WO2022195736A1 - Groupe d'électrodes et batterie de stockage au plomb - Google Patents

Groupe d'électrodes et batterie de stockage au plomb Download PDF

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Publication number
WO2022195736A1
WO2022195736A1 PCT/JP2021/010697 JP2021010697W WO2022195736A1 WO 2022195736 A1 WO2022195736 A1 WO 2022195736A1 JP 2021010697 W JP2021010697 W JP 2021010697W WO 2022195736 A1 WO2022195736 A1 WO 2022195736A1
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Prior art keywords
electrode
separator
negative electrode
lead
electrode group
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PCT/JP2021/010697
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English (en)
Japanese (ja)
Inventor
夏己 宮下
真輔 小林
和也 丸山
拓弥 及川
Original Assignee
昭和電工マテリアルズ株式会社
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Priority to JP2023506458A priority Critical patent/JPWO2022195736A1/ja
Priority to PCT/JP2021/010697 priority patent/WO2022195736A1/fr
Publication of WO2022195736A1 publication Critical patent/WO2022195736A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • 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
    • H01M50/411—Organic material
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H01M50/437—Glass
    • 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
    • H01M50/44—Fibrous material
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • 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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H01M50/466—U-shaped, bag-shaped or folded

Definitions

  • the present disclosure relates to electrode groups, lead-acid batteries, and the like.
  • a lead-acid battery is one of the conventionally used secondary batteries, and is widely used as a secondary battery for industrial or consumer use due to its reliability and low price.
  • lead-acid batteries for automobiles, lead-acid batteries for electric vehicles, lead-acid batteries for power supply devices, and the like.
  • Lead-acid batteries are recharged as often as desired by the end user.
  • stratification of the electrolyte can occur if the battery is not charged for a long period of time. Stratification occurs due to the property that sulfate ions (SO 4 2 ⁇ ), which have a large specific gravity, tend to settle to the bottom.
  • SO 4 2 ⁇ sulfate ions
  • Sulfation is a phenomenon in which lead sulfate, which is a discharge product, is difficult to return to a charged state. As sulfation progresses, the battery capacity decreases, crystals adhere to the negative electrode surface, the contact area between the electrode and the electrolyte decreases, and the charging speed slows down. This can reduce the life characteristics of lead-acid batteries.
  • Patent Document 1 describes a technology related to a lead-acid battery separator characterized by laminating an acid-resistant microporous resin film sheet and an acid-resistant non-woven fabric sheet.
  • An object of one aspect of the present disclosure is to provide an electrode group for obtaining a lead-acid battery having excellent charge acceptance. Another aspect of the present disclosure aims to provide a lead-acid battery including the electrode group.
  • a first embodiment of an electrode group includes a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode, wherein the separator is a bag containing the negative electrode.
  • the bag-shaped separator is provided with ribs on the inner surface thereof, and the ribs are arranged on the inner surface in a region facing the active material region of the negative electrode and in the inner surface that does not face the negative electrode active material region. and , and the separator has an oil component content of more than 0% by mass and 12% by mass or less.
  • a second embodiment of an electrode group according to one aspect of the present disclosure includes a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and a glass mat disposed between the positive electrode and the separator.
  • the content of the oil component in the separator is more than 0% by mass and 12% by mass or less.
  • a third embodiment of an electrode group according to one aspect of the present disclosure includes a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode, wherein the positive electrode and the negative electrode in the electrode group are
  • the present invention relates to an electrode group for a lead-acid battery having the same number and having an oil component content of more than 0% by mass and not more than 12% by mass in the separator.
  • a lead-acid battery according to another aspect of the present disclosure relates to a lead-acid battery including the above-described electrode group and a container housing the electrode group.
  • an electrode group for obtaining a lead-acid battery with excellent charge acceptance it is possible to provide a lead-acid battery including the electrode group.
  • FIG. 1 is an end view showing an example of an electrode group and a lead-acid battery.
  • FIG. 2 is an end view showing another example of an electrode group and a lead-acid battery.
  • FIG. 3 is an end view showing another example of an electrode group and a lead-acid battery.
  • the upper limit or lower limit of the numerical range at one stage can be arbitrarily combined with the upper limit or lower limit of the numerical range at another stage.
  • the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
  • “A or B” may include either A or B, or may include both.
  • the materials exemplified in this specification can be used singly or in combination of two or more unless otherwise specified.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. Since specific gravity changes with temperature, it is defined as specific gravity converted at 20° C. in this specification.
  • the electrode group according to this embodiment is an electrode group for a lead-acid battery, and includes a positive electrode (e.g., positive electrode plate) and a negative electrode (e.g., a negative electrode plate) and a separator disposed between the positive electrode and the negative electrode.
  • a lead-acid battery according to this embodiment includes the electrode group according to this embodiment, and a battery case that houses the electrode group.
  • the content of the oil component in the separator is more than 0% by mass and 12% by mass or less based on the total amount of the separator. In this case, excellent charge acceptance can be obtained. It is presumed that the content of the oil component within such a range improves the diffusibility of sulfate ions, resulting in excellent charge acceptance. However, the factor for obtaining excellent charge acceptability is not limited to this content.
  • the charge acceptability can be evaluated using a lead-acid battery having the same number of positive electrodes and the same number of negative electrodes as the comparative lead-acid battery.
  • the oil component is a component that is soluble in acetone (25°C).
  • the oil component can be used to suppress oxidative deterioration of the separator.
  • the oil component may include mineral oil.
  • Mineral oils include paraffinic process oils, lubricating oils, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, petroleum jelly and the like.
  • the content of the oil component in the separator may be within the following ranges based on the total amount of the separator.
  • the content of the oil component is 1% by mass or more, 3% by mass or more, and 5% by mass or more from the viewpoint of easily obtaining excellent life characteristics because it is easy to suppress short circuits caused by deterioration of the separator (oxidative deterioration, etc.). , 6% by mass or more, 7% by mass or more, 7.5% by mass or more, 8% by mass or more, 9% by mass or more, 10% by mass or more, or 11% by mass or more.
  • the content of the oil component may be 11% by mass or less, 10% by mass or less, 9% by mass or less, 8% by mass or less, or 7.5% by mass or less from the viewpoint of easily obtaining excellent charge acceptance. . From these points of view, the content of the oil component may be 1 to 12% by mass, 7 to 12% by mass, 7 to 11% by mass, or 10 to 12% by mass.
  • the content of oil components is the content of components soluble in acetone (25°C).
  • the content of the oil component can be measured by the method described in Examples as the amount of change in mass when the separator is immersed in acetone.
  • the content of the oil component can be adjusted by adjusting the amount of the oil component used when producing the separator.
  • constituent materials of the separator include organic binders and the like.
  • organic binders include olefin resins, acrylic resins, urethane resins, styrene resins, and the like.
  • olefinic resins include polyethylene and polypropylene.
  • the separator need not contain glass.
  • the ash content of the separator may be within the following range.
  • the ash content of the separator may be 30% by weight or more, 40% by weight or more, 50% by weight or more, 55% by weight or more, 60% by weight or more, 63% by weight or more, or 65% by weight or more.
  • the ash content of the separator may be 90 wt% or less, 80 wt% or less, 70 wt% or less, 65 wt% or less, or 63 wt% or less. From these points of view, the ash content of the separator may be 30-90% by weight, 40-80% by weight, or 50-70% by weight.
  • the ash content of the separator can be measured by the method described in Examples.
  • the porosity of the separator may be within the following range.
  • the porosity of the separator may be 30 vol.% or more, 40 vol.% or more, 50 vol.% or more, 55 vol.% or more, 57 vol.% or more, 60 vol.% or more, or 61 vol.% or more.
  • the porosity of the separator may be 90% or less, 80% or less, 70% or less, 65% or less, 61% or less, 60% or less, or 57% or less by volume. From these points of view, the porosity of the separator may be 30-90% by volume, 40-80% by volume, or 50-70% by volume.
  • the porosity of the separator can be measured by the method described in Examples.
  • the separator placed between the positive electrode and the negative electrode at least part of the separator should be placed between the positive electrode and the negative electrode.
  • the electrode group may have multiple separators.
  • the separator may be bag-shaped or sheet-shaped.
  • the bag-shaped separator can accommodate an electrode (positive electrode or negative electrode) and has an internal space that accommodates the electrode (positive electrode or negative electrode).
  • the "bag-shaped separator” at least a part (part or all) of each of one surface and the other surface of the electrodes is covered in the internal space, and the electrode group is accommodated in the lead-acid battery, and the lower part in the vertical direction It is sufficient that the electrodes are held in the internal space by supporting the electrodes in .
  • the bag-shaped separator may have an opening for accommodating the electrode (an opening through which the electrode can be inserted).
  • the opening direction of the opening for accommodating the electrode (the height direction of the container in the state where the electrode group is accommodated in the lead-acid battery (for example, the vertical direction); the same applies hereinafter) At least part (part or all) may be sealed.
  • the bag-shaped separator may be configured by folding back a single base material (a mode in which the folded back portion of the base material is the sealing portion), and is composed of a plurality of base materials and is arranged in the opening direction. It may be an embodiment in which the base materials are joined to each other at the portion located on the lower side (an embodiment in which the joint portion between the base materials is the sealing portion).
  • the end portion (the side of the bag-shaped separator when the electrode group is housed in the lead-acid battery) in a direction that intersects (for example, orthogonally) with the opening direction and is substantially parallel to the inner surface (main surface) of the separator. At least one (one end or both ends) may be sealed, and the end may be sealed at the joint between the base materials.
  • the joint portion between the base materials may be a welded portion, a pressure-bonded portion (mechanical seal portion), or the like.
  • the separator may have ribs on at least one principal surface selected from the group consisting of one surface and the other surface, and the bag-shaped separator may have ribs on at least one principal surface selected from the group consisting of the inner surface and the outer surface. may be placed.
  • a rib may be arranged on the negative electrode side surface (main surface) of the separator. If the contact area between the negative electrode and the separator is large, dendrite short-circuiting may reduce the life characteristics. On the other hand, since the ribs are arranged on the negative electrode side surface, the contact area between the negative electrode and the separator can be reduced, and excellent life characteristics can be easily obtained. The ribs may not be arranged on the negative electrode side surface (main surface) of the separator.
  • the ribs may not be arranged on the positive electrode side surface (principal surface) of the separator. In this case, an increase in the distance between the positive electrode and the negative electrode is suppressed, so that excellent charge acceptance is likely to be obtained.
  • ribs may be arranged on the positive electrode side surface (main surface) of the separator.
  • the rib may be a long member extending in one direction, and may extend in the opening direction (the height direction of the container when the electrode group is housed in the lead-acid battery (for example, the vertical direction)).
  • the expression relating to the rib extending in the height direction of the battery case when the electrode group is housed in the battery case means that the rib extends from the bottom (bottom) of the battery case toward the top.
  • the ribs may extend in a direction perpendicular to the bottom surface of the container, or may extend in a direction inclined with respect to a line perpendicular to the bottom surface of the container.
  • the separator can have at least one rib, and may have a plurality of ribs.
  • the rib may be arranged in a region facing the active material region of the electrode, or may be arranged in a region facing the active material region of the electrode and a region not facing the active material region of the electrode.
  • An “electrode active material region” is a region in which an active material is disposed in an electrode (positive electrode or negative electrode).
  • the inner surfaces of the separator are closer to each other toward the end (the inner space is narrower). become).
  • the inner surface of the separator and the electrode for example, the active material region of the electrode
  • the separator and the electrode are likely to come into contact with each other.
  • the ribs arranged on the inner surface of the bag-like separator are the active material regions of the electrodes in a direction that intersects (for example, orthogonally) the opening direction of the opening for accommodating the electrode (for example, the negative electrode) and that is substantially parallel to the inner surface.
  • the rib may include a rib arranged in the second space.
  • a plurality of ribs extending in the opening direction of the opening for accommodating the electrode are arranged in a direction (eg, orthogonal) that intersects (eg, perpendicular to) the opening direction. may be spaced apart from one end to the other end of the inner surface of the bag-shaped separator (excluding the joint between the base materials) in the direction that intersects the opening direction and is substantially parallel to the inner surface of the bag-shaped separator. . In this case, even if the electrodes are misaligned, it is easy to reduce the contact area between the electrodes and the separator after the misalignment.
  • the plurality of ribs may be arranged at approximately equal intervals.
  • the rib spacing may be 0.1-10 mm, 0.5-5 mm, 0.5-1 mm, or 1-5 mm.
  • the separator may have a base portion and ribs arranged on at least one surface (principal surface) of the base portion.
  • the base portion thickness T, the rib height H, or the ratio H/T of the rib height H to the base portion thickness T (rib height H/base portion T thickness) is excellent. From the viewpoint of easily obtaining charge acceptance, the following ranges may be used.
  • the thickness T of the base portion may be 0.01 mm or more, 0.05 mm or more, 0.1 mm or more, 0.15 mm or more, or 0.2 mm or more.
  • the thickness T of the base portion may be 0.5 mm or less, 0.4 mm or less, 0.3 mm or less, 0.25 mm or less, or 0.2 mm or less. From these points of view, the thickness T of the base portion may be 0.01-0.5 mm, 0.05-0.4 mm, or 0.1-0.3 mm.
  • the rib height H may be 0.01 mm or more, 0.05 mm or more, 0.1 mm or more, or 0.15 mm or more.
  • the rib height H may be 0.5 mm or less, 0.4 mm or less, 0.3 mm or less, 0.2 mm or less, or 0.15 mm or less. From these points of view, the rib height H may be 0.01-0.5 mm, 0.05-0.4 mm, or 0.1-0.3 mm. All rib heights in the separator may be within these ranges.
  • the ratio H/T may be 0.1 or more, 0.3 or more, 0.5 or more, 0.7 or more, or 0.75 or more.
  • the ratio H/T may be 2 or less, 1.5 or less, 1 or less, less than 1, 0.8 or less, or 0.75 or less. From these points of view, the ratio H/T may be 0.1-2, 0.3-1.5, or 0.5-1.
  • the electrode group may have a plurality of positive electrodes and may have a plurality of negative electrodes.
  • the number of positive electrodes and negative electrodes in the electrode group may or may not be the same. If the number of positive and negative electrodes is not equal, there may be more negative electrodes than positive electrodes.
  • the number of positive electrodes or negative electrodes in the electrode group may be 5 or more, 6 or more, 7 or more, or 8 or more.
  • the number of positive or negative electrodes in the electrode group may be 10 or less, 9 or less, 8 or less, or 7 or less.
  • the number of positive electrodes or negative electrodes in the electrode group may be 5-10, 6-9, or 7-8. At least one (one or both) of the outermost electrodes in the electrode group may be a negative electrode.
  • the positive electrode has a positive electrode current collector and a positive electrode active material supported by the positive electrode current collector.
  • the negative electrode has a negative electrode current collector and a negative electrode active material supported by the negative electrode current collector.
  • the positive electrodes and the negative electrodes may be alternately arranged with separators interposed therebetween.
  • a member obtained by removing the positive electrode current collector from the positive electrode is referred to as a “positive electrode active material”, and a member obtained by removing the negative electrode current collector from the negative electrode is referred to as a “negative electrode active material”.
  • the positive electrode current collector serves as a conductive path for current from the positive electrode active material and holds the positive electrode active material.
  • the negative electrode current collector serves as a conductive path for current from the negative electrode active material and holds the negative electrode active material.
  • the negative electrode current collector may be the same as or different from the positive electrode current collector.
  • Materials constituting the current collector include lead alloys such as lead-calcium-tin alloys and lead-antimony-arsenic alloys. Depending on the application, selenium, silver, bismuth, etc. may be added to the current collector.
  • the current collector has, for example, a grid shape, and may be a cast grid, an expanded grid, or the like.
  • a current collector can be obtained by forming a lead alloy into a grid shape by a gravity casting method, an expanding method, a punching method, or the like.
  • a plurality of positive electrodes may be electrically connected to each other by connecting the ears provided on the positive electrode current collector to each other via a strap.
  • the strap of the positive electrode may be provided with a positive pole for connecting the positive electrode to the positive terminal.
  • a plurality of negative electrodes may be electrically connected to each other by connecting the tabs provided on the negative electrode current collector to each other via a strap.
  • the negative electrode strap may be provided with a negative pole for connecting the negative electrode to the negative terminal.
  • the positive electrode active material can contain ⁇ -PbO 2 as the Pb component.
  • the positive electrode active material may contain ⁇ -PbO 2 or may not contain ⁇ -PbO 2 .
  • the positive electrode active material can contain Pb components other than PbO 2 (for example, PbSO 4 ), additives, and the like, if necessary.
  • Additives that can be included in the positive electrode active material include carbon materials (excluding carbon fibers), short reinforcing fibers, and the like.
  • carbon materials include carbon black and graphite.
  • carbon black include furnace black, channel black, acetylene black, thermal black, and ketjen black.
  • the reinforcing short fibers include acrylic fibers, polyethylene fibers, polypropylene fibers, polyethylene terephthalate fibers, carbon fibers, and the like.
  • the negative electrode active material can contain Pb as a Pb component.
  • the negative electrode active material may include porous Spongy Lead.
  • the negative electrode active material can contain Pb components other than Pb (for example, PbSO 4 ), additives, and the like, if necessary.
  • Additives that can be contained in the negative electrode active material include resins having a sulfo group and/or a sulfonate group, barium sulfate, carbon materials (excluding carbon fibers), short reinforcing fibers, and the like.
  • resins having a sulfo group and/or a sulfonate group include ligninsulfonic acid, ligninsulfonate (eg sodium ligninsulfonate), condensates of phenols, aminoarylsulfonic acid and formaldehyde (eg bisphenol and aminobenzene condensate of sulfonic acid and formaldehyde) and the like.
  • the negative electrode active material may contain at least one selected from the group consisting of ligninsulfonic acid, ligninsulfonate, and bisphenol resin from the viewpoint of easily obtaining excellent charge acceptance, and particularly excellent charge acceptance can be obtained. From the viewpoint of ease of use, a bisphenol-based resin may be contained.
  • carbon materials include carbon black and graphite. Examples of carbon black include furnace black, channel black, acetylene black, thermal black, and ketjen black. Examples of the reinforcing short fibers include acrylic fibers, polyethylene fibers, polypropylene fibers, polyethylene terephthalate fibers, carbon fibers, and the like.
  • the positive electrode active material and the negative electrode active material can be obtained by aging and drying an active material paste containing active material raw materials to obtain an unformed active material, and then forming the unformed active material.
  • the positive electrode and the negative electrode can be obtained by aging and drying an active material paste supported by a current collector to obtain an unformed active material, and then forming the unformed active material.
  • the active material paste may contain solvent and/or sulfuric acid. Examples of solvents include water (eg, ion-exchanged water), organic solvents, and the like.
  • the unformed positive electrode active material may contain tribasic lead sulfate as a main component. Raw materials for the positive electrode active material include lead powder and red lead (Pb 3 O 4 ).
  • the unformed negative electrode active material may contain tribasic lead sulfate as a main component. Lead powder etc. are mentioned as a raw material of a negative electrode active material.
  • the electrode group may have a glass mat placed between the positive electrode and the separator. In this case, it is easy to obtain excellent life characteristics by suppressing dropout of the active material in the positive electrode.
  • a glass mat is a member containing glass, for example, a member obtained by processing glass fibers into a mat.
  • the glass mat may contain a resin material and may contain an acrylic resin.
  • the electrode group may have multiple glass mats.
  • the electrode group may be a laminate of a positive electrode, a glass mat, a separator and a negative electrode. The glass mat does not have to be bag-like. In addition, the electrode group may not have the glass mat arranged between the positive electrode and the separator.
  • the glass mat may cover at least part of the active material region of the positive electrode, and may cover the entire active material region (region where the positive electrode active material is arranged) of the positive electrode (at least one positive electrode).
  • the electrode group according to the first embodiment includes a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode, the separator being a bag-shaped separator that accommodates the negative electrode, and the inner surface of the bag-shaped separator.
  • the ribs are arranged on the inner surface in a region facing the negative electrode active material region and the inner surface in a region not facing the negative electrode active material region, and the oil component content in the separator is more than 0% by mass and 12% by mass or less.
  • at least one rib may be arranged in each of the region facing the negative electrode and the region not facing the negative electrode.
  • the ribs are arranged on the inner surface of the bag-shaped separator, the contact area between the electrode and the separator can be reduced, making it easy to obtain excellent life characteristics.
  • the charge acceptability may decrease.
  • the lead-acid battery according to the first embodiment it is possible to obtain excellent charge acceptance by obtaining the above-described effect resulting from the content of the oil component. That is, according to the lead-acid battery according to the first embodiment, both excellent charge acceptance and life characteristics can be achieved.
  • the electrode group according to the second embodiment has a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and a glass mat disposed between the positive electrode and the separator.
  • the content is more than 0% by mass and 12% by mass or less.
  • the electrode group according to the third embodiment has a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode, the positive electrode and the negative electrode in the electrode group are the same number, and the separator contains an oil component
  • the amount is more than 0% by mass and 12% by mass or less.
  • the active material utilization rate of the positive electrode is lower than the active material utilization rate of the negative electrode. Therefore, in order to increase the active material utilization rate of the positive electrode, it is desirable that the electrode group has one more negative electrode than the positive electrode. .
  • the number of positive electrodes and negative electrodes may be adjusted to the same number by increasing the number of positive electrodes by one in order to improve the cold cranking performance, the utilization rate of the active material of the positive electrode may decrease and the charge acceptance performance may decrease.
  • the electrode group according to the third embodiment it is possible to obtain an excellent charge acceptability even if the number of positive electrodes and negative electrodes is the same, by obtaining the effect caused by the content of the oil component described above. .
  • the electrode group according to the first embodiment may or may not have a glass mat placed between the positive electrode and the separator.
  • the number of positive electrodes and negative electrodes may or may not be the same.
  • the number of positive electrodes and negative electrodes may or may not be the same.
  • the lead-acid battery according to this embodiment may include a plurality of electrode groups.
  • at least one electrode group among the plurality of electrode groups is the electrode group according to the first embodiment, the electrode group according to the second embodiment, or the electrode group according to the third embodiment. may have
  • the container in the lead-acid battery according to this embodiment is hollow and has an internal space for accommodating the electrode group.
  • the lead-acid battery according to this embodiment may include a lid that seals the container.
  • the lid body may be provided with a control valve for controlling the pressure in the container, a positive electrode terminal for connecting the positive electrode to the outside, and a negative electrode terminal for connecting the negative electrode to the outside.
  • the lead-acid battery according to this embodiment may include a spacer member arranged between the electrode group and the battery case (the inner wall of the battery case).
  • a laminate of a glass mat and another sheet different from the glass mat can be used as the spacer member.
  • the frictional force between the electrode group and the spacer member is increased, so that when the electrode group is inserted into the container, the operation of the lead-acid battery is reduced. Since it is easy to suppress positional displacement of the electrode group at times, etc., it is easy to obtain excellent charge acceptance.
  • a pulp sheet or the like can be used as a sheet different from the glass mat.
  • the glass mat and other sheets may be adhered to each other.
  • the glass mat and other sheets can be adhered together with an adhesive.
  • the glass mat may be arranged so as to be positioned on the electrode group side (so that the glass mat faces the electrode group) from the viewpoint of further suppressing the positional deviation of the electrode group. Further, when the electrode group has a positive electrode as the outermost electrode, the glass mat may face the outermost electrode (positive electrode) from the viewpoint of easily obtaining excellent life characteristics by suppressing dropout of the active material in the positive electrode.
  • the lead-acid battery according to this embodiment includes a spacer member disposed between the electrode group and the container, and the spacer member is a laminate of a glass mat and another sheet different from the glass mat.
  • the glass mat of the spacer member may be arranged on the side of the electrode group.
  • the electrode group may have the positive electrode as the outermost electrode, and the glass mat of the spacer member may face the outermost electrode (positive electrode).
  • the lead-acid battery according to this embodiment may include an electrolytic solution.
  • the electrolyte can be contained in a battery case.
  • the electrolytic solution may contain sulfuric acid and may contain sulfate ions.
  • the electrolyte may contain metal ions such as aluminum ions.
  • the specific gravity of the electrolyte (after chemical conversion) may be within the following range.
  • the specific gravity of the electrolytic solution is 1.35 or less, 1.33 or less, 1.32 or less, 1.31 or less, 1.3 or less, 1.29 or less, 1.28 from the viewpoint of easily obtaining excellent charge acceptance. 1.27 or less, or 1.26 or less.
  • the specific gravity of the electrolyte may be 1.23 or higher, 1.24 or higher, 1.25 or higher, 1.26 or higher, 1.27 or higher, or 1.28 or higher. From these points of view, the specific gravity of the electrolyte may be 1.23-1.35, 1.25-1.3, or 1.26-1.28.
  • the specific gravity of the electrolytic solution can be measured by the method described in Examples.
  • FIGS. 1 to 3 show a lead-acid battery including an electrode group having a bag-shaped separator, and are end views of the electrode group and the lead-acid battery in the opening direction of the bag-shaped separator.
  • a lead-acid battery 100 shown in FIG. 1 includes an electrode group 10, an electrolytic solution (not shown), and a battery case (not shown) containing the electrode group 10 and the electrolytic solution.
  • the electrode group 10 includes a plurality of positive electrodes 20, a plurality of negative electrodes 30, a plurality of separators 40 arranged between the positive electrodes 20 and the negative electrodes 30, and a plurality of glass mats 50 arranged between the positive electrodes 20 and the separators 40. and have
  • the positive electrodes 20 and negative electrodes 30 are alternately arranged with separators 40 and glass mats 50 interposed therebetween.
  • the negative electrode 30 is accommodated in the internal space of the separator 40 which is a bag-shaped separator.
  • the negative electrode 30 has one side 30 a and the other side 30 b , and the one side 30 a and the other side 30 b are covered with the separator 40 .
  • the separator 40 has an opening (opening on the front side of the paper surface) for accommodating the negative electrode 30 .
  • the separator 40 has an inner surface 42 on the negative electrode 30 side and an outer surface 44 on the positive electrode 20 side.
  • the inner surface 42 has a region 42 a facing the active material region of the negative electrode 30 and a region 42 b not facing the active material region of the negative electrode 30 .
  • a plurality of ribs 46 are arranged on the inner surface 42 of the separator 40, and the ribs 46 are arranged in the regions 42a and 42b, respectively.
  • the ribs 46 extend in the opening direction of the separator 40 (perpendicular to the paper surface), and extend from one end to the other end of the inner surface 42 of the separator 40 in a direction orthogonal to the opening direction and substantially parallel to the inner surface 42 of the separator 40. are spaced apart from each other.
  • No ribs are arranged on the outer surface 44 , and the outer surface 44 is in close contact with the glass mat 50 .
  • the glass mat 50 covers the entire active material region of the positive electrode 20 .
  • the lead-acid battery 100a shown in FIG. 2 differs from the lead-acid battery 100 in that the electrode group 10 does not include the glass mat 50. Therefore, the outer surface 44 of the separator 40 is in close contact with the positive electrode 20 in the lead-acid battery 100a.
  • a lead-acid battery 100 b shown in FIG. 3 differs from the lead-acid battery 100 in that the separator 40 does not have ribs 46 . Therefore, the inner surface 42 of the separator 40 is in close contact with the negative electrode 30 in the lead-acid battery 100b.
  • the content of the oil component in the separator 40 exceeds 0% by mass and is 12% by mass or less.
  • Such lead-acid batteries 100, 100a, and 100b can obtain excellent charge acceptance.
  • the automobile, electric vehicle, or power supply device includes the lead-acid battery according to this embodiment.
  • Electric vehicles include electric forklifts, golf carts, and the like.
  • Examples of the power supply include a UPS (Uninterruptible Power Supply), a power supply for disaster prevention (emergency) radio, a power supply for telephones, and the like.
  • UPS Uninterruptible Power Supply
  • a lead-acid battery for an automobile, an electric vehicle or a power supply is provided.
  • Lead powder was used as a raw material for the negative electrode active material. 1% by mass of barium sulfate particles, 0.2% by mass of additive A or additive B shown in Tables 1 and 2, 0.1% by mass of reinforcing short fibers (acrylic fibers), carbon material (oil furnace black ) was mixed with lead powder and then dry mixed (the amount of each component is based on the total weight of the raw material (lead powder) of the negative electrode active material).
  • Additive A was sodium ligninsulfonate (manufactured by Nippon Paper Industries Co., Ltd., trade name "Vanirex N”), and additive B was a bisphenol resin (manufactured by Nippon Paper Industries Co., Ltd., trade name "Bisperz P215").
  • kneading was carried out after adding water.
  • dilute sulfuric acid specifically gravity: 1.28 was added little by little and kneaded to prepare a negative electrode material paste.
  • This negative electrode material paste was filled in a grid (current collector) produced by expanding a rolled sheet made of a lead alloy.
  • the lattice filled with the negative electrode material paste was aged for 24 hours in an atmosphere of 50° C. and 98% humidity. After that, the negative electrode material paste was dried to produce an unformed negative electrode plate including the negative electrode material.
  • the length of the bag-shaped separator in the longitudinal direction of the rib was 122 mm
  • the length of the bag-shaped separator in the direction orthogonal to the longitudinal direction of the rib was 152 mm
  • the thickness T of the base portion of the sheet-like material was 0.2 mm.
  • the rib height H was 0.15 mm and the rib spacing was 1 mm.
  • the amount of oil (content of oil components), ash content, and porosity in the bag-shaped separator were measured by the following procedure. Tables 1 and 2 show the measurement results.
  • the amount of oil As the amount of oil, the amount of change in mass when the sample was immersed in acetone (25°C) was obtained. Specifically, first, the mass of the sample before immersion was measured. Next, acetone was poured into the beaker containing the sample and left for 18 hours while being slowly stirred. After air-drying, the mass of the sample was measured. The mass of the sample before and after immersion was determined as the amount of oil.
  • the amount of change in mass when the sample was heated at a high temperature was obtained. Specifically, first, after drying the sample, the mass of the sample was measured. Next, the crucible containing the sample was heated for 3 hours in a firing furnace maintained at a temperature of 600°C. After that, the crucible containing the sample was allowed to cool in a desiccator, and then the mass of the sample was measured. The mass of the sample before and after heating was determined as the ash content.
  • the porosity was measured using the product name "Autopore IV9520” manufactured by Shimadzu Corporation.
  • a glass mat containing acrylic resin was prepared.
  • the size of the glass mat was 121 mm ⁇ 150 mm.
  • a negative electrode member was obtained by housing an unformed negative electrode plate in a bag-like separator.
  • the ribs were arranged on the inner surface of the bag-shaped separator in a region facing the active material region of the negative electrode plate and a region not facing the active material region of the negative electrode plate.
  • seven unformed positive electrode plates and eight negative electrode members were alternately laminated such that a glass mat was interposed between the positive electrode plates and the negative electrode members.
  • the tabs of the electrode plates of the same polarity were welded together by a cast-on-strap (COS) method to produce an electrode plate group.
  • COS cast-on-strap
  • An unformed 2V single cell battery (equivalent to a D26 size single cell defined in JIS D 5301) was assembled by inserting the electrode plate group into an 80D26 battery case and then welding the lid. After that, an electrolytic solution (sulfuric acid solution) was injected into this battery, and chemical formation was performed at a constant current of 16 A for 18 hours at 40° C. to obtain a lead-acid battery.
  • Table 1 shows the specific gravity of the electrolytic solution after chemical conversion. The specific gravity of the electrolytic solution was measured with a product name "Portable Density Density Meter DA-130N" manufactured by Kyoto Electronics Industry Co., Ltd.
  • Battery B A lead-acid battery was obtained in the same manner as Battery A, except that the number of unformed positive plates was changed to eight and an unformed 12V battery (equivalent to D26 size specified in JIS D 5301) was assembled.
  • Table 2 shows the specific gravity of the electrolytic solution (sulfuric acid solution) after anodization.
  • Electrode group 20... Positive electrode, 30... Negative electrode, 30a... One side, 30b... Other side, 40... Separator, 42... Inner surface, 42a, 42b... Area, 44... Outer surface, 50... Glass mat, 100, 100a, 100b... Lead-acid battery.

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Abstract

Ce groupe d'électrodes (10) pour une batterie de stockage au plomb comprend : des électrodes positives (20) ; des électrodes négatives (30) ; et des séparateurs (40) disposés entre les électrodes positives (20) et les électrodes négatives (30). Les séparateurs (40) sont des séparateurs en forme de sac qui reçoivent les électrodes négatives (30). Des nervures (46) sont disposées sur les surfaces internes (42) des séparateurs (40). Les nervures (46) sont disposées dans des régions (42a) qui sont dans les surfaces internes (42) et qui font face à des régions de matériau actif des électrodes négatives (30) et dans des régions (42b) qui sont dans les surfaces internes (42) et qui ne font pas face aux régions de matériau actif des électrodes négatives (30). La quantité contenue de constituants à base d'huile dans les séparateurs (40) est supérieure à 0 % en masse mais pas supérieure à 12 % en masse.
PCT/JP2021/010697 2021-03-16 2021-03-16 Groupe d'électrodes et batterie de stockage au plomb WO2022195736A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1050337A (ja) * 1996-07-31 1998-02-20 Matsushita Electric Ind Co Ltd 密閉形鉛蓄電池
JP2002519819A (ja) * 1998-06-23 2002-07-02 ダラミック、インク 密閉型鉛蓄電池用隔離板
JP2006114313A (ja) * 2004-10-14 2006-04-27 Matsushita Electric Ind Co Ltd 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
WO2020208909A1 (fr) * 2019-04-08 2020-10-15 株式会社Ｇｓユアサ Séparateur pour batterie de stockage au plomb de type liquide et batterie de stockage au plomb de type liquide
JP2020533741A (ja) * 2017-09-08 2020-11-19 ダラミック エルエルシー 炭素を組み込んでいる改良された鉛蓄電池セパレータ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1050337A (ja) * 1996-07-31 1998-02-20 Matsushita Electric Ind Co Ltd 密閉形鉛蓄電池
JP2002519819A (ja) * 1998-06-23 2002-07-02 ダラミック、インク 密閉型鉛蓄電池用隔離板
JP2006114313A (ja) * 2004-10-14 2006-04-27 Matsushita Electric Ind Co Ltd 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
JP2020533741A (ja) * 2017-09-08 2020-11-19 ダラミック エルエルシー 炭素を組み込んでいる改良された鉛蓄電池セパレータ
WO2020208909A1 (fr) * 2019-04-08 2020-10-15 株式会社Ｇｓユアサ Séparateur pour batterie de stockage au plomb de type liquide et batterie de stockage au plomb de type liquide

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