WO2017013822A1 - 鉛蓄電池 - Google Patents
鉛蓄電池 Download PDFInfo
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- WO2017013822A1 WO2017013822A1 PCT/JP2016/002501 JP2016002501W WO2017013822A1 WO 2017013822 A1 WO2017013822 A1 WO 2017013822A1 JP 2016002501 W JP2016002501 W JP 2016002501W WO 2017013822 A1 WO2017013822 A1 WO 2017013822A1
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- WIPO (PCT)
- Prior art keywords
- positive electrode
- electrode plate
- negative electrode
- region
- active material
- Prior art date
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/64—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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a lead storage battery for starting an automobile.
- lead-acid batteries used for starting automobiles lead-acid batteries used for automobiles that perform idling stop control are discharged to a relatively deep SOC (State Of Charge) region, and thus are required to have durability against repeated deep discharges. It is done.
- SOC State Of Charge
- Patent Documents 1 and 2 disclose a technique for optimizing the pore structure of the positive electrode active material based on the result of a cycle life test including a relatively deep discharge, and the automobile that performs the idling stop control described above. Recalls the possibility of applying to lead-acid batteries for industrial use.
- the present disclosure has been made in view of such problems, and an object thereof is to provide a highly reliable lead-acid battery that can exhibit sufficient cycle life characteristics even when used under relatively severe idling stop control conditions. .
- a lead storage battery includes a positive electrode plate made of a positive electrode lattice and a positive electrode active material, a negative electrode plate made of a negative electrode lattice and a negative electrode active material, and an electrode plate group in which the positive electrode plate and the negative electrode plate are laminated via a separator. And a battery case having a plurality of cell chambers for accommodating the electrode plate group and the electrolyte solution, and a lid for sealing the opening of the battery case.
- the positive electrode active material has a maximum value of pore diameter distribution in a region A of 0.03 ⁇ m or more and 0.1 ⁇ m or less and a region B of 0.2 ⁇ m or more and 1.0 ⁇ m or less, and the maximum value AM of the region A
- the ratio AM / BM of the region B to the local maximum value BM is 0.34 or more and 0.70 or less
- the negative electrode lattice contains 1 ppm or more and 300 ppm or less of bismuth.
- At least a surface of the positive electrode plate is provided with a retainer mat made of a nonwoven fabric such as glass or polyester.
- FIG. 1 is a schematic view schematically showing a lead-acid battery according to an embodiment of the present invention.
- FIG. 1 is a schematic view schematically showing a lead storage battery according to an embodiment of the present invention.
- FIG. 2 is a view showing an example of a negative electrode plate that is a main part of the lead storage battery according to an embodiment of the present invention. .
- a plurality of electrode plate groups 4 in which the positive electrode plate 1 and the negative electrode plate 2 are laminated via the separator 3 are accommodated in a battery case 5 having a plurality of cell chambers 5a together with an electrolytic solution (not shown). The opening is sealed by the lid 6.
- the positive electrode plate 1 is composed of a positive electrode lattice 1a and a positive electrode active material 1b
- the negative electrode plate 2 is composed of a negative electrode lattice 2a and a negative electrode active material 2b.
- the positive electrode active material 1b has a maximum value of pore distribution in a region A of 0.03 ⁇ m to 0.1 ⁇ m and a region B of 0.2 ⁇ m to 1.0 ⁇ m, respectively, and the region
- the ratio AM / BM between the maximum value AM of A and the maximum value BM of the region B is 0.34 or more and 0.70 or less.
- FIG. 3 is a diagram showing an example of the pore distribution of the positive electrode active material, which is the first feature of the embodiment of the present invention.
- the negative electrode lattice 2a includes 1 ppm or more and 300 ppm or less of bismuth.
- the sulfate ion concentration of the electrolyte solution in the upper layer is changed to the sulfate ion of the electrolyte solution in the lower layer while repeated charge and discharge that frequently discharges a large current in an environment where the SOC is less than 100%.
- a phenomenon called so-called stratification occurs that is lower than the concentration. If it does so, it will become difficult to produce
- the lower layer part where the sulfate ion concentration is relatively excessive causes an unbalance that it is difficult to separate the sulfate ion from the lead sulfate (it becomes difficult to charge), and the excess lead sulfate in the lower layer part is deposited and discharged.
- the overall reaction slows down, resulting in a decrease in cycle life characteristics.
- This stratification is eliminated by stirring the electrolyte with the gas generated during the hydrolysis (gas generation) of the electrolyte that occurs at the end of charging.
- the SOC is intentionally controlled to be less than 100%, the end of charge cannot be reached, and thus the above-described effect cannot be expected.
- the first feature is that in the positive electrode active material 1b, the region A of 0.03 ⁇ m or more and 0.1 ⁇ m or less and the region B of 0.2 ⁇ m or more and 1.0 ⁇ m or less have maximum values of pore distribution, respectively.
- the ratio AM / BM of the maximum value AM in the region A and the maximum value BM in the region B is set to 0.34 or more and 0.70 or less.
- metallic lead and lead monoxide are classified, and the maximum value is shifted from region B to a region of 1.0 ⁇ m to 5.0 ⁇ m.
- the region B has a maximum value BM.
- the region A can also have a maximum value AM.
- this ratio AM / BM needs to be 0.34 or more and 0.70 or less. Specifically, if the amount of red lead added to the paste is reduced, AM decreases, and if the amount of red lead increases, AM increases, so by adjusting the amount of red lead during paste preparation, AM / BM can be optimized.
- the second feature is that the negative electrode lattice 2a contains 1 ppm or more and 300 ppm or less of bismuth. Due to the presence of an appropriate amount of bismuth in the negative electrode lattice 2a, the hydrogen overvoltage is reduced, hydrogen gas is easily generated even if the SOC is less than 100%, and the electrolyte is liable to diffuse, resulting in stratification. Will be resolved.
- a lead-acid battery that exhibits sufficient life characteristics while maintaining high capacity even when charging and discharging are repeated in an environment where the SOC is less than 100%. Will be able to provide.
- the effect of the embodiment of the present invention is further enhanced by providing a retainer mat on the surface of the positive electrode plate 1.
- the reason is that the ratio AM / BM is shifted to a relatively large range, so that the positive electrode active material 1b softens and falls off from the positive electrode plate 1 to reduce the capacity (deteriorate cycle life characteristics).
- the physical retention of the retainer mat prevents the positive electrode active material 1b from falling off.
- the lead acid battery produced in the present example is a D26L type lead acid battery defined in JIS D5301.
- Each cell chamber 5a accommodates eight positive electrode plates 1 and nine negative electrode plates 2.
- the positive electrode plate 1, except for the battery C-1, is in a state in which a retainer mat is applied to the surface thereof. The mat and the positive electrode plate 1 are in contact with each other.
- the positive electrode plate 1 is a positive electrode lattice 1a made of a lead alloy sheet (thickness: 1.1 mm) containing calcium, which is a precursor of a positive electrode active material 1b prepared by kneading lead oxide powder with sulfuric acid and purified water. It was prepared by filling (expanded lattice).
- the negative electrode plate 2 is prepared by adding a paste which is a precursor of the negative electrode active material 2b prepared by adding carbon and an organic additive to a lead oxide powder and kneading with sulfuric acid and purified water.
- a negative electrode grid 2a expanded grid made of a lead alloy sheet (thickness 1.1 mm) was prepared.
- the mass ratio of bismuth included in the negative electrode lattice 2a was appropriately changed so as to have the values shown in Table 1.
- the negative electrode plate 2 is accommodated in a polyethylene bag-like separator 3 and alternately stacked with the positive electrode plates 1, and the eight positive electrode plates 1 and nine negative electrode plates.
- the electrode group 4 in which 2 and 2 were laminated via the separator 3 was produced.
- the electrode plate group 4 was accommodated in cell chambers 5a divided into six, and six cells were directly connected. Furthermore, chemical conversion was performed by adding an electrolytic solution composed of dilute sulfuric acid to obtain a lead storage battery.
- Cycle life characteristic After making SOC into 90% with respect to the produced lead acid battery, it evaluated by the following procedure.
- Battery capacity A fully charged battery is discharged at a 5-hour rate current until the terminal voltage reaches 10.5 V, and the amount of discharge electricity at that time is measured.
- Table 1 shows the ratio (%) of the discharge electricity amount of each battery as the battery capacity together with the configuration conditions.
- Contrast batteries A-1 to A-7 Contrast batteries A-1 to A-7.
- Battery A-1 having a ratio AM / BM of less than 0.34 has an extremely small capacity. The reason is that the maximum value AM of the region A in which the capacity of the positive electrode plate 1 is increased is relatively small, but the reason why this ratio has an inflection point at 0.34 is unknown.
- the battery A-7 in which this ratio exceeds 0.70 has deteriorated cycle life characteristics.
- the positive electrode active material 1b was softened. Therefore, it can be seen that the appropriate range of the ratio AM / BM is 0.34 or more and 0.70 or less.
- Contrast batteries B-1 to B-8 Both the battery B-1 in which the amount of bismuth in the negative electrode lattice 2a is less than 1 ppm and the battery B-8 in which the amount of bismuth exceeds 300 ppm have deteriorated cycle life characteristics. As a result of disassembling each battery, it was confirmed that the stratification of the electrolyte was remarkable in the battery B-1, and that the electrolyte was extremely decreased in the battery B-9. Therefore, it can be seen that an appropriate range of bismuth included in the negative electrode lattice 2a is 1 ppm or more and 300 ppm or less.
- both the ratio AM / BM and the amount of bismuth contained in the negative electrode lattice 2a are within an appropriate range. I know what to do.
- the battery C-1 has the same configuration as the battery A-4 except that the retainer mat is not applied to the surface of the positive electrode plate 1 with respect to the battery A-4. is doing. This is because the retainer mat suppresses the falling off of the positive electrode active material 1b by physical holding force, but this effect is not exhibited in the battery C-1 because the retainer mat does not exist.
- the battery C-1 was actually disassembled, it was confirmed that the positive electrode active material 1b was slightly softened and dropped off. Therefore, it is preferable to provide a retainer mat on the surface of the positive electrode plate 1.
- the present invention is useful in a lead storage battery used in an automobile that performs idling stop control.
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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)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
本実施例で作製した鉛蓄電池は、JISD5301に規定するD26Lタイプの大きさの鉛蓄電池である。各セル室5aには、8枚の正極板1と9枚の負極板2とが収容され、正極板1は、電池C-1を除き、リテーナマットが表面に付与された状態であり、リテーナマットと正極板1とが当接している。
作製した鉛蓄電池に対し、SOCを90%にしてから、次の手順で評価した。
A.45Aで59秒間放電する。
B.300Aで1秒間放電する。
C.制限電流100A条件下で60秒間14.0V定電圧充電する。
D.A、B、Cの順に行う充放電サイクルを3600回繰り返した後、リフレッシュ充電として20分間14.0V定電圧充電する。
満充電状態の電池を、5時間率電流で端子電圧が10.5Vに到達するまで放電し、そのときの放電電気量を計測し、電池C-1の放電電気量を100として、各々の電池の放電電気量の比率(%)を電池容量として、構成条件と共に表1に記す。
1a 正極格子
1b 正極活物質
2 負極板
2a 負極格子
2b 負極活物質
3 セパレータ
4 極板群
5 電槽
5a セル室
6 蓋
Claims (2)
- 正極格子と正極活物質とからなる正極板と、
負極格子と負極活物質とからなる負極板と、
前記正極板と前記負極板とをセパレータを介して積層した極板群と、
前記極板群と電解液とを収納するためのセル室を複数個有する電槽と、
前記電槽の開口部を封口する蓋と、からなり、
前記正極活物質は、0.03μm以上0.1μm以下の領域Aと0.2μm以上1.0μm以下の領域Bとに、それぞれ細孔直径分布の極大値を有し、かつ領域Aの極大値AMと領域Bの極大値BMとの比AM/BMが0.34以上0.70以下であり、
前記負極格子は1ppm以上300ppm以下のビスマスを含む、鉛蓄電池。 - 少なくとも前記正極板の表面にリテーナマットを付与した状態である、請求項1に記載の鉛蓄電池。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201680035971.7A CN107683544B (zh) | 2015-07-21 | 2016-05-24 | 铅蓄电池 |
DE112016003283.8T DE112016003283T5 (de) | 2015-07-21 | 2016-05-24 | Bleisäure-speicherbatterie |
JP2017529435A JP6766811B2 (ja) | 2015-07-21 | 2016-05-24 | 鉛蓄電池 |
US15/744,534 US20180205072A1 (en) | 2015-07-21 | 2016-05-24 | Lead acid storage battery |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015143904 | 2015-07-21 | ||
JP2015-143904 | 2015-07-21 |
Publications (1)
Publication Number | Publication Date |
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WO2017013822A1 true WO2017013822A1 (ja) | 2017-01-26 |
Family
ID=57834058
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2016/002501 WO2017013822A1 (ja) | 2015-07-21 | 2016-05-24 | 鉛蓄電池 |
Country Status (5)
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US (1) | US20180205072A1 (ja) |
JP (1) | JP6766811B2 (ja) |
CN (1) | CN107683544B (ja) |
DE (1) | DE112016003283T5 (ja) |
WO (1) | WO2017013822A1 (ja) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01161670A (ja) * | 1987-12-17 | 1989-06-26 | Matsushita Electric Ind Co Ltd | 鉛蓄電池 |
JPH0765822A (ja) * | 1993-08-23 | 1995-03-10 | Matsushita Electric Ind Co Ltd | 鉛蓄電池 |
JPH08339820A (ja) * | 1995-06-09 | 1996-12-24 | Japan Storage Battery Co Ltd | 負極吸収式シ−ル形鉛蓄電池 |
JPH1069900A (ja) * | 1996-08-28 | 1998-03-10 | Matsushita Electric Ind Co Ltd | 鉛蓄電池用極板 |
JPH1173950A (ja) * | 1997-08-28 | 1999-03-16 | Matsushita Electric Ind Co Ltd | 鉛蓄電池の製造法 |
JP2002175798A (ja) * | 2000-12-08 | 2002-06-21 | Japan Storage Battery Co Ltd | 密閉型鉛蓄電池 |
JP2004079198A (ja) * | 2002-08-09 | 2004-03-11 | Japan Storage Battery Co Ltd | 鉛蓄電池 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH079280B2 (ja) * | 1987-09-09 | 1995-02-01 | 三菱電機株式会社 | ガスボンベの安全取扱い装置 |
US4871428A (en) * | 1988-03-24 | 1989-10-03 | C & D Charter Power Systems, Inc. | Method for in situ forming lead-acid batteries having absorbent separators |
JP2536251B2 (ja) * | 1990-07-24 | 1996-09-18 | 新神戸電機株式会社 | 鉛蓄電池 |
KR20090125253A (ko) * | 2007-03-02 | 2009-12-04 | 존슨 컨트롤스 테크놀러지 컴퍼니 | 배터리용 음극 그리드 |
US9997782B2 (en) * | 2014-04-08 | 2018-06-12 | Hitachi Chemical Company, Ltd | Bisphenol-based resin, electrode, lead storage battery, production methods for these, and resin composition |
-
2016
- 2016-05-24 US US15/744,534 patent/US20180205072A1/en not_active Abandoned
- 2016-05-24 DE DE112016003283.8T patent/DE112016003283T5/de active Pending
- 2016-05-24 JP JP2017529435A patent/JP6766811B2/ja active Active
- 2016-05-24 WO PCT/JP2016/002501 patent/WO2017013822A1/ja active Application Filing
- 2016-05-24 CN CN201680035971.7A patent/CN107683544B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01161670A (ja) * | 1987-12-17 | 1989-06-26 | Matsushita Electric Ind Co Ltd | 鉛蓄電池 |
JPH0765822A (ja) * | 1993-08-23 | 1995-03-10 | Matsushita Electric Ind Co Ltd | 鉛蓄電池 |
JPH08339820A (ja) * | 1995-06-09 | 1996-12-24 | Japan Storage Battery Co Ltd | 負極吸収式シ−ル形鉛蓄電池 |
JPH1069900A (ja) * | 1996-08-28 | 1998-03-10 | Matsushita Electric Ind Co Ltd | 鉛蓄電池用極板 |
JPH1173950A (ja) * | 1997-08-28 | 1999-03-16 | Matsushita Electric Ind Co Ltd | 鉛蓄電池の製造法 |
JP2002175798A (ja) * | 2000-12-08 | 2002-06-21 | Japan Storage Battery Co Ltd | 密閉型鉛蓄電池 |
JP2004079198A (ja) * | 2002-08-09 | 2004-03-11 | Japan Storage Battery Co Ltd | 鉛蓄電池 |
Also Published As
Publication number | Publication date |
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CN107683544A (zh) | 2018-02-09 |
DE112016003283T5 (de) | 2018-04-12 |
US20180205072A1 (en) | 2018-07-19 |
JP6766811B2 (ja) | 2020-10-14 |
CN107683544B (zh) | 2021-01-19 |
JPWO2017013822A1 (ja) | 2018-05-10 |
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