JP2015174872A - Bisphenol resin, electrode, lead storage battery and method of producing them, and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bisphenol resin which makes it possible to obtain excellent cycle characteristics in a lead storage battery.SOLUTION: A bisphenol resin is obtained by a reaction between (a) bisphenol F or bisphenol AF, (b) at least one selected from the group consisting of aminobenzenesulfonic acid and aminobenzenesulfonic acid derivative, and (c) at least one selected from the group consisting of formaldehyde and formaldehyde derivative.

Description

  The present invention relates to a bisphenol-based resin, a resin composition, an electrode, a lead storage battery, and a method for producing them.

  BACKGROUND ART Lead-acid batteries for automobiles are widely used for engine starting and power supply for electrical components. In recent years, an idling stop system (hereinafter referred to as “ISS”) that stops the engine when the vehicle is temporarily stopped and restarts when the vehicle starts is being implemented as an effort to protect the environment and improve fuel efficiency. In the lead storage battery used in ISS, the engine is frequently started and stopped repeatedly, so that the number of large current discharges at the start of the engine increases, and the use of electrical components overlaps with the discharge load.

Charging of the lead acid battery for automobiles is constant voltage charging by an alternator. In recent years, the set value of the alternator voltage has been lowered for the purpose of suppressing a decrease in the electrolyte due to water decomposition during charging. Further, in recent years, in addition to adopting such a low charging voltage, a power generation control system called “charging by an alternator during traveling is controlled according to the traveling state of the vehicle and the charged state of the lead storage battery. The system that reduces engine load, improves fuel consumption, and reduces CO ₂ is also employed. In such a system, it is difficult to charge the lead storage battery, and it is difficult to achieve a fully charged state. Under such conditions of use, lead-acid batteries are often not fully charged and used due to excessive discharge.

  If the lead storage battery is not fully charged and the state of low charge continues, a phenomenon (sulfation) in which lead sulfate as an inactive discharge product accumulates on the electrode plate may occur. In such a situation, it is known that battery performance such as cycle characteristics deteriorates because the active material is difficult to be reduced (it is difficult to be charged).

  Moreover, when it is difficult to perform complete charging, a stratification phenomenon occurs in which a difference in concentration of dilute sulfuric acid, which is an electrolytic solution, occurs between the upper and lower portions of the electrode plate in the lead acid battery. In this case, the concentration of dilute sulfuric acid in the lower part of the electrode plate increases and sulfation occurs. For this reason, the reactivity of the lower part of the electrode plate is reduced, and only the upper part of the electrode plate reacts intensively. As a result, deterioration such as weakening of the connection between the active materials progresses, and the active material peels off from the current collector supporting the active material (for example, current collector grid) at the upper part of the electrode plate, so that the battery having cycle characteristics and the like Performance decreases.

  On the other hand, as a means for improving cycle characteristics and the like, the following Patent Document 1 discloses a technique relating to a negative electrode for a lead storage battery obtained by using a negative electrode active material and a condensate of phenols, aminobenzenesulfonic acid and formaldehyde. It is disclosed.

International Publication No. 1997/37393

  By the way, for lead-acid batteries, it is required to further improve battery performance such as cycle characteristics.

  This invention is made | formed in view of the said situation, and it aims at providing the bisphenol-type resin which can acquire the cycling characteristics excellent in the lead acid battery, and its manufacturing method. Another object of the present invention is to provide a resin composition containing the bisphenol-based resin. Furthermore, an object of this invention is to provide the electrode and lead acid battery which are manufactured using an electrode active material and the said bisphenol-type resin, and these manufacturing methods.

  As a result of intensive studies by the present inventors, it has become clear that sufficient cycle characteristics cannot be obtained when the lead-acid battery negative electrode described in Patent Document 1 is used. On the other hand, the present inventors have bisphenol F or bisphenol AF, at least one selected from the group consisting of aminobenzenesulfonic acid and aminobenzenesulfonic acid derivatives, and at least one selected from the group consisting of formaldehyde and formaldehyde derivatives It has been found that the above-mentioned problems can be solved by using a bisphenol-based resin obtained by reacting the above.

  That is, the bisphenol resin according to the present invention includes (a) bisphenol F or bisphenol AF, (b) at least one selected from the group consisting of aminobenzenesulfonic acid and aminobenzenesulfonic acid derivatives, and (c) formaldehyde and formaldehyde. It is obtained by reacting at least one selected from the group consisting of derivatives.

  According to the bisphenol resin according to the present invention, excellent cycle characteristics can be obtained in a lead-acid battery. Moreover, according to the bisphenol resin according to the present invention, excellent charge acceptability can be obtained.

  As described above, in the lead storage battery obtained by using the bisphenol-based resin according to the present invention, it is possible to prevent the reaction product generated in the electrode reaction of the lead storage battery from being coarsened. This is presumably because the specific surface area of the electrode is kept high. However, the factor is not limited to this.

  The weight average molecular weight of the bisphenol-based resin according to the present invention is preferably 1000 to 300,000. In this case, further excellent cycle characteristics can be obtained.

  The resin composition according to the present invention contains the bisphenol-based resin according to the present invention. Also in the resin composition according to the present invention, excellent cycle characteristics can be obtained.

  The electrode according to the present invention is manufactured using an electrode active material and the bisphenol-based resin according to the present invention. The lead acid battery according to the present invention includes the electrode according to the present invention. Even in these, excellent cycle characteristics can be obtained.

  The method for producing a bisphenol-based resin according to the present invention includes (a) bisphenol F or bisphenol AF, (b) at least one selected from the group consisting of aminobenzenesulfonic acid and aminobenzenesulfonic acid derivatives, (c) formaldehyde and A step of reacting at least one selected from the group consisting of formaldehyde derivatives.

  According to the method for producing a bisphenol-based resin according to the present invention, excellent cycle characteristics can be obtained in a lead storage battery. Moreover, according to the manufacturing method of the bisphenol-type resin which concerns on this invention, the outstanding charge acceptance property can be acquired.

  In the method for producing a bisphenol-based resin according to the present invention, the blending amount of component (b) is 0.5 to 1.3 moles per mole of component (a), and the blending amount of component (c) is (a). ) A preferred embodiment is 1.5 to 3.5 mol in terms of formaldehyde with respect to 1 mol of the component. In this case, further excellent cycle characteristics can be obtained.

  The electrode manufacturing method according to the present invention includes a step of manufacturing an electrode using an electrode active material and the bisphenol-based resin obtained by the bisphenol-based resin manufacturing method according to the present invention. The manufacturing method of the lead acid battery which concerns on this invention comprises the process of obtaining an electrode with the manufacturing method of the electrode which concerns on this invention. Even in these, excellent cycle characteristics can be obtained.

  According to the present invention, excellent cycle characteristics can be obtained in a lead storage battery. Moreover, according to this invention, the outstanding charge acceptance property and cycling characteristics can be acquired. ADVANTAGE OF THE INVENTION According to this invention, the application to the lead acid battery of bisphenol-type resin and the application to the lead acid battery of the resin composition containing a bisphenol-type resin can be provided.

  In particular, according to the present invention, excellent characteristics can be obtained in a lead-acid battery having a negative electrode produced using an electrode active material and the bisphenol-based resin. ADVANTAGE OF THE INVENTION According to this invention, the application to the negative electrode of the lead storage battery of a bisphenol-type resin and the application to the negative electrode of the lead storage battery of the resin composition containing a bisphenol-type resin can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the application to the lead storage battery in the motor vehicle of the bisphenol-type resin in a motor vehicle and the application to the lead storage battery in the motor vehicle of the resin composition containing a bisphenol-type resin can be provided. Moreover, according to this invention, since it is excellent in charge acceptance, the lead storage battery which can fully be satisfied as an ISS vehicle use used in a severe environment can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application to the lead storage battery in the ISS vehicle of a bisphenol-type resin and the application to the lead storage battery in the ISS vehicle of the resin composition containing a bisphenol-type resin can be provided.

FIG. 1 is a drawing showing measurement results of ¹ H-NMR spectrum.

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

<Bisphenol resin, resin composition and production method thereof>
The bisphenol-based resin according to this embodiment includes (a) bisphenol F or bisphenol AF (hereinafter sometimes referred to as “(a) component”), and (b) aminobenzenesulfonic acid and aminobenzenesulfonic acid derivatives. At least one selected (hereinafter sometimes referred to as “component (b)”) and (c) at least one selected from the group consisting of formaldehyde and a formaldehyde derivative (hereinafter sometimes referred to as “component (c)”). Obtained by reaction. The resin composition according to the present embodiment contains the bisphenol-based resin according to the present embodiment. The resin composition according to the present embodiment is, for example, a composition containing a bisphenol-based resin and a solvent (such as water), and is a liquid resin solution at 25 ° C. Hereinafter, the components of the resin composition will be described.

((A) component: bisphenol F or bisphenol AF)
Bisphenol F or bisphenol AF is a compound having two hydroxyphenyl groups. Bisphenol F is 4,4′-disidroxydiphenylmethane, and bisphenol AF is 2,2-bis (4-hydroxyphenyl) hexafluoropropane. In bisphenol F or bisphenol AF, 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. These can be used individually by 1 type or in combination of 2 or more types.

((B) component: aminobenzenesulfonic acid and aminobenzenesulfonic acid derivative)
Examples of the aminobenzene sulfonic acid include 2-aminobenzene sulfonic acid (also known as alternilic acid), 3-aminobenzene sulfonic acid (also known as metanylic acid), and 4-aminobenzene sulfonic acid (also known as sulfanilic acid).

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), a sulfo group of aminobenzenesulfonic acid (—SO _3). And compounds in which the hydrogen atom of H) is substituted with an alkali metal (for example, sodium or potassium). Examples of the compounds in which some of the 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 sulfo group of aminobenzenesulfonic acid is substituted 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.

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

  From the viewpoint of further improving the discharge characteristics, the blending amount of the component (b) 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 (a). Preferably, 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, with respect to 1 mol of the component (a), from the viewpoint that the discharge characteristics and cycle characteristics are further improved. 1.1 mol or less is more preferable.

((C) 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. (C) 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 (c), 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 formula (I), n1 represents an integer of 2 to 100. ]

  From the viewpoint of improving the reactivity of the component (b), the amount of the component (c) for obtaining the bisphenol-based resin is preferably 1.5 mol or more with respect to 1 mol of the component (a). 2 mol or more is more preferable, and 2.2 mol or more is still more preferable. The amount of the component (c) in terms of formaldehyde is preferably 3.5 moles or less, preferably 3.3 moles per mole of the component (a), from the viewpoint of excellent solubility of the resulting bisphenol-based resin in a solvent. The following is more preferable, and 3.0 mol or less is still more preferable.

(solvent)
The resin composition according to this embodiment may further contain a solvent. 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 for obtaining a bisphenol-based resin.

  The resin composition according to the present embodiment may further contain a natural resin or a synthetic resin other than the bisphenol-based resin.

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

［式（ＩＩ）中、Ｘ^２は、メチレン基（−ＣＨ₂−）又は２，２−ヘキサフルオロプロピリデン基（−Ｃ（ＣＦ_３）_２−）を示し、Ｒ^２１は、アルカリ金属又は水素原子を示し、Ｒ^２２は、メチロール基（−ＣＨ_２ＯＨ）又は水素原子を示し、Ｒ^２３及びＲ^２４は、それぞれ独立にアルカリ金属又は水素原子を示し、ｎ２は、１〜１５０の整数を示す。また、ベンゼン環を構成する炭素原子に直接結合している水素原子は、炭素数１〜５のアルキル基で置換されていてもよい。］

[In Formula (II), X ² represents a methylene group (—CH ₂ —) or a 2,2-hexafluoropropylidene group (—C (CF ₃ ) ₂ —), and R ²¹ represents an alkali metal or hydrogen An atom, R ²² represents a methylol group (—CH ₂ OH) or a hydrogen atom, R ²³ and R ²⁴ each independently represents an alkali metal or a hydrogen atom, and n 2 represents an integer of 1 to 150. . Moreover, 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. ]

［式（ＩＩＩ）中、Ｘ^３は、メチレン基（−ＣＨ₂−）又は２，２−ヘキサフルオロプロピリデン基（−Ｃ（ＣＦ_３）_２−）を示し、Ｒ^３１は、アルカリ金属又は水素原子を示し、Ｒ^３２は、メチロール基（−ＣＨ_２ＯＨ）又は水素原子を示し、Ｒ^３３及びＲ^３４は、それぞれ独立にアルカリ金属又は水素原子を示し、ｎ３は、１〜１５０の整数を示す。また、ベンゼン環を構成する炭素原子に直接結合している水素原子は、炭素数１〜５のアルキル基で置換されていてもよい。］

[In Formula (III), X ³ represents a methylene group (—CH ₂ —) or a 2,2-hexafluoropropylidene group (—C (CF ₃ ) ₂ —), and R ³¹ represents an alkali metal or hydrogen R ³² represents a methylol group (—CH ₂ OH) or a hydrogen atom, R ³³ and R ³⁴ each independently represent an alkali metal or a hydrogen atom, and n 3 represents an integer of 1 to 150. . Moreover, 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.

  The content of the bisphenol-based resin in the resin composition according to the present embodiment is 70% by mass based on the total mass of nonvolatile components in the resin composition from the viewpoint of improving charge acceptance, discharge characteristics, and cycle characteristics in a balanced manner. The above is preferable, 80 mass% or more is more preferable, and 90 mass% or more is still more preferable.

  The weight average molecular weight of the bisphenol-based resin is preferably 1000 or more, more preferably 2000 or more, from the viewpoint that the cycle characteristics are easily improved by suppressing the bisphenol-based resin from eluting from the electrode into the electrolyte in the lead storage battery. More preferably 3000 or more. The weight average molecular weight of the bisphenol-based resin is preferably 300000 or less, more preferably 250,000 or less, and even more preferably 200000 or less, from the viewpoint that the cycle characteristics are easily improved by suppressing the decrease in the adsorptivity to the electrode active material. .

The weight average molecular weight of the bisphenol-based resin 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.)

  The manufacturing method of the bisphenol-type resin which concerns on this embodiment is equipped with the resin manufacturing process which makes (a) component, (b) component, and (c) component react, and obtains a bisphenol-type resin. The resin composition according to the present embodiment may be a composition obtained in the resin production process, or may be a composition obtained by mixing a bisphenol-based resin and other components after the resin production process.

  The bisphenol-based resin 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 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 cycle characteristics, the blending amount of component (b) is 0.2 to 2.5 moles per mole of component (a), and blending of component (c) The aspect whose quantity is 1.5-3.5 mol in conversion of formaldehyde with respect to 1 mol of (a) component is preferable. (B) The preferable compounding quantity of a component and (c) component is the range mentioned above about each of the compounding quantity of (b) component and (c) component.

  The bisphenol-based resin is preferably obtained by reacting the component (a), the component (b) and the component (c) 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 (a), the component (b) and the component (c) 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 13 or less, more preferably 11 or less, and still more preferably 9.5 or less from the viewpoint of suppressing the hydrolysis of the group derived from the component (b) of the bisphenol-based resin. The pH of the reaction solution can be measured by, for example, Twin pH manufactured by AS ONE Corporation. The pH is defined as the pH at 25 ° C.

  Since it is easy to adjust the pH as described above, the compounding amount of the strongly basic compound is preferably 1.01 mol or more, more preferably 1.02 mol or more, relative to 1 mol of the component (b). 03 mol or more is more preferable. From the same viewpoint, the compounding amount of the strongly basic compound is preferably 1.6 mol or less, more preferably 1.2 mol or less, still more preferably 1.1 mol or less with respect to 1 mol of the component (b). Examples of the strongly basic compound include sodium hydroxide and potassium hydroxide.

  In this embodiment, the reaction product (reaction solution) obtained by the method for producing a bisphenol-based resin may be used as it is for the production of an electrode described later, or the bisphenol-based resin obtained by drying the reaction product is used as a solvent (water Etc.) and may be used for the production of an electrode to be described later.

  The pH of the resin composition (for example, a resin solution that is liquid at 25 ° C.) is preferably alkaline (greater than 7) from the viewpoint of excellent solubility of the bisphenol-based resin in a solvent (such as water), and 7.1. The above is more preferable. The pH of the resin composition is preferably 12 or less, more preferably 11 or less, and even more preferably 10 or less from the viewpoint of further improving the wettability of the resin composition to an electrode active material (lead, lead oxide, etc.). Moreover, when using the composition obtained in a resin manufacturing process as a resin composition, it is preferable that pH of a resin composition is the said range. The pH of the resin composition can be measured by, for example, Twin pH manufactured by AS ONE Corporation. The pH is defined as the pH at 25 ° C.

  The synthesis reaction of the bisphenol-based resin is sufficient if the (a) component, the (b) component, and the (c) component react to obtain a bisphenol-based resin. For example, the (a) component, (b) component, and (c) The components may be reacted at the same time, or the remaining one component may be reacted after reacting two of the components (a), (b) and (c).

  The synthesis reaction of the bisphenol-based resin is preferably performed in two steps as follows. In the first stage reaction, for example, the component (b), a solvent (water, etc.) and a basic compound (for example, a strong basic compound) are charged and stirred, and the hydrogen atom of the sulfo group in the component (b) is alkali metal. To obtain an alkali metal salt of the component (b). 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 the component (b) 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, 30 minutes.

  In the second-stage reaction, for example, the bisphenol-based resin is obtained by adding the components (a) and (c) to the reaction product obtained in the first stage and causing a condensation reaction. 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 (a), (b) and (c). The temperature of the reaction system is preferably 100 ° C. or less from the viewpoint of suppressing side reactions. The reaction time is, for example, 3 to 20 hours.

<Electrode, lead acid battery, and manufacturing method thereof>
The electrode according to the present embodiment is manufactured using an electrode active material and the bisphenol resin according to the present embodiment or a resin composition containing the bisphenol resin. The manufacturing method of the electrode which concerns on this embodiment is equipped with the process of manufacturing an electrode using the bisphenol-type resin obtained by the manufacturing method of the bisphenol-type resin which concerns on this embodiment. The electrode includes, for example, an electrode layer containing an electrode active material and a current collector that supports the electrode layer. The electrode is, for example, a negative electrode (a negative electrode plate or the like) for a lead storage battery.

  The lead storage battery according to the present embodiment includes the electrode according to the present embodiment. Examples of the lead storage battery according to this embodiment include a liquid lead storage battery and a sealed lead storage battery, and a liquid lead storage battery is preferable. The method for manufacturing a lead storage battery according to the present embodiment includes, for example, an electrode manufacturing process for obtaining an electrode by the electrode manufacturing method according to the present embodiment, and an assembly process for obtaining a lead storage battery by assembling components including the electrode. Yes.

  In the electrode manufacturing process, for example, after filling an electrode paste into a current collector (for example, current collector grid), aging and drying are performed to obtain an unformed electrode. The electrode paste contains, for example, an electrode active material and a bisphenol-based resin, and may further contain other predetermined additives. When the electrode is a negative electrode, the negative electrode active material is preferably lead powder (PbO). Examples of the additive include barium sulfate, a carbon material, and reinforcing short fibers (acrylic fiber, polyethylene fiber, polypropylene fiber, polyethylene terephthalate fiber, carbon fiber, etc.). Examples of the carbon material include carbon black and graphite. Examples of carbon black include furnace black, channel black, acetylene black, thermal black, and ketjen black.

  When the electrode according to this embodiment is a negative electrode, the negative electrode paste can be obtained, for example, by the following method. First, a mixture is obtained by adding and mixing a bisphenol-type resin or a resin composition containing the bisphenol-type resin and, if necessary, an additive to lead powder. Next, negative sulfuric acid paste is obtained by adding dilute sulfuric acid and a solvent (such as water) to this mixture and kneading.

  In the negative electrode paste, when barium sulfate is used, the compounding amount of barium sulfate is preferably 0.01 to 1% by mass based on the total mass of the negative electrode active material. Moreover, when using a carbon material, the compounding quantity of a carbon material has preferable 0.2-1.4 mass% on the basis of the total mass of a negative electrode active material. The compounding amount of the bisphenol-based resin according to the present embodiment or the resin composition containing the bisphenol-based resin is preferably 0.01 to 2% by mass in terms of resin solids based on the total mass of the negative electrode active material, 0.05-1 mass% is more preferable, and 0.1-0.5 mass% is still more preferable.

  Examples of the material of the current collector include a lead-calcium-tin alloy, a lead-calcium alloy, and alloys obtained by adding a small amount of arsenic, selenium, silver, bismuth, or the like to these.

  The aging conditions are preferably 15 to 60 hours in an atmosphere at a temperature of 35 to 85 ° C. and a humidity of 50 to 98 RH%. Drying conditions are preferably 15 to 30 hours at a temperature of 45 to 80 ° C.

When the electrode which concerns on this embodiment is a negative electrode, the positive electrode (positive electrode plate etc.) for lead acid batteries can be obtained by the following method, for example. First, after adding a reinforcing short fiber to lead powder (PbO) which is an electrode active material, water and dilute sulfuric acid are added. This is kneaded to produce a positive electrode paste. In producing the positive electrode paste, red lead (Pb ₃ O ₄ ) may be added. After filling this positive electrode paste into a current collector (for example, current collector grid), aging and drying are performed to obtain an unformed positive electrode. In the positive electrode 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 lead powder. The type of current collector, aging conditions, and drying conditions are almost the same as in the case of the negative electrode.

  In the assembly process, for example, the negative electrode and the positive electrode produced as described above are alternately stacked via separators, and electrode plates having the same polarity are connected with a strap to obtain a plate group. This electrode group is arranged in a battery case to produce an unformed battery. Next, dilute sulfuric acid is added to the non-chemical cell to perform chemical conversion treatment. Subsequently, after removing the diluted sulfuric acid once, a lead storage battery is obtained by adding an electrolytic solution (sulfuric acid or the like). The specific gravity (converted to 20 ° C.) of sulfuric acid is preferably 1.25 to 1.35.

  Examples of the material of the separator include polyethylene and glass fiber. The chemical conversion conditions and the specific gravity of sulfuric acid can be adjusted according to the properties of the electrode active material. The chemical conversion treatment is not limited to being performed in the assembly process, and may be performed in the electrode manufacturing process.

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

<Preparation of negative electrode plate>
[Example 1]
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: 55.56 mol [1000.0 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 F: 1.00 mol [200.2 parts by mass]
Paraformaldehyde (manufactured by Mitsui Chemicals): 3.00 mol [90.1 parts by mass] (in terms of formaldehyde)

The resin mixture was obtained by making the 2nd liquid mixture (pH = 9.6) react at 90 degreeC for 4 hours. The bisphenol-based resin contained in the resin solution obtained in Example 1 was isolated by low-temperature drying (60 ° C.) under reduced pressure, and a ¹ H-NMR spectrum was measured. The measurement result of ¹ H-NMR spectrum is shown in FIG.

The weight average molecular weight of the bisphenol-based resin obtained in Example 1 was measured by GPC under the following conditions. The weight average molecular weight measured using GPC was 4000. (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.)

After completion of the reaction, the pH of the resin solution was measured under the following measurement conditions. (Conditions for pH measurement)
Testing machine: Twin pH (manufactured by ASONE 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 resin solution was sucked with a dropper, and 0.1 to 0.3 mL was dropped onto the sensor part. The pH at the end of measurement on the screen was taken as the measured value.

  Based on the total mass of the lead powder, 0.2 mass% of the bisphenol resin obtained in Example 1 in terms of solid content, 0.2 mass% of furnace black, and 1.0 mass% of barium sulfate are lead. Dry added after adding to flour. Next, the mixture was kneaded while adding dilute sulfuric acid (specific gravity 1.26 (converted at 20 ° C.)) and water to prepare a negative electrode paste. The negative electrode paste was filled into an expanded current collector (lead-calcium-tin alloy) having a thickness of 0.6 mm to produce a negative electrode plate. The negative electrode plate was aged for 18 hours in an atmosphere of a temperature of 50 ° C. and a humidity of 95% according to a normal method, and then dried in an atmosphere of a temperature of 50 ° C. to obtain an unformed negative electrode plate.

[Example 2]
A negative electrode plate was obtained in the same manner as in Example 1 except that the components for obtaining the bisphenol-based resin were changed to the components shown in Table 1. Further, the weight average molecular weight of the bisphenol-based resin and the pH of the resin solution were measured in the same manner as in Example 1. In Table 1, the amount of paraformaldehyde is a formaldehyde equivalent.

[Comparative Example 1]
A negative electrode plate was obtained in the same manner as in Example 1 except that the bisphenol-based resin was not used.

[Comparative Example 2]
A negative electrode plate was obtained in the same manner as in Example 1 except that the components for obtaining the bisphenol-based resin were changed to the components shown in Table 1. Further, as in Example 1, the weight average molecular weight of the bisphenol-based resin and the pH of the resin solution were measured. In Table 1, the blending amount of 37 mass% formalin is a blending amount in terms of formaldehyde.

<Preparation of positive electrode plate>
After adding 0.01% by mass of reinforcing short fibers (polyethylene fibers) to the lead powder based on the total mass of the lead powder, dry mixing was performed. Next, dilute sulfuric acid (specific gravity 1.26 (converted at 20 ° C.)) and water were added and kneaded to prepare a positive electrode paste. A positive electrode current collector (lead-calcium-tin alloy) made of a cast grid is filled with a positive electrode paste and left to mature for 18 hours in an atmosphere at a temperature of 50 ° C. and a humidity of 95%, and then an atmosphere at a temperature of 50 ° C. It dried below and obtained the unchemically formed positive electrode plate.

<Battery assembly>
After laminating 6 unformed negative plates and 5 unformed positive plates through polyethylene separators so that unformed negative plates and unformed positive plates are alternately laminated, the same polarity electrode plate The electrode plates were made by connecting them with a strap. The electrode plate group was inserted into the battery case to assemble a 2V single cell battery. After dilute sulfuric acid (specific gravity 1.28 (converted at 20 ° C.)) was poured into this battery, it was formed in a 50 ° C. water bath under an electric current of 1.0 A for 15 hours. And after discharging | emitting dilute sulfuric acid, the dilute sulfuric acid of specific gravity 1.28 (20 degreeC conversion) was inject | poured again and the lead acid battery was obtained.

<Evaluation of battery characteristics>
About said 2V single cell battery, charge acceptance, discharge characteristics, and cycling characteristics were measured as follows. The measurement results of charge acceptability, discharge characteristics, and cycle characteristics of Comparative Example 2 were set to 100, and each characteristic was relatively evaluated. The results are shown in Table 1.

(Charge acceptance)
5 seconds after the state of charge of the battery has reached 90%, that is, 10% of the battery capacity is discharged from the fully charged state and charged at a constant voltage of 2.33 V. The current value of was measured. The larger the current value after 5 seconds, the better the initial charge acceptance.

(Discharge characteristics)
As discharge characteristics, a constant current discharge was performed at −15 ° C. at 5 C, and the discharge duration until the battery voltage reached 1.0 V was measured. The longer the discharge duration, the better the battery. The C means discharge current value (A) / battery capacity (Ah).

(Cycle characteristics)
The cycle characteristics were evaluated by a method according to a Japanese Industrial Standard light load life test (JIS D 5301). The larger the number of cycles, the higher the durability.

  In the example, it can be confirmed that the cycle characteristics are greatly improved as compared with the comparative example. Further, the charge acceptability and the discharge characteristics remain almost the same as those in Comparative Example 2, and it can be confirmed that the performance as, for example, an ISS vehicle can be sufficiently satisfied. Thus, in the Examples, it can be confirmed that excellent charge acceptability, discharge characteristics, and cycle characteristics are compatible.

  ADVANTAGE OF THE INVENTION According to this invention, the bisphenol-type resin which can acquire the outstanding cycling characteristics in lead acid battery, and its manufacturing method can be provided. Moreover, according to this invention, the resin composition containing the said bisphenol-type resin can be provided. Furthermore, according to this invention, the electrode manufactured using an electrode active material and the said bisphenol-type resin, lead acid battery, and these manufacturing methods can be provided.

Claims (9)

(A) bisphenol F or bisphenol AF, (b) at least one selected from the group consisting of aminobenzenesulfonic acid and aminobenzenesulfonic acid derivatives, and (c) at least one selected from the group consisting of formaldehyde and formaldehyde derivatives, A bisphenol-based resin obtained by reacting The bisphenol-type resin of Claim 1 whose weight average molecular weights are 1000-300000. A resin composition comprising the bisphenol-based resin according to claim 1. The electrode manufactured using an electrode active material and the bisphenol-type resin of Claim 1 or 2. A lead acid battery comprising the electrode according to claim 4. (A) bisphenol F or bisphenol AF, (b) at least one selected from the group consisting of aminobenzenesulfonic acid and aminobenzenesulfonic acid derivatives, and (c) at least one selected from the group consisting of formaldehyde and formaldehyde derivatives, The manufacturing method of the bisphenol-type resin provided with the process made to react. The amount of component (b) is 0.5 to 1.3 moles per mole of component (a), and the amount of component (c) is formaldehyde relative to 1 mole of component (a). The manufacturing method of the bisphenol-type resin of Claim 6 which is 1.5-3.5 mol in conversion. The manufacturing method of an electrode provided with the process of manufacturing an electrode using an electrode active material and the bisphenol-type resin obtained by the manufacturing method of the bisphenol-type resin of Claim 6 or 7. The manufacturing method of a lead storage battery provided with the process of obtaining an electrode with the manufacturing method of the electrode of Claim 8.

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