WO2020100213A1 - Plaque d'électrode, corps de réseau cristallin, et accumulateur au plomb - Google Patents

Plaque d'électrode, corps de réseau cristallin, et accumulateur au plomb Download PDF

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Publication number
WO2020100213A1
WO2020100213A1 PCT/JP2018/041968 JP2018041968W WO2020100213A1 WO 2020100213 A1 WO2020100213 A1 WO 2020100213A1 JP 2018041968 W JP2018041968 W JP 2018041968W WO 2020100213 A1 WO2020100213 A1 WO 2020100213A1
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WIPO (PCT)
Prior art keywords
electrode plate
active material
lattice
lead storage
height
Prior art date
Application number
PCT/JP2018/041968
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English (en)
Japanese (ja)
Inventor
平野　貴之
Original Assignee
日立化成株式会社
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Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to PCT/JP2018/041968 priority Critical patent/WO2020100213A1/fr
Priority to JP2020556497A priority patent/JP7220371B2/ja
Publication of WO2020100213A1 publication Critical patent/WO2020100213A1/fr
Priority to JP2023005693A priority patent/JP2023033539A/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • 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 an electrode plate, a grid and a lead storage battery.
  • Lead-acid batteries are widely used for industrial purposes, such as automobile batteries, backup power sources, and main power sources for electric vehicles.
  • an idling stop system vehicle hereinafter referred to as "ISS vehicle" equipped with a system that stops the engine during power generation control, signal waiting, etc. has been actively studied for the purpose of carbon dioxide emission regulation measures, fuel consumption reduction, etc.
  • lead-acid batteries are required to have characteristics suitable for ISS vehicle applications.
  • PSOC Partial State Of Charge
  • Patent Document 1 a lead-acid battery provided with a positive electrode plate having an active material specific surface area of 6 m 2 / g or more and a negative electrode plate to which a predetermined material is added is used under PSOC. It is disclosed to improve the life (cycle performance).
  • Another object of the present invention is to provide a grid body and an electrode plate that can provide a lead acid battery having excellent cycle performance.
  • the present inventors have found that when the length of the electrode plate in the vertical direction (the height direction of the lead storage battery) when the lead storage battery is installed horizontally is below a specific value, the cycle performance is The inventors have found that it is remarkably improved and have completed the present invention.
  • One aspect of the present invention is an electrode plate for a lead storage battery, which includes a lattice body having a lattice portion and an ear portion provided on one end side of the lattice portion, and an electrode active material held by the lattice body. And an active material filling portion, wherein the length of the active material filling portion in the height direction of the lead storage battery is 100 mm or less.
  • the width of the active material filled portion may be 136 mm or more. In this case, cycle performance tends to be further improved.
  • the grid may be formed of an alloy containing lead, tin and calcium.
  • a lattice body using this alloy (Pb-Sn-Ca-based alloy) is useful for further improving cycle performance. Further, since it is possible to improve strength, reduce self-discharge, and improve storage characteristics, it is particularly preferably used as a maintenance-free type grid (collector) for a lead storage battery.
  • the ears of the lattice may be located closer to the center of the lattice.
  • cycle performance tends to be further improved. Since the ears are located closer to the center of the lattice, the distance from the ears to the furthest active material is shortened, and the utilization rate of the electrode active material is more likely to be uniformized within the electrode plate surface. It is estimated that the cycle performance will be further improved.
  • the ratio of the height of the active material filled portion to the width of the active material filled portion may be 0.64 to 0.74. In this case, cycle performance tends to be further improved.
  • the electrode plate on the side surface may be a positive electrode plate (electrode plate for positive electrode). If the electrode plate on the side surface is used for the positive electrode plate, the effect of improving the cycle performance due to the suppression of the formation of mud can be remarkably obtained because the active material is likely to be mud-like in the positive electrode.
  • the grid body may be an expanded grid body.
  • the active material is likely to fall off. Therefore, when the lattice is the expanded lattice, the effect of the present invention tends to be more remarkable.
  • One aspect of the present invention is a grid body used for an electrode plate of a lead storage battery, comprising a grid portion and an ear portion projecting from one end side of the grid portion, and the grid portion in a height direction of the lead storage battery. Relates to a lattice body having a length of 100 mm or less.
  • the lattice part in the lattice body on the above side is a portion filled with the electrode active material. Therefore, when the grid body of the present invention is used for an electrode plate of a lead storage battery, the length of the active material filled portion in the height direction of the lead storage battery can be easily set to 100 mm or less. Therefore, according to the grid body of the present invention, it is possible to easily obtain a lead storage battery having excellent cycle performance and an electrode plate used for the lead storage battery.
  • the width of the lattice portion may be 136 mm or more. In this case, a sufficient amount of the electrode active material can be filled, and as a result, cycle performance can be further improved.
  • the grid on the above side may be formed of an alloy containing lead, tin and calcium.
  • the cycle performance tends to be further improved, and strength can be improved, self-discharge can be reduced, and storage characteristics can be improved.
  • the ears of the lattice on the side surface may be located closer to the center of the lattice. In this case, cycle performance tends to be further improved.
  • the ratio of the height of the lattice portion to the width of the lattice portion may be 0.64 to 0.74. In this case, cycle performance tends to be further improved.
  • the grid on the side surface may be a grid used for the positive electrode plate of the lead storage battery. Since the active material is likely to be mud-like in the positive electrode, when the lattice on the side surface is used in the positive electrode plate, the effect of suppressing the mud-like improvement in cycle performance is remarkably obtained.
  • the lattice on the above-mentioned side may be an expanded lattice.
  • the active material is likely to fall off. Therefore, when the lattice is the expanded lattice, the effect of the present invention tends to be more remarkable.
  • One aspect of the present invention relates to a lead storage battery including an electrode plate including the above-described electrode plate or the above-described grid, and an active material filling portion made of an electrode active material held by the grid.
  • the present invention it is possible to provide a lead storage battery having excellent cycle performance. Further, according to the present invention, it is possible to provide a grid body and an electrode plate that can provide a lead storage battery having excellent cycle performance.
  • FIG. 1 is a perspective view showing the overall configuration and internal structure of a lead storage battery according to an embodiment.
  • FIG. 2 is a perspective view showing an electrode group included in the lead storage battery of FIG.
  • FIG. 3 is a front view showing an electrode plate included in the electrode group of FIG.
  • FIG. 4 is a front view showing a grid body (current collector) included in the electrode plate of FIG.
  • FIG. 5 is a cross-sectional view taken along line VV of FIG. 1, showing an electrode group and its internal structure.
  • FIG. 6 is a photograph showing the electrode plates after the cycle test of Examples and Comparative Examples and their schematic diagrams.
  • the vertical direction when the lead storage battery is installed horizontally is defined as the height direction of the lead storage battery.
  • the vertical direction when housed in a horizontally installed lead storage battery is defined as the height direction of the electrode plate (the height direction of the grid body).
  • the numerical range indicated by using "to” indicates the range including the numerical values before and after "to” as the minimum value and the maximum value, respectively.
  • FIG. 1 is a perspective view showing the overall configuration and internal structure of a lead storage battery according to an embodiment.
  • the lead storage battery 1 includes a battery case 2 having an open top surface and a lid 3 that closes the opening of the battery case 2.
  • the battery case 2 and the lid 3 are made of polypropylene, for example.
  • the lid 3 is provided with a negative electrode terminal 4, a positive electrode terminal 5, and a liquid port plug 6 that closes a liquid injection port provided in the lid 3.
  • the inside of the battery case 2 is divided by five partition walls, and six cell chambers are formed inside the battery case 2, and the electrode group 7 and A negative pole 8 for connecting the electrode group 7 to the negative terminal 4, a positive pole (not shown) for connecting the electrode group 7 to the positive terminal 5, and an electrolytic solution such as dilute sulfuric acid are stored.
  • the electrolytic solution may further contain aluminum ions in addition to dilute sulfuric acid.
  • concentration of aluminum ions in the electrolytic solution may be, for example, 0.005 mol / L or more and 0.4 mol / L or less.
  • FIG. 2 is a perspective view showing the electrode group 7.
  • the electrode group 7 is arranged between the negative electrode plate (plate-shaped negative electrode) 9 and the positive electrode plate (plate-shaped positive electrode) 10, which are electrode plates, and between the negative electrode plate 9 and the positive electrode plate 10.
  • the negative electrode plate 9 includes a negative electrode current collector (lattice body) 12 and a negative electrode active material filling portion (active material filling portion) 13 made of a negative electrode active material (electrode active material) held by the negative electrode current collector 12. I have it.
  • the positive electrode plate 10 includes a positive electrode current collector (lattice body) 14 and a positive electrode active material filling portion (active material filling portion) 15 made of a positive electrode active material (electrode active material) held by the positive electrode current collector 14. I have it.
  • the negative electrode after formation and the negative electrode current collector are defined as “negative electrode active material”
  • the positive electrode after formation and the positive electrode current collector are defined as “positive electrode active material”.
  • the electrode group 7 has a structure in which a plurality of negative electrode plates 9 and positive electrode plates 10 are alternately laminated with separators 11 in a direction substantially parallel to the opening surface of the battery case 2. That is, the negative electrode plate 9 and the positive electrode plate 10 are arranged such that their main surfaces extend in the direction perpendicular to the opening surface of the battery case 2.
  • each negative electrode current collector 12 of the plurality of negative electrode plates 9 and each positive electrode current collector 14 of the plurality of positive electrode plates 10 have a negative electrode ear portion 12a and a positive electrode ear portion 14a protruding toward the opening side, respectively. is doing.
  • the ears are typically provided so as to project in the vertical direction in a state where the electrode group 7 is housed in a horizontally installed lead storage battery. Therefore, typically, the direction in which the ears protrude and the height direction of the lead storage battery coincide with each other.
  • the negative electrode ears 12 a of the negative electrode current collectors 12 of the plurality of negative electrode plates 9 are collectively welded by the negative electrode strap 16.
  • the positive electrode ear portions 14 a of the positive electrode current collectors 14 of the plurality of positive electrode plates 10 are collectively welded by the positive electrode strap 17.
  • the negative electrode strap 16 is connected to the negative electrode terminal 4 via the negative electrode column 8.
  • the positive electrode strap 17 is connected to the positive electrode terminal 5 via the positive electrode column.
  • the separator 11 is formed in a bag shape and houses the negative electrode plate 9.
  • the separator 11 is made of, for example, polyethylene (PE), polypropylene (PP) or the like.
  • the separator 11 may be a woven fabric, a non-woven fabric, a porous film, or the like formed of these materials, to which inorganic particles such as SiO 2 or Al 2 O 3 are attached.
  • FIG. 3 is a front view showing the electrode plate 20 (negative electrode plate 9, positive electrode plate 10).
  • the active material filling portion 21 (the negative electrode active material filling portion 13 and the positive electrode active material filling portion 15) is formed so as to spread in the height direction and the width direction of the electrode plate 20.
  • the active material filling portion 21 is exposed on both main surfaces of the electrode plate 20, and has a substantially rectangular outer shape when the electrode plate 20 is viewed from the front.
  • the height direction of the electrode plate 20 is the direction that is the vertical direction when the electrode plate 20 is housed in a horizontally installed lead storage battery. Therefore, typically, the direction in which the ears project is the height direction of the electrode plate 20. Further, the width direction of the electrode plate 20 is a direction orthogonal to the height direction of the electrode plate 20 among the directions along the main surface of the electrode plate 20.
  • the height H1 of the active material filling portion 21 is 100 mm or less.
  • the height H1 of the active material filling portion 21 is the length of the active material filling portion 21 in the height direction of the lead storage battery 1, and is typically the length in the direction in which the ears project. Since the height H1 of the active material filling portion 21 is 100 mm or less, the lead storage battery 1 exhibits excellent cycle performance.
  • the height H1 may be 99 mm or less, 98 mm or less, or 97 mm or less from the viewpoint of obtaining more excellent cycle performance.
  • the height H1 may be 94 mm or more or 95 mm or more from the viewpoint of obtaining more excellent cycle performance.
  • the upper limit value and the lower limit value described above may be arbitrarily combined. That is, the height H1 may be 94-100 mm, 95-100 mm, 94-99 mm, 95-99 mm, 94-98 mm, 95-98 mm, 94-97 mm or 95-97 mm.
  • the upper limit value and the lower limit value described individually can be arbitrarily combined.
  • the height H1 is obtained, for example, by measuring the length from the upper end (end on the ear side) to the lower end (end on the side opposite to the ear) of the active material filling portion 21.
  • the maximum value of the height H1 may be 100 mm or less. In the present embodiment, it is preferable that the height H1 be within the above range at all measurement points.
  • the width W1 of the active material filled portion 21 (the length of the active material filled portion 21 in the width direction of the electrode plate 20) W1 is preferably 136 mm or more from the viewpoint of obtaining better cycle performance. From the same viewpoint, the width W1 may be 140 mm or more or 142 mm or more. The upper limit of the width W1 is not particularly limited, but may be, for example, 145 mm or less, 144 mm or less, or 143 mm or less.
  • the width W1 is obtained, for example, by measuring the length of the active material filling portion 21 from one end to the other end in the width direction.
  • the minimum value of the width W1 is preferably 136 mm or more. In the present embodiment, it is preferable that the width W1 be within the above range at all measurement points.
  • both the active material filling portion of the positive electrode plate and the active material filling portion of the negative electrode plate satisfy the above range.
  • the width of the active material filled portion of the positive electrode plate and the width of the active material filled portion of the negative electrode plate may be different from each other.
  • the width of the active material filled portion of the electrode plate accommodated in the bag-shaped separator may be smaller than the width of the active material filled portion of the electrode plate not accommodated in the bag-shaped separator.
  • the ratio of the height H1 of the active material filled portion 21 to the width W1 of the active material filled portion 21 is preferably 0.74 or less from the viewpoint of obtaining more excellent cycle performance. , 0.71 or less, or 0.70 or less.
  • the aspect ratio (H1 / W1) is preferably 0.64 or more, and may be 0.65 or more or 0.66 or more, from the viewpoint of obtaining more excellent cycle performance.
  • the height H1 and the width W1 on both main surfaces are within the above ranges.
  • the thickness (length in the stacking direction) D1 of the active material filled portion 21 may be, for example, 1.0 to 1.9 mm.
  • the range of the thickness D1 of the active material filled portion 21 may be different between the positive electrode plate and the negative electrode plate.
  • the thickness D1 of the active material filled portion 21 of the positive electrode plate may be 1.4 mm or more or 1.5 mm or more, and may be 1.9 mm or less or 1.8 mm or less.
  • the thickness D1 of the active material filled portion 21 of the negative electrode plate may be 1.0 mm or more, 1.1 mm or more, or 1.2 mm or more, 1.8 mm or less, 1.7 mm or less, 1.6 mm or less, or It may be 1.4 mm or less.
  • the electrode active material forming the active material filling portion is a negative electrode active material or a positive electrode active material.
  • the negative electrode active material contains Pb as a Pb component, and may further contain a Pb component other than Pb (for example, PbSO 4 ) and an additive (negative electrode additive), if necessary.
  • the positive electrode active material contains PbO 2 as a Pb component, and may further contain a Pb component other than PbO 2 (for example, PbSO 4 ) and an additive (positive electrode additive), if necessary.
  • Examples of the negative electrode additive include a resin having a sulfo group and / or a sulfonate group, barium sulfate, a carbon material (excluding carbon fiber), and reinforcing short fibers (acrylic fiber, polyethylene fiber, polypropylene fiber, polyethylene terephthalate fiber, Carbon fiber).
  • the resin having a sulfo group and / or a sulfonate group is a lignin sulfonic acid, a lignin sulfonate, and a condensate of a phenol, an aminoaryl sulfonic acid, and formaldehyde (for example, bisphenol, aminobenzene sulfonic acid, and formaldehyde). It may be at least one selected from the group consisting of condensates).
  • the carbon material include carbon black and graphite. Examples of carbon black include furnace black, channel black, acetylene black, thermal black and Ketjen black.
  • positive electrode additives include carbon materials and reinforcing short fibers (acrylic fibers, polyethylene fibers, polypropylene fibers, polyethylene terephthalate fibers, etc.).
  • the carbon material include carbon black and graphite.
  • Examples of carbon black include furnace black, channel black, acetylene black, thermal black and Ketjen black.
  • FIG. 4 is a front view showing the grid 30 (negative electrode current collector 12, positive electrode current collector 14).
  • the lattice body 30 is an expanded lattice body manufactured by the expanding method.
  • the effect of the present invention tends to be more remarkably obtained.
  • the height of the lattice body can be easily adjusted, and the manufacturing cost can be reduced.
  • the lattice body 30 includes a lattice portion 31 and an ear portion 32 provided so as to project from one end side of the lattice portion 31.
  • An upper frame portion 33 is provided above the lattice portion 31, and a lower frame portion 34 is provided below the lattice portion 31.
  • the ear portion 32 projects upward from a part of the upper frame portion 33 (on the side opposite to the lattice portion 31 and the lower frame portion 34) substantially perpendicular to the longitudinal direction of the upper frame portion 33.
  • the ear portion 32 is located closer to the center of the lattice portion 31 when viewed from the front of the lattice body 30. “Toward the center” means that the shortest distance from the center in the width direction of the lattice portion 31 is less than 1 ⁇ 4 of the width W of the lattice portion 31.
  • the lattice portion 31 is a portion filled with the active material, and has lattice bones 31a arranged in a lattice shape and openings 31b defined by the lattice bones 31a.
  • the lattice portion 31 has a substantially rectangular (eg, rectangular or square) outer shape when viewed from the front.
  • the height H of the lattice 30 may be, for example, 104 mm or less, 103 mm or less, 102 mm or less, or 101 mm or less, and may be 98 mm or more or 99 mm or more.
  • the height of the lattice 30 is measured from the lower end of the lower frame portion 34 (the end portion on the side opposite to the ear portion) to the upper end portion of the upper frame portion 33 (the end portion on the ear portion side). Required by that.
  • the height direction of the grid body 30 matches the height direction of the electrode plate 20. Therefore, the height of the grid body 30 may be called the length of the grid body 30 in the height direction of the lead storage battery 1, and is typically the length in the direction in which the ears 32 project. Further, the height of the grid body 30 and the height of the electrode plate 20 are the same. That is, the height of the electrode plate 20 may be in the same range as the height H of the grid body 30 described above.
  • the maximum value of the height H is 104 mm or less. In the present embodiment, it is preferable that the height H be within the above range at all measurement points.
  • the height H2 of the lattice portion 31 may be 100 mm or less, 99 mm or less, 98 mm or less, or 97 mm or less, from the viewpoint of easily obtaining the active material filling portion 21 having the height H1 as described above, 94 mm or more, or It may be 95 mm or more. That is, the height H2 may be 94-100 mm, 95-100 mm, 94-99 mm, 95-99 mm, 94-98 mm, 95-98 mm, 94-97 mm or 95-97 mm.
  • the height H2 is the height of an area defined by an imaginary line connecting the ends of the lattice bones 31a (for example, from the upper end (end on the ear side) to the lower end (end on the side opposite to the ear). ) Up to)) is measured.
  • the maximum value of the height H2 is 100 mm or less. In the present embodiment, it is preferable that the height H2 be within the above range at all measurement points.
  • the width W2 of the lattice portion 31 may be 136 mm or more, 140 mm or more or 142 mm or more, from the viewpoint of easily obtaining the active material-filled portion having the width W1 as described above, and may be 145 mm or less, 144 mm or less or 143 mm or less. You can The width W2 of the lattice portion 31 is the length of the lattice portion in the width direction of the lattice body 30 (the direction along the main surface of the lattice body 30 which is orthogonal to the height direction of the lattice body 30). ..
  • the width W2 is obtained by measuring the width of a region defined by an imaginary line connecting the ends of the lattice bones 31a (for example, the length from one end to the other end of the lattice portion 31 in the width direction).
  • the minimum value of the width W2 is preferably 136 mm or more. In the present embodiment, it is preferable that the width W2 be within the above range at all measurement points.
  • the ratio of the height H2 of the lattice portion 31 to the width W2 of the lattice portion 31 is preferably 0.74 or less and 0.71 from the viewpoint of obtaining more excellent cycle performance. It may be less than or equal to 0.70.
  • the aspect ratio (H2 / W2) is preferably 0.64 or more, and may be 0.65 or more or 0.66 or more, from the viewpoint of obtaining more excellent cycle performance.
  • the height H2 and the width W2 on the both main surfaces are within the above ranges.
  • the thickness (length in the stacking direction) D2 of the lattice portion 31 is, for example, 0.7 to 1.6 mm from the viewpoint of easily obtaining the active material filled portion 21 having the thickness D1 as described above. Good.
  • the range of the thickness D2 of the grid portion 31 may be different between the positive electrode grid body (positive electrode current collector) and the negative electrode grid body (negative electrode current collector).
  • the thickness D2 of the grid portion 31 of the positive electrode current collector may be 1.1 mm or more or 1.2 mm or more, and may be 1.6 mm or less or 1.4 mm or less.
  • the thickness D2 of the grid portion 31 of the negative electrode current collector may be 0.7 mm or more, 0.8 mm or more, or 0.9 mm or more, and 1.3 mm or less, 1.2 mm or less, or 1.1 mm or less. You can The thickness is, for example, the thickness of the intersection of the lattice portions.
  • the grid body 30 (the negative electrode current collector 12 and the positive electrode current collector 14) is made of, for example, a lead alloy.
  • the lead alloy may be an alloy containing tin, calcium, antimony, selenium, silver, bismuth and the like in addition to lead, and specifically, for example, an alloy containing lead, tin and calcium (Pb-Sn). -Ca-based alloy).
  • the lattice body 30 described above includes the size (height, width and thickness) of the sheet (base material) for forming the lattice body 30, the force applied when the sheet is stretched by the expanding method, the production of the expanded lattice body. It can be manufactured by adjusting the number of slits and the like.
  • FIG. 5 is a cross-sectional view taken along the line VV of FIG. 1, showing an electrode group and its internal structure.
  • the electrode in each cell chamber of the battery case 2, the electrode is set so that the height H3 from the bottom wall 2a of the cell chamber to the upper end (end portion on the ear side) of the active material filling portion 21 is 101 mm or less.
  • the plate 20 (electrode group 7) is preferably housed in the cell chamber.
  • the height H3 may be 100 mm or less, 99 mm or less, or 98 mm or less.
  • the height H3 may be 95 mm or more or 96 mm or more from the viewpoint of obtaining more excellent cycle performance.
  • the lead storage battery 1 described above is preferably used as a lead storage battery for idling stop system vehicles or micro hybrid vehicles. That is, one embodiment of the present invention is an application of the above-described lead storage battery 1 to an idling stop system vehicle or a micro hybrid vehicle.
  • the lead storage battery 1 is manufactured, for example, by a manufacturing method including an electrode plate manufacturing process for obtaining an electrode plate (a negative electrode plate and a positive electrode plate) and an assembly process for assembling the constituent members including the electrode plate to obtain the lead storage battery 1.
  • the electrode plate manufacturing process for example, after the grid material 30 (the negative electrode current collector 12 and the positive electrode current collector 14) holds the active material paste (negative electrode active material paste, positive electrode active material paste), aging and drying Thus, an electrode plate (negative electrode plate, positive electrode plate) including an unformed electrode active material (negative electrode active material, positive electrode active material) is obtained.
  • the electrode plate 20 the negative electrode plate 9 and the positive electrode plate 10) of the embodiment can be easily obtained.
  • the active material paste (negative electrode active material paste, positive electrode active material paste) contains, for example, lead powder, an additive, a solvent (eg water or an organic solvent) and sulfuric acid (eg dilute sulfuric acid).
  • the active material paste is obtained, for example, by mixing lead powder and an additive to obtain a mixture, and then kneading the mixture with a solvent and sulfuric acid.
  • the lead powder for example, a lead powder manufactured by a ball mill type lead powder manufacturing machine or a Burton pot type lead powder manufacturing machine (in the ball mill type lead powder manufacturing machine, a mixture of a powder of the main component PbO and scale-like metallic lead). ) Is mentioned.
  • the grid material 30 holds the active material paste, it is desirable to fill the entire grid portion 31 of the grid material 30 with the active material paste, but there is a portion of the grid portion 31 where the active material paste is not filled. May exist. In this case, only the portion filled with the active material paste forms the active material filling portion 21.
  • Aging may be carried out in an atmosphere having a temperature of 35 to 85 ° C. and a humidity of 50 to 98 RH% for 15 to 60 hours.
  • the drying may be performed at a temperature of 45 to 80 ° C. for 15 to 30 hours.
  • the obtained unformed electrode plates (unformed negative electrode plate and unformed positive electrode plate) are laminated via the separator 11, and the ears of the electrode plates of the same polarity are welded with straps.
  • an electrode group This electrode group is arranged in a battery case to produce an unformed lead storage battery.
  • dilute sulfuric acid is put into an unformed lead storage battery, and a direct current is passed to form a battery case.
  • the lead acid battery 1 is obtained by adjusting the specific gravity (20 ° C.) of the sulfuric acid after chemical conversion to an appropriate specific gravity of the electrolytic solution.
  • the specific gravity (20 ° C.) of sulfuric acid used for chemical conversion may be 1.15 to 1.25.
  • the specific gravity (20 ° C.) of sulfuric acid after chemical conversion is preferably 1.25 to 1.33, more preferably 1.26 to 1.30.
  • the chemical conversion conditions and the specific gravity of sulfuric acid can be adjusted according to the size of the electrode plate.
  • the chemical conversion treatment may be performed in the assembly process or the electrode plate manufacturing process (tank formation).
  • the lead storage battery 1 is a liquid lead storage battery, and is configured such that at least the entire electrode active material filled portion is immersed in the electrolyte solution (for example, the liquid surface of the electrolyte solution is the upper portion of the strap).
  • the lead acid battery may be a valve regulated lead acid battery, a sealed lead acid battery, or the like.
  • At least a part of the positive electrode plate included in the lead storage battery is the electrode plate 20, and it is more preferable that at least a part of the positive electrode plate and at least a part of the negative electrode plate are the electrode plate 20.
  • a part of the electrode plate included in the storage battery may be different from the electrode plate 20.
  • all the electrode plates (the negative electrode plate 9 and the positive electrode plate 10) may be the electrode plates 20 described above.
  • the negative electrode plate 9 is housed in the bag-shaped separator 11, but the positive electrode plate 10 may be housed in the bag-shaped separator 11.
  • the shape of the separator 11 may be a shape other than the bag shape (for example, a sheet shape).
  • the lattice body is an expanded lattice body, but the lattice body may be a lattice body manufactured by another manufacturing method.
  • the lattice body may be, for example, a punching lattice body manufactured by a punching method.
  • a rolled sheet made of a lead alloy was subjected to an expanding process to prepare positive electrode current collectors A and B and negative electrode current collectors A and B as a grid.
  • the height of the positive electrode current collector A was 116 mm, the height H2 of the lattice portion was 112 mm, the width W2 was 143 mm, and the thickness D2 was 1.5 mm. Further, the height of the negative electrode current collector A was 116 mm, the height H2 of the lattice portion was 112 mm, the width W2 was 142 mm, and the thickness D2 was 1.0 mm.
  • the height H of the positive electrode current collector B was 99.5 mm, the height H2 of the lattice portion was 95.5 mm, the width W2 was 143 mm, and the thickness D2 was 1.4 mm.
  • the height H of the negative electrode current collector B was 99.5 mm, the height H2 of the lattice portion was 95.5 mm, the width W2 was 142 mm, and the thickness D2 was 1.0 mm.
  • a battery case was prepared, which consisted of a box whose upper surface was open and whose interior was divided into six cell chambers by partition walls.
  • Electrode plate Lead powder was used as a raw material of the negative electrode active material.
  • After adding to the lead powder dry mixing was performed. Next, after adding water, the mixture was kneaded.
  • a negative electrode active material paste was prepared by kneading while adding dilute sulfuric acid having a specific gravity of 1.280 little by little.
  • the negative electrode current collector A obtained above was filled with the negative electrode active material paste, it was aged in an atmosphere of a temperature of 50 ° C. and a humidity of 98% for 24 hours. Then, it dried at the temperature of 50 degreeC for 16 hours, and produced the negative electrode plate which has a non-formed negative electrode active material.
  • the positive electrode current collector A obtained above was filled with the positive electrode active material paste, it was aged for 24 hours in an atmosphere of a temperature of 50 ° C. and a humidity of 98%. Then, it dried at temperature 50 degreeC for 16 hours, and produced the positive electrode plate which has a non-formed positive electrode active material.
  • the height H1 of the active material-filled portion (positive electrode active material-filled portion) of the positive electrode plate was 112 mm
  • the width W1 was 143 mm
  • the thickness D1 was 1.6 mm
  • the height H3 from the bottom wall to the upper end of the active material filled portion was 115 mm.
  • the height H1 of the active material filled portion of the negative electrode plate (negative electrode active material filled portion) is 112 mm
  • the width W1 is 142 mm
  • the thickness D1 is 1.2 mm
  • the active material from the bottom wall of the cell chamber is The height H3 to the upper end of the filling portion was 115 mm.
  • Example 1 Comparative Example except that the type of grid was changed, and that the number of electrode plates was changed so that the opposing area of the electrode plates was equivalent to that of Comparative Example 1 when compared in electrode plate group units.
  • a lead storage battery was prepared in the same manner as in 1. Specifically, instead of the positive electrode current collector A and the negative electrode current collector A, a positive electrode current collector B and a negative electrode current collector B are used, the number of positive electrode plates is 7, and the number of negative electrode plates is 8. did.
  • the height H1 of the active material filled portion (positive electrode active material filled portion) of the positive electrode plate was 95.5 mm
  • the width W1 was 143 mm
  • the thickness D1 was 1.5 mm.
  • the height H3 from the bottom wall of the cell chamber to the upper end of the active material filled portion was 96.3 mm.
  • the height H1 of the active material filled portion (negative electrode active material filled portion) of the negative electrode plate is 95.5 mm
  • the width W1 is 142 mm
  • the thickness D1 is 1.2 mm
  • the height H3 to the upper end of the active material filled portion was 96.3 mm.
  • a lead storage battery (charging capacity: 60 Ah, 20-hour rate current: 3 A) that had been charged was placed in a gas tank in which the bath temperature was set to 25 ° C ⁇ 2 ° C.
  • the following cycle units (a) to (c) were set as one cycle, and (a) to (c) were repeated in this order.
  • (A) Discharged at 15 A (corresponding to 5 times the 20-hour rate current) for 1 hour.
  • the discharge lower limit voltage was set to be higher than 10.0V.
  • B The battery was charged with a constant voltage of 14.8 V (a limiting current of 30 A (equivalent to 10 times the 20-hour rate current)) for 175 minutes.
  • C The battery was charged at 7.5 A (corresponding to 2.5 times the 20-hour rate current) for 5 minutes.
  • This test is a cycle test according to the EN standard. In this test, when the voltage of the lead storage battery fell below 10.5 V, it was determined that the life had reached the end, and the cycle characteristics were evaluated by comparing the number of cycles until the end of the life.
  • the number of cycles of the lead storage battery of Comparative Example 1 was 160, and the number of cycles of the lead storage battery of Example 1 was 220.
  • the electrode plate (positive electrode plate) was taken out from the lead storage battery after the cycle test, and the active material filling part was observed.
  • the electrode plate after the cycle test is shown in FIG. (A1) of FIG. 6 is a photograph showing the electrode plate of Comparative Example 1, and (b1) is a photograph showing the electrode plate of Example 1 (both photographs have the same scale).
  • (A2) and (b2) of FIG. 6 are schematic views of the photographs shown in (a1) and (b2), in which the electrode active material falling portion A, the mudified portion B, and the non-mud in the active material filled portion are shown. It is a figure which shows the shaped part (non-deteriorated part) C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne une plaque d'électrode (20) pour un accumulateur au plomb, comportant : un corps (30) de réseau cristallin équipé d'une partie de réseau cristallin (31) et d'une partie d'oreille (32) disposée de manière à faire saillie sur une face d'extrémité de la partie de réseau cristallin (31) ; et une partie remplie de matériau actif (21) comprenant un matériau actif d'électrode maintenu par le corps (30) de réseau cristallin. La longueur (H1) de la partie remplie de matériau actif (21) dans la direction de la hauteur de l'accumulateur au plomb est inférieure ou égale à 100 mm.
PCT/JP2018/041968 2018-11-13 2018-11-13 Plaque d'électrode, corps de réseau cristallin, et accumulateur au plomb WO2020100213A1 (fr)

Priority Applications (3)

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PCT/JP2018/041968 WO2020100213A1 (fr) 2018-11-13 2018-11-13 Plaque d'électrode, corps de réseau cristallin, et accumulateur au plomb
JP2020556497A JP7220371B2 (ja) 2018-11-13 2018-11-13 電極板、格子体及び鉛蓄電池
JP2023005693A JP2023033539A (ja) 2018-11-13 2023-01-18 格子体及び鉛蓄電池

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PCT/JP2018/041968 WO2020100213A1 (fr) 2018-11-13 2018-11-13 Plaque d'électrode, corps de réseau cristallin, et accumulateur au plomb

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56159065A (en) * 1980-05-13 1981-12-08 Yuasa Battery Co Ltd Grid for lead acid battery
JPS59219854A (ja) * 1983-05-27 1984-12-11 Shin Kobe Electric Mach Co Ltd 鉛蓄電池
JPH10162834A (ja) * 1996-11-28 1998-06-19 Japan Storage Battery Co Ltd 鉛蓄電池
JPH11339787A (ja) * 1998-05-27 1999-12-10 Matsushita Electric Ind Co Ltd 鉛蓄電池とその製造法
JP2002042857A (ja) * 2000-07-28 2002-02-08 Matsushita Electric Ind Co Ltd 密閉形鉛蓄電池
JP2002358955A (ja) * 2001-06-01 2002-12-13 Japan Storage Battery Co Ltd 円筒形鉛蓄電池
JP2003163008A (ja) * 2001-11-26 2003-06-06 Japan Storage Battery Co Ltd 鉛蓄電池
JP2004273400A (ja) * 2003-03-12 2004-09-30 Matsushita Electric Ind Co Ltd 蓄電池用格子体とそれを用いた鉛蓄電池
JP2007305370A (ja) * 2006-05-10 2007-11-22 Matsushita Electric Ind Co Ltd 鉛蓄電池
WO2017159299A1 (fr) * 2016-03-15 2017-09-21 株式会社Ｇｓユアサ Accumulateur au plomb

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56159065A (en) * 1980-05-13 1981-12-08 Yuasa Battery Co Ltd Grid for lead acid battery
JPS59219854A (ja) * 1983-05-27 1984-12-11 Shin Kobe Electric Mach Co Ltd 鉛蓄電池
JPH10162834A (ja) * 1996-11-28 1998-06-19 Japan Storage Battery Co Ltd 鉛蓄電池
JPH11339787A (ja) * 1998-05-27 1999-12-10 Matsushita Electric Ind Co Ltd 鉛蓄電池とその製造法
JP2002042857A (ja) * 2000-07-28 2002-02-08 Matsushita Electric Ind Co Ltd 密閉形鉛蓄電池
JP2002358955A (ja) * 2001-06-01 2002-12-13 Japan Storage Battery Co Ltd 円筒形鉛蓄電池
JP2003163008A (ja) * 2001-11-26 2003-06-06 Japan Storage Battery Co Ltd 鉛蓄電池
JP2004273400A (ja) * 2003-03-12 2004-09-30 Matsushita Electric Ind Co Ltd 蓄電池用格子体とそれを用いた鉛蓄電池
JP2007305370A (ja) * 2006-05-10 2007-11-22 Matsushita Electric Ind Co Ltd 鉛蓄電池
WO2017159299A1 (fr) * 2016-03-15 2017-09-21 株式会社Ｇｓユアサ Accumulateur au plomb

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JP2023033539A (ja) 2023-03-10
JP7220371B2 (ja) 2023-02-10

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