WO2021070231A1 - Plaque d'électrode positive, accumulateur au plomb et procédé de fabrication d'une plaque d'électrode positive et d'un accumulateur au plomb - Google Patents

Plaque d'électrode positive, accumulateur au plomb et procédé de fabrication d'une plaque d'électrode positive et d'un accumulateur au plomb Download PDF

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Publication number
WO2021070231A1
WO2021070231A1 PCT/JP2019/039541 JP2019039541W WO2021070231A1 WO 2021070231 A1 WO2021070231 A1 WO 2021070231A1 JP 2019039541 W JP2019039541 W JP 2019039541W WO 2021070231 A1 WO2021070231 A1 WO 2021070231A1
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WO
WIPO (PCT)
Prior art keywords
positive electrode
electrode plate
active material
electrode active
lead
Prior art date
Application number
PCT/JP2019/039541
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English (en)
Japanese (ja)
Inventor
祐一 利光
隆之 木村
素子 原田
Original Assignee
昭和電工マテリアルズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to PCT/JP2019/039541 priority Critical patent/WO2021070231A1/fr
Priority to JP2020149906A priority patent/JP2021061235A/ja
Publication of WO2021070231A1 publication Critical patent/WO2021070231A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode plate, a lead storage battery, and a method for manufacturing them.
  • Lead-acid batteries are widely used for industrial purposes, for example, as a battery for automobiles, a backup power source, and a main power source for electric vehicles.
  • the positive electrode in a lead storage battery is required to improve the utilization rate of the positive electrode active material held in the current collector.
  • a positive electrode having an excellent utilization rate of the positive electrode active material is used, for example, the amount of the positive electrode active material used to obtain a predetermined discharge capacity can be reduced, and as a result, the weight of the lead storage battery can be reduced.
  • Patent Document 1 in order to increase the utilization rate of the positive electrode active material, basic lead sulfate and graphite are added to the positive electrode active material, and phosphoric acid is 1% by mass or less in the electrolytic solution.
  • the contained lead-acid battery is disclosed.
  • an object of the present invention is to provide a positive electrode plate for a lead storage battery having an excellent utilization rate of a positive electrode active material, and a lead storage battery provided with the positive electrode plate.
  • One aspect of the present invention includes a positive electrode current collector and a positive electrode active material held by the positive electrode current collector, and the positive electrode active material is a fiber having a liquid retention rate of 125% or more (hereinafter, also referred to as “fiber A”). It is a positive electrode plate for a lead storage battery including (referred to as).
  • Another aspect of the present invention includes a step of holding the positive electrode active material in the positive electrode current collector, and the positive electrode active material is a method for producing a positive electrode plate for a lead storage battery, which contains fibers having a liquid retention rate of 125% or more. Is.
  • the fiber A may contain a polymer fiber.
  • Another aspect of the present invention is a lead-acid battery provided with the above-mentioned positive electrode plate.
  • Another aspect of the present invention is a lead-acid battery manufacturing method including a step of manufacturing a positive electrode plate by the above-mentioned manufacturing method and a step of assembling a lead-acid battery including the positive electrode plate.
  • a positive electrode plate for a lead storage battery having an excellent utilization rate of a positive electrode active material, and a lead storage battery provided with the positive electrode plate.
  • FIG. 1 It is a perspective view which shows the overall structure and the internal structure of the lead storage battery which concerns on one Embodiment. It is a perspective view which shows the electrode group of the lead storage battery shown in FIG.
  • FIG. 1 is a perspective view showing the overall configuration and internal structure of the lead storage battery according to the embodiment.
  • the lead-acid battery 1 includes an electric tank 2 having an open upper surface and a lid 3 that closes the opening of the electric tank 2.
  • the battery case 2 and the lid 3 are made of polypropylene, for example.
  • the lid 3 is provided with a negative electrode terminal 4, a positive electrode terminal 5, and a liquid port plug 6 for closing the liquid injection port provided in the lid 3.
  • FIG. 2 is a perspective view showing the electrode group 7.
  • the electrode group 7 includes a negative electrode plate 9, a positive electrode plate 10, and a separator 11 arranged between the negative electrode plate 9 and the positive electrode plate 10.
  • the negative electrode plate 9 includes a negative electrode current collector (negative electrode lattice body) 12 and a negative electrode active material 13 held by the negative electrode current collector 12.
  • the positive electrode plate 10 includes a positive electrode current collector (positive electrode lattice body) 14 and a positive electrode active material 15 held by the positive electrode current collector 14.
  • negative electrode active material negative electrode active material
  • positive electrode plate after chemical conversion from which the positive electrode current collector is removed is referred to as "positive electrode active material”.
  • positive electrode active material the positive electrode plate after chemical conversion from which the positive electrode current collector is removed
  • the electrode group 7 has a structure in which a plurality of negative electrode plates 9 and positive electrode plates 10 are alternately laminated in a direction substantially parallel to the opening surface of the battery case 2 via a separator 11. That is, the negative electrode plate 9 and the positive electrode plate 10 are arranged so that their main surfaces extend in the direction perpendicular to the opening surface of the battery case 2.
  • the ears 12a of each of the negative electrode current collectors 12 in the plurality of negative electrode plates 9 are collectively welded by the negative electrode side strap 16.
  • the ears 14a of each of the positive electrode current collectors 14 of the plurality of positive electrode plates 10 are collectively welded by the positive electrode side strap 17.
  • the negative electrode side strap 16 and the positive electrode side strap 17 are connected to the negative electrode terminal 4 and the positive electrode terminal 5 via the negative electrode column 8 and the positive electrode column, respectively.
  • the separator 11 is formed in a bag shape, for example, and houses the negative electrode plate 9.
  • the separator 11 is made of, for example, polyethylene (PE), polypropylene (PP), or the like.
  • the separator 11 may have inorganic particles such as SiO 2 and Al 2 O 3 adhered to a woven fabric, a non-woven fabric, a porous film, or the like formed of these materials.
  • the negative electrode current collector 12 and the positive electrode current collector 14 are each made of a lead alloy.
  • the lead alloy may be an alloy containing tin, calcium, antimony, selenium, silver, bismuth and the like in addition to lead. Specifically, for example, an alloy containing lead, tin and calcium (Pb-Sn). -Ca-based alloy) may be used.
  • the negative electrode active material 13 contains at least Pb as a Pb component, and further contains a Pb component other than Pb (for example, PbSO 4) and an additive, if necessary.
  • the negative electrode active material 13 preferably contains porous spongy lead.
  • the content of the Pb component may be 90% by mass or more or 95% by mass or more, and may be 99% by mass or less or 98% by mass or less, based on the total mass of the negative electrode active material.
  • the total mass of the negative electrode active material is, for example, the mass of the negative electrode measured after the negative electrode (negative electrode current collector and negative electrode active material) is taken out from the lead storage battery, washed with water, and the negative electrode is sufficiently dried, and the negative electrode current collection. It can be calculated from the difference from the mass of the body. Drying is carried out, for example, at 50 ° C. for 24 hours.
  • additives include resins having a sulfo group and / or a sulfonic acid base, barium sulfate, carbon materials (excluding carbon fibers) and fibers (acrylic fibers, polyethylene fibers, polypropylene fibers, polyethylene terephthalate fibers, carbon fibers, etc.). Can be mentioned.
  • Resins having a sulfo group and / or a sulfonic acid base include lignin sulfonic acid, lignin sulfonate, and a condensate of phenols, aminoaryl sulfonic acid, and formaldehyde (for example, bisphenol, aminobenzene sulfonic acid, and formaldehyde). It may be at least one selected from the group consisting of condensates).
  • the carbon material include carbon black and graphite. Examples of carbon black include furnace black, channel black, acetylene black, thermal black and Ketjen black.
  • Fiber A has a liquid retention rate of 125% or more.
  • the liquid retention rate of the fiber A is preferably as large as possible from the viewpoint of further improving the utilization rate of the positive electrode active material, and specifically, preferably 130% or more, 135% or more, or 140% or more, more preferably. Is 150% or more, 160% or more, or 170% or more.
  • the liquid retention rate of the fiber A may be, for example, 200% or less.
  • the liquid retention rate of the fiber A can be adjusted by, for example, adjusting the degree of shrinkage of the fiber, the surface condition of the fiber, and the like. For example, the greater the shrinkage of the fiber, the higher the liquid retention rate tends to be. Further, the higher the hydrophilicity of the fiber surface, the higher the liquid retention rate tends to be.
  • Fiber A may contain, for example, polymer fiber, carbon fiber and the like.
  • the polymer fiber include polyolefin fiber (fiber containing polyethylene, polypropylene, etc.), polyester fiber (fiber containing polyethylene terephthalate, etc.), and acrylic fiber (fiber containing polyacrylate, polymethacrylate, etc.).
  • the fiber A preferably contains a polymer fiber, more preferably an acrylic fiber, from the viewpoint of obtaining excellent charge / discharge performance (charge acceptance performance, low temperature high rate discharge performance, etc.).
  • the positive electrode active material 15 contains the fiber A, an excellent utilization rate of the positive electrode active material can be obtained.
  • the reason is that when the positive electrode active material 15 contains fibers A having a high liquid retention rate, the sulfate ions in the electrolytic solution are easily diffused into the positive electrode active material 15, so that the positive electrode active material 15 is stable. The present inventors speculate that this is because of the charge / discharge reaction.
  • the lead-acid battery 1 described above includes, for example, a negative electrode plate manufacturing step for manufacturing a negative electrode plate, a positive electrode plate manufacturing step for manufacturing a positive electrode plate, and an assembly step for assembling the lead-acid battery 1 including the negative electrode plate and the positive electrode plate.
  • a negative electrode plate manufacturing step for manufacturing a negative electrode plate for manufacturing a negative electrode plate
  • a positive electrode plate manufacturing step for manufacturing a positive electrode plate for manufacturing a positive electrode plate
  • an assembly step for assembling the lead-acid battery 1 including the negative electrode plate and the positive electrode plate.
  • Manufactured by a manufacturing method The order of the negative electrode plate manufacturing process and the positive electrode plate manufacturing process is arbitrary.
  • the negative electrode active material paste contains, for example, lead powder, additives, solvent (for example, water or organic solvent) and sulfuric acid (for example, dilute sulfuric acid).
  • solvent for example, water or organic solvent
  • sulfuric acid for example, dilute sulfuric acid.
  • the negative electrode active material paste is obtained, for example, by mixing a lead powder and an additive to obtain a mixture, and then adding a solvent and sulfuric acid to the mixture and kneading the mixture.
  • the lead powder includes, for example, lead powder produced by a ball mill type lead powder manufacturing machine or a barton pot type lead powder manufacturing machine (in a ball mill type lead powder manufacturing machine, a mixture of powder of the main component PbO and scaly metal lead). ).
  • Aging may be carried out for 15 to 60 hours in an atmosphere having a temperature of 35 to 85 ° C. and a humidity of 50 to 98 RH%. Drying may be carried out at a temperature of 45 to 80 ° C. for 15 to 30 hours.
  • the positive electrode current collector 14 holds the positive electrode active material 15. Specifically, first, the positive electrode current collector 14 holds the positive electrode active material paste, and the positive electrode active material paste is aged and dried under the same conditions as in the negative electrode plate manufacturing process to obtain an unchemicald positive electrode active material. After obtaining, a non-chemical positive electrode active material is formed.
  • the positive electrode active material paste is, for example, the same lead powder as that used for the negative electrode active material paste, the above-mentioned fiber A, additives added as necessary, a solvent (for example, water or an organic solvent), and sulfuric acid (for example, rare). Sulfuric acid) is contained.
  • the positive electrode active material paste may further contain lead tan (Pb 3 O 4 ) from the viewpoint of shortening the chemical conversion time.
  • the negative electrode plate obtained in the negative electrode plate manufacturing process and the positive electrode plate obtained in the positive electrode plate manufacturing process are laminated via the separator 11, and the current collector of the electrode plates having the same polarity. Is welded with a strap to obtain a group of electrodes. This group of electrodes is arranged in an electric tank to produce an unchemical lead-acid battery. Next, dilute sulfuric acid is put into a non-chemical lead-acid battery, and a direct current is applied to form an electric tank. Subsequently, the lead storage battery 1 is obtained by adjusting the specific gravity (20 ° C.) of the sulfuric acid after chemical conversion to an appropriate specific gravity of the electrolytic solution.
  • the specific gravity (20 ° C.) of sulfuric acid used for chemical conversion may be 1.15 to 1.25.
  • the specific gravity (20 ° C.) of sulfuric acid after chemical conversion is preferably 1.25 to 1.33, more preferably 1.26 to 1.30.
  • the chemical conversion conditions and the specific gravity of sulfuric acid can be adjusted according to the size of the electrode plate.
  • the chemical conversion treatment may be carried out in the assembly process, or may be carried out in each of the negative electrode plate manufacturing process and the positive electrode plate manufacturing process (tank chemical conversion).
  • Example 1> Manufacturing of positive electrode plate
  • lead powder To 100 parts by mass of lead powder, 1.9 parts by mass of acrylic fiber having a liquid retention rate of 179% was added and mixed in a dry manner.
  • 3 parts by mass of water was added to 100 parts by mass of the mixture consisting of lead powder and fiber A, and 9 parts by mass of dilute sulfuric acid (specific gravity 1.28) was added stepwise and kneaded for 1 hour to activate the positive electrode.
  • a material paste was prepared. Since the acrylic fiber used in Example 1 is greatly shrunk, it is considered that it has a high liquid retention rate.
  • an expanded positive electrode current collector produced by expanding a rolled sheet made of a lead alloy was filled with a positive electrode active material paste and then aged in an atmosphere of a temperature of 50 ° C. and a humidity of 98% for 24 hours. .. Then, it was dried at a temperature of 50 degreeC for 16 hours to obtain an unchemical positive electrode plate.
  • Example 2 In the production of the positive electrode plate, the positive electrode plate and the negative electrode plate were produced in the same manner as in Example 1 except that the acrylic fiber having a liquid retention rate of 145% was used instead of the acrylic fiber having a liquid retention rate of 179%. In addition, the lead storage battery was assembled. Since the surface of the acrylic fiber used in Example 2 is treated with hydrophilicity, it is considered that the acrylic fiber has a high liquid retention rate.
  • Example 3 In the production of the positive electrode plate, the positive electrode plate and the negative electrode plate were produced in the same manner as in Example 1 except that the acrylic fiber having a liquid retention rate of 137% was used instead of the acrylic fiber having a liquid retention rate of 179%. In addition, the lead storage battery was assembled. Since the acrylic fiber used in Example 3 is hydrophilically treated, it is considered that it has a high liquid retention rate.
  • 1 lead-acid battery, 9 ... negative electrode plate, 10 ... positive electrode plate, 11 ... separator, 12 ... negative electrode current collector, 13 ... negative electrode active material, 14 ... positive electrode current collector, 15 ... positive electrode active material.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Un aspect de la présente invention concerne une plaque d'électrode positive qui est destinée à un accumulateur au plomb et qui est pourvue : d'un collecteur d'électrode positive ; et d'un matériau actif d'électrode positive maintenu par le collecteur d'électrode positive, le matériau actif d'électrode positive comprenant des fibres ayant un taux de rétention de liquides supérieur ou égal à 125 %.
PCT/JP2019/039541 2019-10-07 2019-10-07 Plaque d'électrode positive, accumulateur au plomb et procédé de fabrication d'une plaque d'électrode positive et d'un accumulateur au plomb WO2021070231A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2019/039541 WO2021070231A1 (fr) 2019-10-07 2019-10-07 Plaque d'électrode positive, accumulateur au plomb et procédé de fabrication d'une plaque d'électrode positive et d'un accumulateur au plomb
JP2020149906A JP2021061235A (ja) 2019-10-07 2020-09-07 正極板、鉛蓄電池及びそれらの製造方法

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PCT/JP2019/039541 WO2021070231A1 (fr) 2019-10-07 2019-10-07 Plaque d'électrode positive, accumulateur au plomb et procédé de fabrication d'une plaque d'électrode positive et d'un accumulateur au plomb

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55139765A (en) * 1979-04-17 1980-10-31 Japan Storage Battery Co Ltd Closed lead storage battery
JPH05198299A (ja) * 1992-01-20 1993-08-06 Japan Storage Battery Co Ltd ペースト式鉛蓄電池
JPH06176761A (ja) * 1992-10-05 1994-06-24 Shin Kobe Electric Mach Co Ltd 鉛蓄電池用極板
JPH0963567A (ja) * 1995-08-28 1997-03-07 Shin Kobe Electric Mach Co Ltd 鉛蓄電池用ペースト式極板及びその製造法
JP2006004688A (ja) * 2004-06-16 2006-01-05 Shin Kobe Electric Mach Co Ltd 鉛蓄電池
WO2016158753A1 (fr) * 2015-03-27 2016-10-06 日本エクスラン工業株式会社 Fibre à base d'acrylonitrile pour électrodes, électrode contenant ladite fibre, et batterie d'accumulateurs au plomb comportant ladite électrode
WO2019181759A1 (fr) * 2018-03-19 2019-09-26 株式会社Ｇｓユアサ Batterie au plomb

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55139765A (en) * 1979-04-17 1980-10-31 Japan Storage Battery Co Ltd Closed lead storage battery
JPH05198299A (ja) * 1992-01-20 1993-08-06 Japan Storage Battery Co Ltd ペースト式鉛蓄電池
JPH06176761A (ja) * 1992-10-05 1994-06-24 Shin Kobe Electric Mach Co Ltd 鉛蓄電池用極板
JPH0963567A (ja) * 1995-08-28 1997-03-07 Shin Kobe Electric Mach Co Ltd 鉛蓄電池用ペースト式極板及びその製造法
JP2006004688A (ja) * 2004-06-16 2006-01-05 Shin Kobe Electric Mach Co Ltd 鉛蓄電池
WO2016158753A1 (fr) * 2015-03-27 2016-10-06 日本エクスラン工業株式会社 Fibre à base d'acrylonitrile pour électrodes, électrode contenant ladite fibre, et batterie d'accumulateurs au plomb comportant ladite électrode
WO2019181759A1 (fr) * 2018-03-19 2019-09-26 株式会社Ｇｓユアサ Batterie au plomb

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