JP4701623B2 - Sealed battery - Google Patents
Sealed battery Download PDFInfo
- Publication number
- JP4701623B2 JP4701623B2 JP2004107612A JP2004107612A JP4701623B2 JP 4701623 B2 JP4701623 B2 JP 4701623B2 JP 2004107612 A JP2004107612 A JP 2004107612A JP 2004107612 A JP2004107612 A JP 2004107612A JP 4701623 B2 JP4701623 B2 JP 4701623B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- diameter
- flange portion
- terminal
- grommet
- 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.)
- Expired - Lifetime
Links
- 238000003860 storage Methods 0.000 claims description 75
- 238000007789 sealing Methods 0.000 claims description 37
- 238000005452 bending Methods 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 45
- 238000007600 charging Methods 0.000 description 27
- 239000007789 gas Substances 0.000 description 22
- 229910052759 nickel Inorganic materials 0.000 description 22
- -1 nickel metal hydride Chemical class 0.000 description 21
- 229910052987 metal hydride Inorganic materials 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
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- 239000011149 active material Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
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- 238000002156 mixing Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
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- 229920005672 polyolefin resin Polymers 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052769 Ytterbium Inorganic materials 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 3
- 239000012792 core layer Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
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- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
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- 239000002562 thickening agent Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229910018007 MmNi Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
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- 239000006260 foam Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000652 nickel hydride Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
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- 238000004804 winding Methods 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 239000003273 ketjen black Substances 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
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- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 208000022133 pulmonary valve agenesis Diseases 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
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- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- 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
Landscapes
- Gas Exhaust Devices For Batteries (AREA)
- Secondary Cells (AREA)
Description
本発明は、１時間未満という極めて短時間で充電可能であって、かつ安全に急速充電を行うことができる密閉形蓄電池に関するものである。 The present invention relates to a sealed storage battery that can be charged in an extremely short time of less than one hour and that can be rapidly charged safely.
ニッケル水素蓄電池やニッケルカドミウム蓄電池などの密閉形アルカリ蓄電池は、充放電サイクル性能、耐過充電性能、耐過放電性能に優れ、単位体積当たりのエネルギー密度が高いところから携帯機器用電源などサイクルサービスに適した電源として重用されている。
近年、これらサイクルサービス用電源である蓄電池に対して、１時間未満という従来の充電では行われていない短時間で充電を完了させたいとの要求が高まっている。しかしながら、従来の密閉形のニッケル水素蓄電池やニッケルカドミウム蓄電池を従来のように単なる定電流充電や定電圧充電によって１時間を切るようなレートの急速充電を行うとすると、充電時に正極から発生する酸素ガスによって蓄電池の内圧が上昇し、かつ、蓄電池の温度が上昇するために、充電中に破裂の虞が生じたり、蓄電池の性能が劣化する虞があるために充電が困難であった。
Sealed alkaline storage batteries such as nickel metal hydride storage batteries and nickel cadmium storage batteries have excellent charge / discharge cycle performance, overcharge resistance performance, and overdischarge resistance performance, and are suitable for cycle services such as power supplies for portable devices due to their high energy density per unit volume. It is heavily used as a suitable power source.
In recent years, there has been a growing demand for these storage batteries, which are power sources for cycle services, to complete charging in a short time that is not performed in conventional charging of less than one hour. However, if the conventional sealed nickel-metal hydride storage battery or nickel cadmium storage battery is charged rapidly at a rate of less than 1 hour by simple constant current charging or constant voltage charging as in the past, oxygen generated from the positive electrode during charging Since the internal pressure of the storage battery is increased by the gas and the temperature of the storage battery is increased, there is a risk of explosion during charging or the performance of the storage battery may be deteriorated, so that charging is difficult.
これらの課題を解決するために、近年、密閉形アルカリ蓄電池の充電制御方式の一つとして、蓄電池に、電池内部の圧力変動に応じて電池の極板と外部端子を結ぶ回路のオン・オフを切り替えるスイッチを内蔵させる方式が提案されている。該スイッチを内蔵することと、従来の密閉形蓄電池に採用されている圧力開放弁を併用することによって、充電時に蓄電池内部の圧力が上昇するのを極力抑え、充放電を繰り返すことによって蓄電池の性能が劣化するのを防ぐと共に万一蓄電池内部の圧力が異常に上昇したときに蓄電池内部に蓄積したガスを放出する方式が提案されている。（例えば、特許文献１参照） In order to solve these problems, as one of charge control methods for sealed alkaline storage batteries in recent years, the storage battery is turned on / off by a circuit that connects the battery electrode plate and external terminals in accordance with the pressure fluctuation inside the battery. A method of incorporating a switch for switching has been proposed. The built-in switch and the combined use of the pressure release valve used in the conventional sealed storage battery suppress the rise of the internal pressure of the storage battery as much as possible during charging, and the performance of the storage battery by repeating charging and discharging. There has been proposed a method for preventing gas from deteriorating and releasing the gas accumulated in the storage battery when the internal pressure of the storage battery rises abnormally. (For example, see Patent Document 1)
また、該文献に記載されているＦｉｇ２Ａ、Ｆｉｇ２Ｂによれば、接続端子２３に小径の透孔３１を設け、常時は弾性体２８で該透孔を封止し、蓄電池内の圧力が前記スイッチの動作圧力を超えてさらに上昇したときに、該透孔３１を通してガスを外部に排出する安全弁の構造が示されている。しかし、蓄電池内の圧力が上昇した状態では接続端子２３が上方に移動し弾性体２８の変形が大きくなって接続端子を押圧する力が強くなっているために、前記接続端子に設けた小径３１の透孔が開口し難く、安全弁の動作圧力が安定しないという欠点があった。 In addition, according to FIG. 2A and FIG. 2B described in this document, a small-diameter through hole 31 is provided in the connection terminal 23, and the through hole is normally sealed with an elastic body 28. The structure of a safety valve that discharges gas to the outside through the through-hole 31 when the operating pressure is further increased is shown. However, in the state where the pressure in the storage battery is increased, the connection terminal 23 moves upward, the deformation of the elastic body 28 increases, and the force pressing the connection terminal increases, so that the small diameter 31 provided on the connection terminal is increased. However, there is a drawback that the operating pressure of the safety valve is not stable.
本発明は、安全弁の動作圧力が安定した急速充電可能な密閉型蓄電池を提供しようとすつものである。 The present invention is intended to provide a fast-chargeable sealed storage battery in which the operating pressure of the safety valve is stable.
前記課題を解決するために、本発明に係る密閉形電池は、密閉形蓄電池内部のガス圧が上昇したときに、電極と外部端子を結ぶ回路をオフにするスイッチと、蓄電池内部の圧力が異常に上昇したときに蓄電池内部に蓄積したガスを開放するための安全弁を備えた密閉形蓄電池であって、電槽の開放端を気密に密閉するグロメットに配置した透孔を挿通する接続端子に設けられた第１端子と、蓄電池内部に固定された第２端子とを備え、前記グロメットの撓み変形に伴う前記第１の端子の移動によって前記第１の端子と前記第２端子とが当接・離脱することによって、前記スイッチが前記電極と前記外部端子を結ぶ回路のオン・オフの切り替えを行うとともに、前記安全弁が、前記グロメットに破断を生ぜしめることによって、ガスを排出すること、および、前記接続端子に円形の内側フランジ部を設け、前記グロメットの外側にあって前記電槽の開放端に固定された封口板を備え、前記封口板に前記内側フランジ部と同心円をなす円形の透孔を設け、該透孔の直径をａｍｍ、前記内側フランジ部の直径をｂ ｍｍとしたときに、１≦ａ−ｂ≦３の関係が成り立つことを特徴とする。 In order to solve the above problems, a sealed battery according to the present invention includes a switch for turning off a circuit connecting an electrode and an external terminal when the gas pressure inside the sealed battery increases, and the pressure inside the battery is abnormal. Is a sealed storage battery equipped with a safety valve for releasing the gas accumulated in the storage battery when the battery is lifted, and provided at a connection terminal through which a through hole arranged in a grommet that hermetically seals the open end of the battery case The first terminal and the second terminal fixed inside the storage battery, and the first terminal and the second terminal are brought into contact with each other by the movement of the first terminal accompanying the bending deformation of the grommet. By disconnecting, the switch turns on and off the circuit connecting the electrode and the external terminal, and the safety valve discharges gas by causing the grommet to break. And a circular inner flange portion on the connection terminal, a sealing plate fixed to the open end of the battery case on the outer side of the grommet, and concentric with the inner flange portion on the sealing plate When a circular through hole is provided, the diameter of the through hole is amm, and the diameter of the inner flange portion is b mm, the relationship 1 ≦ ab ≦ 3 is satisfied.
本発明に係る密閉形蓄電池は、前記接続端子に円形の内側フランジ部を設け、前記グロメットの外側にあって前記電槽の開放端に固定された封口板を備え、前記封口板に前記内側フランジ部と同心円をなす円形の透孔を設け、前記グロメットに前記内側フランジ部と同心円をなす外周及び内周を有するリング状の溝を設け、該透孔の直径をａｍｍ、前記内側フランジ部の直径をｂ ｍｍ、前記溝の前記外周の直径をｃ ｍｍ、前記内周の直径をｄｍｍとしたときに、ａ≦ｃであって、かつ、ｄ≦ｂ＜ａの関係が成り立つことが好ましい。 Hermetically sealed battery according to the present invention is provided with a inner flange portion of the circular before Symbol connecting terminals, comprising the battery container sealing plate which is fixed to an open end which are in the outside of the grommet, the inner to the sealing plate A circular through hole concentric with the flange portion is provided, and a ring-shaped groove having an outer periphery and an inner periphery concentric with the inner flange portion is provided in the grommet, the diameter of the through hole being a mm , the inner flange portion When the diameter of the groove is b mm , the diameter of the outer periphery of the groove is c mm , and the diameter of the inner periphery is d mm , a ≦ c and d ≦ b <a may be satisfied. preferable.
本発明によれば、前記安全弁の動作圧力が安定した急速充電可能な密閉形蓄電池を提供することができる。 By the present invention lever, the operating pressure of the safety valve can provide a stable rapidly rechargeable hermetically sealed battery was.
図１は、本発明の１実施形態に係る密閉形蓄電池１の要部断面図である。正極板、負極板およびセパレータの積層体を捲回してなる捲回式電極群が金属製電槽１３内に収納されている。該金属製電槽１３の開放端は、該開放端部に装着した熱可塑性樹脂の成形体であるグロメット９、該クロメットの中央部に設けた透孔に嵌着した円柱状の接続端子５によって気密に封止されている。キャップ状正極端子２と正極板３は、常時は、正極リ−ド片４、接続端子５、該接続端子５の側面に接合された板状部（外側フランジ部）６、封口板８からなる回路によって結ばれており、電気的に導通状態にある。 FIG. 1 is a cross-sectional view of a main part of a sealed storage battery 1 according to an embodiment of the present invention. A wound electrode group formed by winding a laminate of a positive electrode plate, a negative electrode plate and a separator is housed in the metal battery case 13. The open end of the metallic battery case 13 is formed by a grommet 9 which is a molded body of a thermoplastic resin attached to the open end, and a columnar connection terminal 5 fitted in a through hole provided in the center of the chromet. It is hermetically sealed. The cap-like positive electrode terminal 2 and the positive electrode plate 3 are normally composed of a positive electrode lead piece 4, a connection terminal 5, a plate-like part (outer flange part) 6 bonded to the side surface of the connection terminal 5, and a sealing plate 8. They are connected by a circuit and are in an electrically conductive state.
充電中に蓄電池内部の圧力が上昇した場合、前記グロメット９の水平壁１０が図の上方に向かって撓み、スイッチの第１端子である接続端子５の外側フランジ部６が上方に移動し、スイッチの第２端子である封口板８から離脱する（スイッチがオンからオフに切り替わる）ために正極板３と正極端子２を結ぶ回路が遮断される。
本発明者らは、電池内部のガス圧が上昇したときに電池内部に蓄積したガスを開放するための安全弁と、電池内部のガス圧が上昇したときに電極と外部端子を結ぶ回路をオンからオフに切り替えるスイッチを備えた密閉形蓄電池であって、
前記スイッチの動作圧力をＸ（ＭＰａ）とし、前記安全弁の動作圧力をＹ（ＭＰａ）としたときに、ＸおよびＹ−Ｘを特定の値に設定することによって充電受入率を低下させることなく、急速充電が可能であることを見いだした。
また、Ｙを特定の値とすることによって、電池を破裂させることなく急速充電を行うことができることを見いだした。
When the internal pressure of the storage battery rises during charging, the horizontal wall 10 of the grommet 9 bends upward in the figure, the outer flange portion 6 of the connection terminal 5 that is the first terminal of the switch moves upward, and the switch The circuit connecting the positive electrode plate 3 and the positive electrode terminal 2 is cut off because it is separated from the sealing plate 8 which is the second terminal (the switch is switched from on to off).
The present inventors turn on a safety valve for releasing the gas accumulated inside the battery when the gas pressure inside the battery rises, and a circuit connecting the electrode and the external terminal when the gas pressure inside the battery rises. A sealed battery with a switch to turn off,
When the operating pressure of the switch is X (MPa) and the operating pressure of the safety valve is Y (MPa), the charge acceptance rate is not lowered by setting X and YX to specific values, We found that fast charging is possible.
It was also found that rapid charging can be performed without rupturing the battery by setting Y to a specific value.
具体的には、蓄電池内部の圧力上昇時に極板と外部端子を結ぶ回路を遮断するスイッチ
の動作圧力Ｘを、Ｘ≧１．５ＭＰａとすると、急速充電を行ったときに高い充電受入率が
得られる。充電受入率を高めるためにはＸ≧１．８ＭＰａとすることがさらに好ましい。
Specifically, when the operating pressure X of the switch that cuts off the circuit connecting the electrode plate and the external terminal when the pressure inside the storage battery rises is X ≧ 1.5 MPa , a high charge acceptance rate is obtained when rapid charging is performed. can get. In order to increase the charge acceptance rate, it is more preferable that X ≧ 1.8 MPa .
電池内部のガス圧力上昇時に電極と外部端子を結ぶ回路を遮断する為に作動する電池の
スイッチ装置は、リレーと同様な原理から制作されており、数万回〜数百万回の作動に耐
えうるものの、万が一、故障をした場合、電池が破裂に至るなどの問題が発生する虞れが
ある。このため、万が一の故障を想定して電池の内圧を解放するための安全弁を備えるこ
とは、安全性確保のために欠かせない。
円筒形の密閉形蓄電池の場合、蓄電池内部の圧力が、３．５ＭＰａを超えると電池の封
口カシメ部が内部圧力に耐えきれずに破損してしまう虞があることが分かった。従って安
全弁の動作圧力Ｙを３．５ＭＰａ以下に設定することが望ましい。
円筒形密閉形蓄電池において、この電池の内圧を解放するための安全弁を３．５ＭＰ
ａ≧Ｙとすることによって、電池の破裂を確実に防ぐ事ができる。
Battery switch devices that operate to shut off the circuit that connects the electrode and external terminals when the gas pressure inside the battery rises are manufactured based on the same principle as relays, and can withstand operation of tens of thousands to millions of times. However, in the unlikely event of a failure, there is a risk that problems such as battery explosion may occur. For this reason, it is indispensable for ensuring safety to provide a safety valve for releasing the internal pressure of the battery in case of a failure.
In the case of a cylindrical sealed storage battery, it has been found that if the internal pressure of the storage battery exceeds 3.5 MPa, the sealing caulking portion of the battery cannot withstand the internal pressure and may be damaged. Therefore, it is desirable to set the operating pressure Y of the safety valve to 3.5 MPa or less.
In a cylindrical sealed storage battery, a safety valve for releasing the internal pressure of this battery is installed at 3.5MP.
By setting a ≧ Y, it is possible to reliably prevent the battery from bursting.
また、Ｙ−Ｘ≧０．３ＭＰａとしたときに優れた寿命特性を示した。優れた寿命特性を
得るためにはＸ≦３．０ＭＰａとすることが好ましく、Ｘ≦２．８ＭＰａとすることがさ
らに好ましい。
Moreover, when it was set as Y-X> = 0.3MPa , the outstanding lifetime characteristic was shown. In order to obtain excellent life characteristics, X ≦ 3.0 MPa is preferable, and X ≦ 2.8 MPa is more preferable.
本発明電池の安全弁の機構は、蓄電池内部の圧力が前記Ｙを超えたときに、前記グロメット９の水平壁１０に破断を生ぜしめることによって前記水平壁に生じた破断箇所を通して蓄電池内部に蓄積したガスを放出するものである。内部に蓄積されたガスは、水平壁の破断箇所およびキャップ状端子２に設けた透孔１４を経由して外部に放出される。
本発明に係る密閉形蓄電池のようにグロメット９の撓み変形に応じてオン・オフの切り替えを行うスイッチを備え、また、グロメット９の水平壁１０に破断させてガスを放出する安全弁を備える蓄電池においては、前記グロメット９が蓄電池内部の圧力の上昇に応じて敏感に撓み、所定の圧力で破断し、且つ、繰り返し撓み変形しても塑性変形し難い材料からなることが好ましい。具体的にはポリプロピレン（ＰＰ）やポリエチレン（ＰＥ）が好適であり、なかでも、ポリプロピレンがクリープ変形が小さいので好ましい材料である。また、グロメット９が容易に撓み変形し、かつ、３．５ＭＰａ以下の所定の圧力で破断を生じさせるにはグロメットの９の水平壁１０の厚さを特定の範囲に設定することが好ましい。具体的には、グロメット９の水平壁１０の厚さを０．３〜１．０ｍｍとするのが好ましく、０．３〜０．６ｍｍとするのがさらに好ましい。また、グロメット９の水平壁１０の直径ｅを出きるだけ大きくすることにより、該水平壁１０がより敏感に撓み易くなるが、１．５ＭＰａ以上の所定の圧力でスイッチをオフに切り替えるには、前記水平壁１０の直径ｅと電槽の内径の比（ｅ／電槽の内径）を０．５以上にすることが好ましく、０．６以上にすることがさらに好ましい。このことによって動作圧力の安定したスイッチを備える密閉形蓄電池とすることができるので好ましい。
When the pressure inside the storage battery exceeds Y, the safety valve mechanism of the battery of the present invention causes the horizontal wall 10 of the grommet 9 to rupture and accumulates in the storage battery through the ruptured portion generated in the horizontal wall. It emits gas. The gas accumulated inside is discharged to the outside through the broken portion of the horizontal wall and the through hole 14 provided in the cap-shaped terminal 2.
In a storage battery comprising a switch that switches on and off according to the bending deformation of the grommet 9 as in the sealed storage battery according to the present invention, and a safety valve that breaks the horizontal wall 10 of the grommet 9 to release gas. The grommet 9 is preferably made of a material that flexes sensitively as the internal pressure of the storage battery increases, breaks at a predetermined pressure, and hardly undergoes plastic deformation even when repeatedly deformed. Specifically, polypropylene (PP) and polyethylene (PE) are preferred, and polypropylene is a preferred material because of its small creep deformation. Moreover, it is preferable to set the thickness of the horizontal wall 10 of the grommet 9 within a specific range in order to cause the grommet 9 to be easily bent and deformed and to be broken at a predetermined pressure of 3.5 MPa or less. Specifically, the thickness of the horizontal wall 10 of the grommet 9 is preferably 0.3 to 1.0 mm, and more preferably 0.3 to 0.6 mm. In addition, by increasing the diameter e of the horizontal wall 10 of the grommet 9 as much as possible, the horizontal wall 10 is more susceptible to bending, but in order to switch the switch off at a predetermined pressure of 1.5 MPa or more, The ratio of the diameter e of the horizontal wall 10 to the inner diameter of the battery case (e / inner diameter of the battery case) is preferably 0.5 or more, and more preferably 0.6 or more. This is preferable because a sealed storage battery including a switch having a stable operating pressure can be obtained.
また、前記本発明に係る密閉形蓄電池の安全弁の機構においては、前記封口板８の中央部に円形の透孔を設け、前記接続端子５の下端部（電池にとって内側端部）に円形の内側フランジ部７を設け、前記封口板８の透孔の外周と内側フランジ部７の外周が電池を真上（正極端子側）から見たときに同心円になるように配置し、封口板８の透孔の直径をａｍｍ、内側フランジ部７の直径をｂｍｍとしたときに、ａ−ｂを１〜３ｍｍに設定することによって、安全弁の動作圧力の安定した安全弁を備える密閉形蓄電池が得られるので好ましい。 In the safety valve mechanism of the sealed storage battery according to the present invention, a circular through hole is provided in the central portion of the sealing plate 8, and a circular inner side is provided at the lower end portion (inner end portion for the battery) of the connection terminal 5. A flange portion 7 is provided, and the outer periphery of the through hole of the sealing plate 8 and the outer periphery of the inner flange portion 7 are arranged so as to be concentric when the battery is viewed from directly above (positive electrode terminal side). When the diameter of the hole is amm and the diameter of the inner flange portion 7 is bmm, by setting ab to 1 to 3 mm, a sealed storage battery having a safety valve with a stable operating pressure of the safety valve can be obtained, which is preferable. .
この作用の機構については必ずしも完全に解明されてはいないが、蓄電池内部の圧力が上昇して、グロメット９の水平壁１０が上方に向かって撓んだときに封口板８に設けた透孔のエッジと内側フランジブ７のエッジとで水平壁が挟まれた状態となり、水平壁１０が押し切られるので、単に水平壁１０が伸びて破断するのに比べて破断が生じるときの圧力が安定したものと考えられる。 Although the mechanism of this action has not been completely elucidated, when the pressure inside the storage battery rises and the horizontal wall 10 of the grommet 9 bends upward, the through holes provided in the sealing plate 8 Since the horizontal wall is sandwiched between the edge and the edge of the inner flange 7 and the horizontal wall 10 is pushed out, the pressure when the breakage occurs is stable compared to the horizontal wall 10 simply extending and breaking. Conceivable.
さらに、前記グロメット９の水平壁１０に、前記封口板８の透孔および内側フランジ部７と同心円状のリング状の溝１１を設け、且つ、該溝１１の外径をｃｍｍ、内径をｄｍｍとしたときに、ａ≦ｃであって、かつ、ｄ≦ｂ＜ａとすると、安全弁の動作圧力がさらに安定するので好ましい。この作用機構については必ずしも完全に解明されてはいないが、水平壁１０のうち溝１１を設けた部分は肉厚が小さいので、撓み変形が生じ易く該肉薄部分に前記封口板８に設けた透孔のエッジと内側フランジブ７のエッジがより強く肉薄部を圧接するためと考えられる。なお、溝１１の深さは特に限定されるものではないが溝１１の深さと水平壁の肉厚の比（溝１１の深さ／水平壁の肉厚）を０．２〜０．８に設定することが好ましく、０．５〜０．８に設定するのがさらに好ましい。該比が０．２未満では溝を設けた効果が得られず、０．８を超えると該溝を設けた部分の強度が低くなって、蓄電池をシールする工程で破断を生じる虞がある。また、該溝１１のの断面形状は特に限定されるものではなく、図１に示したように長方形の他断面形状が半円状、Ｕ字状などの溝も有効である。さらに、溝１１は、図１のように水平壁１０の内面の他に外面に設けても同様の効果が得られる。 Further, a ring-shaped groove 11 concentric with the through hole of the sealing plate 8 and the inner flange portion 7 is provided in the horizontal wall 10 of the grommet 9, and the outer diameter of the groove 11 is c mm and the inner diameter is dmm. When a ≦ c and d ≦ b <a, the operating pressure of the safety valve is more stable, which is preferable. Although the mechanism of this operation is not completely elucidated, the portion of the horizontal wall 10 where the groove 11 is provided is small in thickness, so that it is likely to bend and deform, and the transparent plate provided on the sealing plate 8 is provided in the thin portion. The reason is that the edge of the hole and the edge of the inner flange 7 are more strongly pressed against the thin portion. The depth of the groove 11 is not particularly limited, but the ratio of the depth of the groove 11 to the thickness of the horizontal wall (depth of the groove 11 / thickness of the horizontal wall) is set to 0.2 to 0.8. It is preferable to set, and it is more preferable to set to 0.5-0.8. If the ratio is less than 0.2, the effect of providing the groove cannot be obtained, and if it exceeds 0.8, the strength of the portion provided with the groove is lowered, and there is a possibility that breakage may occur in the process of sealing the storage battery. Further, the cross-sectional shape of the groove 11 is not particularly limited, and as shown in FIG. 1, a groove in which the other cross-sectional shape of the rectangle is semicircular or U-shaped is also effective. Further, the same effect can be obtained by providing the groove 11 on the outer surface in addition to the inner surface of the horizontal wall 10 as shown in FIG.
詳細な説明は省くが、本発明の好ましい実施形態によれば、１ＩｔＡを超える充電で２００％以上（充電電気量／蓄電池の定格容量の比が２００％以上である）の充電を実施するような、通常想定していない充電を行った場合でも、通常の電池は内部圧力の上昇により開弁して大きく寿命が低下してしまうのに対して、本発明電池では内部圧力の上昇に伴い電流遮断するスイッチが作動して寿命の低下を防止できることが分かった。 Although a detailed description is omitted, according to a preferred embodiment of the present invention , charging of 200% or more (ratio of charged electricity / rated capacity of storage battery is 200% or more) by charging exceeding 1 ItA is performed. Even when charging that is not normally assumed, a normal battery opens due to an increase in internal pressure and the service life is greatly reduced, whereas in the battery of the present invention, current interruption occurs as the internal pressure increases. It turns out that the switch which operates can prevent the fall of a lifetime.
上述のような構成にすれば、安全弁が簡単な構成となり安価で、充電器の故障時も極めて安全な電池と、充電制御装置の必要のない充電器で充電できる電池が得られる。 With the above-described configuration, a safety valve is simple and inexpensive, and a battery that is extremely safe even when a charger fails and a battery that can be charged by a charger that does not require a charging control device are obtained.
本発明が適用し得る密閉形蓄電池は特に限定されるものではないが、他の蓄電池と比較して耐過充電性、高率充放電特性の良いニッケル水素電池やニッケルカドミウム電池などのアルカリ蓄電池に適用することによって大きな効果が得られる。従って、以下アルカリ蓄電池のうちのニッケル水素蓄電池を例に採って詳細な説明をする。
ニッケル水素蓄電池においては、正極活物質として、水酸化ニッケルに水酸化亜鉛、水酸化コバルトを混合したものが用いられるが、これらを共沈法によって均一に分散せしめて得た水酸化ニッケル複合水酸化物の使用が好ましい。
水酸化ニッケル複合酸化物以外の添加物には、導電性改質剤として水酸化コバルト、酸化コバルト等を用いるが、前期水酸化ニッケル複合酸化物に水酸化コバルトを被覆したものや、これらの水酸化ニッケル複合酸化物の一部を酸素または含酸素気体、または、Ｋ2Ｓ2Ｏ8、次亜塩素酸などの薬剤を用いて酸化したものを用いることができる。
さらに、添加剤としては酸素過電圧を向上させる物質としてＹ、Ｙｂ等の希土類元素の酸化物や水酸化物を用いることができる。
Although the sealed storage battery to which the present invention can be applied is not particularly limited, it is suitable for alkaline storage batteries such as nickel hydride batteries and nickel cadmium batteries, which have better overcharge resistance and high rate charge / discharge characteristics than other storage batteries. A great effect can be obtained by applying. Therefore, the nickel hydride storage battery of the alkaline storage batteries will be described in detail below as an example.
In nickel metal hydride storage batteries, a mixture of nickel hydroxide, zinc hydroxide, and cobalt hydroxide is used as the positive electrode active material. The nickel hydroxide composite hydroxide obtained by uniformly dispersing these by coprecipitation method. The use of products is preferred.
For additives other than nickel hydroxide composite oxide, cobalt hydroxide, cobalt oxide or the like is used as a conductive modifier. A part of the nickel oxide composite oxide that has been oxidized using oxygen or oxygen-containing gas, or a chemical such as K 2 S 2 O 8 or hypochlorous acid can be used.
Further, as an additive, an oxide or hydroxide of rare earth elements such as Y and Yb can be used as a substance for improving oxygen overvoltage.
負極活物質としては、ニッケル水素電池の場合、
主構成要素である水素吸蔵合金は、水素吸蔵が可能な、一般にＡＢ２系、またはＡＢ５系と呼ばれる合金であれば、その組成には特別の制限はない。
特に好ましくは、ＡＢ５型の合金のＭｍＮｉ５（Ｍｍは希土類元素の混合物）のＮｉの一部をＣｏ、Ｍｎ、Ａｌ、Ｃｕ等で置換した合金が、優れた充放電サイクル寿命特性と高い放電容量を持つので好ましい。
防蝕添加剤として、イットリウム、イッテルビウム、エルビウムの他に、ガドリニウム、セリウムの酸化物や水酸化物を添加したり、予め水素吸蔵合金にこれらの元素を金属として含有させてもよい。
As a negative electrode active material, in the case of a nickel metal hydride battery,
The composition of the hydrogen storage alloy as the main component is not particularly limited as long as it is an alloy generally called AB 2 or AB 5 capable of storing hydrogen.
Particularly preferably, an alloy in which a part of Ni of MmNi 5 (Mm is a mixture of rare earth elements) of an AB 5 type alloy is substituted with Co, Mn, Al, Cu, etc. has excellent charge / discharge cycle life characteristics and high discharge. It is preferable because it has a capacity.
In addition to yttrium, ytterbium and erbium, gadolinium and cerium oxides and hydroxides may be added as anticorrosive additives, or these elements may be preliminarily contained in the hydrogen storage alloy as metals.
正極活物質の粉体及び負極材料の粉体は、平均粒子サイズ５０μｍ以下であることが望ましい。
特に、負極活物質である水素吸蔵合金の粉体は、密閉型ニッケル水素電池の高出力特性を向上する目的で粒径は４０μｍ以下の小さいもの方が良いが、高いサイクル寿命を得るためには粒径が２０μｍを下回らないことが望ましい。
本発明による水素吸蔵合金内部にＮｉ含有比率の大きい層を合金の表層と内部に５０ｎｍ以上４００ｎｍ以下で配置した場合、大きい粒径でも優れた高率放電性能が得られるため、平均粒径としては３０μｍから５０μｍがより好ましい。
It is desirable that the positive electrode active material powder and the negative electrode material powder have an average particle size of 50 μm or less.
In particular, the powder of the hydrogen storage alloy, which is the negative electrode active material, should have a small particle size of 40 μm or less for the purpose of improving the high output characteristics of the sealed nickel-metal hydride battery. It is desirable that the particle size not be less than 20 μm.
When a layer having a large Ni content is arranged in the surface layer and inside of the alloy in the hydrogen storage alloy according to the present invention at 50 nm or more and 400 nm or less, an excellent high rate discharge performance can be obtained even with a large particle size. 30 μm to 50 μm is more preferable.
粉体を所定の形状で得るためには各種の粉砕機や分級機が用いられる。
例えば乳鉢、ボールミル、サンドミル、振動ボールミル、遊星ボールミル、ジェットミル、カウンタージェトミル、旋回気流型ジェットミル等が用いられる。粉砕時には水、あるいはアルカリ金属水酸化物の水溶液を用いて湿式粉砕を用いることもできる。
分級方法としては、特に限定はなく、篩や風力分級機などが使用でき、また、乾式、湿式ともに必要に応じて用いられる。
Various pulverizers and classifiers are used to obtain the powder in a predetermined shape.
For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a planetary ball mill, a jet mill, a counter jet mill, a swirling air flow type jet mill, or the like is used. At the time of pulverization, wet pulverization may be used using water or an aqueous solution of an alkali metal hydroxide.
The classification method is not particularly limited, and a sieve, an air classifier, or the like can be used. Both dry and wet methods are used as necessary.
以上、正極及び負極の主要構成成分である正極活物質および負極活物質について詳述したが、前記正極及び負極には、前記主要構成成分の他に、導電剤、結着剤、増粘剤、フィラー等が、他の構成成分として含有されてもよい。 As described above, the positive electrode active material and the negative electrode active material which are main components of the positive electrode and the negative electrode have been described in detail. In addition to the main component, the positive electrode and the negative electrode include a conductive agent, a binder, a thickener, A filler etc. may be contained as another structural component.
導電剤としては、電池性能に悪影響を及ぼさない電子伝導性材料であれば限定されない。 通常、鱗状黒鉛，鱗片状黒鉛，土状黒鉛等の天然黒鉛、人造黒鉛、カーボンブラック、アセチレンブラック、ケッチェンブラック、カーボンウイスカー、炭素繊維、気相成長炭素、金属（銅，ニッケル，金等）粉、金属繊維等の導電性材料を１種またはそれらの混合物として含ませることができる。 The conductive agent is not limited as long as it is an electron conductive material that does not adversely affect battery performance. Usually, natural graphite such as scaly graphite, scaly graphite, earthy graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon whisker, carbon fiber, vapor grown carbon, metal (copper, nickel, gold, etc.) Conductive materials such as powder and metal fibers can be included as one kind or a mixture thereof.
これらの導電剤の中では、電子伝導性及び塗工性の観点よりアセチレンブラックが望ましい。
導電剤の添加量は、正極または負極の総重量に対して０．１重量％〜１０重量％が好ましい。特にアセチレンブラックを０．１〜０．５μｍの超微粒子に粉砕して用いると必要炭素量を削減できるため望ましい。
これらの混合方法は、物理的な混合であり、その理想とするところは均一混合である。
そのため、Ｖ型混合機、Ｓ型混合機、擂かい機、ボールミル、遊星ボールミルといったような粉体混合機を乾式、あるいは湿式で使用することが可能である。
Among these conductive agents, acetylene black is desirable from the viewpoints of electron conductivity and coatability.
The addition amount of the conductive agent is preferably 0.1% by weight to 10% by weight with respect to the total weight of the positive electrode or the negative electrode. In particular, it is desirable to use acetylene black by pulverizing into ultrafine particles of 0.1 to 0.5 μm because the required carbon amount can be reduced.
These mixing methods are physical mixing, and the ideal is uniform mixing.
Therefore, a powder mixer such as a V-type mixer, an S-type mixer, a grinder, a ball mill, or a planetary ball mill can be used in a dry or wet manner.
前記結着剤としては、通常、ポリテトラフルオロエチレン（ＰＴＦＥ），ポリフッ化ビニリデン，ポリエチレン，ポリプロピレン等の熱可塑性樹脂、エチレン−プロピレン−ジエンターポリマー（ＥＰＤＭ），スルホン化ＥＰＤＭ，スチレンブタジエンゴム（ＳＢＲ）、フッ素ゴム等のゴム弾性を有するポリマーを１種または２種以上の混合物として用いることができる。
結着剤の添加量は、正極または負極の総重量に対して０．１〜３重量％が好ましい。
As the binder, thermoplastic resins such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR) are usually used. ), Polymers having rubber elasticity such as fluoro rubber can be used as one kind or a mixture of two or more kinds.
The addition amount of the binder is preferably 0.1 to 3% by weight with respect to the total weight of the positive electrode or the negative electrode.
前記増粘剤としては、通常、カルボキシメチルセルロース、メチルセルロース等の多糖類等を１種または２種以上の混合物として用いることができる。
増粘剤の添加量は、正極または負極の総重量に対して０．１〜３重量％が好ましい。
As said thickener, polysaccharides, such as carboxymethylcellulose and methylcellulose, can be normally used as 1 type, or 2 or more types of mixtures.
The addition amount of the thickener is preferably 0.1 to 3% by weight with respect to the total weight of the positive electrode or the negative electrode.
フィラーとしては、電池性能に悪影響を及ぼさない材料であれば特に制限はない。通常、ポリプロピレン，ポリエチレン等のオレフィン系ポリマー、炭素等が用いられる。
フィラーの添加量は、正極または負極の総重量に対して添加量は５重量％以下が好ましい。
The filler is not particularly limited as long as it does not adversely affect battery performance. Usually, olefinic polymers such as polypropylene and polyethylene, carbon and the like are used.
The addition amount of the filler is preferably 5% by weight or less with respect to the total weight of the positive electrode or the negative electrode.
正極および負極は、それぞれ前記活物質、導電剤および結着剤を水やアルコール、トルエン等の有機溶媒に混合させた後、得られた混合物を下記に詳述する集電体の上に塗布し、乾燥することによって、好適に作製される。
前記塗布方法については、例えば、アプリケーターロールなどのローラーコーティング、スクリーンコーティング、ドクターブレード方式、スピンコーティング、バーコータ等の手段を用いて任意の厚みおよび任意の形状に塗布することが望ましいが、これらに限定されるものではない。
The positive electrode and the negative electrode were mixed with the active material, the conductive agent and the binder in an organic solvent such as water, alcohol and toluene, respectively, and then the obtained mixture was applied on the current collector described in detail below. It is preferably produced by drying.
About the application method, for example, it is desirable to apply to any thickness and any shape using means such as roller coating such as applicator roll, screen coating, doctor blade method, spin coating, bar coater, etc. Is not to be done.
ニッケル水素電池の正極用集電体としては、構成された電池に悪影響を及ぼさない電子伝導体であれば特に選ぶところはない。
例えば、ニッケルやニッケルメッキを行った鋼板を好適に用いることができ、発泡体、繊維群の形成体、凸凹加工を施した３次元基材の他に、パンチング鋼板等の２次元基材が用いられる。
厚さの限定は特にないが、５〜７００μｍのものが用いられる。これら集電体の中で、正極としては、アルカリに対する耐食性と耐酸化性に優れているＮｉを、集電性に優れた構造である多孔体構造の発泡体としたものを使用することが好ましい。
また、
As the current collector for the positive electrode of the nickel metal hydride battery, there is no particular choice as long as it is an electronic conductor that does not adversely affect the constructed battery.
For example, nickel or a nickel-plated steel plate can be suitably used, and a two-dimensional base material such as a punched steel plate can be used in addition to a foam, a formed group of fibers, and a three-dimensional base material subjected to uneven processing. It is done.
The thickness is not particularly limited, but a thickness of 5 to 700 μm is used. Among these current collectors, it is preferable to use, as the positive electrode, a porous structure foam made of Ni, which has excellent corrosion resistance and oxidation resistance against alkali, and has a structure excellent in current collection. .
Also,
また、負極用集電体としては、安価で、且つ電導性に優れる鉄または鋼の箔ないし板をパンチング加工し、耐還元性向上のためにＮｉメッキを施した、多孔板を使用することが好ましい。
鋼板のパンチングの孔径は１．７ｍｍ以下、開口率４０％以上であることが好ましく、これにより少量の結着剤でも負極活物質と集電体との密着性は優れたものとなる。
焼成炭素繊維、導電性高分子の他に、接着性、導電性および耐酸化性向上の目的で集電体のニッケルの表面をＮｉ粉末やカーボンや白金等を付着させて処理したものを用いることができる。
これらの材料については表面を酸化処理することも可能である。
Moreover, as the current collector for the negative electrode, it is possible to use a porous plate obtained by punching an iron or steel foil or plate that is inexpensive and excellent in electrical conductivity and plated with Ni for improving reduction resistance. preferable.
The punching hole diameter of the steel sheet is preferably 1.7 mm or less and the opening ratio is 40% or more, and thereby the adhesion between the negative electrode active material and the current collector is excellent even with a small amount of binder.
In addition to the calcined carbon fiber and conductive polymer, the nickel surface of the current collector should be treated with Ni powder, carbon, platinum, etc. attached for the purpose of improving adhesion, conductivity and oxidation resistance. Can do.
The surface of these materials can be oxidized.
ニッケル水素電池のセパレータとしては、既知の優れた高率放電特性を示す多孔膜や不織布等を、単独あるいは併用することができる。
セパレータを構成する材料としては、例えばポリエチレン，ポリプロピレン等に代表されるポリオレフィン系樹脂や、ナイロンを挙げることができる。
セパレータの空孔率は強度、ガス透過性の観点から８０体積％以下が好ましい。
また、充放電特性の観点から空孔率は２０体積％以上が好ましい。セパレータは親水化処理を施す事が好ましい。
例えば、ポリエチレンなどのポリオレフィン系樹脂繊維の表面に親水基のグラフト重合処理、スルフォン化処理、コロナ処理、ＰＶＡ処理を施したり、これらの処理を既に施された繊維を混合したシートを用いても良い。
As a separator for a nickel metal hydride battery, a known porous film or nonwoven fabric exhibiting excellent high rate discharge characteristics can be used alone or in combination.
Examples of the material constituting the separator include polyolefin resins typified by polyethylene and polypropylene, and nylon.
The porosity of the separator is preferably 80% by volume or less from the viewpoint of strength and gas permeability.
Further, the porosity is preferably 20% by volume or more from the viewpoint of charge / discharge characteristics. The separator is preferably subjected to a hydrophilic treatment.
For example, a hydrophilic group graft polymerization treatment, sulfonation treatment, corona treatment, PVA treatment may be applied to the surface of a polyolefin resin fiber such as polyethylene, or a sheet obtained by mixing fibers that have already undergone these treatments may be used. .
ニッケル水素電池の電解液としては、一般にアルカリ電池等への使用が提案されているものが使用可能である。
水を溶媒とし、溶質としてはカリウム、ナトリウム、リチウムの水酸化物の単独またはそれら２種以上の混合物を溶解したもの等を挙げることができるがこれらに限定されるものではない。
合金への防食剤や、正極での過電圧向上のためや、負極の耐食性の向上や、自己放電向上の為の電解液への添加剤として、イットリウム、イッテルビウム、エルビウム、カルシウム、硫黄、亜鉛等の化合物を単独またはそれら２種以上混合して添加することができる。
As the electrolyte solution for the nickel-metal hydride battery, those generally proposed for use in alkaline batteries and the like can be used.
Water may be used as a solvent, and the solute may be, but not limited to, potassium, sodium, lithium hydroxide dissolved in a mixture of two or more thereof.
Anticorrosives for alloys, overvoltages at the positive electrode, corrosion resistance of the negative electrode, and additives to the electrolyte for improving self-discharge, such as yttrium, ytterbium, erbium, calcium, sulfur, zinc, etc. The compounds can be added alone or in admixture of two or more.
電解液中の電解質塩の濃度としては、高い電池特性を有する電池を確実に得るためには、水酸化カリウムを５〜７ｍｏｌ／ｌ、水酸化リチウムを０．５〜０．８ｍｏｌ／ｌ含む水溶液が好ましい。 The concentration of the electrolyte salt in the electrolyte solution is an aqueous solution containing 5 to 7 mol / l potassium hydroxide and 0.5 to 0.8 mol / l lithium hydroxide in order to reliably obtain a battery having high battery characteristics. Is preferred.
本発明に係る密閉型ニッケル水素蓄電池は、
電解液を、例えば、セパレータと正極と負極とを積層する前または積層した後に注液し、最終的に、外装材で封止することによって好適に作製される。
また、正極と負極とが密閉形ニッケル水素蓄電池用セパレータを介して積層された発電要素を巻回してなる密閉型ニッケル水素蓄電池においては、電解質は、前記巻回の前後に発電要素に注液されるのが好ましい。
注液法としては、常圧で注液することも可能であるが、真空含浸方法や加圧含浸方法や遠心含浸法も使用可能である。
The sealed nickel-metal hydride storage battery according to the present invention is
For example, the electrolytic solution is preferably prepared by pouring before or after laminating the separator, the positive electrode, and the negative electrode, and finally sealing with an exterior material.
In a sealed nickel-metal hydride storage battery in which a power generation element in which a positive electrode and a negative electrode are stacked via a separator for a sealed nickel-metal hydride battery is wound, the electrolyte is injected into the power generation element before and after the winding. It is preferable.
As the injection method, it is possible to inject at normal pressure, but a vacuum impregnation method, a pressure impregnation method, and a centrifugal impregnation method can also be used.
密閉形ニッケル水素蓄電池の外装体の材料としては、ニッケルメッキした鉄やステンレススチール、ポリオレフィン系樹脂等またはこれらの複合体が挙げられる。 Examples of the material of the outer package of the sealed nickel-metal hydride battery include nickel-plated iron, stainless steel, polyolefin resin, and the like, or a composite thereof.
密閉形ニッケル水素蓄電池の構成、形状については特に限定されるものではなく、正極、負極および単層又は複層のセパレータを有するコイン電池やボタン電池、角形電池、扁平形電池、さらに、ロール状の正極、負極およびセパレータを有する円筒形電池等が一例として挙げられる。 The configuration and shape of the sealed nickel-metal hydride storage battery are not particularly limited, and a coin battery or button battery having a positive electrode, a negative electrode, and a single-layer or multi-layer separator, a square battery, a flat battery, and a roll-shaped battery Examples include a cylindrical battery having a positive electrode, a negative electrode, and a separator.
前記グロメット９の透孔に挿通させた接続端子５の側面と透孔の壁面を気密に当接させるには、グロメット９の透孔の壁面を圧縮するように接続端子に当接させることが好ましく、そのために、透孔の壁の外側に金属製のリングをはめ、該金属製リングによって透孔の壁を締め付ける方法が適用できる。また、接続端子５の側面に石油ピッチやポリオレフィンの樹脂をコートすると機密性が更に向上するうえに電解液の這い上がりを抑制する効果があるところから好ましい。 In order to make the side surface of the connection terminal 5 inserted through the through hole of the grommet 9 and the wall surface of the through hole airtightly contact, it is preferable to contact the connection terminal so as to compress the wall surface of the through hole of the grommet 9. Therefore, a method in which a metal ring is fitted to the outside of the through hole wall and the through hole wall is fastened by the metal ring can be applied. Also, it is preferable to coat the side face of the connection terminal 5 with petroleum pitch or polyolefin resin since the confidentiality is further improved and the electrolyte is prevented from creeping up.
円柱状の接続端子５の材質としては、
耐食性があり、通電路として機能すれば何でも良く、鉄にニッケルメッキしたものや、ニッケルが、アルカリ金属の溶液に対する耐食性に優れ、電池内部の圧力上昇時にグロメット９の水平壁を破断する十分な強度を有することから好ましい。
As a material of the cylindrical connection terminal 5,
Anything is acceptable as long as it has corrosion resistance and can function as a current path. Nickel-plated iron or nickel has excellent corrosion resistance against alkali metal solutions, and has sufficient strength to break the horizontal wall of the grommet 9 when the pressure inside the battery rises. Is preferable.
リング状の封口板８としては、
強度と耐食性の観点からニッケルまたはニッケルメッキを施した鉄が好ましく、ニッケルメッキの厚みを５μｍ以上とすることが好ましい。
As the ring-shaped sealing plate 8,
From the viewpoint of strength and corrosion resistance, nickel or iron with nickel plating is preferable, and the thickness of nickel plating is preferably 5 μm or more.
弾性体１２は、蓄電池内部の圧力上昇によって電気回路を遮断するスイッチの動作圧力を規定する機能を有するものであって、その材質としては、
金属バネ、弾性ゴムなどが好適に用いることができる。
また、その構造としては、
金属バネとしては、コイルスプリング、板バネが好適に用いることができ、弾性ゴムとしては、作動圧の安定する円柱形状やレンズ型が好ましい。
The elastic body 12 has a function of defining an operating pressure of a switch that cuts off an electric circuit due to an increase in pressure inside the storage battery.
A metal spring, elastic rubber, or the like can be preferably used.
In addition, as its structure,
As the metal spring, a coil spring or a leaf spring can be suitably used, and as the elastic rubber, a cylindrical shape or a lens type with stable operating pressure is preferable.
以下に、ニッケル水素蓄電池を例に採った実施例に基づき本発明をさらに詳細に説明するが、本発明は以下の記載により限定されるものではなく、試験方法や構成する電池の正極活物質、負極材料、正極、負極 、電解質、セパレータ並びに電池形状等は任意である。
（実施例１）
Hereinafter, the present invention will be described in more detail on the basis of an example taking a nickel-metal hydride storage battery as an example, but the present invention is not limited by the following description, the test method and the positive electrode active material of the battery to be configured, The negative electrode material, the positive electrode, the negative electrode, the electrolyte, the separator, the battery shape, and the like are arbitrary.
Example 1
（密閉形ニッケル水素蓄電池の作製）
図１に示したスイッチと安全弁を備えたＡＡサイズの密閉形ニッケル水素蓄電池を作製した。
（スイッチおよび安全弁の構成）
前記図１に示したグロメット９は、ポリプロピレン製の成形体とした。該グロメットの水平壁１０の肉厚を０．５ｍｍ、直径ｅを１０ｍｍとした。該直径ｅの大きさは円筒形金属製電槽の内径１４ｍｍを１とすると０．７１に相当し、グロメットの蓄電池の内部圧力を受け止める部分が十分に大きい面積を有するようにした。グロメット９の中央部に設けた透孔に直径１．８ｍｍ、ニッケル製の円柱状接続端子５を挿通させ、該接続端子５の側面を透孔の壁面と気密に当接させた。なお、接続端子５の一旦に直径ｂが３．５ｍｍの内側フランジ部７を形成し、外径７．５ｍｍ、厚さ０．４ｍｍのニッケル製ドーナツ状板を接続端子５の側面に接合させて外側フランジ部６を形成した。中央部分に直径ａが５．５ｍｍの透孔を設けた厚さ０．４ｍｍのニッケル製板を封口板８とした。また、接続端子５とキャップ状正極端子２の間に合成ゴム製の弾性体１２を配置した。蓄電池内部の圧力が異常に上昇したときには前記水平壁１０に破断箇所が生成し、蓄電池内部に蓄積したガスが該破断箇所および透孔１４を通って外部に放出される。
(Production of sealed nickel-metal hydride storage battery)
An AA size sealed nickel-metal hydride storage battery equipped with the switch and safety valve shown in FIG. 1 was produced.
(Configuration of switch and safety valve)
The grommet 9 shown in FIG. 1 was a polypropylene molded body. The wall thickness of the horizontal wall 10 of the grommet was 0.5 mm, and the diameter e was 10 mm. The size of the diameter e corresponds to 0.71 when the inner diameter of the cylindrical metal battery case is 1, and the portion for receiving the internal pressure of the grommet storage battery has a sufficiently large area. A cylindrical connection terminal 5 made of nickel having a diameter of 1.8 mm was inserted into a through hole provided in the central portion of the grommet 9, and the side surface of the connection terminal 5 was brought into airtight contact with the wall surface of the through hole. The inner flange 7 having a diameter b of 3.5 mm is formed once at the connection terminal 5, and a nickel donut plate having an outer diameter of 7.5 mm and a thickness of 0.4 mm is joined to the side surface of the connection terminal 5. An outer flange portion 6 was formed. A sealing plate 8 was a nickel plate having a thickness of 0.4 mm in which a through hole having a diameter a of 5.5 mm was provided in the central portion. Further, an elastic body 12 made of synthetic rubber was disposed between the connection terminal 5 and the cap-like positive electrode terminal 2. When the pressure inside the storage battery rises abnormally, a breakage point is generated in the horizontal wall 10, and the gas accumulated inside the storage battery is released to the outside through the breakage point and the through hole 14.
外側フランジ部６は、正極に接続された接続端子５と封口板８とを接続又は遮断するリレースイッチとして働く。
該実施例では、前記のように、封口板８の透孔の直径ａを、内側フランジ部６の直径ｂより２ｍｍ大きくなるように形成した。
The outer flange portion 6 functions as a relay switch that connects or disconnects the connection terminal 5 connected to the positive electrode and the sealing plate 8.
In this embodiment, as described above, the diameter a of the through hole of the sealing plate 8 was formed to be 2 mm larger than the diameter b of the inner flange portion 6.
（水酸化ニッケル粒子の合成）
硫酸ニッケルと硫酸亜鉛および硫酸コバルトを、それぞれの金属の水酸化物が後記の質量比となるように溶解した水溶液に、硫酸アンモニウムと苛性ソーダ水溶液を添加してアンミン錯体を生成させた。反応系を激しく撹拌しながら更に苛性ソーダを滴下し、反応系のｐＨを１２±０．２に制御して芯層母材となる球状高密度水酸化ニッケル粒子を、水酸化物の質量比がニッケル：亜鉛：コバルト＝９３：５：２となるように合成した。
前記高密度水酸化ニッケル粒子を、苛性ソーダでｐＨ１２±０．２に制御したアルカリ性水溶液に投入した。該溶液を撹拌しながら、所定濃度の硫酸コバルト、アンモニアを含む水溶液を滴下した。 この間、苛性ソーダ水溶液を適宜滴下して反応浴のｐＨを１２．０±０．２の範囲に維持した。約１時間ｐＨを前記の範囲に保持し、水酸化ニッケル粒子表面にＣｏを含む水酸化物から成る表面層を形成させた。該水酸化物の表面層の比率は芯層母粒子（以下単に芯層と記述する）に対して７ｗｔ％であった。次いで、前記表面層を有する水酸化ニッケル粒子５０ｇを、温度１１０℃の３０ｗｔ％の苛性ソーダ水溶液に投入し、充分に攪拌した。
続いて表面層に含まれるコバルトの水酸化物の当量に対して過剰のＫ２Ｓ２Ｏ８を添加し、粒子表面から酸素ガスが発生するのを確認した。活物質粒子をろ過し、水洗、乾燥した。
(Synthesis of nickel hydroxide particles)
An ammonium complex and an aqueous caustic soda solution were added to an aqueous solution in which nickel sulfate, zinc sulfate, and cobalt sulfate were dissolved so that each metal hydroxide had a mass ratio described later, thereby forming an ammine complex. While vigorously stirring the reaction system, caustic soda is further added dropwise, the pH of the reaction system is controlled to 12 ± 0.2, and spherical high density nickel hydroxide particles serving as the core layer base material are mixed with a mass ratio of hydroxide of nickel. : Zinc: Cobalt = 93: 5: 2.
The high-density nickel hydroxide particles were put into an alkaline aqueous solution controlled to pH 12 ± 0.2 with caustic soda. While stirring the solution, an aqueous solution containing cobalt sulfate and ammonia at predetermined concentrations was added dropwise. During this time, an aqueous caustic soda solution was appropriately added dropwise to maintain the pH of the reaction bath in the range of 12.0 ± 0.2. The pH was kept in the above range for about 1 hour, and a surface layer made of a hydroxide containing Co was formed on the surface of the nickel hydroxide particles. The ratio of the surface layer of the hydroxide was 7 wt% with respect to the core layer mother particles (hereinafter simply referred to as the core layer). Next, 50 g of nickel hydroxide particles having the surface layer were put into a 30 wt% aqueous sodium hydroxide solution at a temperature of 110 ° C., and sufficiently stirred.
Subsequently, excess K 2 S 2 O 8 was added to the equivalent of cobalt hydroxide contained in the surface layer, and it was confirmed that oxygen gas was generated from the particle surface. The active material particles were filtered, washed with water and dried.
（正極板の作製）
前記活物質粒子にカルボキシメチルセルローズ（ＣＭＣ）水溶液を添加して前記活物質粒子：ＣＭＣ溶質＝９９．５：０．５のペースト状とし、該ペーストを４５０ｇ／ｍ2のニッケル多孔体（住友電工社製、商品名ニッケルセルメット＃８）に充填した。
その後８０℃で乾燥した後、所定の厚みにプレスし、表面にポリテトラフロロエチレンコーティングを行い幅３４ｍｍ（内、無塗工部１ｍｍ）長さ２６０ｍｍの容量２０００ｍＡｈのニッケル正極板とした。
(Preparation of positive electrode plate)
A carboxymethyl cellulose (CMC) aqueous solution is added to the active material particles to form a paste of the active material particles: CMC solute = 99.5: 0.5, and the paste is a 450 g / m 2 nickel porous body (Sumitomo Electric Industries, Ltd.). The product name, nickel cermet # 8) was filled.
Then, after drying at 80 ° C., it was pressed to a predetermined thickness, and the surface was coated with polytetrafluoroethylene to obtain a nickel positive electrode plate having a capacity of 2000 mAh and a width of 34 mm (inside, uncoated part 1 mm) and a length of 260 mm.
（負極板の作製）
粒径３５μｍのＡＢ５形希土類系のＭｍＮｉ３．６Ｃｏ０．６Ａｌ０．３Ｍｎ０．３５の組成を有する水素吸蔵合金とスチレンブタジエン共重合体エマルジョンとを乾量基準の質量比で９９．３５：０．６５の割合で混合し、水で分散してペースト状にし、ブレードコーターを用いて、鉄にニッケルメッキを施したパンチング鋼板に塗布した後、８０℃で乾燥し、所定の厚みにプレスして幅３４ｍｍ（内、無塗工部１ｍｍ）長さ２６０ｍｍの容量３２００ｍＡｈの水素吸蔵合金負極板とした。
(Preparation of negative electrode plate)
A AB 5 type rare earth-based MmNi 3.6 Co 0.6 Al 0.3 Mn 0.35 composition having a particle size of 35 μm and a styrene-butadiene copolymer emulsion in a mass ratio of 99 on a dry basis is 99. .35: 0.65 mixed, dispersed in water to form a paste, applied to a punched steel sheet with nickel plated on iron using a blade coater, dried at 80 ° C., and given thickness To a hydrogen storage alloy negative electrode plate having a width of 34 mm (inside, uncoated portion 1 mm) and a length of 260 mm and a capacity of 3200 mAh.
前記の水素吸蔵合金負極板と、スルフォン化処理を施した厚み１２０μｍのポリプロピレンの不織布状セパレータと、前記ニッケル極板とを組み合わせてロール状に巻回し、６．８ｍｏｌ／ｌの水酸化カリウムと０．８ｍｏｌ／ｌの水酸化リチウムを溶解したアルカリ電解液を注液し、本発明電池の安全弁を具備するＡＡ形の密閉型ニッケル水素蓄電池を作製した。
この電池を４０℃１２時間の保管処理の後、０．０２ＩｔＡにて６００ｍＡｈ充電し、さらに０．１ＩｔＡで１２時間充電した。さらに０．２ＩｔＡで１Ｖまで放電した後、０．１ＩｔＡで１２時間充電、０．２ＩｔＡで１Ｖまで放電する操作を４回繰り返し、初期容量とした。このようにして得られた電池を実施例１とする。
The hydrogen storage alloy negative electrode plate, a sulfonated polypropylene nonwoven fabric separator having a thickness of 120 μm, and the nickel electrode plate were combined and wound into a roll, and 6.8 mol / l potassium hydroxide and 0 An alkaline electrolyte in which 8 mol / l lithium hydroxide was dissolved was injected to prepare an AA-type sealed nickel-metal hydride storage battery having a safety valve for the battery of the present invention.
This battery was stored at 40 ° C. for 12 hours, charged with 0.02 ItA for 600 mAh, and further charged with 0.1 ItA for 12 hours. Further, after discharging to 0.2V at 1 It, charging to 0.1 ItA for 12 hours and discharging to 0.2 V at 0.2 ItA were repeated 4 times to obtain an initial capacity. The battery thus obtained is referred to as Example 1.
（スイッチの動作圧力、安全弁の動作圧力の測定）
前記密閉形電池の電槽底部に穴を開け、内圧を測定するための気体の圧力を測定できるセンサーとアルゴンガスを圧入するための加圧治具を取り付け、クロロプレン製Ｏリングによって気密を維持するようにした後、エポキシ樹脂で取り付け部位周囲を固めてを用いて完全に気密を維持できるようにした。
この圧力センサーと加圧治具を取り付けた本発明電池１を用いて、アルゴンガスを、電池に対し４１．８立方センチメートル／分（ｃｃ／ｍｉｎ）の速度でアルゴンガスを注入して、通電経路が遮断される 圧力を測定したところ、１．５ＭＰａであった。
また、引き続きアルゴンガスを圧入する加圧力を大きくして、電池の内圧を解放するための安全弁が作動する圧力を測定したところ、３．４ＭＰａであった。
(Measurement of switch operating pressure and safety valve operating pressure)
A hole is made in the bottom of the battery case of the sealed battery, a sensor capable of measuring the pressure of the gas for measuring the internal pressure, and a pressurizing jig for injecting argon gas are attached, and airtightness is maintained by a chloroprene O-ring. After that, the periphery of the attachment site was hardened with an epoxy resin so that it could be kept completely airtight.
Using the battery 1 of the present invention to which the pressure sensor and the pressurizing jig are attached, argon gas is injected into the battery at a rate of 41.8 cubic centimeters / minute (cc / min), and the energization path is When the pressure to be cut off was measured, it was 1.5 MPa.
Further, the pressure at which the safety valve for releasing the internal pressure of the battery was activated was measured by continuously increasing the pressurizing pressure for injecting argon gas, and it was 3.4 MPa.
（充電受入率の評価）
実施例１に係る電池を周囲温度２０℃において１．６２Ｖの定電圧を印加して１５分間充電した後１時間放置し、０．２ＩｔＡで１Ｖまで放電した。該放電で得られた放電容量を前記初期容量で割った値を充電受入率とした。
(Evaluation of charge acceptance rate)
The battery according to Example 1 was charged with a constant voltage of 1.62 V at an ambient temperature of 20 ° C., charged for 15 minutes, then left for 1 hour, and discharged to 1 V at 0.2 ItA. A value obtained by dividing the discharge capacity obtained by the discharge by the initial capacity was defined as a charge acceptance rate.
（充放電サイクル試験）
実施例電池１を周囲温度２０℃において１．６２Ｖの定電圧を印加して１５分間充電した後１時間放置し、１ＩｔＡで１Ｖまで放電した。該充放電操作を繰り返し実施し、放電容量が該サイクル試験における１サイクル目の放電容量の６０％にまで低下したサイクル数をもってその電池のサイクル寿命とした。該電池を実施例１とする。
(Charge / discharge cycle test)
Example Battery 1 was charged at a constant voltage of 1.62 V at an ambient temperature of 20 ° C. and charged for 15 minutes, then left for 1 hour and discharged to 1 V at 1 ItA. The charge / discharge operation was repeated, and the cycle number of the battery was defined as the cycle number at which the discharge capacity was reduced to 60% of the discharge capacity at the first cycle in the cycle test. This battery is referred to as Example 1.
（実施例２）
弾性体１２として、１．８ＭＰａの電池内圧力により、充電電流を遮断、接続することが可能なスイッチ機構として働くような、応力を有する弾性体を用いたこと以外は実施例１と同じ構成とした。該電池を実施例２とする。
（実施例３）
弾性体１２として、２．２ＭＰａの電池内圧力により、充電電流を遮断、接続することが可能なスイッチ機構として働くような、応力を有する弾性体を用いたこと以外は実施例１と同じ構成とした。該電池を実施例３とする。
（実施例４）
弾性体１２として、２．８ＭＰａの電池内圧力により、充電電流を遮断、接続することが可能なスイッチ機構として働くような、応力を有する弾性体を用いたこと以外は実施例１と同じ構成とした。該電池を実施例４とする。
（実施例５）
弾性体１２として、３．０ＭＰａの電池内圧力により、充電電流を遮断、接続することが可能なスイッチ機構として働くような、応力を有する弾性体を用いたこと以外は実施例１と同じ構成とした。該電池を実施例５とする。
(Example 2)
The elastic body 12 has the same configuration as that of Example 1 except that an elastic body having a stress that works as a switch mechanism capable of interrupting and connecting a charging current with a pressure in the battery of 1.8 MPa is used. did. This battery is referred to as Example 2.
(Example 3)
The elastic body 12 has the same configuration as that of the first embodiment except that an elastic body having a stress that works as a switch mechanism capable of interrupting and connecting a charging current with a pressure in the battery of 2.2 MPa is used. did. This battery is referred to as Example 3.
Example 4
The elastic body 12 has the same configuration as that of the first embodiment except that an elastic body having a stress that works as a switch mechanism capable of interrupting and connecting a charging current with a battery internal pressure of 2.8 MPa is used. did. This battery is referred to as Example 4.
(Example 5)
The elastic body 12 has the same configuration as that of Example 1 except that an elastic body having a stress that works as a switch mechanism capable of interrupting and connecting a charging current with a battery internal pressure of 3.0 MPa is used. did. This battery is referred to as Example 5.
（参考例５）
弾性体１２として、１．４ＭＰａの電池内圧力により、充電電流を遮断、接続すること
が可能なスイッチ機構として働くような、応力を有する弾性体を用いたこと以外は、実施
例１と同じ構成とした。該電池を参考例５とする。
( Reference Example 5 )
The same configuration as that of Example 1 except that an elastic body having a stress that works as a switch mechanism capable of interrupting and connecting a charging current with a pressure in the battery of 1.4 MPa is used as the elastic body 12. It was. This battery is referred to Reference Example 5 .
実施例１〜実施例５、参考例５に係る密閉形蓄電池を各々１０ケづつ作製し、充電受入
率およびサイクル性能を評価した。表１に充電受入率およびサイクル寿命の１０ヶの平均
値を示す。
る。参考例５の場合は、スイッチの動作圧力Ｘを低く設定したために、充電中スイッチが
オフにある時間が長く、充電受入率が低くなったものと考えられる。実施例の中でも、Ｘ
を１．８ＭＰａ以上とした実施例２〜実施例５において充電受入率が８０％を超えている
ので好ましい。また、スイッチの動作圧力Ｘを高くするに従いサイクル寿命が低下する傾
向にあることがわかる。スイッチの動作圧力を高く設定すると、充電時に蓄電池の温度上
昇幅が大きくなるために蓄電池の性能低下が速まったものと考えられる。スイッチの動作
圧力Ｘが３．０ＭＰａをこえると、サイクル寿命が低下する虞がある。同動作圧力が３．
０ＭＰａ以下では５００サイクル近いサイクル寿命が得られ、さらに２．８ＭＰａ以下で
は５００サイクルを超えるサイクル寿命が得られるので好ましい。以上のことから、スイ
ッチの動作圧力Ｘを１．５Ｍｐａ以上、３．０ＭＰａ以下、さらには１．８ＭＰａ以上、
２．８ＭＰａ以下に設定することが好ましい。
Ten sealed batteries according to Examples 1 to 5 and Reference Example 5 were produced, and the charge acceptance rate and cycle performance were evaluated. Table 1 shows 10 average values of the charge acceptance rate and the cycle life.
In Examples 2 to 5 in which the pressure is 1.8 MPa or more, the charge acceptance rate exceeds 80%, which is preferable. It can also be seen that the cycle life tends to decrease as the operating pressure X of the switch increases. If the operating pressure of the switch is set high, it is considered that the performance deterioration of the storage battery is accelerated because the temperature rise of the storage battery becomes large during charging. If the operating pressure X of the switch exceeds 3.0 MPa, the cycle life may be reduced. The operating pressure is 3.
A cycle life of nearly 500 cycles can be obtained at 0 MPa or less, and a cycle life exceeding 500 cycles can be obtained at 2.8 MPa or less. From the above, the operating pressure X of the switch is 1.5 MPa or more, 3.0 MPa or less, further 1.8 MPa or more,
It is preferable to set it to 2.8 MPa or less.
（実施例６）
前記実施例３において、グロメット９の水平壁１０に、深さ０．３ｍｍの長方形の断面形状を有するリング状の溝１１を形成したこと以外は実施例３と同じ構成とした。なお溝の外径ｃを６.５ｍｍ、内径ｄを３．０ｍｍとした。該電池を実施例６とする。なお、該実施例６の安全弁の動作圧力は２．５Ｍｐａ（Ｙ−Ｘ＝０．３Ｍｐａ）であった。
（実施例７）
前記実施例３において、グロメット９の水平壁１０に、深さ０．２５ｍｍの長方形の断面形状を有するリング状の溝１１を形成したこと以外は実施例３と同じ構成とした。なお溝の外径ｃを６.５ｍｍ、内径ｄを３．０ｍｍとした。該電池を実施例７とする。なお、該実施例７の安全弁の動作圧力は２．８Ｍｐａ（Ｙ−Ｘ＝０．６Ｍｐａ）であった。
(Example 6)
In Example 3, the same structure as Example 3 was adopted except that a ring-shaped groove 11 having a rectangular cross-sectional shape with a depth of 0.3 mm was formed on the horizontal wall 10 of the grommet 9. The outer diameter c of the groove was 6.5 mm, and the inner diameter d was 3.0 mm. This battery is referred to as Example 6. The operating pressure of the safety valve of Example 6 was 2.5 Mpa (Y-X = 0.3 Mpa).
(Example 7)
In Example 3, the same configuration as that of Example 3 was adopted except that a ring-shaped groove 11 having a rectangular cross-sectional shape having a depth of 0.25 mm was formed on the horizontal wall 10 of the grommet 9. The outer diameter c of the groove was 6.5 mm, and the inner diameter d was 3.0 mm. This battery is referred to as Example 7. The operating pressure of the safety valve of Example 7 was 2.8 Mpa (Y-X = 0.6 Mpa).
（参考例６）
前記実施例３において、グロメット９の水平壁１０に、深さ０．３５ｍｍの長方形の断
面形状を有するリング状の溝１１を形成したこと以外は実施例３と同じ構成とした。なお
、溝の外径ｃを６．５ｍｍ、内径ｄを３．０ｍｍとした。該電池を参考例６とする。該参考例６の安全弁の動作圧力は２．４ＭＰａ（Ｙ−Ｘ＝０．２ＭＰａ）であった。
( Reference Example 6 )
In Example 3, the same configuration as that of Example 3 was adopted except that a ring-shaped groove 11 having a rectangular cross-sectional shape with a depth of 0.35 mm was formed on the horizontal wall 10 of the grommet 9. The outer diameter c of the groove was 6.5 mm, and the inner diameter d was 3.0 mm. This battery is referred to Reference Example 6 . The operating pressure of the safety valve of Reference Example 6 was 2.4 MPa (Y-X = 0.2 MPa ).
実施例６、実施例７、参考例６に係る蓄電池を各々１０ケづつ作製しサイクル性能を評
価した。表２に該評価の試験結果を１０ヶの平均値で示す。
なった。また、詳細は省くが、サイクル寿命のバラツキも大であった。参考例６の場合は
、サイクル回数が浅い時点で充電中に安全弁が開弁してしまうものが散見された。このこ
とは、安全弁の動作圧力Ｙとスイッチの動作圧力Ｘが接近しているため、充電中に蓄電池
の内部圧力が上昇したときに安全弁が開弁したものと考えられる。これに対して実施例３
では１０ケ中１ヶのみ４７０サイクル目で安全弁が開弁し残りの９ヶは全て５００サイク
ル経過時点でもで開弁しなかった。また、実施例７、実施例３は全ての電池において５０
０サイクル経過時点で安全弁が開弁しなかった。このことから、安全弁の動作圧力Ｙとス
イッチの動作圧力Ｘの差を０．３ＭＰａ以上に設定するのが良く、０．６ＭＰａ以上に設
定するのが好ましい。
Ten storage batteries according to Example 6, Example 7, and Reference Example 6 were produced, and the cycle performance was evaluated. Table 2 shows the test results of the evaluation as an average value of 10 pieces.
Then, only one of the 10 valves opened the safety valve at the 470th cycle, and the remaining nine did not open even after the 500th cycle. Moreover, Example 7 and Example 3 are 50 in all batteries.
The safety valve did not open when 0 cycle passed. Therefore, the difference between the operating pressure Y of the safety valve and the operating pressure X of the switch is preferably set to 0.3 MPa or more, and preferably set to 0.6 MPa or more.
（実施例８）
封口板８の透孔の直径ａを６.５ｍｍ、接続端子５の内側フランジ部７の直径ｂを、５.５ｍｍ（ａ−ｂ＝１ｍｍ）とした。それ以外は実施例７と同じとした。該実施例電池を実施例電池８とする。
（実施例９）
封口板８の透孔の直径ａを６.５ｍｍ、接続端子５の内側フランジ部７の直径ｂを、３.５ｍｍ（ａ−ｂ＝３ｍｍ）とした。それ以外は実施例７と同じとした。該実施例電池を実施例電池９とする。
(Example 8)
The diameter a of the through hole of the sealing plate 8 was 6.5 mm, and the diameter b of the inner flange portion 7 of the connection terminal 5 was 5.5 mm (ab = 1 mm). Otherwise, it was the same as Example 7. The example battery is referred to as Example battery 8.
Example 9
The diameter a of the through hole of the sealing plate 8 was 6.5 mm, and the diameter b of the inner flange portion 7 of the connection terminal 5 was 3.5 mm (ab = 3 mm). Otherwise, it was the same as Example 7. The example battery is referred to as Example battery 9.
（参考例１）
封口板８の透孔の直径ａを６.５ｍｍ、接続端子５の内側フランジ部７の直径ｂを、５．９ｍｍ（ａ−ｂ＝０．６ｍｍ）とした。それ以外は実施例７と同じとした。該実施例電池を参考例電池１とする。
（参考例２）
封口板８の透孔の直径ａを６.５ｍｍ、接続端子５の内側フランジ部７の直径ｂを、３．０ｍｍ（ａ−ｂ＝３．５ｍｍ）とした。それ以外は実施例７と同じとした。該実施例電池を参考例電池２とする。
(Reference Example 1)
The diameter a of the through hole of the sealing plate 8 was 6.5 mm, and the diameter b of the inner flange portion 7 of the connection terminal 5 was 5.9 mm (ab = 0.6 mm). Otherwise, it was the same as Example 7. This example battery is referred to as Reference Example Battery 1.
(Reference Example 2)
The diameter a of the through hole of the sealing plate 8 was 6.5 mm, and the diameter b of the inner flange portion 7 of the connection terminal 5 was 3.0 mm (ab = 3.5 mm). Otherwise, it was the same as Example 7. This example battery is referred to as Reference Example Battery 2.
実施例電池７、実施例電池８、実施例電池９、参考例電池１、参考例電池２を各々２０ヶづつ作製し、安全弁の動作圧力を測定した。該側定結果（平均値、最大値、最小値）を表３に示す。
また、ａ−ｂが３ｍｍを超えたときも、安全弁の動作圧力が高く、かつ、バラツキが大きくなる。これは、封口板８の透孔のエッジと内側フランジ部７のエッジの間間の間隔が大きすぎるため、上昇した蓄電池内部の圧力によって水平壁が変形して斜めになるために、封口板８の透孔のエッジと内側フランジ部７のエッジの間でグロメットの水平壁１０を押し切り難くなったためと考えられる。このことから、１ｍｍ≦ａ−ｂ≦３ｍｍとすることが好ましい。
Example battery 7, Example battery 8, Example battery 9, Reference example battery 1 and Reference example battery 2 were produced 20 each, and the operating pressure of the safety valve was measured. The determined results (average value, maximum value, minimum value) are shown in Table 3.
Moreover, when ab exceeds 3 mm, the operating pressure of the safety valve is high and the variation becomes large. This is because the gap between the edge of the through hole of the sealing plate 8 and the edge of the inner flange portion 7 is too large, and the horizontal wall is deformed and becomes slanted by the increased pressure inside the storage battery. This is probably because it is difficult to push the horizontal wall 10 of the grommet between the edge of the through hole and the edge of the inner flange portion 7. Therefore, it is preferable that 1 mm ≦ ab ≦ 3 mm.
（参考例３）
前記実施例７において溝の外径ｃを５．０ｍｍ、内径ｄを３．０ｍｍとした以外は実施例７と同じ構成とした。該実施例を参考例３とする。
（参考例４）
前記実施例７において溝の外径ｃを６.５ｍｍ、内径ｄを３．７ｍｍとした以外は実施例７と同じ構成とした。該実施例を参考例４とする。
(Reference Example 3)
Example 7 was the same as Example 7 except that the outer diameter c of the groove was 5.0 mm and the inner diameter d was 3.0 mm. This example will be referred to as Reference Example 3.
(Reference Example 4)
Example 7 was the same as Example 7 except that the outer diameter c of the groove was 6.5 mm and the inner diameter d was 3.7 mm. This example will be referred to as Reference Example 4.
参考例３、参考例４を各々２０ヶづつ作製し、安全弁の動作圧力を測定した。実施例７の結果と合わせて表４に該側定結果（平均値、最大値、最小値）を示す。
本発明の請求項１〜４に記載の密閉型電池の安全弁を備えた蓋構造では、充電効率特性及び安全性の優れた密閉型電池が得られる。特に、ニッケル水素電池の場合には、充電制御装置を有さない安価な充電器を使用することができる。
また、本発明の請求項４に記載の密閉型電池の安全弁を備えた蓋構造では、安全弁の動作圧力のバラツキを少なくすることが可能になり、産業上の利用可能性は極めて大きい。
In the lid structure including the sealed battery safety valve according to claims 1 to 4 of the present invention, a sealed battery having excellent charging efficiency characteristics and safety can be obtained. In particular, in the case of a nickel metal hydride battery, an inexpensive charger that does not have a charge control device can be used.
Moreover, in the lid structure provided with the safety valve for the sealed battery according to claim 4 of the present invention, it is possible to reduce the variation in the operating pressure of the safety valve, and the industrial applicability is extremely large.
２ 正極端子
５ 接続端子
６ 外側フランジ部
７ 内側フランジ部
８ 封口板
９ グロメット
１０ 水平壁
１１ 溝
2 Positive terminal 5 Connection terminal 6 Outer flange portion 7 Inner flange portion 8 Sealing plate 9 Grommet 10 Horizontal wall 11 Groove
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004107612A JP4701623B2 (en) | 2004-03-31 | 2004-03-31 | Sealed battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004107612A JP4701623B2 (en) | 2004-03-31 | 2004-03-31 | Sealed battery |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2005294046A JP2005294046A (en) | 2005-10-20 |
| JP2005294046A5 JP2005294046A5 (en) | 2007-04-26 |
| JP4701623B2 true JP4701623B2 (en) | 2011-06-15 |
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ID=35326745
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004107612A Expired - Lifetime JP4701623B2 (en) | 2004-03-31 | 2004-03-31 | Sealed battery |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026615A (en) * | 1990-08-06 | 1991-06-25 | Eveready Battery Company, Inc. | Electrochemical cell with disconnect switch device |
| JPH0883600A (en) * | 1994-09-13 | 1996-03-26 | Nikkiso Co Ltd | Safety device for secondary battery and nonaqueous electrolyte secondary battery having safety device |
| JPH08293293A (en) * | 1995-04-20 | 1996-11-05 | Mitsubishi Cable Ind Ltd | Safety device for sealed battery |
| JP2002521805A (en) * | 1998-07-29 | 2002-07-16 | デュラセル インコーポレイテッド | End cap assembly for alkaline cell |
| US20020119364A1 (en) * | 2000-10-20 | 2002-08-29 | Bushong William H. | Method and apparatus for regulating charging of electrochemical cells |
| JP2002543565A (en) * | 1999-04-27 | 2002-12-17 | エヴァレディー バッテリー カンパニー インコーポレイテッド | Electrochemical cell with low profile seal assembly with anti-release vent |
-
2004
- 2004-03-31 JP JP2004107612A patent/JP4701623B2/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026615A (en) * | 1990-08-06 | 1991-06-25 | Eveready Battery Company, Inc. | Electrochemical cell with disconnect switch device |
| JPH0883600A (en) * | 1994-09-13 | 1996-03-26 | Nikkiso Co Ltd | Safety device for secondary battery and nonaqueous electrolyte secondary battery having safety device |
| JPH08293293A (en) * | 1995-04-20 | 1996-11-05 | Mitsubishi Cable Ind Ltd | Safety device for sealed battery |
| JP2002521805A (en) * | 1998-07-29 | 2002-07-16 | デュラセル インコーポレイテッド | End cap assembly for alkaline cell |
| JP2002543565A (en) * | 1999-04-27 | 2002-12-17 | エヴァレディー バッテリー カンパニー インコーポレイテッド | Electrochemical cell with low profile seal assembly with anti-release vent |
| US20020119364A1 (en) * | 2000-10-20 | 2002-08-29 | Bushong William H. | Method and apparatus for regulating charging of electrochemical cells |
| JP2004517440A (en) * | 2000-10-20 | 2004-06-10 | レイオバック コーポレイション | Method and apparatus for regulating charging of an electrochemical cell |
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