WO2020066764A1 - Électrode négative pour batterie au plomb, et batterie au plomb - Google Patents

Électrode négative pour batterie au plomb, et batterie au plomb Download PDF

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Publication number
WO2020066764A1
WO2020066764A1 PCT/JP2019/036445 JP2019036445W WO2020066764A1 WO 2020066764 A1 WO2020066764 A1 WO 2020066764A1 JP 2019036445 W JP2019036445 W JP 2019036445W WO 2020066764 A1 WO2020066764 A1 WO 2020066764A1
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negative electrode
lead
electrode mixture
storage battery
lead storage
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PCT/JP2019/036445
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English (en)
Japanese (ja)
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優作 小嶋
和成 安藤
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株式会社Ｇｓユアサ
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Priority to CN201980062814.9A priority Critical patent/CN112753114B/zh
Priority to JP2020548529A priority patent/JP7318653B2/ja
Priority to SG11202102513RA priority patent/SG11202102513RA/en
Publication of WO2020066764A1 publication Critical patent/WO2020066764A1/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
    • 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 negative electrode for a lead storage battery and a lead storage battery.
  • Lead storage batteries are widely used in various applications such as in-vehicle and industrial use.
  • lead-acid batteries for vehicles are used as a power source for driving a cell motor and a power source for in-vehicle electric devices.
  • Patent Literature 1 proposes a lead storage battery in which ligninsulfonic acid sodium salt, barium sulfate, and oil furnace black are added to a negative electrode active material.
  • a lead storage battery provided in a vehicle (idling stop vehicle) employing these systems has a higher charge / discharge frequency than a power storage element provided in a conventional vehicle. It is also required that more power can be charged in a short time.
  • a lead storage battery for an idling stop vehicle is required to be capable of efficient charging.
  • conventional lead-acid batteries cannot sufficiently meet this demand.
  • SBA Battery Industry Association Standard
  • the present invention has been made based on the above circumstances, and an object thereof is to provide a negative electrode for a lead storage battery that can improve the charging efficiency of a lead storage battery, and a lead storage battery with good charging efficiency. is there.
  • One embodiment of the present invention made to solve the above problem includes a negative electrode mixture containing lead, and a peak near a diffraction angle of 31.2 ° in an X-ray diffraction spectrum of the negative electrode mixture present on the surface.
  • the lead-acid battery negative electrode (A) has a ratio of the peak height near the diffraction angle of 30.3 ° to the height is 0.05 or more.
  • Another embodiment of the present invention has a negative electrode mixture containing lead, wherein at least a part of the negative electrode mixture present on the surface has a flaky shape, and the aspect ratio of the flaky shape is 3
  • This is a lead-acid battery negative electrode (B) having a size of 10 or more and 10 or less.
  • a lead storage battery including the lead storage battery negative electrode (A) or the lead storage battery negative electrode (B).
  • the present invention it is possible to provide a negative electrode for a lead storage battery that can improve the charging efficiency of the lead storage battery, and a lead storage battery with good charging efficiency.
  • FIG. 1 is an exploded perspective view, partially cut away, showing an external appearance and an internal structure of a lead storage battery according to an embodiment of the present invention.
  • FIG. 2 is an X-ray diffraction spectrum of the negative electrode mixture present on the surface of the lead storage battery of Example 4.
  • FIG. 3 is an X-ray diffraction spectrum of the negative electrode mixture present on the surface of the lead storage battery of Comparative Example 5.
  • FIG. 4 is an electron micrograph of the negative electrode mixture on the surface of the lead storage battery of Example 4.
  • FIG. 5 is an electron micrograph of the negative electrode mixture on the surface of the lead storage battery of Comparative Example 5.
  • the lead-acid battery negative electrode according to one embodiment of the present invention has a negative electrode mixture containing lead, and has a peak height near a diffraction angle of 31.2 ° in an X-ray diffraction spectrum of the negative electrode mixture present on the surface.
  • the lead-acid battery negative electrode (A) has a peak height ratio near the diffraction angle of 30.3 ° with respect to the negative electrode (A).
  • the lead-acid battery negative electrode (A) can improve the charging efficiency of the lead-acid battery.
  • the reason for this is not clear, but the following is presumed. It is known that lead sulfate, which is coarsened in the negative electrode mixture by repeating charge and discharge, is one of the causes of lowering charge acceptability and the like. Lead sulfate present in the negative electrode mixture or on the surface of the negative electrode mixture is reduced during charging and is eluted into the electrolytic solution. However, as charging and discharging are repeated, lead sulfate is less likely to be reduced and eluted, and coarsening proceeds.
  • the negative electrode mixture is formed into a shape in which lead sulfate can be easily reduced and eluted, it is considered that lead sulfate is prevented from becoming coarse and charging efficiency is improved.
  • the peak near the diffraction angle of 30.3 ° in the X-ray diffraction spectrum appears when a scaly shape (a shape in which scaly projections are formed) is formed in the negative electrode mixture containing lead.
  • the inventors have found that.
  • the negative electrode mixture present on the surface includes such a scale-like material, it is considered that lead sulfate is generated in narrow gaps of the scale-like shape, so that it is difficult to coarsen.
  • the surface of the negative electrode for a lead-acid battery refers to the surface facing the positive electrode when incorporated in the lead-acid battery, and the negative electrode mixture present on the surface refers to the negative electrode mixture exposed on the surface facing the positive electrode.
  • the X-ray diffraction spectrum of the negative electrode mixture present on the surface is a value measured by the following method.
  • the lead storage battery is set to a fully charged state (SOC 100%).
  • the charging conditions for making the lead storage battery fully charged are as follows. In the case of a liquid (vent) battery, constant current charging is performed in a water tank at 25 ° C. at 0.2 C until the voltage reaches 2.5 V / cell, and then constant current charging is performed at 0.2 C for 2 hours.
  • a constant current constant voltage charge of 0.2C, 2.23V / cell is performed in an air tank at 25 ° C, and the charge current at the time of the constant voltage charge becomes 1mC or less.
  • 1C is a current value at which the nominal capacity of the battery is discharged in one hour. For example, if the battery has a nominal capacity of 30Ah, 1C is 30A.
  • the fully charged lead storage battery is disassembled, the negative electrode is taken out, and washed with running water for 4 hours. Thereafter, vacuum drying is performed at a drying temperature of 70 ° C. and a degree of vacuum of about 150 kPa for 12 hours. II.
  • a negative electrode mixture is collected from the surface of the negative electrode mixture in an amount of 0.048 g per 1 cm 2 with a spatula, and pulverized in a mortar. 2 g of the pulverized negative electrode mixture is filled in a sample table, and the measurement is performed.
  • the lead-acid battery negative electrode according to another embodiment of the present invention has a negative electrode mixture containing lead, and at least a part of the negative electrode mixture present on the surface has a flaky shape, and the flaky shape.
  • the lead-acid battery negative electrode (B) having an aspect ratio of 3 or more and 10 or less.
  • the lead-acid battery negative electrode (B) can also improve the charging efficiency of the lead-acid battery. Although the reason for this is not clear, it is presumed that the reason is the same as that for the negative electrode (A) for a lead storage battery described above.
  • the scaly shape simply refers to a thin shape, and its planar shape is not particularly limited.
  • the aspect ratio of the scale-like shape is a value measured by the following method.
  • a mass of the negative electrode mixture is collected from the negative electrode that has been subjected to the same pretreatment as in “I. Pretreatment” described above.
  • the lump of the collected negative electrode mixture is divided to obtain a fracture surface.
  • Gold deposition is performed on the fracture surface of the obtained negative electrode mixture.
  • the negative electrode mixture is put into an electron microscope device, and the fracture surface is observed. The observation conditions by the electron microscope are shown below.
  • the maximum width and the maximum thickness are obtained for the scale-like shape present on the surface, and the ratio of the maximum width to the maximum thickness (maximum width / maximum thickness) is defined as the aspect ratio.
  • Measuring equipment TOPCON scanning electron microscope SM-300 Acceleration voltage: 15 kV Magnification: 50 times, 100 times, 500 times, 1000 times, 2000 times (of these magnifications, the magnification at which the shape of the negative electrode mixture present on the surface can be observed most clearly is adopted)
  • the specific surface area of the negative electrode mixture of the negative electrode for a lead storage battery (A) and the negative electrode for a lead storage battery (B) is preferably 0.55 m 2 / g or more and 0.8 m 2 / g or less. By doing so, the charging efficiency becomes better. This is presumably because, when the specific surface area of the negative electrode mixture is within the above range, lead sulfate generated in the gaps between the negative electrode mixtures is more easily dissolved.
  • the specific surface area of the negative electrode mixture is a value (BET specific surface area) measured by the following method.
  • a mass of the negative electrode mixture is collected from the negative electrode that has been subjected to the same pretreatment as in “I. Pretreatment” described above.
  • the collected negative electrode mixture (about 3.5 g) is put into the measurement cell.
  • a measurement cell is attached to the apparatus, and measurement is performed under the following conditions.
  • Measuring device Specific surface area / pore distribution measuring device manufactured by Shimadzu Corporation TriStar 3000 Measurement conditions: BET 8-point method
  • Adsorption gas Nitrogen
  • the specific surface area of the negative electrode mixture of the negative electrode for the lead-acid battery (A) and the negative electrode for lead-acid battery (B) is less than 0.6 m 2 / g or more 0.75 m 2 / g. By doing so, the charging efficiency is further improved.
  • the lead storage battery according to one embodiment of the present invention is a lead storage battery including the lead storage battery negative electrode (A) or the lead storage battery negative electrode (B).
  • the lead storage battery includes the negative electrode (A) for a lead storage battery or the negative electrode (B) for a lead storage battery according to one embodiment of the present invention described above, and thus has high charging efficiency.
  • the lead storage battery is for an idling stop vehicle. Since the lead battery has high charging efficiency, it can be suitably used for an idling stop vehicle that requires efficient charging in a short time.
  • a negative electrode plate as an example of a negative electrode (A) for a lead storage battery according to an embodiment of the present invention includes a negative electrode current collector and a negative electrode mixture. The negative electrode mixture is held on the negative electrode current collector.
  • the negative electrode current collector is usually in a grid plate shape.
  • the negative electrode current collector may be formed by casting lead (Pb) or a lead alloy, or may be formed by processing a lead or lead alloy sheet. Examples of the processing method include expanding and punching.
  • the lead alloy used for the negative electrode current collector includes a Pb-Sb-based alloy, a Pb-Ca-based alloy, and a Pb-Ca-Sn-based alloy. These lead or lead alloys may further contain elements such as Ba, Ag, Al, Bi, As, Se, and Cu as additional elements.
  • the negative electrode current collector may have a lead alloy layer having a different composition, and a plurality of lead alloy layers may be provided.
  • the negative electrode mixture contains lead.
  • Lead is a component that functions as a negative electrode active material, and is usually the main component in a negative electrode mixture.
  • the content of lead in the negative electrode mixture can be, for example, 90% by mass or more and 99.99% by mass or less. Part or all of the lead in the negative electrode mixture may be present as lead sulfate, lead oxide, or the like.
  • the negative electrode mixture may contain a carbonaceous material such as carbon black, and other additives such as barium sulfate and lignin, if necessary.
  • the ratio of the peak height near the diffraction angle 30.3 ° to the peak height near the diffraction angle 31.2 ° is 0.05 or more. It is.
  • the peak near the diffraction angle of 31.2 ° is a reference peak that appears strongly in general lead.
  • the ratio of the peak height near the diffraction angle of 30.3 ° to the peak height near the diffraction angle of 31.2 ° is large, it is considered that the lead becomes lead oxide and grows in a scale shape.
  • the peak near the diffraction angle of 31.2 ° may be a peak appearing within 31.2 ° ⁇ 0.3 ° or a peak appearing within 31.2 ° ⁇ 0.1 °.
  • the peak near the diffraction angle of 30.3 ° may be a peak appearing in 30.3 ° ⁇ 0.3 ° or a peak appearing in 30.3 ° ⁇ 0.1 °.
  • the lower limit of the ratio of the peak heights is 0.05, preferably 0.1, more preferably 0.15. By increasing the peak height ratio, the charging efficiency is further improved.
  • the upper limit of the peak height ratio is, for example, 1, and may be 0.5, 0.4, or 0.3.
  • the ratio of the peak height near the diffraction angle 30.3 ° to the peak height near the diffraction angle 31.2 ° is 0.05 or more.
  • at least a part of the negative electrode mixture present on the surface has a flaky shape. It is presumed that the component constituting this flaky shape is a component containing lead.
  • the plane shape of the scaly negative electrode mixture is not particularly limited, but may be, for example, a fan shape or a semicircle. As a minimum of the aspect ratio of this scale-like shape, 3 is preferred and 5 is more preferred. On the other hand, the upper limit of the aspect ratio may be 10, for example, or may be 8 or 7.
  • the number of the scaly shapes is preferably 50% or more. , 70% or more, and even more preferably 90% or more.
  • the classification based on the difference in the shape of the negative electrode mixture is performed from an image of an electron microscope obtained under the conditions for measuring the above-mentioned “spectral shape aspect ratio”.
  • the specific surface area lower limit of the negative electrode mixture for example 0.4 m 2 / g or 0.5 m 2 / g and may be, but preferably is 0.55m 2 / g, 0.6m 2 / g and more preferably .
  • the specific surface area limit of the negative electrode mixture for example, 1 m 2 / g and may be, but preferably 0.8m 2 / g, 0.75m 2 / g is more preferable.
  • the specific surface area of the negative electrode mixture is equal to or less than the above upper limit, the charging efficiency is further improved, for example, by suppressing an electrolytic reaction for generating gas.
  • the negative electrode plate is obtained by subjecting an unformed negative electrode plate to a chemical conversion treatment.
  • An unformed negative electrode plate is usually produced using a lead powder mainly composed of lead monoxide, which is a raw material of a negative electrode active material.
  • the negative electrode current collector is filled with the negative electrode mixture paste, and the mixture is aged and dried according to a conventional method to prepare an unformed negative electrode plate.
  • the negative electrode mixture paste is, for example, a mixture of carbon black, lignin and barium sulfate in a predetermined ratio as an additive to a lead powder mainly composed of lead monoxide, and then water and 50% diluted sulfuric acid in a predetermined ratio. It can be obtained by mixing. Aging and drying of the unformed negative electrode plate are preferably performed at a temperature higher than room temperature and high humidity.
  • a negative electrode plate in which the lead powder becomes spongy lead is obtained.
  • the formation can be performed by charging the electrode group in a state in which the electrode group including the unformed negative electrode plate is immersed in the electrolytic solution containing sulfuric acid in the battery case of the lead storage battery. However, the formation may be performed before assembling the lead storage battery or the electrode plate group. By the formation, spongy lead is generated and can be used as a negative electrode plate.
  • the negative electrode mixture having the above-mentioned peak height ratio that is, the negative electrode mixture having at least a portion of the negative electrode mixture present on the surface in a scaly shape is a chemical conversion condition or an additive to the negative electrode mixture.
  • the specific surface area of the carbon black used can be 70 to 240 m 2 / g, and preferably 100 to 200 m 2 / g.
  • the average particle diameter of the barium sulfate used can be 0.1 to 0.5 ⁇ m, preferably 0.2 to 0.4 ⁇ m.
  • the average molecular weight of the lignin used can be from 1,000 to 10,000, preferably from 3,000 to 8,000.
  • the addition amount of carbon black can be, for example, 0.1 to 1% by mass based on the lead powder.
  • the addition amount of barium sulfate can be, for example, 1 to 5% by mass based on the lead powder.
  • the addition amount of lignin can be, for example, 0.01 to 0.5% by mass based on the lead powder.
  • the specific surface area of the negative electrode mixture can be adjusted by the particle size, specific surface area, etc. of each component used, chemical conversion treatment conditions, and the like.
  • ⁇ Negative electrode for lead storage battery (B)> In the lead-acid battery negative electrode (B) according to one embodiment of the present invention, at least a part of the negative electrode mixture present on the surface has a flaky shape, and the flaky shape has an aspect ratio of 3 or more and 10 or less. In the X-ray diffraction spectrum of the negative electrode mixture on the surface, the ratio of the peak height near the diffraction angle 30.3 ° to the peak height near the diffraction angle 31.2 ° is not limited to 0.05 or more. Is the same as that of the above-described lead-acid battery negative electrode (A). The specific form, preferred form, and manufacturing method of the lead-acid battery negative electrode (B) can be the same as those of the lead-acid battery negative electrode (A) described above.
  • the aspect ratio of the scale-like shape in the lead storage battery electrode (B) 4 is preferable, and 5 is more preferable.
  • the aspect ratio is equal to or more than the lower limit, the charging efficiency is further improved.
  • the upper limit of the aspect ratio may be 10, or may be 8 or 7.
  • a lead storage battery includes a negative electrode plate as a negative electrode, a positive electrode plate as a positive electrode, and an electrolyte.
  • a separator is arranged between the negative electrode plate and the positive electrode plate. The negative electrode plate, the positive electrode plate, and the separator are immersed in the electrolytic solution.
  • the lead storage battery may be a liquid lead storage battery or a control valve lead storage battery, but is preferably a liquid lead storage battery.
  • the negative electrode plate As the negative electrode plate, the negative electrode for a lead storage battery (A) or the negative electrode for a lead storage battery (B) according to one embodiment of the present invention described above is used.
  • the positive electrode plate can be classified into a paste type, a clad type, and the like.
  • the paste-type positive electrode plate usually includes a grid plate-shaped positive electrode current collector and a positive electrode mixture.
  • the positive electrode mixture is held on the positive electrode current collector.
  • the positive electrode current collector may be formed in the same manner as the negative electrode current collector, and can be formed by casting lead or a lead alloy or processing a lead or lead alloy sheet.
  • the clad-type positive electrode plate includes a plurality of porous tubes, a core bar inserted into each tube, a positive electrode mixture filled in the tube where the core bar is inserted, and an articulation connecting the plurality of tubes. Is provided.
  • a lead alloy used for the positive electrode current collector a Pb-Ca-based alloy, a Pb-Ca-Sn-based, or the like is preferable in terms of corrosion resistance and mechanical strength.
  • the positive electrode current collector may have a lead alloy layer having a different composition, and a plurality of lead alloy layers may be provided. It is preferable to use a Pb-Sb alloy for the cored bar.
  • the positive electrode mixture contains a positive electrode active material (usually, lead dioxide or lead sulfate).
  • the positive electrode mixture may contain additives such as tin sulfate and lead red as needed, in addition to the positive electrode active material.
  • An unformed paste-type positive electrode plate is obtained by filling a positive electrode current collector with a positive electrode mixture paste obtained by an ordinary method, aging and drying the same as in the case of the negative electrode plate.
  • the positive electrode mixture paste can be prepared by kneading lead powder, additives, water, sulfuric acid, and the like. Thereafter, an unformed positive electrode plate is formed.
  • the clad-type positive electrode plate is formed by filling a lead glass or a slurry-like lead powder into a porous glass tube into which a core metal has been inserted, and connecting a plurality of tubes in a continuous manner.
  • the electrolyte is an aqueous solution containing sulfuric acid.
  • the electrolytic solution may further contain metal ions such as sodium ions.
  • the electrolyte may be gelled if necessary.
  • the degree of gelation is not particularly limited. An electrolyte in a gel state from a sol having fluidity may be used, or an electrolyte in a gel state without fluidity may be used.
  • the lower limit of the specific gravity of the electrolyte at 20 ° C. in the fully charged lead storage battery is, for example, 1.1 g / cm 3 , and preferably 1.2 g / cm 3 .
  • the upper limit of the specific gravity is, for example, 1.4 g / cm 3 , and preferably 1.35 g / cm 3 .
  • the separator As the separator, a nonwoven fabric sheet, a microporous membrane, or the like is used. The thickness and the number of separators interposed between the negative electrode plate and the positive electrode plate may be appropriately selected according to the distance between the electrodes.
  • the nonwoven fabric sheet is a sheet mainly composed of a polymer fiber or a glass fiber. For example, 60% by mass or more is formed of a fiber component.
  • the microporous membrane is obtained by extruding a composition containing, for example, a polymer powder, a silica powder, and an oil into a sheet, and then extracting the oil to form pores.
  • the material constituting the separator preferably has acid resistance, and the polymer component is preferably a polyolefin such as polyethylene or polypropylene.
  • the lead storage battery has good charging efficiency. Therefore, the lead storage battery can be widely used for various uses in which a general lead storage battery is used, such as for an automobile. In particular, the battery can be suitably used for an idling stop vehicle that requires repeated charging and discharging and requires excellent charging efficiency.
  • FIG. 1 shows an external view of an example of the lead storage battery according to the embodiment of the present invention.
  • the lead storage battery 1 includes an electrode group 11, an electrolytic solution (not shown), and a battery case 12 for accommodating them.
  • the inside of the battery case 12 is partitioned by a partition 13 into a plurality of cell chambers 14.
  • Each of the cell chambers 14 accommodates one electrode group 11 one by one.
  • the opening of the battery case 12 is sealed with a lid 15 having a negative electrode terminal 16 and a positive electrode terminal 17.
  • the lid 15 is provided with a liquid port plug 18 for each cell chamber. At the time of rehydration, the rehydration liquid is supplied by removing the liquid port plug 18.
  • the liquid port plug 18 may have a function of discharging gas generated in the cell chamber 14 to the outside of the battery.
  • the negative electrode plate group 11 is configured by laminating a plurality of negative electrode plates 2 and positive electrode plates 3 with a separator 4 interposed therebetween.
  • a bag-shaped separator 4 that accommodates the negative electrode plate 2 is shown, but the form of the separator is not particularly limited.
  • a negative electrode shelf 6 for connecting a plurality of negative electrodes 2 in parallel is connected to a through connector 8, and a positive electrode shelf 5 for connecting a plurality of positive electrodes 3 in parallel is provided. It is connected to the positive pole 7.
  • the positive pole 7 is connected to a positive terminal 17 outside the lid 15.
  • the negative pole 9 is connected to the negative shelf 6, and the through-connector 8 is connected to the positive shelf 5.
  • the negative pole 9 is connected to a negative terminal 16 outside the lid 15.
  • Each penetrating connector 8 passes through a through hole provided in the partition wall 13 and connects the electrode groups 11 of the adjacent cell chambers 14 in series.
  • the present invention is not limited to the above-described embodiment, and can be embodied with various modifications and improvements in addition to the above-described aspects.
  • the positive electrode and the negative electrode are described as the positive electrode plate and the negative electrode plate, respectively.
  • the positive electrode and the negative electrode are not limited to the plate shape, respectively.
  • Example 1 (1) Preparation of unformed negative electrode plate To a lead powder mainly composed of lead monoxide, 0.3 mass% of carbon black having a specific surface area of 165 m 2 / g and barium sulfate having an average particle diameter of 0.3 ⁇ m were added. 2.1% by mass and 0.05% by mass of lignin having a mass average molecular weight of 6000 were added. Water and 50% diluted sulfuric acid were further added to the mixture and kneaded to obtain a negative electrode mixture paste. The negative electrode mixture paste was filled in a mesh portion of an expanded lattice made of a Pb—Ca—Sn alloy, aged and dried to obtain an unformed negative electrode plate.
  • Electrode plate is accommodated in a bag-like separator formed of a microporous polyethylene film, and seven unformed negative electrode plates and six unformed positive electrode plates are used. Groups were formed.
  • the electrode group was housed in a battery case made of polypropylene together with the electrolytic solution, and subjected to chemical conversion in the battery case to assemble the liquid lead storage battery of Example 1. The formation was carried out with an electric charge of 3.3 Ah / g with respect to the negative electrode mixture.
  • Example 2 A lead-acid battery of Example 2 was assembled in the same manner as in Example 1 except that the amount of lignin added was 0.07% by mass.
  • Example 3 The lead of Example 3 was prepared in the same manner as in Example 1 except that 0.3% by mass of carbon black having a specific surface area of 140 m 2 / g was added as the carbon black, and the amount of lignin added was 0.10% by mass. The storage battery was assembled.
  • Example 4 A lead-acid battery of Example 4 was assembled in the same manner as in Example 1, except that the amount of lignin added was 0.10% by mass.
  • Example 5 The lead of Example 5 was prepared in the same manner as in Example 1 except that 0.3% by mass of carbon black having a specific surface area of 183 m 2 / g was added as the carbon black, and the amount of lignin added was 0.10% by mass. The storage battery was assembled.
  • Example 6 The lead of Example 6 was prepared in the same manner as in Example 1 except that 0.3% by mass of carbon black having a specific surface area of 140 m 2 / g was added as the carbon black, and the added amount of lignin was 0.15% by mass. The storage battery was assembled.
  • Example 7 A lead-acid battery of Example 7 was assembled in the same manner as in Example 1 except that the amount of lignin added was 0.15% by mass.
  • Example 8 The lead of Example 8 was prepared in the same manner as in Example 1 except that 0.3% by mass of carbon black having a specific surface area of 183 m 2 / g was added as the carbon black, and the amount of lignin added was 0.15% by mass. The storage battery was assembled.
  • Example 9 A lead-acid battery of Example 9 was assembled in the same manner as in Example 1, except that the amount of lignin added was 0.20% by mass.
  • Example 10 A lead-acid battery of Example 10 was assembled in the same manner as Example 1 except that the amount of lignin added was 0.25% by mass.
  • a lead-acid battery of Comparative Example 1 was assembled in the same manner as in Example 1 except that 0.05% by mass of lignin was added.
  • Comparative Example 2 A lead-acid battery of Comparative Example 2 was assembled in the same manner as Comparative Example 1 except that 0.07% by mass of lignin having an average molecular weight of 12,000 was added as lignin.
  • Comparative Example 3 A lead-acid battery of Comparative Example 3 was assembled in the same manner as Comparative Example 1 except that 0.10% by mass of lignin having an average molecular weight of 12,000 was added as lignin.
  • Comparative Example 4 A lead-acid battery of Comparative Example 4 was assembled in the same manner as Comparative Example 1 except that 0.15% by mass of lignin having an average molecular weight of 12000 was added as lignin.
  • Comparative Example 5 A lead-acid battery of Comparative Example 5 was assembled in the same manner as Comparative Example 1 except that 0.20% by mass of lignin having an average molecular weight of 12000 was added as lignin.
  • Comparative Example 6 A lead-acid battery of Comparative Example 6 was assembled in the same manner as Comparative Example 1 except that 0.25% by mass of lignin having an average molecular weight of 12000 was added as lignin.
  • Table 1 shows the shapes and the aspect ratios based on the shapes.
  • “normal” means a lump or sphere having a low aspect ratio.
  • FIG. 4 shows an electron micrograph of the surface of the negative electrode mixture in the lead storage battery of Example 4.
  • An electron micrograph of the surface of the negative electrode mixture in the lead storage battery of Comparative Example 5 is shown in FIG. FIG. 4 shows that in Example 4, a plurality of scale-like projections (scale-like shapes) were formed on the surface.
  • FIG. 5 shows that in Comparative Example 5, such a scaly shape was not formed.
  • Table 1 shows the evaluation results.
  • the IS life in Table 1 is shown as a relative value based on Comparative Example 1 (100%).
  • the lead storage batteries of Examples 1 to 10 all had an IS life of 130% or more, and had good charging efficiency.
  • the specific surface area of the negative electrode mixture is 0.55 m 2 / g or more and 0.8 m 2 / g or less, or when the peak height ratio in the X-ray diffraction spectrum is higher, It can be seen that the IS life is longer.
  • the lead storage batteries of Comparative Examples 1 to 6 in which the surface shape of the negative electrode mixture was not scaly and the peak height ratio in the X-ray diffraction spectrum was low were all short in IS life and insufficient in charging efficiency. It became.
  • the lead storage battery of the present invention is used as a power source for automobiles, motorcycles, electric vehicles (forklifts and the like), industrial power storage devices, and the like, and is particularly suitably used as a power source for idling stop vehicles.

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

Un aspect de la présente invention concerne une électrode négative pour une batterie au plomb, ladite électrode négative ayant un mélange d'électrode négative qui comprend du plomb, le spectre de diffraction des rayons X du mélange d'électrode négative présent dans une surface, le rapport de la hauteur de pic à proximité d'un angle de diffraction de 30,3° à la hauteur de pic près d'un angle de diffraction de 31,2° étant supérieur ou égal à 0,05.
PCT/JP2019/036445 2018-09-25 2019-09-18 Électrode négative pour batterie au plomb, et batterie au plomb WO2020066764A1 (fr)

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CN201980062814.9A CN112753114B (zh) 2018-09-25 2019-09-18 铅蓄电池用负极及铅蓄电池
JP2020548529A JP7318653B2 (ja) 2018-09-25 2019-09-18 鉛蓄電池用負極及び鉛蓄電池
SG11202102513RA SG11202102513RA (en) 2018-09-25 2019-09-18 Negative electrode for lead-acid battery, and lead-acid battery

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JP2018179410 2018-09-25
JP2018-179410 2018-09-25

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JP2001043861A (ja) * 1999-07-30 2001-02-16 Furukawa Battery Co Ltd:The 鉛蓄電池用正極板及び鉛蓄電池
JP2010113932A (ja) * 2008-11-06 2010-05-20 Panasonic Corp 鉛蓄電池用極板およびこれを用いた制御弁式鉛蓄電池
JP2016046118A (ja) * 2014-08-22 2016-04-04 株式会社日本触媒 電極及びそれを用いて構成される電池

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JP5219360B2 (ja) * 2006-12-14 2013-06-26 新神戸電機株式会社 鉛蓄電池
US8972966B2 (en) * 2012-01-05 2015-03-03 Lenovo (Singapore) Pte. Ltd. Updating firmware in a hybrid computing environment
JP6165710B2 (ja) * 2012-03-23 2017-07-19 株式会社東芝 非水電解質二次電池用負極活物質、非水電解質二次電池及び電池パック
JP6311799B2 (ja) * 2014-11-27 2018-04-18 日立化成株式会社 鉛蓄電池
JP2016152077A (ja) * 2015-02-16 2016-08-22 信越化学工業株式会社 非水電解質二次電池用負極活物質及び非水電解質二次電池、並びに非水電解質二次電池用負極材の製造方法
JP6136080B2 (ja) * 2015-02-18 2017-05-31 株式会社Ｇｓユアサ 鉛蓄電池
JP2017162754A (ja) * 2016-03-11 2017-09-14 東レ株式会社 鉛蓄電池用電極およびこれを用いた鉛蓄電池

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001043861A (ja) * 1999-07-30 2001-02-16 Furukawa Battery Co Ltd:The 鉛蓄電池用正極板及び鉛蓄電池
JP2010113932A (ja) * 2008-11-06 2010-05-20 Panasonic Corp 鉛蓄電池用極板およびこれを用いた制御弁式鉛蓄電池
JP2016046118A (ja) * 2014-08-22 2016-04-04 株式会社日本触媒 電極及びそれを用いて構成される電池

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CN112753114A (zh) 2021-05-04
JP7318653B2 (ja) 2023-08-01
JPWO2020066764A1 (ja) 2021-08-30
CN112753114B (zh) 2023-09-19
SG11202102513RA (en) 2021-04-29

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