CN107026271B - Positive electrode plate for lead storage battery, and method for manufacturing positive electrode plate for lead storage battery - Google Patents

Positive electrode plate for lead storage battery, and method for manufacturing positive electrode plate for lead storage battery Download PDF

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Publication number
CN107026271B
CN107026271B CN201710061705.8A CN201710061705A CN107026271B CN 107026271 B CN107026271 B CN 107026271B CN 201710061705 A CN201710061705 A CN 201710061705A CN 107026271 B CN107026271 B CN 107026271B
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positive electrode
grid
electrode plate
lead
density
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CN107026271A (en
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小渕晋
藤田晃平
枦晃法
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GS Yuasa International Ltd
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GS Yuasa International Ltd
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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
    • H01M4/64—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
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • 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
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in 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
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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
    • H01M4/82—Multi-step processes for manufacturing carriers 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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

Abstract

The invention provides a positive plate for a lead storage battery, which can improve the service life performance and the initial capacity of the lead storage battery. A positive electrode plate for a lead-acid battery, comprising a punched grid (10) having a grid frame and a positive electrode material (20), wherein corners (15C) of a cross section of the grid frame perpendicular to an extending direction of the punched grid (10) are deformed, and the positive electrode material (20) has a density of 4.1[ g/cm ] when formed3]The above.

Description

Positive electrode plate for lead storage battery, and method for manufacturing positive electrode plate for lead storage battery
Technical Field
The present invention relates to a positive electrode plate for a lead-acid battery, and a method for manufacturing a positive electrode plate for a lead-acid battery.
Background
Conventionally, as a current collector used in a lead-acid battery, there is a grid made by stretching a lead alloy sheet having staggered slits formed therein. A pull-grid has a great limitation on the design of the configuration of the grid frame (grid stack) in nature of its method of manufacture. Therefore, it is difficult to optimize the arrangement of the grid frame so that the potential distribution in the entire plate becomes more uniform. In the expanded grid, since the imbalance of the potential distribution of the entire electrode plate is likely to increase, local corrosion occurs, and as a result, the life of the electrode plate is shortened. Further, a cast grid is used as a current collector used in a lead-acid battery. The casting grid is manufactured by pouring molten lead into a mould of the grid and compacting it. The cast grid has a higher degree of freedom in designing the arrangement of the grid frame than the grid. However, in the case of a cast grid, if an attempt is made to reduce the thickness of the grid, it is difficult for the molten lead to flow well when the molten lead is poured into a mold of the grid, and therefore, there is a problem that it is difficult to reduce the thickness of the grid.
A punched grid is known as a current collector that can solve these problems (see patent document 1 below). The punched grid is produced by punching a rolled sheet made of a lead alloy. Compared to pull grids, cast grids, stamped grids allow a more free design of the grid. In addition, the punched grid can make the thickness of the grid thinner than a cast grid.
Patent document 2 below describes a method for producing a negative electrode grid (grid). It is to be understood that any number of modified grid line shapes may be selected in order to impart improved paste adhesion characteristics to the negative grid electrode that are superior to the quadrilateral cross section produced by the punching process. According to various exemplary embodiments, the modified gridlines have a substantially diamond shape, a hexagonal shape, an octagonal shape, or an elliptical shape ". Further, it is described that the adhesion between the paste (negative electrode active material) and the punched grid can be improved by forming the grid cross section of the grid frame (grid line) of the punched grid on the negative electrode side into a square shape, a hexagonal shape, or an octagonal shape.
Patent document 3 (jp 2013 a 140677 a) discloses that "in a liquid lead storage battery for an idling stop vehicle, a positive electrode active material has a density of 4.4g/cm in a state in which formation of the positive electrode active material is completed3～4.8g/cm3And 0.05 to 1.0 mass% of Sn "in terms of metallic Sn. Further, it is described that "the density of the formed positive electrode active material is set to 4.4g/cm3～4.8g/cm3Thereby, durability when used in a state of insufficient charge can be improved. Since the capacity of the flooded lead acid battery decreases as a result, the capacity decrease is suppressed by including 0.05 to 1.0 mass% of Sn in terms of metallic Sn in the positive electrode active material.
As disclosed in patent document 3, when the lead acid battery is used in a state of incomplete charge (psoc) like a lead acid battery for an idling stop vehicle, the density of the positive electrode material is increased to improve the life performance. On the other hand, if the density of the positive electrode material is increased, the initial capacity is decreased.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2014-235844
Patent document 2: japanese Kokai publication No. 2010-520607
Patent document 3: japanese patent laid-open publication No. 2013-140677
Disclosure of Invention
In order to improve the life performance of lead-acid batteries used in PSOCs, the present inventors considered to further improve the density of the positive electrode material by using a punched grid as the positive electrode current collector, which has a longer life than a pulled grid. However, increasing the density of the positive electrode material decreases the utilization rate of the positive electrode material, and thus the initial capacity decreases. As described in patent document 3, although the initial capacity is improved by adding Sn to the positive electrode material, the addition of Sn to the positive electrode material tends to decrease the electrolyte as the lead-acid battery is used. The present inventors have studied to improve the initial capacity by a method other than adding Sn to the positive electrode material in order to avoid a decrease in the electrolytic solution with the use of the lead-acid battery.
The invention aims to provide a lead storage battery with high service life performance and improved initial capacity under PSOC.
The positive electrode plate for a lead-acid battery disclosed in the present specification includes a punched grid having a grid frame, and a positive electrode material, wherein corners of a cross section perpendicular to an extending direction of the grid frame are deformed, and a density of the positive electrode material when the positive electrode material has been formed is 4.1g/cm3The above.
According to the positive electrode plate disclosed in the present specification, the life performance and initial capacity of the lead-acid battery can be improved.
Drawings
FIG. 1 is a plan view of a positive electrode current collector according to an embodiment
FIG. 2 is a cross-sectional view of the positive plate (the cross-section is a quadrangle)
FIG. 3 is a sectional view of the positive plate (octagonal section)
FIG. 4 is a cross-sectional view of the positive electrode plate (the cross-section is a non-polygonal shape with rounded corners)
FIG. 5 is a view showing a cross-sectional shape of a grid frame (roughly octagonal)
Description of the symbols
Positive electrode current collector (punched grid)
Frame bone
A grid framework
Corner part of 15C
Positive electrode material (positive active material)
Paste-filled layer
Detailed Description
(outline of the present embodiment)
Embodiments of the present invention are shown below. In carrying out the present invention, the embodiments may be appropriately modified according to common knowledge of those skilled in the art and the disclosure of the prior art. Hereinafter, the positive electrode material is referred to as a positive electrode active material, and the negative electrode material is referred to as a negative electrode active material. The positive electrode plate is composed of a positive electrode current collector and a positive electrode active material (positive electrode material), the negative electrode plate is composed of a negative electrode current collector and a negative electrode active material, and the solid components other than the current collectors belong to the active material (electrode material). In addition, the grid is one form of a current collector.
The lead-acid battery of the present invention includes a group of electrode plates including, for example, a negative electrode plate containing lead as an active material main component, a positive electrode plate containing lead dioxide as an active material main component, and a porous separator interposed between the electrode plates, and the group of electrode plates is housed in an electrolytic cell and immersed in a flowable electrolyte containing dilute sulfuric acid as a main component.
The positive electrode plate of the present invention is formed by filling a grid portion of a current collector made of a Pb-Sb alloy, a Pb-Ca-Sn alloy, or the like, with a paste-like active material. These respective components can be selected from appropriately known components according to the purpose and use.
The positive electrode current collector 10 is made of a lead alloy having a lath-like structure. The lead alloy having a lath structure is, for example, a lead alloy obtained by rolling. When a lead alloy is rolled to be thin, lead particles constituting a metal structure contained in the original lead alloy are crushed, and a lath-like structure appears in the direction of progress of rolling. When the current collector is manufactured by casting, the lead alloy constituting the current collector does not have a lath-like structure. The lead alloy with the lath-shaped structure has the advantage of high strength.
The corner 15C of the grid frame 15 of the positive electrode current collector 10, which is a cross section perpendicular to the extending direction thereof, is deformed. The phrase "the corner portion 15C of the cross section is deformed" means that the shape of the corner portion 15C of the cross section of the grid frame 15 is deformed from a rectangular shape shown in fig. 2 to a diagonal shape shown in fig. 3 or a shape other than a rectangular shape such as a circular shape shown in fig. 4. Particularly preferred is a shape that deforms more gently than a right angle. In fig. 3 and 4, an example in which all of the 4 corner portions 15C are deformed is shown, but only a part of the corner portions 15C may be deformed. The cross-sectional views of the positive electrode plate shown in fig. 2 to 4 are cross-sectional views taken along the line a-a in fig. 1, and are cross-sectional views of the 1 st sub-frame 16 of the grid frame 15 cut on a vertical plane with respect to the extending direction (vertical direction in fig. 1). Hereinafter, unless otherwise specified, the cross section of the grid frame 15 perpendicular to the extending direction will be simply referred to as "cross section of the grid frame".
The cross-sectional shape of the grid frame 15 is a polygon of at least pentagon, a substantially polygon of at least pentagon, or a non-polygon. "polygonal" means a shape in which all sides are composed of straight lines and have the same number of vertices as the number of sides. The term "substantially polygonal" refers to a shape that can be substantially regarded as a polygon, such as a polygon having the same number of vertices as the number of sides, even if the sides are not straight lines. Fig. 5 shows a substantially octagonal shape in which some of the sides L1 to L4 are curved outward. When the cross-sectional shape of the grill frame 15 is a polygon of at least pentagon, or a substantially polygon of at least pentagon, all internal angles are preferably at least 90 °.
The term "non-polygonal" refers to the following 2 shapes.
(1) Shapes consisting of curves only
(2) A shape combining straight lines and curved lines (excluding substantially polygonal shapes)
(1) For example, circular, elliptical, etc. Further, (2) includes, for example, a shape in which all of the 4 corner portions 15C are curved as shown in fig. 4, and a shape in which a part of the 4 corner portions 15C are curved. In addition, the elliptical shape is also included.
As shown in fig. 1, the positive electrode current collector 10 includes an ear portion 13 and a grid frame 15 connected to the ear portion 13. The lug portions 13 may be directly connected to the grid frame 15 or may be connected to the grid frame 15 via the frame members 12. The arrangement of the grill frame 15 is arbitrary, but the grill frame 15 is preferably substantially linear. This is because, with such a configuration, the current path to the ear portion 13 can be further shortened, and the resistance can be reduced.
The lug portion 13 protrudes outward of the positive electrode current collector 10. The lug portions 13 are provided for connecting the positive electrode plates to each other via a tape not shown. The positive electrode current collector 10 may have the frame 12 at the first side 12A, and the positive electrode current collector 10 may have the frame 12 at the second side 12B facing the first side 12A. The positive electrode collector 10 may have the frame members 12 in the third side 12C and the fourth side 12D that connect the end of the first side 12A and the end of the second side 12B. The positive electrode current collector 10 preferably has a frame 12 on the first side 12A, the second side 12B, the third side 12C, and the fourth side 12D. With such a configuration, the extension of the positive electrode plate can be suppressed even when charge and discharge are repeated.
The positive electrode current collector 10 is manufactured by cutting (1-time processing) and removing a portion excluding the lug portion 13, the frame member 12, and the grid frame 15 from a rolled sheet made of a lead alloy having a lath-like structure. The current collector thus manufactured has through-holes 18. The 1-time processing is, for example, press processing such as punching, water jet processing, laser processing, or the like. Since a large amount of processing can be performed at low cost if the press working is a punching working or the like, the 1-time processing is preferably performed by a press working such as a punching working.
However, in the positive electrode current collector 10 after 1-time processing, the cross section of the grid frame 15 is rectangular, and the shape of the corner portion 15C is a right-angled shape as shown in fig. 2. Therefore, the positive electrode current collector 10 is manufactured by performing a process (2 processes) of deforming the corner portion 15C of the cross section of the grid frame 15. Specifically, the corner portion 15C of the cross section of the grid frame 15 is deformed into a shape other than a rectangular shape such as a diagonal shape shown in fig. 3 or a circular shape shown in fig. 4 by 2 passes of machining. The entire cross section including the corner portion 15C may be processed 2 times, and the cross section of the grid frame 15 may be deformed into a circular or elliptical shape by such processing. The 2-time processing may be performed only on a part of the grid frames or may be performed on all the grid frames, but is preferably performed on all the grid frames. When the positive electrode current collector 10 has the frame 12, the frame 12 can be processed 2 times because the cross section of the frame 12 is also rectangular after 1 processing. The 2-time working is, for example, press working, cutting working, polishing working, or the like. Since a large amount of processing can be performed at low cost if the press working is performed, the 2-time processing is preferably performed by press working. The 1 st processing and the 2 nd processing may be performed separately or simultaneously.
The negative electrode plate is formed by filling a grid portion of a current collector made of a Pb-Sb alloy, a Pb-Ca-Sn alloy, or the like, with a paste-like active material. These respective components can be selected from known components as appropriate according to the purpose and use. The negative electrode current collector is any of a cast grid, a pulled grid, a punched grid, and the like.
The positive electrode plate and the negative electrode plate can be manufactured through an active material paste production step, a filling step, a curing step, a drying step, and a chemical conversion step.
In the active material paste preparation step, dilute sulfuric acid and an additive are added to lead powder at a predetermined ratio and kneaded to prepare active material pastes for a positive electrode and a negative electrode. The positive electrode active material paste may contain Sn.
In the filling step, the positive electrode collector and the negative electrode collector are respectively filled with the respective active material pastes. Thus, undried positive and negative electrode plates were obtained.
The curing step is a step of curing the undried positive and negative electrode plates. The undried plate is cured in an atmosphere of moderate humidity and temperature. Thereafter, the dried positive electrode plate and the dried negative electrode plate were obtained.
The drying step is a step of drying the uncured positive and negative electrode plates.
In the chemical conversion step, the dried positive electrode plate and negative electrode plate are placed in a dilute sulfuric acid electrolyte and subjected to oxidation and reduction by direct current. Thus, the formed positive and negative electrode plates were obtained.
In the present invention, the density of the positive electrode material at the time of formation was set to 4.1g/cm3The above. When the positive electrode plate is produced, the density of the positive electrode material when formed can be adjusted by adjusting the amount of water contained in the positive electrode active material paste. Specifically, the density of the positive electrode material when formed can be adjusted by adjusting the amount of water contained in the positive electrode active material paste in the active material paste production step.
The density of the positive electrode material was measured as follows. And disassembling and taking out the fully charged electrode, and washing and drying. The electrode material was measured in an unpulverized state by mercury intrusion method for an apparent volume v per 1g and a total pore volume u per 1 g. The apparent volume v is the sum of the solid volume of the electrode material and the volume of the closed pores. The electrode material was filled in a container having a known volume V1, and the volume V2 corresponding to a pore diameter of 100 μm or more was measured by mercury intrusion method. The mercury was continuously introduced, and the total pore volume u was measured to obtain the apparent volume V of (V1-V2) -u, and the density d of the positive electrode material was determined by using the value of d 1/(V + u) 1/(V1-V2). In the measurement by the mercury intrusion method, the pressure was increased to a maximum pressure of 4.45psia (30.7Kpa), the contact angle was 130 °, and the surface tension of mercury was 484 dynes/cm. The fully charged state is a state in which the terminal voltage during charging measured every 15 minutes for 3 consecutive times shows a certain value (± 0.01V), and charging is performed at a current rate of 5 hours.
< one embodiment >
Hereinafter, an embodiment of the present invention will be described.
(Positive plate)
The positive electrode plate is a so-called paste type, and includes a positive electrode current collector 10 (punched grid) made of a lead alloy produced by punching and a positive electrode active material 20.
The positive electrode current collector 10 was obtained by punching (1-time processing) a rolled sheet made of an antimony-free Pb — Ca — Sn alloy having a lath-like structure.
The positive electrode current collector 10 shown in fig. 1 has a frame 12 (a generic name for 12A to 12D). The frame 12 has a first side 12A, a second side 12B, a third side 12C, and a fourth side 12D. The first side 12A and the second side 12B of the frame 12 extend in the left-right direction and face each other in the up-down direction. The third side 12C and the fourth side 12D of the frame 12 extend in the vertical direction, and respectively connect the left end and the right end of the first side 12A and the second side 12B. Further, an ear portion 13 is provided on the first side portion 12A.
The lattice frame 15 includes the 1 st subchondral bone 16 and the 2 nd subchondral bone 17. A plurality of 1 st sub-ribs 16 are provided so as to linearly extend between the first side portion 12A and the second side portion 12B. A plurality of the 2 nd sub-bones 17 are arranged so as to intersect the 1 st sub-bone 16.
The 2 nd sub-bone 17 includes an orthogonal bone orthogonal to the 1 st sub-bone 16 and an oblique bone inclined at a predetermined angle with respect to the 1 st sub-bone 16.
In the positive electrode current collector 10 obtained by punching, the cross section of the grid frame 15 is rectangular as shown in fig. 2 unless the cross section of the grid frame 15 is deformed. The positive electrode collector 10 is subjected to press working to obtain a positive electrode collector in which the cross-sectional shape of the grid frame 15 is deformed into an octagonal shape as shown in fig. 3. In the following description, the positive electrode current collector whose cross-sectional shape of the grid frame 15 is not deformed is referred to as "10A", and the positive electrode current collector whose cross-sectional shape of the grid frame 15 is deformed into an octagonal shape is referred to as "10B".
The positive electrode active material paste is prepared by mixing lead oxide by a ball milling method, synthetic resin fibers of a reinforcing material, water, and sulfuric acid. The positive electrode active material paste was filled in the positive electrode current collector 10A and the positive electrode current collector 10B, and was subjected to aging, drying, and formation to produce a positive electrode plate having a width of 100mm, a height of 110mm, and a thickness of 1.4 mm. As shown in fig. 2 and 3, the positive electrode active material 20 is filled (over paste) so as to cover the grid frame 15 of the positive electrode current collectors 10A and 10B. The thickness t2 phase of the positive electrode active material 20 is "1.4 mm" as an example, whereas the thickness t1 of the positive electrode current collectors 10A, 10B is "1.0 mm" as an example, and one side of the thickness t3 of the paste filling layer 20A is 0.2 mm. The amount of water contained in the positive electrode active material paste was adjusted so that the density of the positive electrode active material when the positive electrode active material paste was formed was 3.5g/cm3、4.2g/cm3、4.4g/cm3、4.7g/cm3The positive electrode plate of (1). The positive electrode active material may not be impregnated with the positive electrode current collector 10.
(negative plate)
The negative electrode paste was prepared by mixing lead oxide based on a ball milling method, barium sulfate, wood, carbon black, synthetic resin fiber of a reinforcing material, water and sulfuric acid. The paste was filled in a grid-type negative electrode current collector made of antimony-free Pb — Ca — Sn alloy, and the paste was cured, dried, and converted to produce a negative electrode plate.
(construction of Battery)
6 positive electrode plates and 7 negative electrode plates accommodated in the bag-shaped separator were alternately stacked. As the spacer, a spacer generally used as a spacer for a liquid lead storage battery can be used. For example, a sheet mainly composed of polyolefin having micropores, and a matte spacer mainly composed of resin or glass fibers can be used. The tabs of the stacked positive electrode plates and the tabs of the stacked negative electrode plates are connected by positive electrode strips and negative electrode strips by a cast-on-strap method, respectively, to produce a group of electrode plates. 6 plate groups were connected in series and stored in a polypropylene cell, and sulfuric acid was added to prepare a flooded lead acid battery having an electrolyte specific gravity of 1.285.
(measurement of initial Capacity)
Lead batteries using the positive electrode current collector 10A for the positive electrode plate and lead batteries using the positive electrode current collector 10B for the positive electrode plate were prepared, and the 5-hour rate capacity was measured as the initial capacity. The 5-hour rate capacity was measured according to JIS D5301(2006 version). The 5-hour rate capacity of the lead-acid battery using the positive electrode current collector 10B was "X1", and the 5-hour rate capacity of the lead-acid battery using the positive electrode current collector 10A was "X2", and the rate of change Z in the 5-hour rate capacity was calculated by the following equation (1). The 5-hour rate capacity change rate Z indicates a 5-hour rate capacity change rate when the cross-sectional shape of the louver frame 15 is changed from the quadrilateral shape to the octagonal shape, and indicates that the 5-hour rate capacity improvement effect due to the change in the cross-sectional shape of the louver frame 15 is greater as the value is larger. The results are shown in Table 1.
Z＝(X1-X2)/X2×100·····(1)
[ Table 1]
Density (g/cm) of positive electrode active material3) 5-hour Rate Change in Capacity Z (%)
3.5 3
4.2 11
4.4 12
4.7 12
The density of the positive electrode active material was 3.5g/cm3In this case, the rate of change Z in capacity at 5 hours was 3%. On the other hand, the density of the positive electrode active material was 4.1g/cm3Above this, it is particularly 4.2g/cm3In the above case, the 5-hour rate of change Z of the capacity is 11 to 12% and 3.5g/cm3The density of the positive electrode active material is significantly higher than that of the positive electrode active material. Thus, the density of the positive electrode active material was 3.5g/cm3When the density of the positive electrode active material was 4.1g/cm3Above this, especially 4.2g/cm3In the above case, the rate of change in the 5-hour rate capacity caused by the deformation of the cross-sectional shape of the grid frame 15 is greatly different. The same result is obtained also when the cross-sectional shape of the grid frame 15 is formed into a hexagonal shape or a non-polygonal shape such as a circular shape at the corner 15C shown in fig. 4. It has not been known so far that the effect of improving the capacity at a rate of 5 hours is increased by deforming the shape of the cross section of the grid frame 15 in the range of the specific positive electrode active material density, which has not been expected from the conventional technical common knowledge. In addition, since there are many factors affecting the initial capacity of a lead-acid battery, the density of the positive electrode active material is set to 4.1g/cm3Above, especially 4.2g/cm3The above combination with the deformation of the shape of the cross section of the grill frame 15 requires a considerable amount of trial and error to obtain it, and is not easily conceivable by those skilled in the art. By setting the density at the formed time to 4.1g/cm3Above, preferably 4.2g/cm3The positive electrode plate configured by combining the positive electrode active material and the punched grid in which the cross-sectional shape of the grid frame 15 is deformed is used for a lead-acid battery, and thus a lead-acid battery having excellent life performance under PSOC and also excellent initial capacity can be formed.
If the density of the positive electrode active material is set to 4.3g/cm3The above is more preferable because the effect of improving the capacity at a rate of 5 hours is more remarkable. If the density of the positive electrode active material is set to 4.4g/cm3The above is particularly preferable because the effect of improving the capacity at a rate of 5 hours is particularly remarkable.
If the density of the positive electrode active material exceeds 5.0g/cm3Then initial capacitySince the effect of the reduction becomes large, the positive electrode active material density is preferably 5.0g/cm3Hereinafter, in order to decrease the initial capacity within a practical range, it is more preferable that the positive electrode active material density is 4.8g/cm3The following.
The positive electrode plate of the present embodiment is suitably used for a lead-acid battery for idling stop in which the positive electrode active material has a high density in order to improve the life performance under PSOC.
The present invention can be implemented by the following means.
(1) A positive electrode plate for a lead-acid battery, the positive electrode plate comprising a punched grid having a grid frame, and a positive electrode material, wherein corners of a cross section of the grid frame perpendicular to an extending direction are deformed, and a density of the positive electrode material when the positive electrode material is formed is 4.1g/cm3]The above.
(2) A positive electrode plate for a lead-acid battery, the positive electrode plate comprising a punched grid having a grid frame, and a positive electrode material, wherein the grid frame has a cross-sectional shape perpendicular to the extending direction of any one of a polygon of at least five sides, a substantially polygon of at least five sides, and a non-polygon, and the positive electrode material has a density of 4.1[ g/cm ] when formed3]The above.
(3) A positive electrode plate for a lead-acid battery, the positive electrode plate comprising a grid made of a lead alloy having a lath-like structure, the grid having a grid frame, corners of a cross section of the grid frame perpendicular to an extending direction of the grid frame being deformed, and a positive electrode material having a density of 4.1[ g/cm ] when formed3]The above.
(4) A positive electrode plate for a lead-acid battery, the positive electrode plate comprising a grid made of a lead alloy having a lath-like structure, the grid having a grid frame, the grid frame having a cross-sectional shape perpendicular to an extending direction of any one of a polygon of at least pentagon, a substantially polygon of at least pentagon, and a non-polygon, the positive electrode material having a density of 4.1[ g/cm ] when formed3]The above.
(5) Any one of (1) to (4)The positive electrode plate according to, wherein the positive electrode material has a density of 4.2[ g/cm ] when formed3]The above.
(6) The positive electrode plate according to any one of (1) to (4), wherein the positive electrode material has a density of 4.3[ g/cm ] when formed3]The above.
(7) The positive electrode plate according to any one of (1) to (4), wherein the positive electrode material has a density of 4.4[ g/cm ] when formed3]The above.
(8) The positive electrode plate according to any one of (1) to (7), wherein the positive electrode material has a density of 5.0[ g/cm ] when formed3]The following.
(9) The positive electrode plate according to any one of (1) to (7), wherein the positive electrode material has a density of 4.8[ g/cm ] when formed3]The following.
(10) A lead-acid battery comprising the positive electrode plate according to any one of (1) to (9).
(11) A method for manufacturing a positive electrode plate for a lead acid battery comprising a grid and a positive electrode material, wherein the grid is formed from a lead alloy sheet by forming a grid frame by cutting, corners of a cross section perpendicular to an extending direction of the grid frame are deformed, and the density of the positive electrode material when formed is set to 4.1g/cm3]The above.
(12) The method for manufacturing a positive electrode plate for a lead-acid battery according to the item (11), wherein the grid is a grid made of a lead alloy having a lath-like structure.
(13) The method for manufacturing a positive electrode plate for a lead-acid battery according to (11) or (12), wherein the cutting is a press working.
(14) The method for manufacturing a positive electrode plate for a lead-acid battery according to the above (11) or (12), wherein the cutting is punching.
(15) The method for manufacturing a positive electrode plate for a lead-acid battery according to any one of (11) to (14), wherein corners of a cross section perpendicular to an extending direction of the grid frame are deformed by press working.

Claims (17)

1. A positive electrode plate for a lead-acid battery, the positive electrode plate comprising:
a blanking grid with a grid frame, and
a positive electrode material for a positive electrode,
the cross-sectional shape of the grid frame perpendicular to the extending direction is any one of a polygon of at least a pentagon, a substantially polygon of at least a pentagon, and a non-polygon,
the density of the positive electrode material when formed is 4.1g/cm3]Above and 5.0[ g/cm ]3]The following.
2. A positive electrode plate for a lead-acid battery, the positive electrode plate comprising:
a grid composed of a lead alloy having a lath-like structure, and
a positive electrode material for a positive electrode,
the grid is provided with a grid framework,
the cross-sectional shape of the grid frame perpendicular to the extending direction is any one of a polygon of at least a pentagon, a substantially polygon of at least a pentagon, and a non-polygon,
the density of the positive electrode material when formed is 4.1g/cm3]Above and 5.0[ g/cm ]3]The following.
3. The positive electrode plate according to claim 1 or 2, wherein the density of the positive electrode material when formed is 4.2[ g/cm3]The above.
4. The positive electrode plate according to claim 1 or 2, wherein the density of the positive electrode material when formed is 4.3[ g/cm3]The above.
5. The positive electrode plate according to claim 1 or 2, wherein the density of the positive electrode material when formed is 4.4[ g/cm3]The above.
6. The positive electrode plate according to claim 1 or 2, wherein the density of the positive electrode material when formed is 4.8[ g/cm3]The following.
7. The positive electrode plate according to claim 3, wherein the density of the positive electrode material when formed is 4.8[ g/cm3]The following.
8. The positive electrode plate according to claim 4, wherein the density of the positive electrode material when formed is 4.8[ g/cm3]The following.
9. The positive electrode plate according to claim 5, wherein the density of the positive electrode material when formed is 4.8[ g/cm3]The following.
10. A lead-acid battery comprising the positive electrode plate according to any one of claims 1 to 9.
11. A method for manufacturing a positive plate for a lead storage battery, which is a method for manufacturing a positive plate for a lead storage battery composed of a grid and a positive electrode material,
the grid is formed from a sheet of lead alloy by forming a grid frame using a cutting process,
deforming corners of a cross section of the grid frame perpendicular to an extending direction, the cross section of the grid frame perpendicular to the extending direction having a shape of any one of a polygon of at least five sides, a substantially polygon of at least five sides, and a non-polygon,
the density of the positive electrode material when formed was set to 4.1[ g/cm ]3]Above and 5.0[ g/cm ]3]The following.
12. The method for manufacturing a positive electrode plate for a lead-acid battery according to claim 11, wherein the grid is made of a lead alloy having a lath-like structure.
13. The method for manufacturing a positive electrode plate for a lead-acid battery according to claim 11 or 12, wherein the cutting process is a press process.
14. The method for manufacturing a positive electrode plate for a lead-acid battery according to claim 11 or 12, wherein the cutting process is a blanking process.
15. The method for manufacturing a positive electrode plate for a lead-acid battery according to claim 11 or 12, wherein corners of a cross section perpendicular to an extending direction of the grid frame are deformed by press working.
16. The method for manufacturing a positive electrode plate for a lead-acid battery according to claim 13, wherein corners of a cross section perpendicular to an extending direction of the grid frame are deformed by press working.
17. The method for manufacturing a positive electrode plate for a lead-acid battery according to claim 14, wherein corners of a cross section perpendicular to an extending direction of the grid frame are deformed by press working.
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