid in the electrolytic solution and tends to _{gradually change to lead sulfate (PbSO 4).} Examples of the raw material for the negative electrode active material include lead powder and the like. As the lead powder, for example, lead powder produced by a ball mill type lead powder manufacturing machine or a barton pot type lead powder manufacturing machine (in a ball mill type lead powder manufacturing machine, a mixture of a powder of the main component PbO and scaly metal lead). Can be mentioned. The unchemical negative electrode material is composed of, for example, basic lead sulfate and metallic lead, and a lower oxide.

[Negative electrode additive]
The negative electrode material further contains an additive. In the lead storage battery according to the present embodiment, the negative electrode material contains (A) a bisphenol resin and may contain (B) other additives. The (A) bisphenol resin is composed of, for example, (a) a bisphenol compound and (b) an amino acid, an amino acid derivative, an aminoalkyl sulfonic acid, an aminoalkyl sulfonic acid derivative, an aminoaryl sulfonic acid and an aminoaryl sulfonic acid derivative. Examples thereof include a resin obtained by reacting at least one selected from the group with at least one selected from the group consisting of (c) formaldehyde and a formaldehyde derivative.
Hereinafter, the bisphenol resin (A) will be described in detail, but the present invention is not limited thereto.

<(A) Bisphenol resin>
(Component (a): bisphenol compound)
A bisphenol compound is a compound having two hydroxyphenyl groups. Examples of the bisphenol compound include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as "bisphenol A"), bis (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl). Etan, 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, and bis (4-hydroxyphenyl) sulfone (Hereinafter referred to as "bisphenol S").

The bisphenol compound may be used alone or in combination of two or more. As the bisphenol compound, bisphenol A is preferable from the viewpoint of further excellent charge acceptability, and bisphenol S is preferable from the viewpoint of further excellent discharge characteristics.

As the bisphenol compound, it is preferable to use bisphenol A and bisphenol S in combination from the viewpoint of improving charge acceptability, discharge characteristics and cycle characteristics in a well-balanced manner. In this case, the blending amount of bisphenol A for obtaining (A) bisphenol resin is 70 mol based on the total amount of bisphenol A and bisphenol S from the viewpoint of improving charge acceptability, discharge characteristics and cycle characteristics in a well-balanced manner. % Or more is preferable, 75 mol% or more is more preferable, and 80 mol% or more is further preferable. The blending amount of bisphenol A is preferably 99 mol% or less, more preferably 98 mol% or less, and more preferably 97 mol, based on the total amount of bisphenol A and bisphenol S, from the viewpoint of improving charge acceptability, discharge characteristics and cycle characteristics in a well-balanced manner. % Or less is more preferable.

(Component (b): Amino acid, amino acid derivative, aminoalkyl sulfonic acid, aminoalkyl sulfonic acid derivative, aminoaryl sulfonic acid and aminoaryl sulfonic acid derivative)
Examples of amino acids include glycine, alanine, phenylalanine, aspartic acid and glutamic acid. Examples of the amino acid derivative include an alkali metal salt in which the hydrogen atom of the carboxyl group of the amino acid is replaced with an alkali metal. Among amino acids and amino acid derivatives, glutamic acid and its alkali metal salts are particularly preferable. Examples of the alkali metal salt include sodium salt and potassium salt.

Examples of the aminoalkyl sulfonic acid and the aminoalkyl sulfonic acid derivative include compounds represented by the following general formula (I). ^{Examples of the aminoalkyl sulfonic acid include compounds in which X 1} is a hydrogen atom in the following general formula (I). The aminoalkyl sulphonic acid derivatives, for example, X ¹ in the following general formula (I) include alkali metal salts is an alkali metal.

［式（Ｉ）中、Ｒ^１は、水素原子又は炭化水素基を示し、Ｘ^１は、アルカリ金属又は水素原子を示し、ｎ１は、０〜３の整数を示す。］

[In formula (I), R ¹ represents a hydrogen atom or a hydrogen atom, X ¹ represents an alkali metal or a hydrogen atom, and n1 represents an integer of 0 to 3. ]

^{Examples of the hydrocarbon group of R 1} in the formula (I) include a linear, branched or cyclic hydrocarbon group. Examples of the linear or branched hydrocarbon group include a linear or branched alkyl group. Examples of the cyclic hydrocarbon group include an alicyclic hydrocarbon group. The number of carbon atoms of the hydrocarbon group is preferably 1 or more from the viewpoint of improving charge acceptability, discharge characteristics and cycle characteristics in a well-balanced manner. The number of carbon atoms of the hydrocarbon group is preferably 6 or less, more preferably 5 or less, still more preferably 3 or less, from the viewpoint of improving charge acceptability, discharge characteristics and cycle characteristics in a well-balanced manner.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group and isopentyl. Examples include groups, t-pentyl groups, n-hexyl groups, isohexyl groups, s-hexyl groups and t-hexyl groups. Examples of the alicyclic hydrocarbon group include an alicyclic alkyl group, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. The R ^1, charge acceptance, in view of discharge characteristics and cycle characteristics are improved in good balance, a hydrogen atom, and preferably a linear or branched alkyl group having 1 to 6 carbon atoms, a hydrogen atom and a methyl group Is more preferable.

The alkali metal of X ¹ in formula (I), include for example, sodium and potassium. As X ¹ , sodium is preferable from the viewpoint of improving charge acceptability, discharge characteristics and cycle characteristics in a well-balanced manner. As n1, 0 to 2 is preferable, and 0 or 1 is more preferable, from the viewpoint of improving charge acceptability, discharge characteristics, and cycle characteristics in a well-balanced manner.

Examples of the aminoalkyl sulfonic acid include aminomethane sulfonic acid, 2-aminoethane sulfonic acid, 3-aminopropane sulfonic acid, and 2-methylamino ethane sulfonic acid, and 2-amino ethane sulfonic acid is preferable.

Examples of the aminoaryl sulfonic acid include aminobenzene sulfonic acid and aminonaphthalene sulfonic acid. Examples of the aminoaryl sulfonic acid derivative include an aminobenzene sulfonic acid derivative and an aminonaphthalene sulfonic acid derivative.

Examples of the aminobenzene sulfonic acid include 2-aminobenzene sulfonic acid (also known as alteranic acid), 3-aminobenzene sulfonic acid (also known as metanyl acid), and 4-aminobenzene sulfonic acid (also known as sulfanic acid).

Examples of the aminobenzene sulfonic acid derivative include a compound in which some hydrogen atoms of aminobenzene sulfonic acid are substituted with an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms), and a sulfo group of aminobenzene sulfonic acid. hydrogen atom (-SO 3 _H) and the alkali metal salts substituted with an alkali metal (e.g. sodium or potassium). Examples of the compound in which some hydrogen atoms of aminobenzenesulfonic acid are substituted with an alkyl group include 4- (methylamino) benzenesulfonic acid, 3-methyl-4-aminobenzenesulfonic acid, and 3-amino-4-. Examples thereof include methylbenzene sulfonic acid, 4- (ethylamino) benzenesulfonic acid, and 3- (ethylamino) -4-methylbenzenesulfonic acid. Examples of the alkali metal salt in which the hydrogen atom of the sulfo group of aminobenzenesulfonic acid is replaced with an alkali metal include sodium 2-aminobenzenesulfonate, sodium 3-aminobenzenesulfonate, sodium 4-aminobenzenesulfonate, and 2. Examples include potassium-potassium aminobenzenesulfonate, potassium 3-aminobenzenesulfonate, and potassium 4-aminobenzenesulfonate.

Examples of aminonaphthalene sulfonic acid include 4-amino-1-naphthalene sulfonic acid (p-form), 5-amino-1-naphthalene sulfonic acid (ana-form), and 1-amino-6-naphthalene sulfonic acid (ε). -Body, 5-amino-2-naphthalene sulfonic acid), 6-amino-1-naphthalene sulfonic acid (ε-form), 6-amino-2-naphthalene sulfonic acid (amphi-form), 7-amino-2- Aminonaphthalene monosulfonic acid such as naphthalene sulfonic acid, 8-amino-1-naphthalene sulfonic acid (peri-form), 1-amino-7-naphthalene sulfonic acid (kata-form, 8-amino-2-naphthalene sulfonic acid) 1-Amino-3,8-naphthalenedisulfonic acid, 3-amino-2,7-naphthalenedisulfonic acid, 7-amino-1,5-naphthalenedisulfonic acid, 6-amino-1,3-naphthalenedisulfonic acid, 7 Aminonaphthalenedisulfonic acid such as −amino-1,3-naphthalenedisulfonic acid; Aminonaphthalene such as 7-amino-1,3,6-naphthalentrisulfonic acid and 8-amino-1,3,6-naphthalentrisulfonic acid Examples include trisulfonic acid.

Examples of the aminonaphthalene sulfonic acid derivative include a compound in which some hydrogen atoms of aminonaphthalene sulfonic acid are substituted with an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms), and a sulfo group of aminonaphthalene sulfonic acid. hydrogen atom (-SO 3 _H) and the alkali metal salts substituted with an alkali metal. Examples of the alkali metal salt include mono-alkali metal salt and di-alkali metal salt. As the alkali metal salt, sodium salt and potassium salt are preferable, and sodium salt is more preferable, from the viewpoint of improving charge acceptability, discharge characteristics and cycle characteristics in a well-balanced manner.

As the aminonaphthalenesulfonic acid and the aminonaphthalenesulfonic acid derivative, a compound represented by the following general formula (II) is preferable from the viewpoint of improving charge acceptability, discharge characteristics and cycle characteristics in a well-balanced manner. The alkali metal of R ^2, include for example, sodium and potassium. n2 is preferably 1 or 2, and more preferably 1 from the viewpoint of improving charge acceptability, discharge characteristics, and cycle characteristics in a well-balanced manner. If n2 is 2 or 3, R ² may be identical to one another or may be different.

［式（ＩＩ）中、Ｒ^２は、アルカリ金属又は水素原子を示し、ｎ２は、１〜３の整数を示す。］

[In formula (II), R ² represents an alkali metal or a hydrogen atom, and n2 represents an integer of 1 to 3. ]

As the component (b), one type can be used alone or two or more types can be used in combination. As the component (b), aminoalkyl sulfonic acid, aminoalkyl sulfonic acid derivative, aminoaryl sulfonic acid and aminoaryl sulfonic acid derivative are preferable, and 2-aminoethane sulfonic acid is preferable from the viewpoint of further improving charge acceptability and cycle characteristics. , 4-Aminobenzene sulfonic acid, and 7-amino-2-naphthalene sulfonic acid sodium are more preferable.

The blending amount of the component (b) for obtaining the (A) bisphenol resin is preferably 0.5 mol or more, more preferably 0.6 mol or more, with respect to 1 mol of the component (a) from the viewpoint of further improving the discharge characteristics. It is preferable, 0.8 mol or more is more preferable, and 0.9 mol or more is particularly preferable. The blending amount of the component (b) is preferably 1.3 mol or less, more preferably 1.2 mol or less, and more preferably 1.1 mol with respect to 1 mol of the component (a) from the viewpoint of further improving the discharge characteristics and cycle characteristics. The following is more preferable.

(Component (c): formaldehyde and formaldehyde derivative)
As the 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. (C)
As the component, one kind may be used alone or two or more kinds may be used in combination. Formaldehyde and formaldehyde derivatives may be used in combination.

As the component (c), a formaldehyde derivative is preferable, and paraformaldehyde is more preferable, from the viewpoint that excellent cycle characteristics can be easily obtained. Paraformaldehyde has a structure as shown in the following general formula (III), for example.
HO (CH ₂ O) _n3 H ... (III)
[In formula (III), n3 represents an integer of 2 to 100. ]

The formaldehyde-equivalent amount of the component (c) for obtaining the (A) bisphenol resin is preferably 2 mol or more with respect to 1 mol of the component (a) from the viewpoint of improving the reactivity of the component (b). .2 mol or more is more preferable, and 2.4 mol or more is further preferable. The amount of the component (c) in terms of formaldehyde is preferably 3.5 mol or less, preferably 3.2 mol or less, with respect to 1 mol of the component (a) from the viewpoint of excellent solubility of the (A) bisphenol resin in the solvent. More preferably, 3 mol or less is further preferable.

When aminoalkyl sulfonic acid, aminoalkyl sulfonic acid derivative, aminoaryl sulfonic acid or aminoaryl sulfonic acid derivative is used as the component (b), the bisphenol resin (A) is a structural unit represented by the following formula (IV). In addition, it is preferable to have at least one selected from the group consisting of structural units represented by the following formula (V).

［式（ＩＶ）中、Ｘ^４は、２価の基を示し、Ａ^４は、アルキレン基又はアリーレン基を示し、Ｒ^４１は、アルカリ金属又は水素原子を示し、Ｒ^４２は、メチロール基（−ＣＨ_２ＯＨ）を示し、Ｒ^４３及びＲ^４４は、それぞれ独立にアルカリ金属又は水素原子を示し、ｎ４１は、１〜６００の整数を示し、ｎ４２は、１〜３の整数を示し、ｎ４３は、０又は１を示す。］

[In formula (IV), X ⁴ represents a divalent group, A ⁴ represents an alkylene group or an arylene group, R ⁴¹ represents an alkali metal or a hydrogen atom, and R ⁴² represents a methylol group (-). CH ₂ OH), R ⁴³ and R ⁴⁴ each independently represent an alkali metal or hydrogen atom, n41 represents an integer from 1 to 600, n42 represents an integer from 1 to 3, and n43 represents an integer from 1 to 3. Indicates 0 or 1. ]

［式（Ｖ）中、Ｘ^５は、２価の基を示し、Ａ^５は、アルキレン基又はアリーレン基を示し、Ｒ^５１は、アルカリ金属又は水素原子を示し、Ｒ^５２は、メチロール基（−ＣＨ_２ＯＨ）を示し、Ｒ^５３及びＲ^５４は、それぞれ独立にアルカリ金属又は水素原子を示し、ｎ５１は、１〜６００の整数を示し、ｎ５２は、１〜３の整数を示し、ｎ５３は、０又は１を示す。］

[In formula (V), X ⁵ represents a divalent group, A ⁵ represents an alkylene group or an arylene group, R ⁵¹ represents an alkali metal or a hydrogen atom, and R ⁵² represents a methylol group (-). CH ₂ OH), R ⁵³ and R ⁵⁴ independently represent alkali metal or hydrogen atoms, n51 represents an integer from 1 to 600, n 52 represents an integer from 1 to 3, and n53 is. Indicates 0 or 1. ]

When an amino acid or an amino acid derivative is used as the component (b), the bisphenol resin (A) is composed of a group consisting of a structural unit represented by the following formula (VI) and a structural unit represented by the following formula (VII). It is preferable to have at least one selected.

［式（ＶＩ）中、Ｘ^６は、２価の基を示し、Ａ^６は、アルキレン基又はアリーレン基を示し、Ｒ^６１は、アルカリ金属又は水素原子を示し、Ｒ^６２は、メチロール基（−ＣＨ_２ＯＨ）を示し、Ｒ^６３及びＲ^６４は、それぞれ独立にアルカリ金属又は水素原子を示し、ｎ６１は、１〜６００の整数を示し、ｎ６２は、１〜３の整数を示し、ｎ６３は、０又は１を示す。］

[In formula (VI), X ⁶ represents a divalent group, A ⁶ represents an alkylene group or an arylene group, R ⁶¹ represents an alkali metal or a hydrogen atom, and R ⁶² represents a methylol group (-). CH ₂ OH), R ⁶³ and R ⁶⁴ independently represent alkali metal or hydrogen atoms, n61 represents an integer from 1 to 600, n62 represents an integer from 1 to 3, and n63 is. Indicates 0 or 1. ]

［式（ＶＩＩ）中、Ｘ^７は、２価の基を示し、Ａ^７は、アルキレン基又はアリーレン基を示し、Ｒ^７１は、アルカリ金属又は水素原子を示し、Ｒ^７２は、メチロール基（−ＣＨ_２ＯＨ）を示し、Ｒ^７３及びＲ^７４は、それぞれ独立にアルカリ金属又は水素原子を示し、ｎ７１は、１〜６００の整数を示し、ｎ７２は、１〜３の整数を示し、ｎ７３は、０又は１を示す。］

[In formula (VII), X ⁷ represents a divalent group, A ⁷ represents an alkylene group or an arylene group, R ⁷¹ represents an alkali metal or a hydrogen atom, and R ⁷² represents a methylol group (-). CH ₂ OH), R ⁷³ and R ⁷⁴ independently represent alkali metal or hydrogen atoms, n71 represents an integer from 1 to 600, n72 represents an integer from 1 to 3, and n73 is. Indicates 0 or 1. ]

The ratio of the structural unit represented by the formula (IV) and the structural unit represented by the formula (V) is not particularly limited and may change depending on the synthesis conditions and the like. As the bisphenol resin (A), a resin having only one of the structural unit represented by the formula (IV) and the structural unit represented by the formula (V) may be used. The ratio of the structural unit represented by the formula (VI) and the structural unit represented by the formula (VII) is not particularly limited and may change depending on the synthesis conditions and the like. As the bisphenol resin (A), a resin having only one of the structural unit represented by the formula (VI) and the structural unit represented by the formula (VII) may be used.

Examples of X ⁴ , X ⁵ , X ⁶ and X ⁷ include an alkylidene group (methylidene group, ethylidene group, isopropylidene group, sec-butylidene group, etc.), a cycloalkylidene group (cyclohexylidene group, etc.), and a phenylalkylidene group. Organic groups such as (diphenylmethylidene group, phenylethylidene group, etc.); sulfonyl groups are mentioned, and an isopropylidene group (-C (CH ₃ ) _2- ) group is preferable from the viewpoint of further excellent charge acceptability, and discharge characteristics. _{A sulfonyl group (-SO 2-} ) is preferable from the viewpoint of further excellence. X ⁴ , X ⁵ , X ⁶ and X ⁷ may be substituted with a halogen atom such as a fluorine atom. When X ⁴ , X ⁵ , X ⁶ and X ⁷ are cycloalkylidene groups, the hydrocarbon ring may be substituted with an alkyl group or the like.

Examples of A ⁴ , A ⁵ , A ⁶ and A ⁷ include an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group and a butylene group; and a divalent arylene group such as a phenylene group and a naphthylene group. Can be mentioned. The arylene group may be substituted with an alkyl group or the like.

Examples of the alkali metals of R ⁴¹ , R ⁴³ , R ⁴⁴ , R ⁵¹ , R ⁵³ , R ⁵⁴ , R ⁶¹ , R ⁶³ , R ⁶⁴ , R ⁷¹ , R ⁷³ and R ^{74 include sodium and potassium.} n41, n51, n61 and n71 are preferably 5 to 300 from the viewpoint of further excellent cycle characteristics and solubility in a solvent. n42, n52, n62 and n72 are preferably 1 or 2, and more preferably 1 from the viewpoint of improving charge acceptability, discharge characteristics and cycle characteristics in a well-balanced manner. Although n43, n53, n63 and n73 vary depending on the production conditions, 0 is preferable from the viewpoint of further excellent cycle characteristics and (A) excellent storage stability of the bisphenol resin.

The weight average molecular weight of the (A) bisphenol resin is preferably 3000 or more from the viewpoint that the cycle characteristics can be easily improved by suppressing the elution of the (A) bisphenol resin from the electrode into the electrolytic solution in the lead storage battery. 10,000 or more is more preferable, 20,000 or more is further preferable, and 30,000 or more is particularly preferable. The weight average molecular weight of the bisphenol resin (A) is preferably 200,000 or less, preferably 150,000 or less, from the viewpoint that the cycle characteristics can be easily improved by suppressing the decrease in adsorptivity to the electrode active material and the decrease in dispersibility. Is more preferable, and 100,000 or less is further preferable.

The weight average molecular weight of the bisphenol resin (A) can be measured, for example, by gel permeation chromatography (hereinafter referred to as “GPC”) under the following conditions.
(GPC condition)
Equipment: High Performance Liquid Chromatograph LC-2200 Plus (manufactured by JASCO Corporation)
Pump: PU-2080
Differential refractometer: RI-2031
Detector: Ultraviolet-visible absorptiometer UV-2075 (λ: 254 nm)
Column oven: CO-2065
Columns: 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 velocity: 0.6 mL / min Molecular weight Standard sample: Polyethylene glycol (Molecular weight: 1.10 x 10 ⁶ , 5.80 x 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 Toso Co., Ltd., 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.)

The bisphenol resin (A) can be obtained, for example, by reacting the component (a), the component (b) and the component (c) in a reaction solvent. The reaction solvent is preferably water (for example, ion-exchanged water). Organic solvents, catalysts, additives and the like may be used to accelerate the reaction.

In the resin manufacturing process for obtaining the bisphenol-based resin (A), the blending amount of the component (b) is 0.5 to 1.3 mol with respect to 1 mol of the component (a) from the viewpoint of further improving the cycle characteristics, and It is preferable that the blending amount of the component (c) is 2 to 3.5 mol in terms of formaldehyde with respect to 1 mol of the component (a). The preferable blending amount of the component (b) and the component (c) is in the above-mentioned range for each of the blending amounts of the component (b) and the component (c).

The bisphenol resin (A) is prepared by reacting the components (a), (b) and (c) under basic conditions (alkaline conditions) from the viewpoint that a sufficient amount of the (A) bisphenol resin can be easily obtained. It is preferable to obtain by. In order to adjust to basic conditions, a basic compound may be used. Examples of the basic compound include sodium hydroxide, potassium hydroxide and sodium carbonate. The basic compound may be used alone or in combination of two or more. Among the basic compounds, sodium hydroxide and potassium hydroxide are preferable from the viewpoint of excellent reactivity.

If the reaction solution at the time of reaction is neutral (pH = 7), the reaction for producing the (A) bisphenol resin may be difficult to proceed, and if the reaction solution is acidic (pH <7), side reactions may occur. May progress. Therefore, the pH of the reaction solution at the time of the reaction is preferably alkaline (more than 7) from the viewpoint of suppressing the progress of the side reaction while proceeding with the formation reaction of the (A) bisphenol resin. 1 or more is more preferable, and 7.2 or more is further preferable. The pH of the reaction solution is preferably 13 or less, more preferably 10 or less, still more preferably 9 or less, from the viewpoint of suppressing the progress of hydrolysis of the group derived from the component (b) of the (A) bisphenol resin. .. The pH of the reaction solution can be measured by, for example, Twin pH manufactured by AS ONE Corporation. pH is defined as pH at 25 ° C.

Since it is easy to adjust the pH as described above, the blending amount of the strong basic compound is preferably 1.01 mol or more, more preferably 1.02 mol or more, and 1.03 mol or more with respect to 1 mol of the component (b). More preferred. From the same viewpoint, the blending amount of the strong basic compound is preferably 1.1 mol or less, more preferably 1.08 mol or less, and further preferably 1.07 mol or less with respect to 1 mol of the component (b). Examples of the strong basic compound include sodium hydroxide and potassium hydroxide.

In the present embodiment, the reaction product (reaction solution) obtained in the production of the (A) bisphenol resin may be used as it is in the production of the electrode described later, or the reaction product may be dried and obtained (A). A bisphenol resin may be dissolved in a solvent (water or the like) and used for manufacturing an electrode described later.

The pH of the resin solution containing the bisphenol resin (for example, a liquid resin solution at 25 ° C.) is alkaline from the viewpoint of excellent solubility of the bisphenol resin in a solvent (water or the like) (7). It is preferable, and 7.1 or more is more preferable. The pH of the resin solution is preferably 10 or less, more preferably 9 or less, still more preferably 8.5 or less, from the viewpoint of improving the storage stability of the resin composition. In particular, when the reaction product obtained in the resin production step is used as the resin solution, the pH of the resin solution is preferably in the above range. The pH of the resin solution can be measured by, for example, Twin pH manufactured by AS ONE Corporation. pH is defined as pH at 25 ° C.

In the synthetic reaction of the (A) bisphenol-based resin, it is sufficient that the component (a), the component (b) and the component (c) react to obtain the (A) bisphenol-based resin. For example, the component (a) and (b). ) And (c) may be reacted at the same time, or two of the components (a), (b) and (c) may be reacted and then the remaining one component may be reacted.

The synthesis reaction of the bisphenol resin (A) is preferably carried out in two steps as follows.
In the reaction of the first step, for example, the component (b), the solvent (water, etc.) and the basic compound are charged and then stirred, and the hydrogen atom of the sulfo group in the component (b) is replaced with an alkali metal or the like (b). ) Obtain an alkali metal salt of the component. This makes it easier to suppress side reactions in the condensation reaction described below. 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 the component (b) in a solvent (water or the like). The temperature of the reaction system is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, and even more preferably 65 ° C. or lower, from the viewpoint of suppressing side reactions. The reaction time is, for example, 30 minutes.

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

The (A) bisphenol resin can be obtained by drying the reaction product thus obtained to remove the solvent (water or the like) and the unreacted component (c). The drying method is not particularly limited, but a method in which the temperature of the (A) bisphenol resin is 100 ° C. or lower is preferable from the viewpoint of preventing the self-curing reaction of the (A) bisphenol resin. Examples of the drying method include vacuum drying, freeze drying and spray drying.

The lead-acid battery according to the present invention is excellent in charge acceptability because the negative electrode material contains (A) bisphenol resin. Further, the lead-acid battery according to the present invention is excellent in ISS cycle characteristics because the negative electrode material contains (A) bisphenol resin, so that the selvage portion of the negative electrode current collector is less likely to break and suddenly reaches the end of its life. Although it is not clear why the selvage portion of the negative electrode current collector is less likely to break due to the inclusion of the (A) bisphenol resin in the negative electrode material, the potential of the selvage portion is higher than the potential of dissolution and precipitation of lead sulfate. It is presumed that the potential changes and the ears are less likely to break.

[(B) Other additives]
The negative electrode material may contain (B) other additives. Examples of the other additive (B) include barium sulfate, a carbon material (carbon conductive material), and short reinforcing fibers.

[Carbon material (carbon conductive material)]
Examples of the carbonaceous conductive material include graphite, carbon black, activated carbon, carbon fibers, carbon nanotubes and the like. The amount of the carbonaceous conductive material added is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the negative electrode active material (lead spongy metal) in a fully charged state. Graphite is preferable from the viewpoint of improving charge acceptability, and scaly graphite is more preferable from the viewpoint of further improving charge acceptability. The average primary particle size of the scaly graphite is preferably 100 μm to 500 μm, more preferably 100 μm to 350 μm, and even more preferably 100 μm to 220 μm from the viewpoint of improving charge acceptability.

The scaly graphite referred to here refers to the one described in JIS M 8601 (2005). The electrical resistivity of scaly graphite is 0.02 Ω · cm or less, which is an order of magnitude smaller than around 0.1 Ω · cm of carbon blacks such as acetylene black. Therefore, by using scaly graphite instead of the carbon blacks used in the conventional lead-acid battery, the electric resistance of the negative electrode active material can be lowered and the charge acceptance performance can be improved.

Here, the average primary particle size of scaly graphite is determined in accordance with the laser diffraction / scattering method described in JIS M8511 (2005). A commercially available surfactant polyoxyethylene octylphenyl ether (for example, manufactured by Roche Diagnostics Co., Ltd .: Triton) is used as a dispersant using a laser diffraction / scattering type particle size distribution measuring device (manufactured by Nikkiso Co., Ltd .: Microtrack 9220FRA). An appropriate amount of the scaly graphite sample is put into an aqueous solution containing 0.5 vol% of X-100), and 40 W ultrasonic waves are irradiated for 180 seconds with stirring, and then the measurement is performed. The value of the obtained average particle diameter (median diameter: D50) is defined as the average primary particle diameter.

[Short fiber for reinforcement]
Examples of the reinforcing short fibers include acrylic fibers, polyethylene fibers, polypropylene fibers, polyethylene terephthalate fibers, carbon fibers and the like.

(Electrolytic solution)
The electrolytic solution preferably contains sulfuric acid and aluminum ions, and can be obtained, for example, by mixing 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 of the electrolytic solution (which may contain aluminum ions) (since the specific gravity changes depending on the temperature, it is defined as the specific density converted at 20 ° C. in the present specification. The same applies hereinafter) is within the following range. It is preferable to have. The specific gravity of the electrolytic solution is preferably 1.25 or more, more preferably 1.28 or more, further preferably 1.285 or more, still more preferably 1.29 or more, from the viewpoint of suppressing permeation short circuit or freezing and further excellent discharge characteristics. Especially preferable. The specific gravity of the electrolytic solution is preferably 1.33 or less, more preferably 1.32 or less, further preferably 1.315 or less, and particularly preferably 1.31 or less, from the viewpoint of further improving charge acceptability and cycle characteristics. 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 Denshi Kogyo Co., Ltd.

The aluminum ion concentration of the electrolytic solution is preferably 0.01 mol / L or more, more preferably 0.02 mol / L or more, still more preferably 0.03 mol / L or more, from the viewpoint of further improving charge acceptability and ISS cycle characteristics. .. The aluminum ion concentration of the electrolytic solution is preferably 0.2 mol / L or less, more preferably 0.15 mol / L or less, still more preferably 0.13 mol / L or less, from the viewpoint of further improving charge acceptability and ISS cycle characteristics. .. The aluminum ion concentration of the electrolytic solution can be measured by, for example, ICP inductively coupled plasma emission spectroscopy (high frequency inductively coupled plasma emission spectroscopy).

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, but under any low SOC, in the electrolytic solution of crystalline lead sulfate which is a discharge product. It is considered that this is because the solubility in the electrode is increased or the diffusivity of the electrolytic solution into the electrode active material is improved due to the high ionic conductivity of the aluminum ions.

Further, although the mechanism by which the ISS cycle characteristics are improved when the aluminum ion concentration of the electrolytic solution is within the predetermined range is not known in detail, the potential of the ear portion of the negative electrode plate is higher than the potential of dissolution and precipitation of lead sulfate. It is presumed that the potential remains high and the ears are less likely to break.

(Separator)
Examples of the separator include a separator made of at least one selected from glass, pulp, and synthetic resin. Among the separators, it is preferable to use a synthetic resin from the viewpoint of further suppressing a short circuit. Further, among the synthetic resins, polyolefin is particularly preferable.

<Manufacturing method of lead-acid battery>
The method for manufacturing a lead-acid battery according to the present embodiment includes, for example, an electrode manufacturing step for obtaining electrodes (positive electrode and negative electrode) and an assembly step for assembling constituent members including the electrodes to obtain a lead-acid battery.

In the electrode manufacturing process, for example, an electrode material paste (positive electrode material paste and negative electrode material paste) is filled in a current collector (for example, a current collector lattice such as a cast lattice or an expanded lattice), and then aged and dried. Thereby, an unchemical electrode is obtained. The positive electrode material paste contains, for example, a raw material (lead powder or the like) for 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 a bisphenol-based resin, and may further contain other additives.

The positive electrode material paste can be obtained, for example, by the following method. First, an additive (short fiber for reinforcement, etc.) and water are added to the raw material of the positive electrode active material. Next, dilute sulfuric acid is added and then kneaded to obtain a positive electrode material paste. _{In producing the positive electrode material paste, lead tan (Pb 3} O ₄ ) may be used as a raw material for the positive electrode active material from the viewpoint of shortening the chemical conversion time. An unchemicald positive electrode can be obtained by filling the current collector with this positive electrode material paste and then aging and drying it.

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 raw material (lead powder, etc.) of the positive electrode active material. More preferably, 0.05 to 0.3% by mass.

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

The negative electrode current collector of the lead storage battery according to the present embodiment will be described. Examples of the composition of the current collector include lead-calcium-tin alloy, lead-calcium alloy and lead-antimony alloy. A current collector can be obtained by forming these lead alloys in a grid pattern by a gravity casting method, an expanding method, a punching method, or the like.

The negative electrode current collector includes a grid portion and a strip-shaped portion connected to the upper and lower edges thereof. Of the strip-shaped portions, the upper forehead portion is connected to the strip-shaped portion on the upper edge side, and the upper forehead portion is formed with an ear portion for collecting electricity.

The selvage portion of the negative electrode current collector according to the present invention has a surface layer of Sn or Sn alloy. The surface layer is preferably formed from an alloy containing 50% by mass or more of Sn from the viewpoint of improving the ISS cycle characteristics. The surface layer is more preferably formed from Sn from the viewpoint of further improving the ISS cycle characteristics. Since the surface layer is formed of Sn or a Sn alloy, it is possible to provide a lead storage battery having a long life performance that does not suddenly reach the end of its life under PSOC.

Since the surface layer is formed of Sn or Sn alloy, the reason why it is possible to provide a lead-acid battery having a long life performance that does not suddenly reach the end of its life under PSOC is the charge / discharge cycle in ISS vehicle applications and the like. It is presumed that this is because the ears of the negative electrode current collector are less likely to break when the above steps are repeated. Although the cause of the selvage breakage is not clear, it is considered that the selvage rupture is likely to occur due to the lead sulfate formation of the selvage and the repeated dissolution and precipitation of the lead sulfate. Therefore, it is considered that selvage breakage is less likely to occur by setting the surface where the selvage and the electrolytic solution come into contact with a potential higher than the potential at which lead sulfate is repeatedly dissolved and precipitated.

If the surface layer is formed of Sn or a Sn alloy, even if it contains a metal other than Pb and Sn, it is less likely to cause selvage fracture and has the effect of improving the ISS cycle characteristics.

In the present invention, the surface layer is formed on the ear portion, and the surface layer may also be formed on the upper forehead portion.

Examples of the method of forming the surface layer on the selvage portion include a rolling method and a hot-dip plating method. The rolling method is a method in which a material on which a surface layer is formed (for example, a metal plate or an alloy plate) and a material on which a surface layer is formed (a metal sheet or an alloy sheet) are superposed and rolled. .. On the other hand, the hot-dip plating method is a method in which the selvage portion is immersed in a melting tank in which the material forming the surface layer is melted and plated. Of these methods, the rolling method is preferable in the present invention.

The method of forming the surface layer by the rolling method may be, for example, the following method. A Sn sheet for forming a surface layer or an alloy sheet containing Sn is superposed on both sides of a plate-shaped lead alloy (base material) and rolled with a rolling roller to produce a rolled sheet (a rolled sheet is produced). Process). Next, when the rolled sheet is expanded by an expanding machine while adjusting the position of the rolled sheet so that the surface layer is formed at the position of the ear of the negative electrode current collector (expanding method), the surface is located at the position of the ear. A layered negative electrode current collector is obtained. In this rolling method, the thickness of the surface layer can be easily adjusted by adjusting the thickness of the alloy as the base material, the thickness of the sheet as the surface layer, or the thickness of the sheet after rolling. The thickness of the surface layer after rolling is preferably 10 μm or more and 60 μm or less from the viewpoint of manufacturing.

In the electrode manufacturing process, for example, an electrode material paste (positive electrode material paste and negative electrode material paste) is filled in a current collector (for example, a current collector lattice such as a cast lattice or an expanded lattice), and then aged and dried. Thereby, an unchemical electrode is obtained. The positive electrode material paste contains, for example, a raw material (lead powder or the like) for the positive electrode active material, and may further contain other additives. The negative electrode material paste contains a raw material (lead powder, etc.) for the negative electrode active material, (A) a bisphenol resin, and may further contain (B) other additives.

The positive electrode material paste can be obtained, for example, by the following method. First, an additive (short fiber for reinforcement, etc.) and water are added to the raw material of the positive electrode active material. Next, dilute sulfuric acid is added and then kneaded to obtain a positive electrode material paste. _{In producing the positive electrode material paste, lead tan (Pb 3} O ₄ ) may be used as a raw material for the positive electrode active material from the viewpoint of shortening the chemical conversion time. An unchemicald positive electrode can be obtained by filling the current collector with this positive electrode material paste and then aging and drying it.

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 raw material (lead powder, etc.) of the positive electrode active material. More preferably, 0.05 to 0.3% by mass.

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

The negative electrode material paste can be obtained, for example, by the following method. First, an additive (resin having a sulfone group and / or a sulfonic acid base, reinforcing short fibers, barium sulfate, etc.) is added to the raw material of the negative electrode active material and dry-mixed to obtain a mixture. Then, sulfuric acid (dilute sulfuric acid or the like) and a solvent (water such as ion-exchanged water, an organic solvent, etc.) are added to this mixture and kneaded to obtain a negative electrode material paste. An unmodified negative electrode can be obtained by filling a current collector (for example, a current collector lattice such as a cast lattice or an expanded lattice) with this negative electrode material paste, and then aging and drying.

When a resin having a sulfone group and / or a sulfonic acid base (bisphenol resin or the like), a carbon material, reinforcing short fibers or barium sulfate is used in the negative electrode material paste, the blending amount of each component is preferably in the following range. The blending amount of the resin having a sulfone group and / or a sulfonic acid base is preferably 0.01 to 2.0% by mass in terms of resin solid content based on the total mass of the raw material (lead powder, etc.) of the negative electrode active material. , 0.05 to 1.0% by mass, more preferably 0.1 to 0.5% by mass, and particularly preferably 0.1 to 0.3% by mass. The blending amount of the carbon material is preferably 0.1 to 3% by mass, more preferably 0.2 to 1.4% by mass, based on the total mass of the raw material (lead powder or the like) of the negative electrode active material. The blending amount of the reinforcing short fibers is preferably 0.05 to 0.15% by mass based on the total mass of the raw material (lead powder or the like) of the negative electrode active material. The blending amount of barium sulfate is preferably 0.01 to 2.0% by mass, more preferably 0.01 to 1.0% by mass, based on the total mass of the raw material (lead powder or the like) of the negative electrode active material.

The aging conditions for obtaining an unmodified negative electrode are preferably 15 to 30 hours in an atmosphere having a temperature of 45 to 65 ° C. and a humidity of 70 to 98 RH%. The drying conditions are preferably 15 to 30 hours at a temperature of 45 to 60 ° C.

In the assembling step, for example, the unchemical negative electrode and the positive electrode produced as described above are alternately laminated via a separator, and the electrode plates having the same polarity are connected (welded, etc.) to the strap to obtain a electrode plate group. .. This group of plates is arranged in the battery case to produce an unmodified battery. Next, a lead storage battery is obtained by injecting dilute sulfuric acid into the unconverted battery and then applying a direct current to perform chemical conversion. Normally, a lead-acid battery having a predetermined specific density can be obtained only by energizing, but for the purpose of shortening the energizing time, dilute sulfuric acid may be removed once after chemical conversion, and then an electrolytic solution may be injected.

The chemical conversion conditions and the specific gravity of sulfuric acid can be adjusted according to the properties of the electrode active material. Further, the chemical conversion treatment is not limited to being carried out after the assembly step, and may be carried out after aging and drying in the electrode manufacturing step (tank chemical conversion).

Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the following examples.

[Synthesis Example 1]
<Making bisphenol resin>
[Synthesis example (bisphenol, aminobenzenesulfonic acid, formaldehyde condensate)]
After adding 4.2 parts by mass (0.105 mol) of sodium hydroxide and 79.26 parts by mass (4.4 mol) of ion-exchanged water to a 500 mL separable flask equipped with a Dimroth condenser, a mechanical stirrer and a thermometer, 150 rpm (=) An aqueous sodium hydroxide solution was prepared by stirring with ^{min -1) for 5 minutes.} 17.32 parts by mass (0.1 mol) of 4-aminobenzenesulfonic acid was added to this aqueous sodium hydroxide solution, and the mixture was stirred at 25 ° C. for 30 minutes to obtain a uniform aqueous solution. After adding 9.09 parts by mass of paraformaldehyde (formaldehyde equivalent, 0.3 mol, manufactured by Mitsui Chemicals, Inc.) to this aqueous solution, the mixture was stirred for 5 minutes to dissolve paraformaldehyde to obtain a uniform aqueous solution. After adding 21.92 parts by mass (0.096 mol) of bisphenol A and 1.04 parts by mass (0.004 mol) of bisphenol S to this aqueous solution, the aqueous solution is stirred for 10 hours while heating using an oil bath set at 90 ° C. Got As a result of measuring the pH of the aqueous solution at the start of the reaction immediately after adding bisphenol A and bisphenol S under the following measurement conditions, the pH was 8.6.

After transferring the obtained aqueous solution to a heat-resistant container, the aqueous solution was put into a vacuum dryer set at 60 ° C. Next, a bisphenol-based resin powder (bisphenol, aminobenzenesulfonic acid, formaldehyde condensate) was obtained by drying under a reduced pressure of 1 kPa or less for 10 hours. As a result of measuring the weight average molecular weight of the bisphenol resin obtained in Synthesis Example 1 by GPC under the following conditions, the weight average molecular weight was 53,900.

(PH measurement conditions)
Testing machine: Twin pH (manufactured by AS ONE Corporation)
Calibration solution: pH 6.86 (25 ° C), pH 4.01 (25 ° C)
Measurement temperature: 25 ° C
Measurement procedure: Two-point calibration was performed using a calibration solution. After cleaning the sensor part of the testing machine, the measurement solution was sucked up with a dropper, and 0.1 to 0.3 mL was added dropwise to the sensor part. The pH at the time when the indication of the end of measurement appeared on the screen was taken as the measured value.

(GPC condition)
Equipment: High Performance Liquid Chromatograph LC-2200 Plus (manufactured by JASCO Corporation)
Pump: PU-2080
Differential refractometer: RI-2031
Detector: Ultraviolet-visible absorptiometer UV-2075 (λ: 254 nm)
Column oven: CO-2065
Columns: 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 velocity: 0.6 mL / min Molecular weight Standard sample: Polyethylene glycol (Molecular weight: 1.10 x 10 ⁶ , 5.80 x 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 Toso Co., Ltd., 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.)

<Manufacturing lead-acid batteries>
[Example 1]
(Manufacturing of positive electrode plate)
_{Lead powder and lead tan (Pb 3} O ₄ ) were used as raw materials for the positive electrode active material. The raw material of the positive electrode active material, 0.07% by mass of short reinforcing fibers (acrylic fibers) based on the total mass of the raw material of the positive electrode active material, and water were added and kneaded. Subsequently, dilute sulfuric acid having a specific gravity of 1.280 (20 ° C. equivalent, the same applies hereinafter) was added little by little and kneaded to prepare a positive electrode active material paste. This positive electrode active material paste was filled in an expandable current collector produced by expanding a rolled sheet made of a lead alloy, and then aged in an atmosphere of 50 ° C. and 98% humidity for 24 hours. Then, it was dried to prepare an unchemical positive electrode plate.

(Manufacturing of negative electrode current collector)
The negative electrode current collector was prepared as follows. As the base material of the negative electrode current collector, a plate-shaped lead-0.05 mass% calcium-0.5 mass% tin alloy having a thickness of 12 mm was used. As a metal sheet for forming the surface layer, a Sn sheet having a thickness of 0.2 mm was used. A rolled sheet having a thickness of 0.9 mm was produced by superimposing a Sn sheet on both sides of the lead-0.05 mass% calcium-0.5 mass% tin alloy and rolling with a rolling roller. The thickness of the surface layer formed on the rolled sheet was about 15 μm.

While adjusting the position of the rolled sheet so that the Sn layer is provided at the position of the ear of the negative electrode current collector, the rolled sheet is expanded by a reciprocal expanding machine, and the Sn layer is formed on the ear of the negative electrode current collector. Was produced.

(Manufacturing of negative electrode plate)
Lead powder was used as a raw material for the negative electrode active material. 0.2% by mass of the bisphenol resin produced in Synthesis Example 1, 0.1% by mass of short reinforcing fibers (acrylic fibers), 1.0% by mass of barium sulfate, and 0.2 of carbonaceous conductive material (furness black). A mass% mixture was added to the lead powder and then dry-mixed (the blending amount is a blending amount based on the total mass of the raw material of the negative electrode active material). Next, water was added and then kneaded. Subsequently, dilute sulfuric acid having a specific density of 1.280 was added little by little and kneaded to prepare a negative electrode active material paste. The current collector produced by the above method was filled with this negative electrode active material paste, and then aged in an atmosphere of 50 ° C. and 98% humidity for 24 hours. Then, it was dried to prepare an unchemical negative electrode plate.

(Battery assembly)
An unchemical negative electrode plate was inserted into a polyethylene separator processed into a bag shape. Next, eight non-chemical positive electrode plates and nine non-chemical negative electrode plates inserted into the bag-shaped separator were alternately laminated. Subsequently, the ears of the plates having the same polarity were welded to each other by a cast-on-strap (COS) method to prepare a group of plates. The electrode plate group was inserted into an electric tank to assemble a 2V single cell battery (corresponding to a D26 size single cell specified in JIS D 5301). Dilute sulfuric acid with a specific density of 1.280 was injected into this battery. Then, a lead storage battery was obtained by chemical conversion in a water tank at 35 ° C. under the condition of an energizing current of 20 A for 20 hours.

[Examples 2 to 4, Comparative Examples 1 to 4]
Examples 2 and 3 are Examples except that dilute sulfuric acid having a specific gravity of 1.280 in which aluminum sulfate anhydride is dissolved so that the concentration of aluminum ions in the electrolytic solution has the concentration shown in Table 1 is injected into the battery. A lead storage battery was produced in the same manner as in 1. Further, in Example 4, a lead storage battery was produced in the same manner as in Example 3 except that the surface layer provided for the negative electrode current collector used for the negative electrode plate was changed to a Pb—Sn (50% by mass) alloy layer. .. In Comparative Example 2, a lead-acid battery was produced in the same manner as in Example 1 except that a commercially available sodium lignin sulfonate (trade name: Vanillex N, manufactured by Nippon Paper Industries, Ltd.) was used instead of the bisphenol resin. Comparative Example 3 was the same as in Example 1 except that a commercially available sodium lignin sulfonate (trade name: Vanillex N, manufactured by Nippon Paper Industries, Ltd.) was used instead of the bisphenol resin without forming a surface layer. A lead storage battery was manufactured. In Comparative Example 4, a lead storage battery was produced in the same manner as in Example 1 except that the surface layer was not formed.

<Evaluation of battery characteristics>
For the lead-acid battery, charge acceptability, low-temperature high-rate discharge performance, and ISS cycle characteristics were measured as follows. The charge acceptability, low-temperature high-rate discharge performance, and ISS cycle characteristics were relatively evaluated with the measurement results of Comparative Example 3 as 100, respectively. The results are shown in Table 1.

(Charge acceptability)
In the produced battery, a constant current discharge was performed at 25 ° C. and 10.4 A for 30 minutes, the battery was left for 12 hours, and then charged at a constant voltage of 2.41 V for 60 seconds under a current limit of 100 A, and 5 seconds after the start of charging. The current value of was measured.

(Low temperature and high rate discharge performance)
In the prepared battery, the battery temperature was adjusted to −15 ° C., constant current discharge was performed at 300 A, and the discharge duration until the cell voltage fell below 1.0 V was measured.

(ISS cycle characteristics)
The ISS cycle evaluation was performed as follows. Adjust the atmospheric temperature so that the battery temperature becomes 25 ° C, perform constant current discharge for 45A-59 seconds and 300A-1 second, and then perform constant current / constant voltage charging for 100A-2.33V-60 seconds. A cycle test was performed. During the test, the cycle was restarted after being left for 40 hours every 3600 cycles. This test is a cycle test that simulates how lead-acid batteries are used in ISS vehicles. In this cycle test, the amount of charge is small compared to the amount of discharge, so if charging is not completed, the charge will gradually become insufficient, and as a result, the voltage for the first second when discharged for 1 second with a discharge current of 300 A will be It gradually decreases. That is, if the negative electrode is polarized during constant current / constant voltage charging and switches to constant voltage charging at an early stage, the charging current is attenuated and charging becomes insufficient. In this life test, when the voltage at the first second when discharging 300 A was less than 1.2 V, it was determined that the battery life was reached.

In Example 1 in which the negative electrode material contains a bisphenol resin and the ear portion of the negative electrode current collector has a surface layer, the negative electrode material contains a bisphenol resin but the surface layer is provided on the ear portion of the negative electrode current collector. Compared to Comparative Example 1 which does not have it and Comparative Example 2 which has a surface layer on the selvage of the negative electrode current collector but contains sodium lignin sulfonate which is not a bisphenol resin in the negative electrode material, the ISS cycle characteristics are larger. You can see that it improves. The reason for this is that the Sn or Sn alloy is formed as the surface layer, and the negative electrode material contains a bisphenol resin, so that the potential of the ear portion changes to a higher potential than the dissolution / precipitation potential of lead sulfate, and the ear It is presumed that the ISS cycle characteristics could be further improved because the corrosion and breakage of the part were suppressed.

Further, from Examples 2 and 3, it can be seen that the charge acceptability and the ISS cycle characteristics are further improved by containing aluminum ions in the electrolytic solution.

Claims (9)

A positive electrode, a negative electrode, and an electrolytic solution are provided, the positive electrode has a positive electrode material and a positive electrode current collector, the negative electrode has a negative electrode material and a negative electrode current collector, and the negative electrode material is a bisphenol resin and a negative electrode activity. A lead storage battery containing a substance, the negative electrode current collector has an ear portion, and a surface layer of Sn or a Sn alloy is formed on the ear portion (however, the positive electrode current collector and the negative electrode). A method for manufacturing (excluding those in which at least one of the current collectors has a frame bone all around).
A step of preparing the negative electrode current collector is provided.
Wherein the step of preparing a negative electrode current collector is a step of preparing a substrate, on the substrate, Bei example a step of forming a layer made of Sn or a Sn alloy of said surface layer,
The bisphenol resin is at least selected from the group consisting of (a) bisphenol compounds and (b) amino acids, amino acid derivatives, aminoalkyl sulfonic acids, aminoalkyl sulfonic acid derivatives, aminoaryl sulfonic acids and aminoaryl sulfonic acid derivatives. A method for producing a lead storage battery, which is a resin obtained by reacting one type with at least one selected from the group consisting of (c) formaldehyde and a formaldehyde derivative. The step of forming a layer made of Sn or a Sn alloy includes a step of superimposing a Sn sheet for forming the surface layer on both surfaces of the base material or an alloy sheet containing Sn and rolling with a rolling roller. The method for manufacturing a lead storage battery according to claim 1. The method for manufacturing a lead-acid battery according to claim 2, wherein the step of forming a layer made of Sn or a Sn alloy further includes a step of developing a rolled sheet obtained in the rolling step by an expanding method. The method for manufacturing a lead-acid battery according to claim 1, wherein the step of forming a layer made of Sn or Sn alloy is a step of hot-dip plating Sn or Sn alloy on the ear portion of the base material. The method for manufacturing a lead-acid battery according to any one of claims 1 to 4, wherein both the positive electrode current collector and the negative electrode current collector are expanded lattice bodies. The method for producing a lead storage battery according to any one of claims 1 to 5, wherein the electrolytic solution contains aluminum ions. The method for manufacturing a lead-acid battery according to any one of claims 1 to 6 , wherein the lead-acid battery is a lead-acid battery used under a partially charged state. The method for manufacturing a lead-acid battery according to any one of claims 1 to 7 , wherein the lead-acid battery is a lead-acid battery for an idling stop system vehicle. The method for manufacturing a lead-acid battery according to any one of claims 1 to 7 , wherein the lead-acid battery is a lead-acid battery for a micro-hybrid vehicle.