阅读说明：本技术 铅蓄电池及其制造方法 (Lead storage battery and method for manufacturing the same ) 是由 铃木启太 武部智纪 竹内久喜 松本谅 松村祥太 于 2020-02-19 设计创作，主要内容包括：铅蓄电池(100)具备正极(10)、负极(20)及电解液(40),正极(10)具有用于保持活性物质的管(10a),负极(20)具有含有表面活性剂的负极材料,电解液(40)中与负极材料的表面活性剂不同的表面活性剂的总含量为0.1质量％以下。(A lead storage battery (100) is provided with a positive electrode (10), a negative electrode (20), and an electrolyte (40), wherein the positive electrode (10) has a tube (10a) for holding an active material, the negative electrode (20) has a negative electrode material containing a surfactant, and the total content of surfactants different from the surfactant of the negative electrode material in the electrolyte (40) is 0.1 mass% or less.)

1. A lead-acid battery comprising a positive electrode, a negative electrode and an electrolyte,

the positive electrode has a tube for holding an active material,

the negative electrode has a negative electrode material containing a surfactant,

the total content X of the surfactant different from the surfactant of the negative electrode material in the electrolyte solution is 0.1 mass% or less.

2. The lead-acid battery according to claim 1,

the tube contains a surfactant different from the surfactant of the anode material.

3. A lead-acid battery comprising a positive electrode, a negative electrode and an electrolyte,

the positive electrode has a tube for holding an active material,

the negative electrode has a negative electrode material containing a surfactant different from the dialkyl sulfosuccinic acid,

the content X of the dialkyl sulfosuccinic acid in the electrolyte is 0.1 mass% or less.

4. The lead-acid battery according to claim 3,

the tube contains dialkyl sulfosuccinic acid.

5. The lead storage battery according to any one of claims 1 to 4,

the content X is more than 0 mass% and 0.1 mass% or less.

6. The lead storage battery according to any one of claims 1 to 4,

the content X is 0 mass%.

7. The lead storage battery according to any one of claims 1 to 6,

the surfactant of the negative electrode material contains lignosulfonate.

8. The lead storage battery according to any one of claims 1 to 7,

the tube comprises glass.

9. A method for manufacturing a lead-acid battery having a positive electrode, a negative electrode and an electrolyte,

the method for manufacturing a lead-acid battery includes a chemical conversion treatment step of performing chemical conversion treatment of the positive electrode and the negative electrode,

The positive electrode has a tube for holding an active material,

the negative electrode has a negative electrode material containing a surfactant,

after the chemical conversion treatment step, the positive electrode and the negative electrode are brought into contact with the electrolytic solution in a state where a total content X of surfactants different from the surfactant of the negative electrode material in the electrolytic solution is 0.1 mass% or less.

10. The method for manufacturing a lead-acid battery according to claim 9,

after the chemical conversion treatment step, the tube contains a surfactant different from the surfactant of the negative electrode material.

11. A method for manufacturing a lead-acid battery having a positive electrode, a negative electrode and an electrolyte,

the method for manufacturing a lead-acid battery includes a chemical conversion treatment step of performing chemical conversion treatment of the positive electrode and the negative electrode,

the positive electrode has a tube for holding an active material,

the negative electrode has a negative electrode material containing a surfactant different from the dialkyl sulfosuccinic acid,

after the chemical conversion treatment step, the positive electrode and the negative electrode are brought into contact with the electrolyte solution in a state where the content X of the dialkyl sulfosuccinic acid in the electrolyte solution is 0.1 mass% or less.

12. The method for manufacturing a lead-acid battery according to claim 11,

after the chemical conversion treatment process, the pipe contains a dialkyl sulfosuccinic acid.

13. The method for manufacturing a lead storage battery according to any one of claims 9 to 12,

the content X is more than 0 mass% and 0.1 mass% or less.

14. The method for manufacturing a lead storage battery according to any one of claims 9 to 12,

the content X is 0 mass%.

15. The method for manufacturing a lead-acid battery according to any one of claims 9 to 14, further comprising a step of washing the tube with water before the chemical conversion treatment step.

16. The method for manufacturing a lead-acid battery according to any one of claims 9 to 15, further comprising a step of removing the 1 st electrolytic solution used in the chemical conversion treatment step and bringing the 2 nd electrolytic solution into contact with the positive electrode and the negative electrode after the chemical conversion treatment step.

17. The method for manufacturing a lead storage battery according to any one of claims 9 to 16,

the surfactant of the negative electrode material contains lignosulfonate.

18. The method for manufacturing a lead storage battery according to any one of claims 9 to 17,

The tube comprises glass.

Technical Field

The present invention relates to a lead storage battery and a method for manufacturing the same.

Background

Lead-acid batteries are widely used as secondary batteries for industrial or domestic use, and in particular, backup lead-acid batteries for electric vehicles (for example, lead-acid batteries for automobiles, so-called batteries (batteries)), UPSs (Uninterruptible Power supplies), disaster-prevention (emergency) wireless Power supplies, telephone Power supplies, and the like are in great demand.

In lead storage batteries, a tube for holding an active material is sometimes used. For example, a lead-acid battery includes an electrode having a tube for holding an active material, a plug (current collector) inserted into the tube, and an electrode material filled between the tube and the plug (see, for example, patent document 1 below).

Prior art documents

Patent document

Patent document 1: japanese laid-open patent publication No. 8-203506

Disclosure of Invention

Technical problem to be solved by the invention

A lead-acid battery having a tube for holding an active material is required to have excellent discharge performance.

The present invention has been made in view of such circumstances, and an object thereof is to provide a lead acid battery having excellent discharge performance and a method for manufacturing the same.

Means for solving the technical problem

A lead-acid battery according to embodiment 1 of the present invention includes a positive electrode having a tube for holding an active material, a negative electrode having a negative electrode material containing a surfactant, and an electrolyte solution in which a total content X of a surfactant different from the surfactant in the negative electrode material is 0.1 mass% or less.

Embodiment 2 of the lead-acid battery according to one aspect of the present invention includes a positive electrode having a tube for holding an active material, a negative electrode having a negative electrode material containing a surfactant different from dialkyl sulfosuccinic acid, and an electrolyte solution in which the content X of dialkyl sulfosuccinic acid is 0.1 mass% or less.

A method for manufacturing a lead-acid battery according to a first embodiment of the present invention is a method for manufacturing a lead-acid battery including a positive electrode having a tube for holding an active material, a negative electrode having a negative electrode material containing a surfactant, and an electrolyte, the positive electrode and the negative electrode being in contact with the electrolyte in a state where a total content X of the surfactant different from the surfactant in the electrolyte is 0.1 mass% or less after the chemical conversion treatment step.

A method for manufacturing a lead-acid battery according to a second aspect of the present invention is a method for manufacturing a lead-acid battery including a positive electrode, a negative electrode, and an electrolytic solution, the method for manufacturing a lead-acid battery including a chemical conversion treatment step of performing chemical conversion treatment of the positive electrode and the negative electrode, the positive electrode having a tube for holding an active material, the negative electrode having a negative electrode material containing a surfactant different from dialkyl sulfosuccinic acid, the positive electrode and the negative electrode being in contact with the electrolytic solution in a state where a content X of dialkyl sulfosuccinic acid in the electrolytic solution is 0.1 mass% or less after the chemical conversion treatment step.

Effects of the invention

According to the present invention, a lead-acid battery having excellent discharge performance and a method for manufacturing the same can be provided.

Drawings

Fig. 1 is a schematic cross-sectional view illustrating a lead-acid battery according to an embodiment of the present invention.

Fig. 2 is a schematic cross-sectional view illustrating a lead-acid battery according to an embodiment of the present invention.

Detailed Description

Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

In addition, the specific gravity varies with temperature, and is therefore defined as a specific gravity in terms of 20 ℃. In the present specification, the numerical range shown by the term "to" means a range including the numerical values before and after the term "to" as the minimum value and the maximum value, respectively. In the numerical ranges recited in the present specification, the upper limit or the lower limit of the numerical range in one stage may be arbitrarily combined with the upper limit or the lower limit of the numerical range in another stage. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples. "a or B" may include both a and B as long as they include both. Unless otherwise specified, one or a combination of two or more of the materials described in this specification can be used. In the case where a plurality of substances corresponding to the respective components are present in the composition, the content of each component in the composition indicates the total amount of the plurality of substances present in the composition unless otherwise specified. The term "step" includes not only an independent step but also a step included in the term as long as the desired action of the step can be achieved even when the step is not clearly distinguished from other steps.

In the present specification, the weight average molecular weight can be measured, for example, by gel permeation chromatography (hereinafter, referred to as "GPC") under the following conditions.

(GPC conditions)

The device comprises the following steps: high performance liquid chromatograph LC-2200Plus (manufactured by JASCO Corporation)

A pump: PU-2080

Differential refractometer: RI-2031

A detector: ultraviolet visible absorption photometer UV-2075 (lambda: 254nm)

Column oven: CO-2065

A chromatographic column: TSKgel SuperAW (4000), TSKgel SuperAW (3000), TSKgel SuperAW (2500) (manufactured by TOSOH CORPORATION)

Column temperature: 40 deg.C

Eluent: methanol solution containing LiBr (10mM) and triethylamine (200mM)

Flow rate: 0.6 mL/min

Molecular weight standards: polyethylene glycol (molecular weight: 1.10X 10)⁶、5.80×10⁵、2.55×10⁵、1.46×10⁵、1.01×10⁵、4.49×10⁴、2.70×10⁴、2.10×10⁴(ii) a Manufactured by TOSOH corporation), diethylene glycol (molecular weight: 1.06X 10²(ii) a KISHIDA CHEMICAL co., ltd., product), dibutylhydroxytoluene (molecular weight: 2.20X 10²(ii) a KISHIDA CHEMICAL Co., Ltd.)

< lead storage battery >

A lead-acid battery according to this embodiment (including embodiment 1 and embodiment 2 described later, and the same applies hereinafter) includes a positive electrode having a tube for holding an active material, a negative electrode having a negative electrode material containing a surfactant, and an electrolyte. In the lead-acid battery according to embodiment 1, the total content X of the surfactant different from the surfactant of the negative electrode material in the electrolytic solution is 0.1 mass% or less. In the lead-acid battery according to embodiment 2, the negative electrode has a negative electrode material containing a surfactant different from the dialkyl sulfosuccinic acid, and the content X of the dialkyl sulfosuccinic acid in the electrolyte is 0.1 mass% or less. According to the lead-acid battery of the present embodiment, excellent discharge performance can be obtained.

When a tube for holding an active material is produced, a surfactant different from the surfactant used for the negative electrode material may be used for the purpose of improving affinity between constituent materials of the tube, affinity between the electrolyte and the tube at the time of chemical conversion, or the like. For example, when a surfactant is used when a resin material such as a phenol resin, an acrylic resin, or an epoxy resin is held on a base material constituting a tube, the resin material is easily held on the base material. With respect to such a surfactant for pipes, the present inventors found that: in a lead-acid battery obtained by immersing a tube in an electrolyte, a surfactant remaining on the tube may be eluted into the electrolyte and discharge performance may be degraded by the influence of the eluted surfactant. The reason for this deterioration in discharge performance is not necessarily clear, but the present inventors presume that: the surfactant used in the production of the tube is more likely to be eluted into the electrolyte than the surfactant of the negative electrode material, and the discharge performance is lowered because the surfactant eluted into the electrolyte inhibits the discharge reaction. However, the reason why the discharge performance is deteriorated is not limited to this reason. On the other hand, in the lead-acid battery according to embodiment 1, the total content X of the surfactant different from the surfactant of the negative electrode material in the electrolytic solution is 0.1 mass% or less, whereby excellent discharge performance can be obtained. In the lead-acid battery according to embodiment 2, the negative electrode has a negative electrode material containing a surfactant different from the dialkyl sulfosuccinic acid, and the content X of the dialkyl sulfosuccinic acid in the electrolyte is 0.1 mass% or less, whereby excellent discharge performance can be obtained.

From the viewpoint of obtaining excellent discharge performance, the content X is 0.1 mass% or less based on the total mass of the electrolyte. The content X is a content in the electrolyte of the lead-acid battery after chemical conversion, for example, a content in the electrolyte when charging and discharging are performed. Therefore, when the electrolyte solution is replaced after the chemical conversion treatment, the newly supplied electrolyte solution is the target of the content X as the electrolyte solution at the time of charge and discharge. Examples of methods for reducing the content X include: a method of cleaning (e.g., water washing) a tube after manufacturing the tube using a surfactant (dialkyl sulfosuccinic acid or the like); a method of replacing the electrolyte after the chemical conversion treatment; a method of reducing the amount of a surfactant (e.g., dialkyl sulfosuccinic acid) used in producing a pipe; a method of performing a chemical conversion treatment while circulating an electrolytic solution, and the like.

The content X in the electrolyte solution of embodiment 1 is targeted at the total amount of all surfactants different from the surfactant of the negative electrode material. That is, in the electrolyte solution according to embodiment 1, a surfactant having a content exceeding 0.1 mass% is not present as a surfactant other than the surfactant contained in the negative electrode material. The content X can be confirmed by determining the content of each surfactant after determining the kind of the surfactant contained in the electrolytic solution. In the electrolyte solution according to embodiment 2, the content X of the dialkyl sulfosuccinic acid is 0.1 mass% or less, and the content of the surfactant other than the dialkyl sulfosuccinic acid is arbitrary.

The content X is preferably within the following range based on the total mass of the electrolytic solution. From the viewpoint of easily obtaining excellent discharge performance, the content X is preferably less than 0.1% by mass, more preferably 0.09% by mass or less, further preferably 0.08% by mass or less, particularly preferably 0.07% by mass or less, very preferably 0.06% by mass or less, very preferably 0.05% by mass or less, and further more preferably 0.02% by mass or less. The content X may be 0 mass% or more than 0 mass%. The content X may be more than 0 mass% and 0.1 mass% or less, or may be 0 mass%. The content X can be measured by high performance liquid chromatography (HPL C).

The negative electrode material contains a surfactant from the viewpoint that the reaction area of the electrode material is easily maintained at a high level during charge and discharge cycles, and excellent discharge performance is easily obtained. The surfactant of the negative electrode material preferably contains an anionic surfactant from the viewpoint of easily obtaining excellent discharge performance. As the surfactant of the negative electrode material, a resin having at least one selected from the group consisting of a sulfo group and a sulfonate group (a resin having a sulfo group and/or a sulfonate group) can be used. Examples of the resin having a sulfo group and/or a sulfonate group include lignin sulfonic acid, lignin sulfonate, and condensates of phenols, aminoarylsulfonic acid, and formaldehyde. Examples of the lignosulfonate include alkali metal salts of lignosulfonate and the like. Examples of the phenols include bisphenol compounds such as bisphenol. Examples of the aminoarylsulfonic acid include aminobenzenesulfonic acid and aminonaphthalenesulfonic acid.

The surfactant of the negative electrode material preferably contains a lignosulfonate from the viewpoint of easily obtaining excellent discharge performance. From the viewpoint of easily obtaining excellent discharge performance, the lignosulfonate preferably contains at least one selected from the group consisting of potassium lignosulfonate and sodium lignosulfonate. The lignosulfonate may contain at least one selected from the group consisting of lignosulfonate with a quinoid structure and lignosulfonate with a stilbene structure.

The molecular weight (for example, weight average molecular weight) of the surfactant of the negative electrode material is preferably in the following range. The molecular weight of the surfactant of the negative electrode material is preferably 3000 or more, more preferably 5000 or more, and even more preferably 7000 or more, from the viewpoint of easily maintaining a high reaction area of the electrode material during charge and discharge cycles. The molecular weight of the surfactant of the negative electrode material is preferably 100000 or less, more preferably 50000 or less, and even more preferably 30000 or less, from the viewpoint of being easily soluble in water and easily exhibiting the effect of inhibiting aggregation of the active material. From these viewpoints, the molecular weight of the surfactant of the negative electrode material is preferably 3000 to 100000.

The content of the surfactant in the negative electrode material (negative electrode material after chemical conversion) is preferably in the following range with respect to 100 parts by mass of the negative electrode active material. The content of the surfactant is preferably 0.4 parts by mass or less, more preferably 0.3 parts by mass or less, and still more preferably 0.25 parts by mass or less, from the viewpoint of easily obtaining excellent discharge performance. The content of the surfactant is preferably 0.1 part by mass or more, more preferably 0.15 part by mass or more, further preferably 0.175 part by mass or more, and particularly preferably 0.2 part by mass or more, from the viewpoint of easily obtaining excellent discharge performance. From these viewpoints, the content of the surfactant is preferably 0.1 to 0.4 part by mass. The content of the surfactant can be measured by High Performance Liquid Chromatography (HPLC). For example, lignosulfonates of quinoid structure have an intrinsic peak at 350nm and lignosulfonates of stilbene structure have an intrinsic peak at 370 nm. The surfactant content can be quantified from the calibration curve and the intensity of the intrinsic peak.

The tube may contain a surfactant different from that of the anode material, for example, may contain dialkyl sulfosuccinic acid. For example, the presence of the surfactant in the tube can be confirmed by High Performance Liquid Chromatography (HPLC). As the surfactant for the pipe, a surfactant different from lignosulfonate may be used. The tube and the electrolyte may contain the same surfactant or different surfactants.

The surfactant for the pipe preferably contains at least one selected from the group consisting of anionic surfactants and nonionic surfactants, and more preferably contains an anionic surfactant, from the viewpoint that the resin material is easily held on the base material when the pipe is produced. Examples of the anionic surfactant include alkylsulfosuccinates, fatty acid soaps, rosin soaps, alkylsulfonates, alkylbenzenesulfonates, dialkylarylsulfonates, polyoxyethylene alkylsulfates, and polyoxyethylene alkylarylsulfates. Examples of the nonionic surfactant include polyoxyethylene alkyl aryl ethers, polyoxyethylene sorbitan fatty acid esters, and oxyethylene oxypropylene copolymers. The surfactant for the pipe preferably contains an alkyl sulfosuccinate, more preferably contains at least one selected from the group consisting of monoalkyl sulfosuccinates and dialkyl sulfosuccinates, and even more preferably contains a dialkyl sulfosuccinate, from the viewpoint of facilitating holding of the resin material on the substrate when the pipe is produced. Examples of the dialkyl sulfosuccinate include sodium diheptyl sulfosuccinate, sodium dioctyl sulfosuccinate, and sodium dinonyl sulfosuccinate, and sodium dioctyl sulfosuccinate is preferable from the viewpoint that the resin material is easily held on the base material when the pipe is produced.

The molecular weight (for example, weight average molecular weight) of the surfactant of the tube is preferably within the following range. The molecular weight of the surfactant is preferably 100 or more, more preferably 200 or more, further preferably 300 or more, and particularly preferably 400 or more, from the viewpoint of ease of holding the resin material on the base material when the pipe is produced. The molecular weight of the surfactant is preferably 2000 or less, more preferably 1000 or less, further preferably 800 or less, and particularly preferably 500 or less, from the viewpoint of ease of holding the resin material to the base material when the pipe is produced. From these viewpoints, the molecular weight of the surfactant is preferably 100 to 2000.

After the chemical conversion (after the chemical conversion treatment step described later), the tube may or may not contain a surfactant. The content of the surfactant in the tube (tube of the lead-acid battery after chemical conversion) is preferably in the following range based on the total mass of the tube. From the viewpoint of easily obtaining excellent discharge performance, the content of the surfactant is preferably 2.00% by mass or less, more preferably 1.50% by mass or less, further preferably 1.00% by mass or less, particularly preferably 0.5% by mass or less, very preferably 0.3% by mass or less, very preferably 0.1% by mass or less, further preferably 0.08% by mass or less, further preferably 0.06% by mass or less. The content of the surfactant is preferably 0% by mass or more, more preferably more than 0% by mass, even more preferably 0.01% by mass or more, particularly preferably 0.02% by mass or more, very preferably 0.03% by mass or more, very preferably 0.04% by mass or more, and even more preferably 0.05% by mass or more, from the viewpoint of easily obtaining excellent discharge performance and from the viewpoint of excellent permeability of the electrolyte solution at the time of chemical conversion. From these viewpoints, the content of the surfactant is preferably 0 to 2.0 mass%. The surfactant content in the tube can be determined by High Performance Liquid Chromatography (HPLC).

The lead-acid battery according to the present embodiment includes, for example, an electrolytic cell that houses electrodes (a positive electrode and a negative electrode). The electrolytic bath is filled with an electrolyte. The electrodes may constitute an electrode group. For example, in the electrode group, positive electrodes and negative electrodes are alternately arranged via separators.

The electrode (positive electrode or negative electrode) after chemical conversion has an electrode material (positive electrode material or negative electrode material) containing an active material. Also, the electrode (positive electrode or negative electrode) may have a current collector. The electrode material may be held by a current collector, a tube for holding an active material, or the like. In the present embodiment, the positive electrode material is held by, for example, a tube for holding an active material. The negative electrode material may be held by any of a current collector, a tube for holding an active material, and the like.

The tube for holding the active material is, for example, a tube that can accommodate the plug (current collector) and the electrode material. The mandrel is a rod-like member inserted into the tube, for example, extending in the axial direction of the tube at the center portion of the tube. An electrode material (for example, a positive electrode material) containing an active material is filled between the tube and the mandrel.

The tube for holding the active material may constitute an active material holding member (tube group for holding the active material) provided with a plurality of (for example, 2 to 19) tubes. In the active material holding member, a plurality of tubes are arranged side by side with each other. The structure in which a plurality of tubes are arranged side by side may be obtained by arranging tubes independent of each other side by side, or may be obtained by forming a plurality of through-holes between substrates facing each other. A connecting portion such as a seam (sewn portion) may be disposed between the adjacent tubes.

The shape of the cross section of the tube perpendicular to the axial direction may be circular, elliptical, rounded quadrilateral, or the like. The length of the tube is, for example, 160 to 650 mm. The outer diameter of the tube is, for example, 5 to 12 mm. The inner diameter of the tube is, for example, 5 to 10 mm. The thickness of the tube is, for example, 0.1 to 2 mm.

The tube is formed of a porous body and has pores. The tube may be formed of a base material such as woven fabric or nonwoven fabric. As the material of the base material, a material having acid resistance can be used. Examples of the material of the substrate include: inorganic materials such as glass (e.g., glass fiber), silicon carbide, and alumina; and resins such as polyolefin (e.g., polypropylene or polyethylene), polyester (e.g., polyethylene terephthalate (PET)), Polystyrene (PS), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), and Polycarbonate (PC). The substrate may comprise glass or may comprise a polyolefin. When the substrate is a glass tube containing glass, the content of glass may be 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, or 90 mass% or more based on the total mass of the tube.

In the tube, the resin material may be held on the base material. Examples of the resin material include acrylic resin, epoxy resin, phenol resin, melamine resin, styrene resin, and the like. The resin material may be held on the inner surface or the outer surface of the base material or on the surface within the pores of the base material, or may be adhered to the base material. The resin material may be held on a part of the base material or may be held on the entire base material.

The core rod can be obtained by, for example, die casting. The constituent material of the plug may be any conductive material, and examples thereof include lead alloys such as lead-calcium-tin alloys and lead-antimony-arsenic alloys. The lead alloy may contain selenium, silver, bismuth, and the like. The shape of the cross section of the mandrel perpendicular to the axial direction (longitudinal direction) may be circular, elliptical, or the like. The length of the core rod is, for example, 170 to 650 mm. The diameter of the core rod is, for example, 2.0 to 4.0 mm.

The positive electrode material contains a positive electrode active material after chemical conversion. The chemically converted positive electrode material can be obtained by, for example, chemically converting an chemically unconverted positive electrode material of a raw material containing a positive electrode active material. Examples of the method for obtaining a chemically converted positive electrode material include a method in which a raw material of a positive electrode active material is directly charged into a tube for holding an active material and then chemically converted, a method in which a positive electrode material paste containing a raw material of a positive electrode active material is aged and dried to obtain a non-chemically converted positive electrode material, and then the non-chemically converted positive electrode material is chemically converted, and the like. Examples of the raw material of the positive electrode active material include lead powder and red lead. Examples of the positive electrode active material in the positive electrode material after chemical conversion include lead dioxide.

The positive electrode material may further contain an additive, as necessary. Examples of the additive for the positive electrode material include short reinforcing fibers. Examples of the reinforcing short fibers include acrylic fibers, polyethylene fibers, polypropylene fibers, polyethylene terephthalate fibers (PET fibers), and the like.

The negative electrode material contains a negative electrode active material and the above surfactant after chemical conversion. The chemically converted negative electrode material can be obtained by, for example, chemically converting an electrochemically unconverted negative electrode material of a raw material containing a negative electrode active material. The anode material after chemical conversion can be obtained, for example, as follows: the non-chemically-converted negative electrode material is obtained by aging and drying a negative electrode material paste containing a raw material of a negative electrode active material, and then the non-chemically-converted negative electrode material is chemically converted. As a raw material of the negative electrode active material, lead powder and the like can be cited. Examples of the negative electrode active material in the negative electrode material after chemical conversion include porous Spongy Lead (sponge Lead).

The negative electrode material may further contain an additive (excluding the above surfactant) as necessary. Examples of the additive of the negative electrode material include barium sulfate, short reinforcing fibers, and a carbon material (carbon conductive material). As the short reinforcing fibers, the same short reinforcing fibers as those used for the positive electrode material can be used.

Examples of the carbon material include carbon black and graphite. Examples of the carbon black include furnace black (ketjen black (registered trademark), etc.), channel black, acetylene black, and thermal black.

The material of the separator is not particularly limited as long as it is a material that blocks electrical connection between the positive electrode and the negative electrode and allows the electrolyte to permeate therethrough. Examples of the material of the separator include: microporous polyethylene; mixtures of glass fibers and synthetic resins, and the like.

As the electrolytic solution, sulfuric acid (e.g., dilute sulfuric acid) may be used. The electrolyte may contain aluminum ions, sodium ions, or the like. According to the present embodiment, there is provided an electrolyte solution used for a lead-acid battery including a positive electrode and a negative electrode, the positive electrode having a tube for holding an active material, the negative electrode having a negative electrode material containing a surfactant, and the electrolyte solution having a total content X of a surfactant different from the surfactant of the negative electrode material of 0.1 mass% or less. According to the present embodiment, there can be provided an electrolyte solution used for a lead-acid battery including a positive electrode and a negative electrode, the positive electrode having a tube for holding an active material, the negative electrode having a negative electrode material containing a surfactant different from dialkyl sulfosuccinic acid, and the content X of the dialkyl sulfosuccinic acid in the electrolyte solution being 0.1 mass% or less. According to the present embodiment, the application of the electrolyte to lead-acid batteries for electric vehicles or power supply devices can be provided.

An example of the lead-acid battery according to the present embodiment will be described with reference to fig. 1 and 2. Fig. 1 and 2 are schematic cross-sectional views showing an example of a lead-acid battery. In fig. 1, positive electrodes and negative electrodes are alternately arranged through separators from the front side to the back side of the drawing sheet. Fig. 1(b) is an enlarged view showing a region P in fig. 1 (a). In fig. 1(a), the details of the inside of the tube are not shown. The lead-acid battery shown in fig. 1 and 2 includes an electrolytic bath extending in the vertical direction, and fig. 2 shows a stacked structure of a positive electrode, a negative electrode, and a separator when the lead-acid battery is viewed from above in the vertical direction (from above in the height direction of the electrolytic bath).

The lead acid battery 100 shown in fig. 1 and 2 includes an electrode group 110, an electrolytic cell 120 accommodating the electrode group 110, connecting members 130a and 130b connected to the electrode group 110, poles 140a and 140b connected to the connecting members 130a and 130b, a spout plug 150 closing a liquid inlet of the electrolytic cell 120, and a support member 160 connected to the electrolytic cell 120.

The electrode group 110 includes a plurality of positive electrodes 10, a plurality of negative electrodes 20, and a plurality of separators 30. The positive electrodes 10 and the negative electrodes 20 are alternately arranged via the separators 30. The space around the positive electrode 10 between the separators 30 is filled with the electrolyte 40. The content X in the electrolyte solution 40 is 0.1 mass% or less.

The positive electrode 10 is, for example, a plate-shaped electrode (positive electrode plate), and includes a plurality of tubes 10a for holding an active material, a plug (current collector) 10b, a positive electrode material 10c, a lower connecting holder 10d, an upper connecting holder 10e, and an ear portion 10 f.

The plurality of tubes 10a are arranged side by side with each other, thereby constituting a tube group for holding an active material. Each pipe 10a extends in the height direction (vertical direction) of the electrolytic cell 120. The core rod 10b extends in the axial direction of the tube 10a at the center portion of the tube 10 a. The positive electrode material 10c is filled between the tube 10a and the mandrel 10 b.

The lower connecting seat 10d is connected to one end (lower end in the figure) of the pipe 10a, and the upper connecting seat 10e is connected to the other end (upper end in the figure) of the pipe 10 a. The lower and upper connecting holders 10d and 10e contact the tube 10a and the plug 10b and the positive electrode material 10c disposed in the tube 10a, and hold the tube 10a, the plug 10b, and the positive electrode material 10 c. The lower connecting holder 10d is attached to the bottom-side end of the electrolytic bath 120 in the tube 10a (the end on one end side of the tube 10 a). The lower connecting seat 10d is fitted to an end of the tube 10a, and includes a base portion extending in a direction orthogonal to the axial direction of the tube 10a and a plurality of fitting portions connected to the base portion and fitted to the end of the tube 10 a. The fitting portion is formed with a recess for inserting the end of the mandrel bar 10 b. The upper connecting holder 10e is attached to an end portion of the tube 10a on the upper side of the electrolytic bath 120 (the end on the other end side of the tube 10 a).

One end (lower end in the figure) of the ear portion 10f is connected to the upper link holder 10e, and the other end (upper end in the figure) of the ear portion 10f is connected to the coupling member 130 a. The plug 10b accommodated in the tube 10a is electrically connected to the pole 140a via the upper connecting socket 10e, the ear 10f, and the connecting member 130 a.

The support member 160 has a plurality of protrusions 160a extending in the axial direction of the pipe 10a (the longitudinal direction, for example, the height direction of the electrolytic cell 120), and the lower connecting holder 10d is fixed in contact with the plurality of protrusions 160a (see fig. 1 (a)). That is, the support member 160 supports the bottom surface side portion of the electrolytic cell 120 in the lower connecting holder 10d by the respective protrusions 160 a.

The negative electrode 20 is, for example, a plate-like, for example, a paste-type negative electrode plate. The negative electrode 20 has a negative electrode current collector and a negative electrode material held by the negative electrode current collector. As the negative electrode current collector, a plate-shaped current collector may be used. The compositions of the negative electrode current collector and the core rod 10b of the positive electrode 10 may be the same as each other or may be different from each other. The negative electrode 20 is electrically connected to the pole 140b via the connecting member 130 b.

Method for manufacturing lead-acid battery

The method for manufacturing a lead-acid battery according to the present embodiment is a method for manufacturing a lead-acid battery including a positive electrode, a negative electrode, and an electrolytic solution, and includes a chemical conversion treatment step of performing chemical conversion treatment of the positive electrode and the negative electrode. In embodiment 1, after the chemical conversion treatment step, the positive electrode and the negative electrode are brought into contact with the electrolytic solution in a state where the total content X of the surfactants different from the surfactant of the negative electrode material in the electrolytic solution is 0.1 mass% or less. In embodiment 2, after the chemical conversion treatment step, the positive electrode and the negative electrode are brought into contact with the electrolytic solution in a state where the content X of the dialkyl sulfosuccinic acid in the electrolytic solution is 0.1 mass% or less. According to the method for manufacturing a lead-acid battery of the present embodiment, the lead-acid battery of the present embodiment can be obtained. In the present embodiment, after the chemical conversion treatment step, the tube of the positive electrode and the negative electrode material of the negative electrode are brought into contact with the electrolytic solution.

In the chemical conversion treatment step, for example, the chemical conversion treatment is performed by applying a direct current in a state where the positive electrode and the negative electrode are in contact with the electrolyte. The specific gravity of the electrolyte after chemical conversion is adjusted to an appropriate specific gravity, whereby a lead-acid battery can be obtained. The specific gravity (before chemical conversion) of the electrolyte is, for example, 1.100 to 1.260. The specific gravity of the electrolyte (after chemical conversion) is, for example, 1.265 to 1.310. The chemical conversion treatment may be performed while the electrolytic solution is circulated, or may be performed without circulating the electrolytic solution.

The method for manufacturing a lead-acid battery according to the present embodiment may include a tube manufacturing step of manufacturing a tube. In the case of producing a glass tube, in the tube production process, for example, a tube having a through-hole can be obtained by impregnating a tubular base material containing glass with a resin component (e.g., phenol resin) and then drying the impregnated base material. In the case of manufacturing a resin pipe, in the pipe manufacturing process, for example, at least two sheet-like base materials are arranged to face each other, and then the base materials are cylindrically formed therebetween, whereby a pipe having a through-hole can be obtained. Examples of the method of forming the space between the substrates into a cylindrical shape include: a method of molding by inserting a rod-shaped body between base materials; and a method of impregnating a liquid containing a resin component into a base material and then drying the impregnated base material to swell the base material.

In the tube manufacturing process, the tube may be manufactured using a surfactant, or the tube may be manufactured without using a surfactant. When a pipe is produced using a surfactant, for example, the pipe can be produced while holding the resin material on the base material by immersing the base material in a liquid containing the resin material (phenol resin or the like), the surfactant, and a solvent.

When the surfactant is used in the tube forming step, the amount of the surfactant to be used is preferably within the following range with respect to 100 parts by mass of the solvent. From the viewpoint of easily obtaining excellent discharge performance, the amount of the surfactant to be used is preferably 8 parts by mass or less, more preferably 6 parts by mass or less, further preferably 5 parts by mass or less, particularly preferably 3 parts by mass or less, very preferably 2 parts by mass or less, very preferably 1.8 parts by mass or less, and further preferably 1.5 parts by mass or less. The amount of the surfactant used may be less than 1.5 parts by mass, 1.2 parts by mass or less, or 1.0 part by mass or less. The amount of the surfactant used is preferably 0 part by mass or more, more preferably more than 0 part by mass, further preferably 0.1 part by mass or more, particularly preferably 0.2 part by mass or more, very preferably 0.3 part by mass or more, very preferably 0.5 part by mass or more, further preferably 0.8 part by mass or more, and further preferably 1 part by mass or more, from the viewpoint that a pipe excellent in compressive strength is easily obtained because the surfactant is easily sufficiently impregnated in the pipe, the resin material is easily adhered, and the electrolyte easily permeates at the time of chemical conversion. The amount of the surfactant used may be more than 1 part by mass, 1.2 parts by mass or more, 1.5 parts by mass or more, 2 parts by mass or more, 3 parts by mass or more, or 5 parts by mass or more. From these viewpoints, the content of the surfactant is preferably 0 to 8 parts by mass. The surfactant content in the tube can be determined by High Performance Liquid Chromatography (HPLC).

The method for manufacturing a lead-acid battery according to the present embodiment may include a tube cleaning step of cleaning the tube after the tube manufacturing step and before the chemical conversion treatment step. The tube cleaning step is a step of cleaning a tube containing a surfactant to remove at least a part of the surfactant from the tube. In the tube cleaning step, the tube may be washed with running water, or may be immersed in water, sulfuric acid, or the like. The tube cleaning step may be performed before or after the filling step of filling the tube with the active material (lead powder) in the electrode production step.

The method for manufacturing a lead-acid battery according to the present embodiment may include an electrode manufacturing step of manufacturing electrodes (positive electrode and negative electrode). The electrode manufacturing step includes a positive electrode manufacturing step and a negative electrode manufacturing step.

In the positive electrode producing step, a positive electrode having a mandrel inserted into a tube and a positive electrode material filled between the tube and the mandrel is obtained. In the positive electrode manufacturing process, for example, a raw material of a positive electrode active material is filled between a mandrel and a tube after the mandrel is wrapped with the tube, and further, the lower end of the tube is closed with a lower connecting seat, whereby a positive electrode having a positive electrode material that is not chemically converted can be obtained. In the positive electrode manufacturing process, the upper end of the tube may be plugged with an upper connection seat.

In the negative electrode production step, for example, a negative electrode material paste containing a raw material of a negative electrode active material is filled in a negative electrode current collector (for example, a current collector grid (a cast grid, an expanded grid, or the like)) and then cured and dried, whereby a negative electrode having a negative electrode material that has not been chemically converted can be obtained. The curing is preferably carried out at a temperature of 35 to 85 ℃ and a humidity of 50 to 98 RH% for 15 to 60 hours. The drying is preferably carried out at a temperature of 45 to 80 ℃ for 15 to 30 hours.

The negative electrode material paste may further contain the above-mentioned additive in addition to the raw material of the negative electrode active material, for example. The negative electrode material paste may further contain a solvent and sulfuric acid. Examples of the solvent include water and an organic solvent.

When an additive such as barium sulfate, a carbon material, or short reinforcing fibers is used in the negative electrode material paste, the amount of the additive is preferably within the following range with respect to 100 parts by mass of the raw material of the negative electrode active material. The amount of barium sulfate is, for example, 0.01 to 2 parts by mass. The amount of the carbon material is, for example, 0.1 to 3 parts by mass. The blending amount of the short reinforcing fibers is, for example, 0.01 to 0.3 part by mass.

The method for manufacturing a lead-acid battery according to the present embodiment may include an assembly step of assembling constituent members including electrodes to obtain the lead-acid battery. In the assembly step, for example, an electrode group is obtained by stacking an electrochemically unconverted positive electrode and an electrochemically unconverted negative electrode with a separator interposed therebetween, and welding current collecting portions of the electrodes of the same polarity by a bus bar. The electrode assembly was placed in an electrolytic cell to produce a non-chemically-converted cell. The chemical conversion treatment step may be performed after the assembly step, or may be performed in the electrode production step (tank chemical conversion) before the assembly step.

The method for manufacturing a lead-acid battery according to the present embodiment may include, after the chemical conversion treatment step, an electrolyte replacement step of removing the 1 st electrolyte used in the chemical conversion treatment step and bringing the 2 nd electrolyte into contact with the positive electrode and the negative electrode. In the electrolyte replacement step, the 2 nd electrolyte is supplied after the 1 st electrolyte is removed, whereby the 2 nd electrolyte can be brought into contact with the positive electrode and the negative electrode. As described above, the content X in the 2 nd electrolytic solution is 0.1 mass% or less, and may have each of the above ranges.

Electric vehicle, power supply device, and method for manufacturing same

The electric vehicle or the power supply device according to the present embodiment includes the lead storage battery according to the present embodiment. The method for manufacturing an electric vehicle or a power supply device according to the present embodiment includes a step of obtaining a lead storage battery by the method for manufacturing a lead storage battery according to the present embodiment. The method for manufacturing an electric vehicle or a power supply device according to the present embodiment includes, for example, a step of obtaining a lead storage battery by the method for manufacturing a lead storage battery according to the present embodiment and a step of assembling constituent members including the lead storage battery to obtain an electric vehicle or a power supply device. Examples of the electric vehicle include a forklift, a golf cart, and the like. Examples of the power supply device include a UPS, a disaster prevention (emergency) wireless power supply, and a telephone power supply. According to the present embodiment, a lead-acid battery for an electric vehicle, for example, a lead-acid battery for a forklift is provided. According to the present embodiment, a lead acid battery for a power supply device is provided.

Examples

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

< production of Battery >

(example 1)

Glass yarns each formed by binding alkali glass fibers were woven at a weaving density of 25 stitches/25 mm. In the tubular raw sleeve after weaving, 24 warps, 48 heddles and an inner diameter of 9mm were provided. Then, 100 parts by mass of water (solvent), 17 parts by mass of a phenol resin (trade name: Phenolite IG-1002, manufactured by DIC CORPORATION) and 1 part by mass of a surfactant A (NEOCOL SW-C, manufactured by DKS Co. Ltd., trade name: sodium di (2-ethylhexyl) sulfosuccinate (also called sodium dioctyl sulfosuccinate)) were mixed to obtain a mixed solution. Next, the green sleeve was impregnated with the mixed solution (mixed solution: green sleeve: 1:0.032 (mass ratio)). Then, the raw sleeve was passed through a passage-type heating furnace having an internal temperature of 250 ℃ for 120 seconds to evaporate water and cure the resin component, thereby obtaining a glass tube.

Next, after 15 tubes were arranged, the upper connector holder was attached to the tubes. Then, a plug (cylindrical shape having a diameter of 2.7 mm. phi. times.342 mm in length) made of a lead-antimony (4.0 mass%) -arsenic (0.2 mass%) -tin (0.015 mass%) alloy was inserted into the tube, and lead powder containing lead monoxide as a main component was filled into the tube. Then, sealing was performed by driving the lower connecting socket into the lower end of the tube, thereby obtaining an chemically unconverted positive electrode plate having 15 tubes.

A lead-antimony alloy (antimony content: 3 mass%) was melted, and a gate (dimensions: 283.0mm in the vertical direction, 141.0mm in the horizontal direction, and 4.0mm in thickness) was produced by casting. Then, 100 parts by mass of lead powder containing lead monoxide as a main component were mixed with 0.3 part by mass of barium sulfate, 0.03 part by mass of PET fiber, 0.2 part by mass of surfactant B (sodium lignosulfonate with a stilbene structure, product name: Indul in C manufactured by Ingevisty Co., Ltd.), 8 parts by mass of water and 10 parts by mass of dilute sulfuric acid (specific gravity: 1.260) and kneaded to prepare a negative electrode material paste. Then, after filling the negative electrode material paste into the grid body, the grid body was cured and dried under the following conditions, thereby producing a negative electrode plate that was not chemically converted.

(aging conditions) temperature: 40 ℃ and humidity: 98 RH%, time: 40 hours

(drying conditions) temperature: 60 ℃ and time: 24 hours

After the electrode plate group was produced by alternately laminating the non-chemically-converted positive electrode plates 7 and the non-chemically-converted negative electrode plates 8 with polyethylene separators interposed therebetween, the positive electrode terminal and the negative electrode terminal were welded to the electrode plate group. Next, the cell is sealed after the electrode plate group is inserted into the cell. Then, dilute sulfuric acid (specific gravity: 1.240) was injected from the liquid inlet, and then chemical conversion was performed in the electrolytic cell (without circulating the electrolytic solution), thereby producing a lead-acid battery. The chemical conversion conditions of the electrolytic cell were set to such conditions that the amount of electricity (reference: theoretical chemical conversion amount of positive electrode active material) applied in the water tank was 250% and 36 hours at a water temperature of 40 ℃.

(example 2)

A lead acid battery was produced in the same manner as in example 1, except that the amount of the surfactant a used was changed to 1.5 parts by mass with respect to 100 parts by mass of the solvent, and that all of the electrolyte in the battery was discharged after the cell chemical conversion was performed, and dilute sulfuric acid (specific gravity: 1.280) was refilled from the liquid inlet.

(example 3)

A lead storage battery was produced in the same manner as in example 1, except that the amount of the surfactant a used was changed to 1.5 parts by mass with respect to 100 parts by mass of the solvent.

(example 4)

A lead storage battery was produced in the same manner as in example 2, except that the amount of the surfactant a used was changed to 5.9 parts by mass with respect to 100 parts by mass of the solvent.

Comparative example 1

A lead storage battery was produced in the same manner as in example 1, except that the amount of the surfactant a used was changed to 5.9 parts by mass with respect to 100 parts by mass of the solvent.

< quantification of surfactant >

The lead-acid battery was disassembled, the electrolyte and the tube for holding the active material were taken out, and the contents of the surfactant a in the tube and the electrolyte were measured by High Performance Liquid Chromatography (HPLC). The measurement results are shown in table 1.

< evaluation of discharge Performance >

The rated capacity confirmation test was performed at 0.2 CA. That is, the battery was subjected to constant current charging at a current value of 0.1CA at an ambient temperature of 30 ℃ to 120% of the discharge capacity, thereby being adjusted to a fully charged state. Then, the fully charged lead-acid battery was left in a water tank (temperature: 30 ℃ C.) for 24 hours, and then discharged at 0.2CA to overvoltage of 1.7V, and the discharge capacity (5-hour rate capacity, 0.2CA discharge capacity, rated capacity. unit: Ah) at that time was measured. The discharge capacities were relatively compared with each other with the value of the discharge capacity of comparative example 1 being 100. The results are shown in Table 1.

< evaluation of compressive Strength >

The compressive strength of the tube was evaluated according to the compression ratio measured in the following procedure. The outer diameter of the central portion of the glass tube produced by the above procedure was measured in 0.01mm units using a YSS type schottky thickness measuring instrument manufactured by YASUDA SEIKI SEISAKUSHO ltd. (t 0). Then, the area was set to 4cm²The pressing plate (circular plate) is pressed against the sample. Then, a load of 9.8N was applied to the tube for 1 minute in a direction perpendicular to the longitudinal direction of the tube, and the outer diameter of the central portion at that time was measured (t 1). The compressibility [% ] is measured according to the following formula]. The results are shown in Table 1.

Compressibility ratio (t0-t1)/t0 × 100

[ Table 1]

Description of the symbols

10-positive pole, 10 a-tube, 20-negative pole, 40-electrolyte and 100-lead storage battery.