WO2021084878A1 - Batterie d'accumulateurs au plomb - Google Patents

Batterie d'accumulateurs au plomb Download PDF

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Publication number
WO2021084878A1
WO2021084878A1 PCT/JP2020/032404 JP2020032404W WO2021084878A1 WO 2021084878 A1 WO2021084878 A1 WO 2021084878A1 JP 2020032404 W JP2020032404 W JP 2020032404W WO 2021084878 A1 WO2021084878 A1 WO 2021084878A1
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WIPO (PCT)
Prior art keywords
separator
positive electrode
lead
mass
less
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PCT/JP2020/032404
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English (en)
Japanese (ja)
Inventor
正仁 立澤
悦子 伊藤
和成 安藤
Original Assignee
株式会社Ｇｓユアサ
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Application filed by 株式会社Ｇｓユアサ filed Critical 株式会社Ｇｓユアサ
Priority to CN202080074956.XA priority Critical patent/CN114616698A/zh
Priority to JP2021554114A priority patent/JP7533474B2/ja
Publication of WO2021084878A1 publication Critical patent/WO2021084878A1/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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • 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 lead storage battery.
  • Lead-acid batteries are used for various purposes such as in-vehicle use and industrial use.
  • the lead-acid battery includes a positive electrode plate and a negative electrode plate, a separator interposed between them, and an electrolytic solution.
  • Various performances are required for the components of lead-acid batteries.
  • Patent Document 1 heats a raw material composition composed of a mixture of 20 to 69% by mass of a polyolefin resin, 80 to 40% by mass of an inorganic powder, and 40 to 240% by mass of a mineral oil with respect to a combination thereof.
  • the oil is obtained by melting and kneading to form a sheet having ribs, immersing the oil in a dipping tank of an organic solvent capable of dissolving the oil, extracting and removing a part of the oil, and heating and drying.
  • a ribbed separator for a lead storage battery containing 5 to 30% by mass of oil
  • both the positive electrode plate and the negative electrode plate are provided with an expanded lattice body, and the electrode plate having the polarity of either the positive electrode or the negative electrode is housed in a bag-shaped separator made of a polyolefin synthetic resin sheet such as microporous polyethylene. It has a group of electrode plates laminated with an electrode plate of the other polarity, has a plurality of linear ribs in the vertical direction on the surface of the bag-shaped separator facing the positive electrode plate surface, and houses the electrode plate group.
  • We have proposed a lead-acid battery in which the height of the battery case ribs provided in the vertical direction on the inner wall parallel to the electrode plate surface of the cell chamber is set to be equal to or lower than the height of the linear ribs.
  • Patent Document 3 is a separator for a lead battery containing a microporous polyolefin member.
  • the microporous polyolefin member contains polyethylene, a particle-like filler, and a plasticizer, and the amount of the particle-like filler is 40% by weight or more.
  • polyethylene comprises a polymer having a shishikebab structure containing a plurality of elongated chain crystals and a plurality of folded chain crystals, and proposes a separator having an average repetition or period of the kebab structure of 1 nm to 150 nm. doing.
  • Patent Document 4 describes a binder 5 that can adhere to 30 to 90% by weight of synthetic pulp having a drainage degree of 0.1 sec / g or more and 1.0 sec / g or less at a temperature lower than the melting point or decomposition temperature of the synthetic pulp.
  • a separator for a sealed lead-acid battery having an apparent density of 0.15 g / cm 3 or less under load is described.
  • Described is a method for manufacturing a sealed lead-acid battery, which comprises 005% or more and 1.0% or less, and the time from injection of liquid to the start of battery chemical formation is within 2 hours.
  • Lead-acid batteries are required to have high output and long life.
  • the separator contains oil, oxidative deterioration of the separator is suppressed, which is advantageous from the viewpoint of life performance.
  • the life performance in the high temperature deep discharge life test may be deteriorated.
  • One aspect of the present invention includes a positive electrode plate, a negative electrode plate, and a separator interposed between the positive electrode plate and the negative electrode plate.
  • the positive electrode plate contains a positive electrode material and contains a positive electrode material.
  • the positive electrode material contains an Sb element and contains an Sb element.
  • the content of the Sb element in the positive electrode material is 0.05% by mass or more.
  • the separator relates to a lead-acid battery containing polyolefin and oil and having an apparent density of 0.46 g / cm 3 or more and less than 0.57 g / cm 3.
  • Lead-acid batteries may be used in an undercharged state called a partially charged state (PSOC).
  • PSOC partially charged state
  • IS idling stop
  • ISS idling start / stop
  • lead-acid batteries will be used in PSOC.
  • the electrolytic solution is not agitated because it is unlikely to be overcharged.
  • stratification is likely to occur in which the specific gravity of the electrolytic solution in the upper part of the battery gradually decreases and the specific gravity of the electrolytic solution in the lower part of the battery gradually increases.
  • the electrolytic solution is stratified, the negative electrode material deteriorates in the upper part of the negative electrode plate, the binding force of the negative electrode material decreases, and the capacity decreases. This reduces the service life performance.
  • the positive electrode material of lead-acid batteries contains lead dioxide, which has strong oxidizing power, as a positive electrode active material.
  • a separator containing polyolefin is often used for lead-acid batteries. Separators containing polyolefins tend to deteriorate due to oxidation of polyolefins when they come into contact with the positive electrode material for a long period of time. In a lead-acid battery, when the separator is oxidatively deteriorated, its flexibility decreases, cracks occur, and a short circuit occurs, resulting in a lifetime.
  • the separator containing polyolefin may contain oil as a pore-forming agent or an additive.
  • oil oxidative deterioration of the separator containing polyolefin is suppressed, which is advantageous from the viewpoint of life performance.
  • the resistance of the separator tends to increase because the insulating oil closes the pores of the separator. When the resistance of the separator increases, it is difficult to increase the output.
  • a separator with a low density is used while containing oil, it is expected that the oil can ensure the oxidation resistance of the separator. Further, when a separator having a low density is used, high output can be ensured and the diffusibility of the electrolytic solution is improved, so that stratification of the electrolytic solution is suppressed and the life performance is expected to be improved.
  • the apparent density of the separator containing polyolefin is 0.46 g / cm 3 or more and less than 0.57 g / cm 3 , if a specific amount of Sb element is contained in the positive electrode material, it is excellent in the high temperature deep discharge life test. It was clarified that the life performance can be obtained.
  • the lead-acid battery according to one aspect of the present invention includes a positive electrode plate, a negative electrode plate, and a separator interposed between the positive electrode plate and the negative electrode plate.
  • the positive electrode plate contains a positive electrode material.
  • the positive electrode material contains Sb element, and the content of Sb element in the positive electrode material is 0.05% by mass or more.
  • the separator contains polyolefin and oil and has an apparent density of 0.46 g / cm 3 or more and less than 0.57 g / cm 3.
  • a lead storage battery can secure a high output and a high temperature. Excellent life performance in deep discharge life test can be obtained. That is, in a lead-acid battery, both high output and excellent durability can be achieved at the same time.
  • Oxidative deterioration of the separator generally proceeds when the positive electrode plate surface expanded by repeated charging and discharging of the lead storage battery and the base surface of the separator (that is, the region facing the positive electrode plate of the separator) come into direct contact with each other (Patent Documents). 2 [0013]). Oxidative deterioration on the base surface of the separator is suppressed to some extent when the separator contains oil. However, when a separator having an apparent density of less than 0.57 g / cm 3 is used, it may be difficult to suppress oxidative deterioration of the separator even though the separator contains oil.
  • a positive electrode material containing 0.05% by mass or more of Sb element is used.
  • softening of the positive electrode material is suppressed.
  • the falling off of the positive electrode material is suppressed, and it is considered that the oxidative deterioration of the separator near the lower end portion of the separator is suppressed. Therefore, high output and excellent life performance in the high temperature deep discharge life test can be ensured.
  • the apparent density of the separator may be 0.56 g / cm 3 or less. When the apparent density is in such a range, higher life performance can be ensured in the high temperature deep discharge life test.
  • the oil content in the separator may be 5% by mass or more. In this case, the effect of suppressing oxidative deterioration in the region of the separator facing the positive electrode plate can be enhanced.
  • the total pore volume of the positive electrode material may be 0.08 cm 3 / g or more. In this case, a higher output of the lead-acid battery can be ensured.
  • the total pore volume may be 0.18 cm 3 / g or less. In this case, the life performance in the high temperature deep discharge life test can be further improved.
  • the positive electrode material may contain ⁇ -PbO 2 crystallites and ⁇ -PbO 2 crystallites.
  • Lead-acid batteries are usually liquid (vent type) lead-acid batteries.
  • the lead-acid battery is particularly useful as a lead-acid battery (for example, a lead-acid battery for IS) that is expected to be charged and discharged by PSOC.
  • the lead-acid battery for IS Since the lead-acid battery for IS is unlikely to be overcharged, gassing is unlikely to occur, and the positive electrode material is likely to soften and fall off. Even if the lead-acid battery according to the above aspect is used as such a lead-acid battery for IS, it is possible to suppress oxidative deterioration of the separator due to the detachment of the positive electrode material in the high temperature deep discharge life test.
  • the positive electrode material is usually held by the positive electrode current collector.
  • the positive electrode material is a positive electrode plate obtained by removing a positive electrode current collector. Members such as mats and pacing papers may be attached to the positive electrode plate. Since such a member (also referred to as a sticking member) is used integrally with the positive electrode plate, it is included in the positive electrode plate.
  • the positive electrode material is the one excluding the positive electrode current collector and the sticking member.
  • Total pore volume in positive electrode material The total pore volume of the positive electrode material is the total volume of all pores obtained by the mercury intrusion method.
  • the apparent density of the separator is a value (g / cm 3 ) obtained by dividing the mass of the separator by the apparent volume of the separator.
  • the apparent density of the separator is determined by using a sample obtained by cutting the separator. If the separator has ribs, the sample is cut out from the base where the ribs are not formed.
  • Polyolefin is a polymer containing an olefin as a monomer.
  • Polyolefins include, for example, homopolymers of olefins, copolymers containing monomer units of different olefins, and copolymers containing olefins and copolymerizable monomers as monomer units.
  • a copolymer containing an olefin and a copolymerizable monomer as a monomer unit contains one or more olefins as a monomer unit.
  • the copolymerizable monomer is a polymerizable monomer other than the olefin and copolymerizable with the olefin.
  • Oil refers to a hydrophobic substance that is liquid at room temperature (temperature of 20 ° C. or higher and 35 ° C. or lower) and separates from water. Oils include naturally occurring oils, mineral oils, and synthetic oils.
  • the fully charged state of the lead-acid battery is defined by the definition of JIS D 5301: 2019. More specifically, the terminal voltage during charging or 20 measured every 15 minutes with a current (A) of 1/10 of the value described as the rated capacity of the lead-acid battery in a water tank at 25 ° C. ⁇ 2 ° C.
  • a fully charged state is defined as a state in which the electrolyte density converted to ° C. is charged three times in a row until it shows a constant value with three significant figures.
  • the numerical value described as the rated capacity is a numerical value in which the unit is Ah.
  • the unit of current set based on the numerical value described as the rated capacity is A.
  • a fully charged lead-acid battery is a fully charged lead-acid battery.
  • the lead-acid battery may be fully charged after the chemical conversion, immediately after the chemical conversion, or after a lapse of time from the chemical conversion (for example, after the chemical conversion, the lead-acid battery in use (preferably at the initial stage of use) is fully charged. May be).
  • the battery at the initial stage of use means a battery that has not been used for a long time and has hardly deteriorated.
  • the vertical direction is defined with the side where the selvage is provided as the upper side and the side opposite to the selvage as the lower side.
  • the side facing the upper side of the plate that is, the selvage side
  • the side facing the lower side of the plate is the lower side of the separator.
  • the vertical direction of the electrode plate and the vertical direction of the separator are the same as the vertical direction of the lead storage battery, respectively.
  • the apparent density of the separator is 0.46 g / cm 3 or more.
  • the apparent density of the separator is preferably 0.48 g / cm 3 or more, or 0.49 g / cm 3 or more.
  • Apparent density of the separator is less than 0.57 g / cm 3, it may be 0.56 g / cm 3 or less. When the apparent density is in such a range, high output and high life performance in a high temperature deep discharge life test can be obtained. If Sb element content of the positive electrode material is not less than 0.05 wt%, the apparent density of the separator is equal to or less than 0.56 g / cm 3, at high temperatures deep discharge life test in comparison with the case of 0.57 g / cm 3 Life performance is significantly improved. That is, when the Sb element content of the positive electrode material is 0.05% by mass or more, it can be said that the apparent density of the separator is 0.56 g / cm 3 and is critical in the life performance of the high temperature deep discharge life test.
  • Apparent density of the separator 0.46 g / cm 3 or more 0.57 g / cm less than 3 (or 0.56g / cm 3 or less), 0.48 g / cm 3 or more 0.57 g / cm less than 3 (or 0.56g / cm 3 or less), or may be 0.49 g / cm 3 or more 0.57 g / cm less than 3 (or 0.56 g / cm 3 or less).
  • a resin composition containing a polymer material hereinafter, also referred to as a base polymer
  • a pore-forming agent for example, a polymer material (hereinafter, also referred to as a base polymer), a pore-forming agent, and a penetrant (surfactant) is extruded into a sheet, and then the pore-forming agent is removed. Obtained by doing. By removing at least a part of the pore-forming agent, micropores are formed in the matrix of the base polymer.
  • the resin composition may further contain inorganic particles.
  • the apparent density of the separator is, for example, at least one (typically two or more) of the type of pore-forming agent, the amount of pore-forming agent, the mixing ratio of the base polymer and the pore-forming agent, and the amount of pore-forming agent removed. ) Can be adjusted.
  • At least polyolefin is used as the base polymer.
  • the base polymer polyolefin and other base polymers may be used in combination.
  • the other base polymer is not particularly limited as long as it is used as a separator for a lead storage battery.
  • the ratio of polyolefin to the total base polymer contained in the separator is, for example, 50% by mass or more, 80% by mass or more, or 90% by mass or more.
  • the base polymer may be composed of polyolefin only.
  • polystyrene resin examples include polymers containing at least C 2-3 olefin as a monomer unit.
  • the C2-3 olefin examples include at least one selected from the group consisting of ethylene and propylene.
  • the polyolefin for example, a copolymer containing polyethylene, polypropylene, or C2-3 olefin as a monomer unit (for example, an ethylene-propylene copolymer) is more preferable.
  • polyolefins it is preferable to use at least polyethylene. Polyethylene and other polyolefins may be used in combination.
  • ceramic particles are preferable.
  • the ceramics constituting the ceramic particles include at least one selected from the group consisting of silica, alumina, and titania.
  • the content of the inorganic particles in the separator is, for example, 40% by mass or more, and may be 50% by mass or more.
  • the content of the inorganic particles is, for example, 80% by mass or less, and may be 75% by mass or less or 70% by mass or less.
  • the content of inorganic particles in the separator is 40% by mass or more (or 50% by mass or more) 80% by mass or less, 40% by mass or more (or 50% by mass or more) 75% by mass or less, or 40% by mass or more (or). It may be 50% by mass or more) and 70% by mass or less.
  • the pore-forming agent examples include a liquid pore-forming agent and a solid pore-forming agent. At least oil is used as the pore-forming agent. As the pore-forming agent, one type may be used alone, or two or more types may be used in combination. Oil may be used in combination with other pore-forming agents. A liquid pore-forming agent and a solid pore-forming agent may be used in combination. At room temperature (temperature of 20 ° C. or higher and 35 ° C. or lower), a liquid pore-forming agent is classified as a liquid pore-forming agent, and a solid pore-forming agent is classified as a solid pore-forming agent.
  • liquid pore-forming agent mineral oil, synthetic oil, etc. are preferable.
  • liquid pore-forming agent include paraffin oil and silicone oil.
  • solid pore-forming agent include polymer powder.
  • the amount of the pore-forming agent in the separator may vary depending on the type, so it cannot be said unconditionally, but it is, for example, 30 parts by mass or more per 100 parts by mass of the base polymer.
  • the amount of the pore-forming agent is, for example, 60 parts by mass or less.
  • the oil content in the separator is, for example, 5% by mass or more.
  • the oil content in the separator is preferably 10% by mass or more, more preferably 12% by mass or more, from the viewpoint of suppressing oxidative deterioration in the region facing the positive electrode plate of the separator.
  • the content of the oil in the separator is, for example, 20% by mass or less, and preferably 18% by mass or less.
  • the content of oil in the separator is 5% by mass or more and 20% by mass or less (or 18% by mass or less), 10% by mass or more and 20% by mass or less (or 18% by mass or less), or 12% by mass or more and 20% by mass or less. (Or 18% by mass or less) may be used.
  • the surfactant as the penetrant may be, for example, either an ionic surfactant or a nonionic surfactant.
  • an ionic surfactant or a nonionic surfactant.
  • the surfactant one type may be used alone, or two or more types may be used in combination.
  • the amount of the penetrant in the separator is, for example, 0.1 part by mass or more and 0.5 parts by mass or more per 100 parts by mass of the base polymer.
  • the amount of the penetrant is, for example, 10 parts by mass or less, and may be 5 parts by mass or less.
  • the amount of penetrant in the separator is 0.1 parts by mass or more (or 0.5 parts by mass or more), 10 parts by mass or less, or 0.1 parts by mass or more (0.5 parts by mass or more) per 100 parts by mass of the base polymer. It may be 5 parts by mass or less.
  • the content of the penetrant in the separator is, for example, 0.01% by mass or more, and may be 0.1% by mass or more.
  • the content of the penetrant is, for example, 5% by mass or less, and may be 10% by mass or less.
  • the content of the penetrant in the separator is 0.01% by mass or more (0.1 parts by mass or more) 10% by mass or less, or 0.01% by mass or more (0.1 parts by mass or more) 5% by mass or less. There may be.
  • the thickness of the separator is, for example, 0.1 mm or more.
  • the thickness of the separator may be 0.3 mm or less.
  • the thickness of the sticking member shall be included in the thickness of the separator.
  • the separator may be either one having ribs or one having no ribs.
  • the ribbed separator comprises, for example, a base portion and ribs erected from the surface of the base portion.
  • the ribs may be provided on only one surface of the separator or each base portion, or may be provided on both surfaces.
  • the separator may be in the form of a sheet. Further, a sheet bent in a bellows shape may be used as a separator.
  • the separator may be formed in a bag shape, or either a positive electrode plate or a negative electrode plate may be wrapped in a bag-shaped separator. When a bag-shaped separator is used, the lower end portion of the separator is liable to be oxidatively deteriorated due to contact with the fallen positive electrode material. In the above aspect of the present invention, even when such a bag-shaped separator is used, oxidative deterioration at the lower end portion of the separator can be suppressed in the high temperature deep discharge life test.
  • the ribs may be formed on the sheet when the resin composition is extruded. Further, the ribs may be formed by pressing the sheet with a roller having a groove corresponding to each rib after molding the resin composition into a sheet or removing the pore-forming agent.
  • the height of the ribs may be 0.05 mm or more. Further, the height of the rib may be 1.2 mm or less. The height of the rib is the height of the portion protruding from the main surface of the base portion (protruding height).
  • the height of the rib provided in the region of the separator facing the positive electrode plate may be 0.4 mm or more.
  • the height of the rib provided in the region of the separator facing the positive electrode plate may be 1.2 mm or less.
  • the thickness of the base portion is, for example, 0.15 mm or more. In this case, it is easy to secure the strength of the separator. From the viewpoint of suppressing the resistance of the separator to a low level, the thickness of the base portion is preferably 0.25 mm or less, and may be 0.20 mm or less, for example.
  • Separators taken from lead-acid batteries in the early stages of use are used for separator analysis or size measurement.
  • the separator removed from the lead-acid battery is washed and dried prior to analysis or measurement.
  • the separator taken out from the lead storage battery is immersed in pure water for 1 hour to remove sulfuric acid in the separator.
  • the separator is taken out from the immersed liquid and allowed to stand for 16 hours or more in an environment of 25 ° C. ⁇ 5 ° C. to dry.
  • the separator is taken out from the fully charged lead storage battery.
  • the apparent density of the separator is determined by the following procedure. First, in the region of the separator facing the electrode plate, the base portion is processed into a strip of 100 mm ⁇ 10 mm so as not to include ribs, and a sample (hereinafter referred to as sample A) is prepared. The vertical and horizontal sizes and thicknesses of sample A are measured, and the volume of sample A is determined from these measured values. The apparent density is calculated by measuring the mass of sample A and dividing by volume. The apparent density is obtained for a plurality of samples (for example, 20 samples), and the average value is calculated. The obtained average value is used as the apparent density of the separator.
  • Sample A (Content of penetrant in separator) A part of Sample A prepared in the same manner as above is collected, weighed accurately, and then dried at room temperature (temperature of 20 ° C. or higher and 35 ° C. or lower) in a reduced pressure environment lower than atmospheric pressure for 12 hours or more. The dried product is placed in a platinum cell, set in a thermogravimetric analyzer, and heated from room temperature to 800 ° C. ⁇ 1 ° C. at a heating rate of 10 K / min. The weight loss when the temperature is raised from room temperature to 250 ° C. ⁇ 1 ° C.
  • the thickness of the separator is obtained by measuring and averaging the thicknesses of five arbitrarily selected points in the cross-sectional photograph of the separator.
  • the thickness of the base portion is obtained by measuring and averaging the thickness of the base portion at five arbitrarily selected points in the cross-sectional photograph of the separator.
  • the height of the rib is obtained by averaging the height from one main surface of the base portion of the rib measured at 10 arbitrarily selected points of the rib in the cross-sectional photograph of the separator.
  • Positive electrode plate a paste type positive electrode plate is used.
  • the positive electrode current collector contained in the positive electrode plate may be formed by casting lead (Pb) or a lead alloy, or may be formed by processing a lead or a lead alloy sheet. Examples of the processing method include expanding processing and punching processing. It is preferable to use a grid-shaped current collector as the positive electrode current collector because it is easy to support the positive electrode material.
  • the lead alloy used for the positive electrode current collector Pb-Ca-based alloys and Pb-Ca-Sn-based alloys are preferable in terms of corrosion resistance and mechanical strength.
  • the positive electrode current collector may have lead alloy layers having different compositions, and may have a plurality of alloy layers. It is preferable to use a Pb—Ca alloy or a Pb—Sb alloy for the core metal.
  • the positive electrode material contains a positive electrode active material (lead dioxide or lead sulfate) whose capacity is developed by a redox reaction.
  • the positive electrode material contains the Sb element.
  • the positive electrode material may contain other additives (reinforcing material, etc.), if necessary.
  • the positive electrode material usually contains ⁇ -PbO 2 crystallites and ⁇ -PbO 2 crystallites.
  • the ⁇ / ⁇ ratio is in such a range, the ratio of active ⁇ -PbO 2 crystallites is relatively large, so that the initial capacity decrease of the lead storage battery can be suppressed and a high initial capacity can be secured. it can.
  • the ⁇ / ⁇ ratio may be 0.05 or more or 0.1 or more.
  • the ⁇ / ⁇ ratio may be 0.13 or more, 0.18 or more, or 0.2 or more.
  • the ⁇ / ⁇ ratio can be controlled, for example, by adjusting at least one of the temperature at the time of chemical conversion and the specific gravity of the electrolytic solution at the time of chemical conversion.
  • the ⁇ / ⁇ ratio is 0.05 or more (or 0.1 or more) 0.6 or less, 0.13 or more (or 0.18 or more) 0.6 or less, 0.2 or more. 0.6 or less, 0.05 or more (or 0.1 or more) 0.55 or less, 0.13 or more (or 0.18 or more) 0.55 or less, 0.2 or more and 0.55 or less, 0.05 or more (Or 0.1 or more) 0.5 or less, 0.13 or more (or 0.18 or more) 0.5 or less, 0.2 or more and 0.5 or less, 0.05 or more (or 0.1 or more) 0. It may be 2 or less, or 0.13 or more (or 0.18 or more) and 0.2 or less.
  • the content of Sb element in the positive electrode material is 0.05% by mass or more.
  • the content of the Sb element in the positive electrode material is, for example, 0.6% by mass or less, 0.5% by mass or less, or 0.3% by mass. It may be as follows.
  • the positive electrode plate in which the positive electrode material contains the Sb element can be formed, for example, by using an antimony compound (for example, an oxide, a salt, etc.) as an additive.
  • an antimony compound for example, an oxide, a salt, etc.
  • Examples of the reinforcing material of the additive include fibers (inorganic fibers, organic fibers, etc.).
  • the resin (or polymer) constituting the organic fiber include acrylic resin, polyolefin resin (polypropylene resin, polyethylene resin, etc.), and polyester resin (including polyalkylene allylate (polyethylene terephthalate, etc.)).
  • celluloses cellulose, cellulose derivatives (cellulose ether, cellulose ester, etc.), etc.
  • Cellulose also includes rayon.
  • the amount of the reinforcing material in the positive electrode material is, for example, 0.03% by mass or more.
  • the amount of the reinforcing material in the positive electrode material is, for example, 0.5% by mass or less.
  • the total pore volume of the positive electrode material is, for example, 0.08 cm 3 / g or more, and may be 0.09 cm 3 / g or more. When the total pore volume is in such a range, the diffusibility of sulfate ions is increased, so that it is easy to secure a higher output.
  • the total pore volume of the positive electrode material may be, for example, 0.2 cm 3 / g or less. When the total pore volume of the positive electrode material is 0.18 cm 3 / g or less, the contact between the lead and lead sulfate particles is likely to be maintained even after repeated charging and discharging. Therefore, the effect of suppressing the softening and falling off of the positive electrode material by setting the content of the Sb element to 0.05% by mass or more is further enhanced. Therefore, it is easy to secure even higher life performance in the high temperature deep discharge life test.
  • Total pore volume of the positive electrode material 0.08 cm 3 / g or more (or 0.09 cm 3 / g or more) 0.2 cm 3 / g or less, or 0.08 cm 3 / g or more (or 0.09 cm 3 / g or more) 0.18 cm 3 / g or less may be used.
  • the unchemical paste type positive electrode plate is obtained by filling the positive electrode current collector with the positive electrode paste, aging and drying.
  • the positive electrode paste is prepared by adding water and sulfuric acid to lead powder, an antimony compound, and if necessary, other additives (reinforcing material, etc.) and kneading.
  • a positive electrode plate can be obtained by forming an unchemical positive electrode plate.
  • the chemical conversion can be carried out by charging the electrode plate group in a state where the electrode plate group including the unchemical positive electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery. However, chemical conversion may be performed before assembling the lead-acid battery or the electrode plate group.
  • the positive electrode material is recovered from the positive electrode plate by the following procedure. First, the fully charged lead-acid battery is disassembled, and the obtained positive electrode plate is washed with water for 3 to 4 hours to remove the electrolytic solution in the positive electrode plate. The positive electrode plate washed with water is dried in a constant temperature bath at 60 ° C. ⁇ 5 ° C. for 5 hours or more. If the positive electrode plate contains a sticking member after drying, the sticking member is removed from the positive electrode plate by peeling.
  • the positive electrode material for analysis hereinafter referred to as sample B
  • sample B the positive electrode material for analysis
  • sample B can be obtained by collecting the positive electrode material from the vicinity of the center of the top, bottom, left and right. Sample B is pulverized as necessary and used for analysis.
  • the crushed sample B is taken and weighed accurately.
  • Mixing ratio (volume ratio) of the aqueous nitrate solution and the aqueous tartrate acid solution 7: 2).
  • Dissolve the solubles while stirring under heating.
  • the resulting mixture is filtered using a membrane filter (average pore size: 0.45 ⁇ m or less).
  • the reinforcing material contained in the positive electrode material is obtained as a solid substance on the filter paper.
  • the obtained solid is washed with water and dried. Measure the mass of the dried product.
  • the ratio (percentage) of the mass of the dried product to the mass of sample B is determined. This ratio corresponds to the amount of
  • the filtrate or diluted filtrate is used as a solution for Sb quantification, and the emission intensity of Sb in the solution is measured by inductively coupled plasma (ICP) emission spectroscopy. Then, the mass of Sb contained in the solution is determined using a calibration curve prepared in advance. The ratio of the Sb mass to the mass of the sample B used for analysis is determined as the content of the Sb element. Analysis by ICP emission spectroscopy is performed using SPECTRO-ARCOS manufactured by Hitachi High-Tech Science Corporation.
  • Total pore volume of positive electrode material Using uncrushed sample B, it is measured by a mercury porosimeter (manufactured by Shimadzu Corporation, Autopore IV9510).
  • the pressure range for measurement is 1 psia ( ⁇ 6.9 kPa) or more and 60,000 psia ( ⁇ 414 MPa) or less.
  • the pore distribution uses a range in which the pore diameter is 3 nm or more and 100 ⁇ m or less.
  • the ⁇ / ⁇ ratio is determined from the intensity ratio of the peaks of each PbO 2 crystallite by measuring the X-ray diffraction (XRD) spectrum using the pulverized sample B.
  • XRD X-ray diffraction
  • the XRD measurement is performed using a fully automatic multipurpose X-ray diffractometer Smart Lab (horizontal goniometer ⁇ - ⁇ type, Cu-K ⁇ ray) manufactured by RIGAKU.
  • the negative electrode plate of a lead storage battery is composed of a negative electrode current collector and a negative electrode material.
  • the negative electrode electrode material is a negative electrode plate obtained by removing the negative electrode current collector.
  • the negative electrode plate may have a sticking member as described above stuck to the negative electrode plate. In this case, the sticking member shall be included in the negative electrode plate.
  • the negative electrode plate includes a sticking member, the negative electrode material is the one excluding the negative electrode current collector and the sticking member.
  • 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 processing and punching processing. It is preferable to use a grid-shaped current collector as the negative electrode current collector because it is easy to support the negative electrode material.
  • the lead alloy used for the negative electrode current collector may be any of a Pb—Sb alloy, a Pb—Ca alloy, and a Pb—Ca—Sn alloy. These leads or lead alloys may further contain, as an additive element, at least one selected from the group consisting of Ba, Ag, Al, Bi, As, Se, Cu and the like.
  • the negative electrode material contains a negative electrode active material (lead or lead sulfate) whose capacity is developed by a redox reaction, and contains a shrink-proofing agent (organic shrink-proofing agent, etc.), a carbonaceous material (carbon black, etc.), barium sulfate, and the like. But it may be.
  • the negative electrode material may contain other additives (reinforcing material, etc.), if necessary.
  • the reinforcing material include fibers (inorganic fibers, organic fibers (organic fibers composed of the resin described for the reinforcing material of the positive electrode electrode material, etc.)).
  • the negative electrode active material in the charged state is spongy lead, but the unchemicald negative electrode plate is usually produced using lead powder.
  • the negative electrode plate can be formed by filling a negative electrode current collector with a negative electrode paste, aging and drying to prepare an unchemicald negative electrode plate, and then forming an unchemicald negative electrode plate.
  • the negative electrode paste is prepared by adding water and sulfuric acid to lead powder, an organic shrink-proofing agent, and various additives as necessary, and kneading them. In the aging step, it is preferable to ripen the unchemicald negative electrode plate at a temperature higher than room temperature and high humidity.
  • Chemical formation can be performed by charging the electrode plate group in a state where the electrode plate group including the unchemical negative electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery. However, chemical conversion may be performed before assembling the lead-acid battery or the electrode plate group. The chemical formation produces spongy lead.
  • the electrolytic solution is an aqueous solution containing sulfuric acid.
  • the electrolytic solution may further contain at least one selected from the group consisting of Na ions, Li ions, Mg ions, and Al ions.
  • the electrolytic solution may be gelled if necessary.
  • the specific weight of the electrolytic solution at 20 ° C. is, for example, 1.10 or more.
  • the specific weight of the electrolytic solution at 20 ° C. may be 1.35 or less. It should be noted that these specific gravity values are values for the electrolytic solution of the ready-made and fully charged lead-acid battery.
  • FIG. 1 shows the appearance of an example of a lead storage battery according to an embodiment of the present invention.
  • the lead-acid battery 1 includes an electric tank 12 that houses a electrode plate group 11 and an electrolytic solution (not shown).
  • the inside of the electric tank 12 is partitioned into a plurality of cell chambers 14 by a partition wall 13.
  • each cell chamber 14 one electrode plate group 11 is stored.
  • the opening of the battery case 12 is closed by a lid 15 including a negative electrode terminal 16 and a positive electrode terminal 17.
  • the lid 15 is provided with a liquid spout 18 for each cell chamber. At the time of rehydration, the liquid spout 18 is removed and the rehydration liquid is replenished.
  • the liquid spout 18 may have a function of discharging the gas generated in the cell chamber 14 to the outside of the battery.
  • the electrode plate group 11 is formed by laminating a plurality of negative electrode plates 2 and positive electrode plates 3 via a separator 4, respectively.
  • the bag-shaped separator 4 that accommodates the negative electrode plate 2 is shown, but the form of the separator is not particularly limited.
  • the negative electrode shelf portion 6 for connecting the plurality of negative electrode plates 2 in parallel is connected to the through connecting body 8, and the positive electrode shelf portion for connecting the plurality of positive electrode plates 3 in parallel. 5 is connected to the positive electrode column 7.
  • the positive electrode column 7 is connected to the positive electrode terminal 17 outside the lid 15.
  • the negative electrode column 9 is connected to the negative electrode shelf 6, and the through connector 8 is connected to the positive electrode shelf 5.
  • the negative electrode column 9 is connected to the negative electrode terminal 16 outside the lid 15.
  • Each through-connecting body 8 passes through a through-hole provided in the partition wall 13 and connects the electrode plates 11 of the adjacent cell chambers 14 in series.
  • life performance in high temperature deep discharge life test In the present specification, the life performance in the high temperature deep discharge life test is evaluated based on the number of cycles to be the life in the high temperature deep discharge life test.
  • the high-temperature deep discharge life test is performed by repeating discharging and charging a lead-acid battery having a rated voltage of 12 V in a fully charged state under the following conditions.
  • (A) to (c) are carried out in an air tank environment of 50 ° C. ⁇ 2 ° C.
  • the output of the lead-acid battery shall be evaluated by the terminal voltage 30 seconds after the start of discharge, which is measured according to the cold cranking current (CCA) test of 10.3 of JIS D 5301: 2019. The larger the voltage value, the higher the output. More specifically, the output of the lead-acid battery is measured by the following procedure.
  • the lead-acid battery Place the fully charged lead-acid battery in a water tank at 25 ° C ⁇ 2 ° C for 5 hours after it is fully charged.
  • the lead-acid battery is then placed in a -18 ° C ⁇ 1 ° C cooling chamber until the electrolyte temperature of one cell in or near the center is -18 ° C ⁇ 1 ° C.
  • the battery is discharged at the rated cold cranking current (CCA) for 30 seconds within 2 minutes. Record the terminal voltage 30 seconds after the start of discharge.
  • CCA cold cranking current
  • CCA is one of the indexes showing the performance of the lead-acid battery.
  • the terminal voltage after 30 seconds is 7 when discharged at a temperature of -18 ° C ⁇ 1 ° C. .
  • the initial capacity of the lead-acid battery can be measured according to the 20-hour rate capacity test of 10.1 of JIS D 5301: 2019. More specifically, the initial capacity of the lead-acid battery is measured by the following procedure.
  • Negative Electrode Plate A negative electrode paste was prepared by mixing lead oxide, carbon black, barium sulfate, lignin, reinforcing material (synthetic resin fiber), water and sulfuric acid.
  • the negative electrode paste was filled in the mesh portion of an expanded lattice made of an antimony-free Pb-Ca—Sn alloy, and aged and dried to obtain an unmodified negative electrode plate having a width of 100 mm, a height of 115 mm, and a thickness of 1.2 mm. ..
  • the amounts of carbon black, barium sulfate, lignin and synthetic resin fibers were 0.3% by mass, 2.1% by mass, 0.1% by mass and 0.1% by mass, respectively, when measured in a fully charged state. Adjusted to mass%.
  • a positive electrode paste was prepared by mixing lead oxide, antimony trioxide, reinforcing material (synthetic resin fiber), water and sulfuric acid.
  • the amount of antimony trioxide added was adjusted so that the Sb element content in the positive electrode material measured by the procedure described above would be the values shown in Tables 1 to 3.
  • the amounts of water and sulfuric acid were adjusted so that the total pore volume of the positive electrode material measured by the procedure described above would be the values shown in Tables 1 to 3.
  • the amount of the reinforcing material in the positive electrode material measured by the procedure described above was 0.15% by mass.
  • the positive electrode paste was filled in the mesh portion of an expanded lattice made of an antimony-free Pb-Ca—Sn alloy, and aged and dried to obtain an unmodified positive electrode plate having a width of 100 mm, a height of 115 mm, and a thickness of 1.6 mm. ..
  • composition of the resin composition containing polyethylene, silica particles, pore-forming agent and penetrant is arbitrary, depending on, for example, at least one selected from the design of the separator, the manufacturing conditions, and the usage of the lead-acid battery. Can be changed to. Further, if necessary, for example, at least one of the amount of the penetrant in the separator and the amount of the pore-forming agent removed is adjusted.
  • a plurality of striped mini-ribs having a protruding height of 0.18 mm were provided on both edges in the width direction of the bag-shaped separator at a pitch of 1 mm.
  • a plurality of striped main ribs having a protruding height of 0.6 mm were provided at a pitch of 9.8 mm in a region inside both edges provided with mini ribs.
  • the total thickness of the separator was 0.8 mm.
  • the content of silica particles in the separator was 60% by mass.
  • the total thickness of the separator, the protruding height of the ribs, the pitch of the ribs, and the content of the silica particles are the values obtained for the separator before the production of the lead-acid battery, but for the separator taken out from the lead-acid battery after production. It is almost the same as the value measured by the procedure described above.
  • Each unchemicald negative electrode plate is housed in a bag-shaped separator, and 7 unchemicald negative electrode plates and 6 unchemicald positive electrode plates are alternately stacked to form a group of electrode plates per cell. did.
  • the ears of the positive electrode plate and the ears of the negative electrode plate were welded to the positive electrode shelf and the negative electrode shelf by a cast-on strap (COS) method, respectively.
  • the electrode plate group is inserted into a polypropylene battery case, an electrolytic solution is injected, and chemical conversion is performed in the battery battery.
  • the rated voltage is 12 V and the rated capacity is 30 Ah (5-hour rate capacity (value described in the rated capacity).
  • Liquid lead-acid batteries E1 to E26 and R1 to R18 of 1/5 of the current (A) when discharged) were assembled. In the battery case, six electrode plates are connected in series.
  • the electrolytic solution a solution in which aluminum sulfate was dissolved in an aqueous sulfuric acid solution was used.
  • the Al ion concentration of the electrolytic solution after chemical conversion was 0.2% by mass.
  • the specific gravity of the electrolytic solution at the time of chemical conversion was adjusted in the range of 1.12 to 1.26 so that the ⁇ / ⁇ ratio in the positive electrode material would be the values shown in Tables 1 to 3.
  • the produced lead-acid battery was fully charged according to the procedure described above and used for the following evaluation.
  • the content of Sb element in the positive electrode material may be changed from 0% by mass to 0.30% by mass.
  • the life performance in the high temperature deep discharge life test does not change at all (R7, R9, R11 and R13).
  • the content of Sb element in the positive electrode electrode material is less than 0.05% by mass, if the apparent density of the separator is reduced to less than 0.57 g / cm 3 , the life performance in the high temperature deep discharge life test deteriorates. (Comparison between R7 and R1 to R6).
  • the apparent density of the separator is 0.46 g / cm 3 or more and less than 0.57 g / cm 3 , so that the high temperature deep discharge life is achieved. Life performance in the test is improved (comparison between R8 and R9 and E1 to E6, comparison between R10 and R11 and E7 to E11, comparison between R12 and R13 and E12 to E16). As described above, the influence (behavior) of the apparent density of the separator on the life performance in the high temperature deep discharge life test when the content of the Sb element in the positive electrode material is 0.05% by mass or more and less than 0.05% by mass. Is very different. Further, in the lead storage batteries E1 to E16, a high output of 100% or more can be secured.
  • the total pore volume of the positive electrode material is preferably 0.08 cm 3 / g or more, 0.09 cm 3 / g or more is more preferable. From the viewpoint of ensuring higher life performance in the high temperature deep discharge life test, the total pore volume of the positive electrode material is preferably 0.18 cm 3 / g or less.
  • the ⁇ / ⁇ ratio in the positive electrode material is 0.55 or less, a higher initial capacitance can be secured.
  • the ⁇ / ⁇ ratio is preferably 0.18 or more or 0.2 or more from the viewpoint of ensuring higher life performance.
  • the lead-acid battery according to the above aspect of the present invention is suitable for IS applications (lead-acid batteries for ISS vehicles, etc.), power sources for starting various vehicles (automobiles, motorcycles, etc.), and the like. Further, the lead-acid battery can be suitably used as a power source for industrial power storage devices (electric vehicles (forklifts, etc.), etc.). It should be noted that these uses are merely examples, and the lead-acid battery according to the above aspect of the present invention is not limited to these uses.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne une batterie d'accumulateurs au plomb comprenant une plaque positive, une plaque négative et un séparateur interposé entre la plaque positive et la plaque négative. La plaque positive comprend un matériau d'électrode positive. Le matériau d'électrode positive contient un élément de Sb. La teneur en élément de Sb à l'intérieur du matériau d'électrode positive est d'au moins 0,05 % en masse. Le séparateur contient une polyoléfine et de l'huile, et sa densité apparente est d'au moins 0,46g/cm3 et inférieure à 0,57g/cm3.
PCT/JP2020/032404 2019-10-28 2020-08-27 Batterie d'accumulateurs au plomb WO2021084878A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06236752A (ja) * 1992-12-17 1994-08-23 Nippon Muki Co Ltd 鉛蓄電池用セパレータ並びにその製造法
JPH1031992A (ja) * 1996-07-16 1998-02-03 Matsushita Electric Ind Co Ltd 鉛蓄電池用セパレータおよびその製造法
JP2001338631A (ja) * 2000-05-29 2001-12-07 Nippon Muki Co Ltd 鉛蓄電池用リブ付きセパレータおよびその製造方法
JP2006140034A (ja) * 2004-11-12 2006-06-01 Matsushita Electric Ind Co Ltd 鉛蓄電池
JP2017079144A (ja) * 2015-10-20 2017-04-27 株式会社Ｇｓユアサ 鉛蓄電池
WO2018229875A1 (fr) * 2017-06-13 2018-12-20 日立化成株式会社 Batterie au plomb de type liquide
WO2019087678A1 (fr) * 2017-10-31 2019-05-09 株式会社Ｇｓユアサ Batterie de stockage au plomb

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06236752A (ja) * 1992-12-17 1994-08-23 Nippon Muki Co Ltd 鉛蓄電池用セパレータ並びにその製造法
JPH1031992A (ja) * 1996-07-16 1998-02-03 Matsushita Electric Ind Co Ltd 鉛蓄電池用セパレータおよびその製造法
JP2001338631A (ja) * 2000-05-29 2001-12-07 Nippon Muki Co Ltd 鉛蓄電池用リブ付きセパレータおよびその製造方法
JP2006140034A (ja) * 2004-11-12 2006-06-01 Matsushita Electric Ind Co Ltd 鉛蓄電池
JP2017079144A (ja) * 2015-10-20 2017-04-27 株式会社Ｇｓユアサ 鉛蓄電池
WO2018229875A1 (fr) * 2017-06-13 2018-12-20 日立化成株式会社 Batterie au plomb de type liquide
WO2019087678A1 (fr) * 2017-10-31 2019-05-09 株式会社Ｇｓユアサ Batterie de stockage au plomb

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