CN117957676A - Lead storage battery - Google Patents
Lead storage battery Download PDFInfo
- Publication number
- CN117957676A CN117957676A CN202280061227.XA CN202280061227A CN117957676A CN 117957676 A CN117957676 A CN 117957676A CN 202280061227 A CN202280061227 A CN 202280061227A CN 117957676 A CN117957676 A CN 117957676A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- mass
- lead
- range
- collector plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000003860 storage Methods 0.000 title claims abstract description 51
- 229910000978 Pb alloy Inorganic materials 0.000 claims abstract description 83
- 239000002253 acid Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 claims abstract description 10
- 238000005266 casting Methods 0.000 claims description 14
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 abstract description 25
- 230000009467 reduction Effects 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000011575 calcium Substances 0.000 description 43
- 229910045601 alloy Inorganic materials 0.000 description 33
- 239000000956 alloy Substances 0.000 description 33
- 229910052791 calcium Inorganic materials 0.000 description 30
- 239000007788 liquid Substances 0.000 description 30
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 29
- 229910052718 tin Inorganic materials 0.000 description 29
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 26
- 229910052797 bismuth Inorganic materials 0.000 description 25
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 24
- 229910052709 silver Inorganic materials 0.000 description 24
- 239000004332 silver Substances 0.000 description 24
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 22
- 229910052788 barium Inorganic materials 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 210000000988 bone and bone Anatomy 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 230000001186 cumulative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- 229910001128 Sn alloy Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009749 continuous casting Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000882 Ca alloy Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910000600 Ba alloy Inorganic materials 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 229910014474 Ca-Sn Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/06—Alloys based on lead with tin as the next major constituent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—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
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a lead storage battery which has excellent high-temperature durability and can inhibit the reduction of the water content of an electrolyte. A lead acid battery comprising a battery case having a battery chamber, a polar plate group accommodated in the battery chamber, and an electrolyte injected into the battery chamber, wherein the polar plate group comprises a plurality of positive and negative plates alternately arranged and a separator arranged between the positive and negative plates, the positive plate comprises a positive electrode mixture containing a positive electrode active material and a positive electrode collector plate (11) comprising a lattice-shaped portion (110) holding the positive electrode mixture, the positive electrode collector plate (11) is formed of a lead alloy containing Ca in a range of 0.035 to 0.08 mass%, 0.50 to 1.0 mass%, ag in a range of 0.003 to 0.035 mass%, bi in a range of more than 0 to 0.02 mass%, and the balance of lead and unavoidable impurities.
Description
Technical Field
The present invention relates to a lead storage battery.
Background
A general lead acid storage battery, namely, a liquid lead acid storage battery includes a battery case having a battery compartment, a polar plate group accommodated in the battery compartment, and an electrolyte injected into the battery compartment. The electrode group has a plurality of positive electrode plates and negative electrode plates alternately arranged, and separators arranged between the positive electrode plates and the negative electrode plates. The positive electrode plate holds a positive electrode mixture containing a positive electrode active material on a current collector. The negative electrode plate has a collector plate holding a negative electrode mixture containing a negative electrode active material. Dilute sulfuric acid was used as the electrolyte. Such liquid lead storage batteries are widely used as batteries for automobiles and the like.
In recent years, an engine room of an automobile has been significantly increased in temperature due to an increase in equipment, a design to exclude a dead space, and the like. Therefore, since the liquid lead acid battery for automobiles is used in an environment where corrosion or growth (deformation due to elongation of the grid) is likely to occur in the positive electrode grid, countermeasures for prolonging the life are strongly demanded. In addition, in many cases, a liquid lead-acid battery for automobiles is used in an overcharged state, and if the liquid lead-acid battery is used in an overcharged state, water in an electrolyte is electrolyzed, and generated hydrogen gas and oxygen gas are discharged to the outside of the battery through a vent hole, so that the water content of the electrolyte is easily reduced.
Patent document 1 describes an alloy composition of a positive electrode collector plate constituting a lead acid battery which is maintenance-free (maintenance such as water replenishment is required only once or less in use, or preferably not at all during the life expectancy of the battery). In addition, as a battery for SLI of an automobile (a battery for starting, lighting, and igniting), in order to provide a maintenance-free lead storage battery which can have a sufficient service life (excellent corrosion resistance of a positive electrode collector plate) even when exposed to a relatively high temperature environment, a positive electrode cell using a lead alloy containing 0.025 to 0.06 mass% of Ca, 0.3 to 0.7 mass% of Sn, and 0.015 to 0.045 mass% of Ag is disclosed.
The positive electrode collector plate constituting the maintenance-free lead acid storage battery has conventionally been formed of a pb—ca alloy, and a lead alloy to which an alloy component such as Sn, ag, ba, cu, bi, se is added is used depending on the application. Among them, it is known that the use of a lead alloy containing Sn or Ag greatly improves the corrosion resistance and creep resistance of the positive electrode collector plate.
Patent document 2 discloses that a positive electrode grid (positive electrode collector plate) composed of a lead alloy containing 0.05 to 0.085 mass% of Ca, 1.2 to 2.0 mass% of Sn, 0.002 to 0.02 mass% of Bi, 0.0001 to 0.002 mass% of Ag, and 0.005 to 0.03 mass% of Al is used in order to obtain a long-life lead storage battery at a high temperature. In addition, it is described that by setting the alloy composition to the above range, a lattice excellent in workability (strength) can be obtained.
As the lead storage battery, a control valve type lead storage battery may be mentioned in addition to the liquid type lead storage battery. The control valve type lead acid battery has a sealed structure including an electrolyte and a laminate body composed of a plurality of positive electrode plates and negative electrode plates alternately arranged and separators arranged between the positive electrode plates and the negative electrode plates. The electrolyte permeates into the glass fiber mat as a separator or is not fluidized by gelation.
The control valve type lead acid battery is often used for backup power supply such as communication, power and disaster prevention, and requires less maintenance frequency. Therefore, it is more important to reduce the water content of the electrolyte than in the case of liquid lead acid batteries, and battery designs have been made in which the water content of the electrolyte is reduced, that is, so-called liquid depletion is not achieved for an early life.
The mechanism of causing the water content of the electrolyte to decrease in the control valve type lead acid battery is as follows. The control valve type lead acid battery has a reaction mechanism that suppresses oxygen generated from the positive electrode plate by electrolysis of water during charging from being absorbed by the negative electrode plate due to oxygen absorbing capacity of the negative electrode active material, generates water from the absorbed oxygen, and emits oxygen generated from the positive electrode plate to the outside of the battery. However, if the amount of oxygen generated in the positive electrode plate exceeds the oxygen absorbing capacity of the negative electrode active material, oxygen in the battery is released from the control valve to the outside of the battery, and the water content of the electrolyte is reduced.
Prior art literature
Patent literature
Patent document 1: U.S. Pat. No. 5,298,350 specification
Patent document 2: japanese patent No. 6406457
Disclosure of Invention
Technical problem to be solved by the invention
However, in the lead storage batteries described in patent documents 1 and 2, there is room for improvement in terms of both high-temperature durability and maintenance-free characteristics (suppression of water content reduction of the electrolyte solution without requiring water replenishment) as lead storage batteries used under severe conditions such as high-temperature environments.
The invention aims to provide a lead storage battery which has excellent high-temperature durability and can inhibit the reduction of the moisture of electrolyte.
Technical scheme for solving technical problems
In order to solve the above-described problems, a first aspect of the present invention provides a lead acid battery having the following structures (1) and (2).
(1) The positive electrode plate has a positive electrode mixture containing a positive electrode active material and a positive electrode collector plate including a lattice-like portion holding the positive electrode mixture.
(2) The positive electrode collector plate is formed of a lead alloy containing Ca in a range of 0.035 to 0.08 mass%, sn in a range of 0.50 to 1.0 mass%, ag in a range of 0.003to 0.035 mass%, bi in a range of more than 0 to 0.02 mass%, and the balance of lead and unavoidable impurities.
A second aspect of the present invention provides a lead acid battery having the above-described structure (1) and the following structure (3).
(3) The positive electrode collector plate is formed of a lead alloy containing Ca in a range of 0.035 to 0.07 mass%, sn in a range of 0.55 to 0.9 mass%, ag in a range of 0.010 to 0.030 mass%, bi in a range of 0.0001 to 0.010 mass%, and the balance of lead and unavoidable impurities.
A third aspect of the present invention provides a lead acid battery having the above-described structure (1) and the following structure (4).
(4) The positive electrode collector plate is formed of a lead alloy containing Ca in a range of 0.035 to 0.06 mass%, sn in a range of 0.60 to 0.8 mass%, ag in a range of 0.015 to 0.025 mass%, bi in a range of 0.0005 to 0.005 mass%, and the balance of lead and unavoidable impurities.
A fourth aspect of the present invention provides a lead acid battery having the above-described structure (1) and the following structure (5).
(5) The positive electrode collector plate is formed of a lead alloy containing Ca in a range of 0.035 to 0.08 mass%, sn in a range of 0.50 to 1.0 mass%, ag in a range of 0.003 to 0.035 mass%, bi in a range of more than 0 to 0.02 mass%, ba in a range of more than 0 to 0.001 mass%, and the balance of lead and unavoidable impurities.
A fifth aspect of the present invention provides a lead acid battery having the above-described structure (1) and the following structure (6).
(6) The positive electrode collector plate is formed of a lead alloy containing Ca in a range of 0.035 to 0.07 mass%, containing Sn in a range of 0.55 to 0.9 mass%, containing Ag in a range of 0.010 to 0.030 mass%, containing Bi in a range of 0.0001 to 0.010 mass%, containing Ba in a range of more than 0 to 0.001 mass%, and the balance being lead and unavoidable impurities.
A sixth aspect of the present invention provides a lead acid battery having the above-described structure (1) and the following structure (7).
(7) The positive electrode collector plate is formed of a lead alloy containing Ca in a range of 0.035 to 0.06 mass%, sn in a range of 0.60 to 0.8 mass%, ag in a range of 0.015 to 0.025 mass%, bi in a range of 0.0005 to 0.005 mass%, ba in a range of more than 0 to 0.001 mass%, and the balance of lead and unavoidable impurities.
In the case where the lead storage batteries according to the first to sixth aspects of the present invention are liquid lead storage batteries, the following structure (11) is provided as the above-described structure (1).
(11) The battery pack is provided with a battery case having a battery chamber, a polar plate group accommodated in the battery chamber, and an electrolyte injected into the battery chamber. The electrode plate group has a plurality of positive electrode plates and negative electrode plates alternately arranged, and separators arranged between the positive electrode plates and the negative electrode plates.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the lead-acid battery of the present invention, it is expected that the high-temperature durability and the water reduction suppression effect of the electrolyte are both high.
Drawings
Fig. 1 is a partial cross-sectional view showing the structure of a lead acid battery according to an embodiment of the present invention.
Fig. 2 is a plan view showing a positive electrode collector plate constituting a lead acid storage battery according to an embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the embodiments described below. In the embodiments described below, technical preferred restrictions are made for the implementation of the present invention, but these restrictions are not a requirement of the present invention.
[ Integral Structure ]
As shown in fig. 1, the liquid lead storage battery of the present embodiment includes a battery case 41 having a battery chamber, a pole plate group 1, a positive electrode terminal 14, a negative electrode terminal 24, an electrolyte (not shown) injected into the battery chamber, and a cover 43 fixed to the battery case 41 so as to block the upper side of the battery chamber. The electrode plate group 1 includes: a laminated body composed of a plurality of positive electrode plates 10 and negative electrode plates 20 alternately arranged, and separators 30 arranged between the positive electrode plates 10 and the negative electrode plates 20; a positive electrode strip 13 connecting the positive electrode plates 10 of the laminate; and a negative electrode belt 23 connecting the negative electrode plates 20 of the laminate.
One electrode group 1 is accommodated in one battery chamber, and the number of positive electrode plates 10 constituting the stacked body of the electrode group 1 is equal to or less than the number of negative electrode plates 20. The number of positive electrode plates 10 may be the same as or greater than the number of negative electrode plates 20.
The positive electrode plate 10 has a positive electrode collector and a positive electrode mixture containing a positive electrode active material. The positive electrode collector plate has rectangular grid portions in which a positive electrode mixture is held, and lugs 12 continuous with the grid portions. Negative electrode plate 20 has a negative electrode collector and a negative electrode mixture containing a negative electrode active material. The negative electrode collector plate has rectangular lattice-shaped portions in which a negative electrode mixture is held, and lugs 22 continuous with the lattice-shaped portions. The positive electrode mixture and the negative electrode mixture are filled in the openings of the grid-shaped portions of the positive electrode collector plate and the negative electrode collector plate, and cover the plate surfaces of the grid-shaped portions.
The stacked body of the electrode group 1 is disposed in the battery case 41 such that the plate surfaces of the grid-like portions of the positive electrode plate 10 and the negative electrode plate 20 extend in the up-down direction of the battery case 41.
The material and manufacturing method of positive electrode collector plate 11 constituting positive electrode plate 10 will be described in detail later. The negative electrode collector constituting negative electrode plate 20 is formed by continuous casting using a Pb-Ca-Sn-based alloy. The separator 30 is a porous film body made of, for example, resin or glass, and may have a flat plate-like base (film body) formed with pleated ribs protruding in a direction perpendicular to the base surface.
The lugs 12 of the plurality of positive electrode plates 10 are connected by positive electrode strips 13, and the lugs 22 of the plurality of negative electrode plates 20 are connected by negative electrode strips 23. One end of the positive electrode terminal 14 is connected to the upper portion of the positive electrode belt 13, one end of the negative electrode terminal 24 is connected to the upper portion of the negative electrode belt 23, and the other end of the positive electrode terminal 14 and the other end of the negative electrode terminal 24 penetrate the cover 43 closing the opening of the battery case 41, and are exposed to the outside of the case constituted by the battery case 41 and the cover 43.
The electrolyte is dilute sulfuric acid having a specific gravity of 1.28 or more and 1.30 or less (in terms of 20 ℃).
[ Concerning positive plate ]
Positive electrode plate 10 has positive electrode collector plate 11 having the shape shown in fig. 2. The positive electrode collector plate 11 includes rectangular grid portions 110 and lugs 12 protruding from above the grid portions 110.
The lattice-shaped portion 110 includes frame bones forming rectangular four sides and a plurality of inner bones connected to the frame bones and located inside the frame bones. The frame bone has: an upper frame rib 111 located above the lattice-like portion 110 and extending in a lateral direction (X direction) which is a direction perpendicular to the stacking direction (Y direction) of the stacked body and the up-down direction (Z direction) of the battery case; a lower frame rib 112 located at the lower side of the lattice-shaped portion 110 and extending in the lateral direction; the pair of vertical frame ribs 113 and 114 extend in the vertical direction (Z direction) of the battery case, that is, in the vertical direction. The plurality of inner bones include a plurality of vertical inner bones 115 extending from the respective positions of the upper frame toward the lower frame, and a plurality of horizontal inner bones 116 connecting the pair of vertical frame 113 and 114.
The positive electrode mixture is filled in all the openings 117 of the grid 110, and a layer made of the positive electrode mixture is present on the entire surface of the grid 110. That is, the positive electrode mixture is held in the lattice-like portion 110.
[ Production method of Positive electrode collector plate ]
As a method for producing the positive electrode collector plate, there are a casting method using a mold, an expanding method for processing a rolled substrate, a punching method, and the like, but a rolled substrate made of a pb—ca—sn alloy (a lead alloy containing Ca and Sn as alloy components) is competitively aged, overaged, and recrystallized during rolling. Therefore, when the positive electrode collector plate made of a pb—ca—sn alloy is a plate obtained by processing a rolled substrate (a plate having a rolled structure), corrosion is likely to occur, and mechanical strength is reduced by corrosion, so that deformation due to elongation of the lattice-like portion is likely to occur. In contrast, the positive electrode collector plate obtained by casting is less likely to deform due to the elongation of the lattice-shaped portion. Therefore, the positive electrode collector plate made of a pb—ca—sn alloy is preferably a plate obtained by casting, that is, a plate having no rolled structure (no rolled structure).
The casting method includes a gravity casting method, a continuous casting method, and the like.
[ Material for Positive electrode collector plate ]
The positive electrode collector plate 11 is produced by casting and is formed of a lead alloy containing Ca in a range of 0.035 mass% to 0.08 mass%, containing Sn in a range of 0.50 mass% to 1.0 mass%, containing Ag in a range of 0.003 mass% to 0.035 mass%, containing Bi in a range of more than 0 and 0.02 mass%, containing Ba in a range of more than 0 and 0.001 mass%, and the remainder being composed of lead and unavoidable impurities.
The actions of the alloy components contained in the lead alloy are described below.
< Ca >, ca
The lead alloy forming the positive electrode collector plate contains calcium, so that the mechanical strength of the positive electrode collector plate is improved. Specifically, when a positive electrode collector plate is produced by casting using a lead alloy, calcium produces a grain refinement effect, and therefore the mechanical strength of the produced positive electrode collector plate is improved. In addition, when the content of calcium is too small, casting failure may occur. On the other hand, when the content of calcium is too large, the necessary corrosion resistance may not be obtained.
When the content of calcium is in the range of 0.035 mass% or more and 0.08 mass% or less, the necessary properties in terms of both mechanical strength and corrosion resistance can be obtained. The content of Ca is preferably in the range of 0.035 mass% to 0.07 mass%, more preferably in the range of 0.035 mass% to 0.06 mass%.
< Sn (tin) >)
The lead alloy forming the positive electrode collector plate contains tin, thereby improving the mechanical strength and corrosion resistance of the positive electrode collector plate. In addition, by increasing the oxygen generation overvoltage of the positive electrode collector plate, oxygen generation from the positive electrode plate due to electrolysis of water can be suppressed. As a result, the reduction in the water content of the electrolyte can be suppressed. If the tin content is too small, these effects cannot be exerted. On the other hand, when the Sn content is too large, the cost becomes high.
When the content of tin is in the range of 0.50 mass% or more and 1.0 mass% or less, the necessary properties can be obtained in all aspects of mechanical strength, corrosion resistance, oxygen generation overvoltage, and cost. The content of Sn is preferably in the range of 0.55 mass% or more and 0.90 mass% or less, and more preferably in the range of 0.60 mass% or more and 0.80 mass% or less.
< Ag (silver) >, and
By containing silver in the lead alloy forming the positive electrode collector plate, the mechanical strength, corrosion resistance, and creep resistance of the positive electrode collector plate are improved. If the silver content is too small, these effects cannot be exerted. On the other hand, if the silver content is too high, the oxygen generation overvoltage of the positive electrode collector plate decreases, the generation of oxygen from the positive electrode plate by electrolysis of water becomes remarkable, and the cost increases.
When the content of silver is in the range of 0.003 mass% or more and 0.035 mass% or less, the necessary properties can be obtained in all aspects of mechanical strength, corrosion resistance and creep resistance, oxygen generation overvoltage and cost. The content of Ag is preferably in the range of 0.010 mass% to 0.030 mass%, more preferably in the range of 0.015 mass% to 0.025 mass%.
< Bi (bismuth) >, a process for preparing the same
By containing bismuth in the lead alloy forming the positive electrode collector plate, the creep resistance of the positive electrode collector plate is improved. If the content of bismuth is too small, this effect cannot be exerted. On the other hand, when the content of bismuth is too large, the oxygen generation overvoltage of the positive electrode collector plate decreases, and the generation of oxygen from the positive electrode plate by electrolysis of water becomes remarkable.
When the content of Bi is in the range of more than 0 (=0.0000 mass%) and not more than 0.02 mass%, the necessary performance can be obtained in terms of both creep resistance and oxygen generation overvoltage. The content of bismuth is preferably in the range of 0.0001% by mass or more and 0.010% by mass or less, and more preferably in the range of 0.0005% by mass or more and 0.005% by mass or less.
< Ba (Ba) >)
The lead alloy forming the positive electrode collector plate contains barium, so that the mechanical strength and corrosion resistance of the positive electrode collector plate are improved. If the content of barium is too small, these effects cannot be exerted. On the other hand, when the content of barium is too large, the cost becomes high.
If the content of Ba is in the range of more than 0 (=0.000 mass%) and 0.001 mass% or less, the effect of improving mechanical strength and corrosion resistance can be obtained while suppressing the cost.
[ Action, effect ]
The liquid lead battery according to the embodiment uses, as the positive electrode collector plate 11, a plate produced by casting and made of a lead alloy containing Ca in a range of 0.035 mass% or more and 0.08 mass% or less, containing Sn in a range of 0.50 mass% or more and 1.0 mass% or less, containing Ag in a range of 0.003 mass% or more and 0.035 mass% or less, containing Bi in a range of more than 0 and 0.02 mass% or less, containing Ba in a range of more than 0 and 0.001 mass% or less, and the remainder being made of lead and unavoidable impurities, and can achieve both high-temperature durability and high suppression effect of water reduction of the electrolyte and also suppress costs.
In the control valve type lead acid battery, the same operational effects as those of the liquid type lead acid battery can be obtained.
Examples
[ Production of Experimental cell ]
As a plurality of liquid lead storage batteries having the same structure as the liquid lead storage battery according to the embodiment, a liquid lead storage battery having a capacity of 36Ah at a5 hour rate, a size of B24, and a nominal voltage of 12V was produced, and a positive electrode collector plate having a different material (alloy composition of lead alloy) was used. The battery compartment has six battery compartments. The structure was the same except for the positive electrode collector plate.
First, as the positive electrode collector plates of nos. 1 to 30, lead alloys having alloy compositions of the respective values shown in table 1 were used, and positive electrode collector plates 11 having shapes shown in fig. 2 were produced by gravity casting. At this time, the positive electrode collector plate of No.2 produced casting failure. Specifically, when the collector plate after casting is transported to the next step, the collector plate is deformed and cannot maintain its shape. A positive electrode collector other than No.2 can be used.
Next, a negative electrode collector plate having substantially the same shape as the positive electrode collector plate 11 was produced by continuous casting using a lead alloy having a Ca content of 0.09 mass%, a Sn content of 0.4 mass%, an Ag content of 0.001 mass% and a Bi content of 0.005 mass% and the remainder consisting of lead and unavoidable impurities.
Next, a positive electrode mixture paste was prepared by kneading lead powder containing lead monoxide as a main component and water with dilute sulfuric acid, and then further mixing and fusing the mixture with necessary additives (that is, by a usual method). Further, a negative electrode mixture paste was prepared by kneading lead powder containing lead monoxide as a main component and water with dilute sulfuric acid, and then mixing and fusing the mixture with necessary additives (that is, by a usual method).
The positive electrode mixture paste thus obtained was uniformly applied and filled over the entire surface of the lattice-shaped portion of the positive electrode current collector plate, and then, the positive electrode plate (before formation) was produced by performing pre-heat drying and aging drying by a usual method. The negative electrode mixture paste thus obtained was uniformly applied and filled over the entire surface of the lattice-like portion of the negative electrode current collector plate, and then, the negative electrode plate (before formation) was produced by performing pre-heat drying and aging drying by a usual method.
Next, for each sample, the negative electrode plate before formation was placed in a polyethylene bag-shaped separator, and 7 separators in which the negative electrode plate before formation was placed and 6 positive electrode plates before formation were alternately laminated, to obtain a laminate. Next, a cast device of COS (cast strip) system was used to form strips, intermediate posts, and terminal posts on the positive and negative electrode plates before formation of each laminate, thereby obtaining a plate group.
Six electrode plate groups are prepared for each sample, and placed in each cell chamber of a cell container, and the liquid lead storage batteries for nos. 1 and 3 to 30 are assembled (before formation) by performing normal steps such as resistance welding of intermediate electrode posts between adjacent cell chambers, thermal welding of the cell container and a lid, injection of an electrolyte into each cell chamber from each injection port, and blocking of the injection port by a liquid plug or the like.
The electrolyte was injected by injecting dilute sulfuric acid having a specific gravity of 1.250 (20 ℃ conversion value) into each cell.
Then, the battery case was formed so that the specific gravity of the electrolyte after the battery case formation was 1.285 (20 ℃ C. Conversion value), whereby two lead storage batteries of Nos. 1 and 3 to 30 were obtained, respectively.
[ Measurement of composition of lead alloy ]
The alloy composition of the positive electrode collector plate (after formation) was measured by disassembling one of the obtained two lead storage batteries.
Specifically, first, the electrode plate group is taken out from two adjacent battery cells (third battery cell) of the battery cells (first battery cell) in which the electrode plate group having the positive electrode terminal post is housed, and the positive electrode plate disposed on the fourth battery cell side is taken out after the electrode plate group is decomposed. Then, the tab portion of the positive electrode collector plate was cut from the removed positive electrode plate, and the surface of the tab portion was polished to expose the metallic luster surface. Then, the ear after polishing was used as a sample, and quantitative analysis was performed by a conventionally known method using a solid-state light-emitting analyzer (OES: PDA-7000 manufactured by Shimadzu corporation).
[ Experiment and evaluation ]
As an experiment for evaluating high temperature durability, "JISD 5301" was performed using the remaining one of the two obtained lead storage batteries at 75 ℃. 2019", a light load life test specified in the following.
Specifically, each lead acid battery was left in a water tank at 75 ℃, and the discharge (240±1 seconds at a discharge current of 25.0±0.1A) and the charge (600±1 seconds at a discharge current of 14.80v±0.03V) were repeated, whereby the amount of liquid reduction (the amount of reduction in water content of the electrolyte) was measured every 480 cycles, and the supply of purified water in the same amount as the amount of liquid reduction and the life was determined. In the life determination, each lead acid battery was continuously discharged for 30 seconds at the rated cold crank starting current, and the life was determined when the 30 th second voltage was 7.2V or less.
Regarding the measurement of the liquid reduction amount, the mass of the battery was measured every 480 cycles, and the reduction amount from the mass before the experiment was calculated as the liquid reduction amount. Then, the cumulative amount of the liquid reduction at the 1920-time end points (the total value of the liquid reduction calculated every 480 times) was investigated. For the sample that reached the life until the number of cycles (the number of repetitions of discharging and charging) reached 1920 times, the cumulative liquid reduction amount was not measured.
Table 1 shows the results of these experiments together with the composition of the lead alloy forming the positive electrode collector plate of each lead acid battery and the determination of the cost of the lead alloy.
The judgment of the cost of the lead alloy is described as "verygood" when the cost is equal to or less than 1.05 times the cost of the lead alloy used in No.1, as "good" when the cost is 1.05 times or more and less than 1.08 times, as "delta" when the cost is 1.08 times or more and less than 1.10 times, and as "x" when the cost is 1.10 times or more.
In addition, since the criterion of the high temperature durability in the experimental results is 2000 cycles or more, it is marked "x" when the number of cycles is less than 2000, it is marked "o" when the number of cycles is 2000 or more and 4000 or less, and it is marked "jingjing" when the number of cycles is more than 4000. The judgment of the liquid reduction characteristics (whether or not the reduction of the electrolyte is suppressed) is indicated as "very good" when the cumulative liquid reduction amount at 1920 cycle time points is 350g or less, indicated as "good" when it exceeds 350g and is less than 400g, and indicated as "good" when it exceeds 400 g.
Further, comprehensive determination based on the experimental results was performed as follows. When all of the judgment is "excellent", the judgment is "excellent". When any one of the high temperature durability, the liquid reducing property, and the cost is determined to be "o", it is referred to as "o". When any one of the high temperature durability, the liquid reducing property, and the cost is determined as "Δ", the determination is made as "Δ". When any one of the high temperature durability, the liquid reducing property, and the cost is determined to be "x", it is referred to as "x".
TABLE 1
The following is apparent from the results in Table 1.
＜No.1＞
The lead acid battery of No.1 was a conventional example based on cost, and as a result, the life obtained in a light load life test (test for evaluating high temperature durability) at 75℃was 1920 cycles, and the cumulative liquid reduction was 400g.
The lead alloy forming the positive electrode collector plate of the lead acid battery of No.1 has a calcium content of 0.090 mass% which is greater than the upper limit of the calcium content of the lead alloy forming the positive electrode collector plate of the lead acid battery of the first embodiment (hereinafter referred to as "first lead alloy"). The tin content of the lead alloy forming the positive electrode collector plate was 1.10 mass% and was greater than the upper limit of the tin content of the first lead alloy. The lead alloy forming the positive electrode collector plate does not contain silver as an essential component of the first lead alloy. The content of bismuth in the lead alloy forming the positive electrode collector plate was 0.0200 mass% and was greater than the upper limit of the content of bismuth in the lead alloy forming the positive electrode collector plate of the lead storage battery according to the second embodiment (hereinafter referred to as "second lead alloy").
In this way, in the lead acid battery of No.1, regarding the composition of the lead alloy forming the positive electrode collector plate, the calcium content is excessive as compared with the first lead alloy, the corrosion resistance of the positive electrode collector plate is insufficient due to the absence of silver, and the performance of suppressing the reduction of the electrolyte is insufficient due to the slightly more bismuth (more bismuth than the second lead alloy).
＜No.2＞
The positive electrode collector plate of No.2 is formed of a lead alloy having a content of tin, silver, bismuth, and barium in the alloy composition within a range of a lead alloy forming the positive electrode collector plate of the lead acid battery of the fifth aspect (hereinafter referred to as "fifth lead alloy"), and having a content of calcium less than a lower limit value of a content of calcium in the lead alloy forming the positive electrode collector plate of the lead acid battery of the fourth aspect (hereinafter referred to as "fourth lead alloy").
The positive electrode collector plate of No.2 is considered to have a calcium content of 0.030 mass% in the lead alloy forming the positive electrode collector plate, and is less than the lower limit of the calcium content of the fourth lead alloy, whereby casting defects are generated.
＜No.3～No.8＞
The content of tin, silver, and bismuth in the lead alloy forming the positive electrode collector plate of the lead storage battery of nos. 3 to 8 are the same in the range of the lead alloy forming the positive electrode collector plate of the lead storage battery of the third embodiment (hereinafter referred to as "third lead alloy") and the lead alloy forming the positive electrode collector plate of the lead storage battery of the sixth embodiment (hereinafter referred to as "sixth lead alloy"), and the content of barium is 0.001 mass% (in the range of the sixth alloy) or 0.000 mass% (in the range of the third alloy), and the content of calcium is different (in the ranges of the first and fourth alloys).
The lead-acid batteries of Nos. 3 to 8 can have excellent high-temperature durability of 2500 cycles or more and particularly excellent liquid-reducing characteristics of 350g or less in the cumulative liquid-reducing amount. In addition, the lead alloy forming the positive electrode collector plate has a higher silver content than the lead storage battery of No.1, but has a lower calcium and tin content, so that the manufacturing cost can be reduced. In particular, since tin is expensive, the tin content can be made about half, and the effect of reducing the material cost is large.
The lead alloys of nos. 3 and 5 to 8, which form the positive electrode collector plates, have the same contents of tin, silver, bismuth and barium (the range of the sixth alloy), and the calcium contents are different in the range of the fourth alloy. The lead alloy forming the positive electrode collector plate of No.7 has a calcium content outside the range of the sixth alloy, and the lead alloy forming the positive electrode collector plate of No.8 has a calcium content outside the range of the fifth alloy.
Among the lead acid batteries of Nos. 3,5 to 8, the lead acid batteries of Nos. 3,5 and 6 have a positive electrode collector plate made of a lead alloy having a content of not only tin, silver, bismuth and barium but also calcium within the range of the sixth alloy, and thus have excellent high-temperature durability of 4000 cycles or more and excellent liquid-reducing characteristics of 350g or less in cumulative liquid-reducing amount.
In addition, when No.4 and No.5, in which the content of barium alone is different from each other, were compared, the lead storage battery of No.5 having a positive electrode collector plate formed of a lead alloy containing 0.001 mass% of barium was superior in high-temperature durability to the lead storage battery of No.4 having a positive electrode collector plate formed of a lead alloy containing no barium (0.000 mass%).
＜No.5、No.9～No.15＞
The lead alloys of the lead batteries of Nos. 5 and 9 to 14, which form the positive electrode collector plate, have different contents of calcium, silver, bismuth and barium in the fourth alloy range and different contents of tin. The lead alloy of No.15, which forms the positive electrode collector plate, contains calcium, bismuth and barium in the fourth alloy, and silver and tin in the fourth alloy.
Among the lead storage batteries of Nos. 5 and 9 to 15, the lead storage batteries of Nos. 5 and 10 to 14 have excellent high-temperature durability of 3000 cycles or more and excellent liquid-reducing characteristics in which the cumulative liquid-reducing amount is less than 400g by having a positive electrode collector plate formed of a lead alloy having not only calcium, silver, bismuth and barium but also tin contents within the range of the fourth alloy. Since the tin content of the alloy forming the positive electrode collector plate of the lead acid battery of No.15 is greater than the upper limit value of the fourth alloy, the manufacturing cost is significantly increased.
Among the lead storage batteries of Nos. 5 and 10 to 14, the lead storage batteries of Nos. 5 and 12 to 14 have a positive electrode collector plate formed of a lead alloy having a content of tin in the range of 0.060 mass% or more and 1.0 mass% in the range of the sixth alloy of calcium, silver, bismuth and barium, and further have excellent high-temperature durability of 4000 cycles or more and particularly excellent liquid-reducing characteristics of 350g or less in the cumulative liquid-reducing amount.
Among the lead storage batteries of nos. 5, 12 to 14, the lead storage batteries of nos. 5 and 12 can be reduced in cost as compared with the lead storage batteries of nos. 13 and 14 by having the positive electrode collector plate formed of a lead alloy having not only calcium, silver, bismuth and barium but also tin contents within the range of the sixth alloy, and are excellent in particularly high-temperature durability of 4500 cycles or more, which is higher than that of the lead storage batteries of nos. 13 and 14. That is, by having the positive electrode collector plate formed of the lead alloy in the range of the sixth alloy, the cost reduction effect, particularly excellent high-temperature durability, and excellent liquid-reducing characteristics are obtained.
＜No.5、No.16～No.23＞
The lead alloys of the lead batteries of Nos. 5 and 16 to 23, which form the positive electrode collector plate, have different contents of calcium, tin, bismuth and barium in the fourth alloy range, and have different contents of silver.
Among the lead storage batteries of Nos. 5 and 16 to 23, the lead storage batteries of Nos. 5 and 19 to 22 have a positive electrode collector plate made of a lead alloy having a content of not only calcium, tin, bismuth and barium but also silver within the range of the fourth alloy, and thus have excellent high-temperature durability of 3000 cycles or more and particularly excellent liquid-reducing characteristics of 350g or less in the cumulative liquid-reducing amount.
Among the lead storage batteries of Nos. 5, 19 to 22, the lead storage batteries of Nos. 5, 19 and 20 have a positive electrode collector plate made of a lead alloy having a content of not only calcium, tin, bismuth and barium but also silver within the range of the sixth alloy, and thus have a particularly excellent high-temperature durability of 4500 cycles or more and a high cost reduction effect.
Further, the lead-acid batteries of nos. 5 and 20 to 22 have a positive electrode collector plate made of a lead alloy in which calcium, tin, bismuth and barium are in the range of the sixth alloy and the silver content is in the range of 0.020 mass% or more and 0.035 mass% or more, and thus have significantly excellent high-temperature durability of 4800 cycles or more.
＜No.5、No.24～No.30＞
The lead alloys of the lead batteries of Nos. 5 and 24 to 30, which form the positive electrode collector plate, have different contents of calcium, tin, silver and barium in the fifth alloy range, and have different contents of bismuth.
Among the lead storage batteries of Nos. 5 and 24 to 30, the lead storage batteries of Nos. 5 and 25 to 29 have excellent high-temperature durability over 3500 cycles and excellent liquid-reducing characteristics in which the cumulative liquid-reducing amount is less than 400g, by having a positive electrode collector plate formed of a lead alloy in which calcium, tin, silver, and barium are in the range of the fifth alloy and the content of bismuth is in the range of the fourth alloy.
Among the lead storage batteries of Nos. 5, 25 to 29, the lead storage batteries of Nos. 5, 26 and 27 have a positive electrode collector plate made of a lead alloy having not only calcium, tin, silver and barium but also a bismuth content within the range of the sixth alloy, and thus have particularly excellent high-temperature durability of 4500 cycles or more, high cost reduction effect and particularly excellent liquid-reducing characteristics of 350g or less in the cumulative liquid-reducing amount.
In the case of manufacturing the lead acid battery of No.24, a positive electrode collector plate was formed using a lead alloy obtained by completely removing Bi from a commercially available lead alloy (containing a small amount of Bi). This bismuth removal step costs a lot, and therefore, the cost increases.
The lead acid battery of No.24 uses the positive electrode collector plate made of a lead alloy described in patent document 1, and has a high-temperature durability as short as 1917 cycles. After the experiment, the battery was disassembled, and as a result, it was confirmed that significant growth occurred in the lattice-like portion of the positive electrode collector plate. Therefore, it is considered that the positive electrode mixture is detached from the lattice-like portion of the positive electrode collector plate, which is a cause of short life.
Description of the reference numerals
1: A polar plate group; 10: a positive plate; 11: a positive electrode collector plate; 12: ear parts of the positive electrode collector plate; 110: grid-like portions of the positive electrode collector plate; 111: an upper frame bone; 112: a lower frame bone; 113: a longitudinal frame bone; 114: a longitudinal frame bone; 115: a longitudinal inner bone; 116: transverse internal bone; 117: an opening portion; 13: a positive electrode belt; 14: a positive electrode terminal; 20: a negative plate; 22: ear parts of the negative electrode collector plate; 23: a negative electrode belt; 24: a negative electrode terminal; 30: a diaphragm; 41: a battery case; 43: and a cover.
Claims (7)
1. A lead-acid battery, which comprises a battery body,
The electrolyte solution and the laminate are provided,
The laminate is composed of a plurality of positive electrode plates and negative electrode plates alternately arranged and separators arranged between the positive electrode plates and the negative electrode plates,
The positive electrode plate has a positive electrode mixture containing a positive electrode active material and a positive electrode collector plate including a lattice-shaped portion holding the positive electrode mixture,
The positive electrode collector plate is formed of a lead alloy containing Ca in a range of 0.035 to 0.08 mass%, sn in a range of 0.50 to 1.0 mass%, ag in a range of 0.003 to 0.035 mass%, bi in a range of more than 0 to 0.02 mass%, and the balance of lead and unavoidable impurities.
2. A lead-acid battery, which comprises a battery body,
The electrolyte solution and the laminate are provided,
The laminate is composed of a plurality of positive electrode plates and negative electrode plates alternately arranged and separators arranged between the positive electrode plates and the negative electrode plates,
The positive electrode plate has a positive electrode mixture containing a positive electrode active material and a positive electrode collector plate including a lattice-shaped portion holding the positive electrode mixture,
The positive electrode collector plate is formed of a lead alloy containing Ca in a range of 0.035 to 0.07 mass%, sn in a range of 0.55 to 0.9 mass%, ag in a range of 0.010 to 0.030 mass%, bi in a range of 0.0001 to 0.010 mass%, and the balance of lead and unavoidable impurities.
3. A lead-acid battery, which comprises a battery body,
The electrolyte solution and the laminate are provided,
The laminate is composed of a plurality of positive electrode plates and negative electrode plates alternately arranged and separators arranged between the positive electrode plates and the negative electrode plates,
The positive electrode plate has a positive electrode mixture containing a positive electrode active material and a positive electrode collector plate including a lattice-shaped portion holding the positive electrode mixture,
The positive electrode collector plate is formed of a lead alloy containing Ca in a range of 0.035 to 0.06 mass%, sn in a range of 0.60 to 0.8 mass%, ag in a range of 0.015 to 0.025 mass%, bi in a range of 0.0005 to 0.005 mass%, and the balance of lead and unavoidable impurities.
4. A lead-acid battery, which comprises a battery body,
The electrolyte solution and the laminate are provided,
The laminate is composed of a plurality of positive electrode plates and negative electrode plates alternately arranged and separators arranged between the positive electrode plates and the negative electrode plates,
The positive electrode plate has a positive electrode mixture containing a positive electrode active material and a positive electrode collector plate including a lattice-shaped portion holding the positive electrode mixture,
The positive electrode collector plate is formed of a lead alloy containing Ca in a range of 0.035 to 0.08 mass%, sn in a range of 0.50 to 1.0 mass%, ag in a range of 0.003 to 0.035 mass%, bi in a range of more than 0 to 0.02 mass%, ba in a range of more than 0 to 0.001 mass%, and the balance of lead and unavoidable impurities.
5. A lead-acid battery, which comprises a battery body,
The electrolyte solution and the laminate are provided,
The laminate is composed of a plurality of positive electrode plates and negative electrode plates alternately arranged and separators arranged between the positive electrode plates and the negative electrode plates,
The positive electrode plate has a positive electrode mixture containing a positive electrode active material and a positive electrode collector plate including a lattice-shaped portion holding the positive electrode mixture,
The positive electrode collector plate is formed of a lead alloy containing Ca in a range of 0.035 to 0.07 mass%, containing Sn in a range of 0.55 to 0.9 mass%, containing Ag in a range of 0.010 to 0.030 mass%, containing Bi in a range of 0.0001 to 0.010 mass%, containing Ba in a range of more than 0 to 0.001 mass%, and the balance being lead and unavoidable impurities.
6. A lead-acid battery, which comprises a battery body,
The electrolyte solution and the laminate are provided,
The laminate is composed of a plurality of positive electrode plates and negative electrode plates alternately arranged and separators arranged between the positive electrode plates and the negative electrode plates,
The positive electrode plate has a positive electrode mixture containing a positive electrode active material and a positive electrode collector plate including a lattice-shaped portion holding the positive electrode mixture,
The positive electrode collector plate is formed of a lead alloy containing Ca in a range of 0.035 to 0.06 mass%, sn in a range of 0.60 to 0.8 mass%, ag in a range of 0.015 to 0.025 mass%, bi in a range of 0.0005 to 0.005 mass%, ba in a range of more than 0 to 0.001 mass%, and the balance of lead and unavoidable impurities.
7. The lead storage battery according to any one of claims 1 to 6, wherein,
The positive electrode collector plate is obtained by casting.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021148853A JP7198890B1 (en) | 2021-09-13 | 2021-09-13 | lead acid battery |
| JP2021-148853 | 2021-09-13 | ||
| PCT/JP2022/030675 WO2023037822A1 (en) | 2021-09-13 | 2022-08-10 | Lead storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117957676A true CN117957676A (en) | 2024-04-30 |
Family
ID=84777491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280061227.XA Pending CN117957676A (en) | 2021-09-13 | 2022-08-10 | Lead storage battery |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7198890B1 (en) |
| CN (1) | CN117957676A (en) |
| WO (1) | WO2023037822A1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040033157A1 (en) * | 2002-08-13 | 2004-02-19 | Johnson Controls Technology Company | Alloy for battery grids |
| JP4515055B2 (en) * | 2003-07-25 | 2010-07-28 | 古河電池株式会社 | Lattice substrate for lead storage battery and lead storage battery using the same |
| JP5858048B2 (en) * | 2011-11-16 | 2016-02-10 | 新神戸電機株式会社 | Lead acid battery |
| CN103199263B (en) * | 2013-03-27 | 2015-08-12 | 奇瑞汽车股份有限公司 | A kind of process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method |
| JP2016085859A (en) * | 2014-10-27 | 2016-05-19 | 日立化成株式会社 | Lead acid storage battery |
-
2021
- 2021-09-13 JP JP2021148853A patent/JP7198890B1/en active Active
-
2022
- 2022-08-10 CN CN202280061227.XA patent/CN117957676A/en active Pending
- 2022-08-10 WO PCT/JP2022/030675 patent/WO2023037822A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023041464A (en) | 2023-03-24 |
| WO2023037822A1 (en) | 2023-03-16 |
| JP7198890B1 (en) | 2023-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2330676B1 (en) | Lead acid storage battery | |
| JP5061451B2 (en) | Anode current collector for lead acid battery | |
| JP5012047B2 (en) | Lead acid battery | |
| WO2006049295A1 (en) | Negative electrode current collector for lead storage battery and lead storage battery including the same | |
| WO2013114822A1 (en) | Lead-acid battery | |
| US20200212504A1 (en) | Compact absorbent glass mat battery | |
| JP5656068B2 (en) | Liquid lead-acid battery | |
| EP3553870A1 (en) | Lead acid storage battery | |
| EP2901511B1 (en) | Lead-acid battery positive plate and alloy therefore | |
| JP4325153B2 (en) | Control valve type lead acid battery | |
| CN117957676A (en) | Lead storage battery | |
| EP3432394A1 (en) | Lead acid storage battery, forged grid and method for producing same | |
| JP5145644B2 (en) | Lead acid battery | |
| JP4904658B2 (en) | Method for producing lead-acid battery | |
| JP4026259B2 (en) | Sealed lead acid battery | |
| JP2024025093A (en) | Lead storage battery | |
| JP7128484B2 (en) | liquid lead acid battery | |
| JP2012138331A (en) | Lead storage battery and idling stop vehicle | |
| CN211320252U (en) | Lead-acid battery | |
| JP2024025092A (en) | Lead storage battery | |
| JP2006114416A (en) | Lead-acid battery | |
| JP2011159551A (en) | Lead-acid storage battery | |
| JP2016171018A (en) | Lead storage battery | |
| JP2022186315A (en) | liquid lead acid battery | |
| JP2023079571A (en) | liquid lead acid battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |