JP3536850B2 - Sealed metal oxide / hydrogen storage battery - Google Patents
Sealed metal oxide / hydrogen storage batteryInfo
- Publication number
- JP3536850B2 JP3536850B2 JP2003005713A JP2003005713A JP3536850B2 JP 3536850 B2 JP3536850 B2 JP 3536850B2 JP 2003005713 A JP2003005713 A JP 2003005713A JP 2003005713 A JP2003005713 A JP 2003005713A JP 3536850 B2 JP3536850 B2 JP 3536850B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- hydrogen storage
- nickel
- metal oxide
- positive electrode
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 56
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 56
- 239000001257 hydrogen Substances 0.000 title claims description 56
- 238000003860 storage Methods 0.000 title claims description 47
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 12
- 150000004706 metal oxides Chemical class 0.000 title claims description 12
- 239000000956 alloy Substances 0.000 claims description 45
- 229910045601 alloy Inorganic materials 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 12
- 150000002910 rare earth metals Chemical class 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 6
- 229910001122 Mischmetal Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229920003002 synthetic resin Polymers 0.000 claims description 4
- 239000000057 synthetic resin Substances 0.000 claims description 4
- 229910004247 CaCu Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 72
- 229910052759 nickel Inorganic materials 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000843 powder Substances 0.000 description 23
- 239000000758 substrate Substances 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000000654 additive Substances 0.000 description 14
- 239000011149 active material Substances 0.000 description 13
- 239000011572 manganese Substances 0.000 description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- -1 and Pm Inorganic materials 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000006104 solid solution Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052793 cadmium Inorganic materials 0.000 description 8
- 238000012856 packing Methods 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 229910052987 metal hydride Inorganic materials 0.000 description 7
- 229910000480 nickel oxide Inorganic materials 0.000 description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 229910008340 ZrNi Inorganic materials 0.000 description 2
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 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
- 229920001577 copolymer Polymers 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910018007 MmNi Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910010380 TiNi Inorganic materials 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005673 polypropylene based resin Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000010969 white metal Substances 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
- Sealing Battery Cases Or Jackets (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金属酸化物を用い
た高容量で軽量な正極ならびに高容量で低水素平衡圧の
水素吸蔵合金の負極を用い、高温での充電特性と信頼性
に優れた密閉式金属酸化物・水素蓄電池に関する。The present invention relates to a high-capacity, light-weight positive electrode using a metal oxide and a high-capacity, low-hydrogen equilibrium pressure hydrogen-absorbing alloy negative electrode, which are excellent in high-temperature charging characteristics and reliability. Closed metal oxide-hydrogen storage battery.
【０００２】[0002]
【従来の技術】常温、常圧付近で可逆的に水素を吸収し
たり放出する水素吸蔵合金を用いた電極は、充放電が可
能でありしかもエネルギー密度の点で古くから知られて
いるカドミウム電極より優れていることから、アルカリ
蓄電池用の新しい負極として注目されてきた。2. Description of the Related Art An electrode using a hydrogen storage alloy that reversibly absorbs and releases hydrogen at or near normal temperature and normal pressure is a cadmium electrode which is chargeable and dischargeable and has been known for a long time in terms of energy density. Because of their superiority, they have attracted attention as new negative electrodes for alkaline storage batteries.
【０００３】とくに、最近の約１０年間は、電池業界の
研究開発も極めて旺盛であり、研究開発の結果、高容量
の二次電池として商品化され、各種のポータブル電子機
器に本格的に使用されはじめた。[0003] In particular, research and development in the battery industry have been extremely vigorous for the past ten years, and as a result of the research and development, they have been commercialized as high-capacity secondary batteries and used in various portable electronic devices in earnest. began.
【０００４】これは主に円筒密閉形で代表される小型の
密閉式電池であり、正極にニッケル酸化物を、負極に水
素吸蔵合金を用いたニッケル・水素蓄電池である。This is a small sealed battery mainly represented by a cylindrical sealed type, and is a nickel-hydrogen storage battery using nickel oxide for a positive electrode and a hydrogen storage alloy for a negative electrode.
【０００５】そしてその構造は、ニッケル正極と水素吸
蔵合金負極の両方の板状電極を樹脂製のセパレータを介
して渦巻状に構成し、ついで金属製の円筒缶に挿入した
後、安全弁を備えた蓋で封口した構造が一般的である。[0005] The structure is such that both a plate electrode of a nickel positive electrode and a plate electrode of a hydrogen storage alloy negative electrode are formed in a spiral shape through a resin separator, and then inserted into a metal cylindrical can, and then provided with a safety valve. A structure sealed with a lid is common.
【０００６】ニッケル正極は、ニッケル・カドミウム電
池で一般に使用されているようなニッケルの焼結基板に
ニッケル塩溶液を含浸させた後、水酸化物に転化する焼
結式電極や、水酸化ニッケルを主材料とする粉末をコバ
ルトやコバルト酸化物等の少量の添加物と共にペースト
状にして三次元のスポンジ状ニッケルからなる高多孔度
の電極基体中に充填し、ついで乾燥したのち加圧成型を
施した電極（以下ＳＭＥ式という。これらは米国特許第
４、2５1、６０３号、同４、9３５、3１８号明細書、特
開昭６２−２９００１９号公報に開示されている。）が
用いられている。[0006] The nickel positive electrode is formed by impregnating a nickel-sintered substrate, such as a nickel-cadmium battery generally, with a nickel salt solution and then converting it to hydroxide, or a nickel electrode. The powder as the main material is made into a paste with a small amount of additives such as cobalt and cobalt oxide, filled into a highly porous electrode substrate made of three-dimensional sponge nickel, dried, and then subjected to pressure molding. (Hereinafter referred to as SME type, which are disclosed in U.S. Pat. Nos. 4,251,603, 4,935,318, and JP-A-62-290019). .
【０００７】一方水素吸蔵合金負極は、ＬｎＮｉ5系
（Ｌｎは原子番号５７から７１迄の希土類金属（Ｌａ、
Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄ
ｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ）またはそれらの混
合物であるミッシュメタル（以下Ｍｍで示す））の水素
吸蔵合金の粉末を三次元のスポンジ状ニッケル多孔体か
らなる基体中に充填する電極（米国特許第４９３５３１
８号明細書に開示されている。）や二次元の穴あき板に
結着剤と共に塗着した電極、またはＴｉをベースにした
ＴｉＮｉ系合金（米国特許第４８４９２０５号明細書に
開示されている。）の粉末を二次元の穴あき金属板に結
着剤と共に塗着した電極や塗着後に焼結する操作を加え
る電極が知られている。他の水素吸蔵合金材料として、
ＺｒをベースにしたＺｒＮｉ系合金も高容量の点で有望
な材料であるとの提案もある（米国特許第４９４６６４
６号明細書に開示されている。）。On the other hand, a hydrogen storage alloy negative electrode is an LnNi 5 type (Ln is a rare earth metal (La,
Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D
An electrode for filling a substrate made of a three-dimensional sponge-like nickel porous body with a powder of a hydrogen-absorbing alloy of a misch metal (hereinafter referred to as Mm) which is y, Ho, Er, Tm, Yb, Lu) or a mixture thereof. (US Pat. No. 4,935,531)
No. 8 discloses it. ) Or a two-dimensional perforated plate coated with a binder, or a powder of Ti-based TiNi-based alloy (disclosed in U.S. Pat. No. 4,849,205). An electrode coated on a metal plate together with a binder and an electrode subjected to an operation of sintering after coating are known. As other hydrogen storage alloy materials,
It has also been proposed that ZrNi-based alloys based on Zr are also promising materials in terms of high capacity (US Pat. No. 4,946,664).
No. 6 discloses it. ).
【０００８】これらの負極はそれぞれ前記したいずれか
の正極と組み合わせ、セパレータを介して渦巻状に巻い
て使用される。また、負極の容量は、正極のそれよりも
大きくするのが一般である。Each of these negative electrodes is used in combination with any one of the above-mentioned positive electrodes and spirally wound through a separator. The capacity of the negative electrode is generally larger than that of the positive electrode.
【０００９】セパレータ材料としては、ニッケル・カド
ミウム電池で一般に使用されているポリアミド系の樹脂
繊維からなる不織布を使用するのが通常であるが、自己
放電の低減に効果が著しいスルフォン化処理を施したポ
リオレフィン系の樹脂繊維からなる不織布の採用はすで
に提案されている。（米国特許第４９３７１１９号明細
書、特開昭６４−５７５６８号公報に開示されてい
る。）電解液は、ニッケル・カドミウム電池に使用され
ているものと同様な、苛性カリ水溶液が主に使用され
る。As a material for the separator, a nonwoven fabric made of polyamide resin fibers generally used in nickel-cadmium batteries is usually used. However, a sulfonation treatment, which has a remarkable effect in reducing self-discharge, is applied. The use of a nonwoven fabric made of a polyolefin resin fiber has already been proposed. (It is disclosed in U.S. Pat. No. 4,937,119 and Japanese Patent Application Laid-Open No. 64-57568.) As the electrolyte, an aqueous solution of potassium hydroxide, which is the same as that used for nickel-cadmium batteries, is mainly used. .
【００１０】なお、この電池系では、使用する水素吸蔵
合金の水素平衡圧以下に電池内の水素分圧が低下する
と、水素吸蔵合金は水素ガスを放出するため、開放型で
使用すると、ガスの逃散による電解液の減少をきたし、
電池性能の劣化と自己放電の増大を引き起こす。In this battery system, when the hydrogen partial pressure in the battery falls below the hydrogen equilibrium pressure of the hydrogen storage alloy used, the hydrogen storage alloy releases hydrogen gas. The electrolyte decreases due to escape,
It causes deterioration of battery performance and increase of self-discharge.
【００１１】従って、安全弁を備えた密閉式電池が構成
される。この電池の安全弁の作動圧は、過充電時の酸素
および水素ガスによる電池の内圧上昇や、酸素・水素ガ
スの反応に伴う温度上昇による水素吸蔵合金の水素ガス
平衡圧の増大による電池の内圧上昇などを考慮して決め
られている。Accordingly, a sealed battery provided with a safety valve is constructed. The operating pressure of the safety valve of this battery is such that the internal pressure of the battery increases due to oxygen and hydrogen gas during overcharge, and the internal pressure of the battery increases due to the increase in the hydrogen gas equilibrium pressure of the hydrogen storage alloy due to the temperature increase due to the reaction between oxygen and hydrogen gas. It is determined in consideration of such factors.
【００１２】今までに提案されてきた電池は、主に小型
で円筒形の密閉式電池であり、電槽や封口部の耐圧強度
にすぐれている。したがって、１Ｃ（その電池を１時間
率で充電する。）のような大電流で過充電を行っても密
閉が維持できる高い安全弁の作動圧を採用することがで
き、開弁圧力は一般には、１０〜３０ｋｇ／ｃｍ2に設
定して用いられている。これは、小型の電池では放熱に
優れることにもよっている。The batteries that have been proposed so far are mainly small and cylindrical sealed batteries, and have excellent pressure resistance of the battery case and the sealing portion. Therefore, it is possible to adopt a high operating pressure of the safety valve that can maintain the seal even when overcharging with a large current such as 1C (the battery is charged at an hourly rate). It is used at a setting of 10 to 30 kg / cm 2 . This is also due to the fact that small batteries have excellent heat dissipation.
【００１３】以上が、すでに実用化され始めた小型のニ
ッケル・水素蓄電池の従来技術の概要である。The above is an outline of the prior art of a small nickel-metal hydride storage battery which has already been put into practical use.
【００１４】[0014]
【発明が解決しようとする課題】しかし、最近になっ
て、家電製品から電気自動車など巾広く移動用電源にエ
ネルギー密度が高く、信頼性も高い中、大容量の電池が
強く要望され出した。However, recently, there has been a strong demand for large-capacity batteries with high energy density and high reliability for power sources for mobile devices such as home appliances and electric vehicles in a wide range.
【００１５】そしてこの要望に対し、金属酸化物・水素
蓄電池は、有望な電池系と考えられる。金属酸化物とし
ては経済性を考えるとニッケル酸化物やマンガン酸化物
が適切であり、このうちニッケル酸化物を用いたニッケ
ル・水素蓄電池では若干試作を試みた報告はあるもの
の、中容量電池（以下容量が１０Ａｈから１００Ａｈと
定義する。）および大容量電池（以下容量が１００Ａｈ
以上と定義する。）に関しては、まだ具体的な電池構成
の提案がほとんどないのが現状である。[0015] In response to this demand, the metal oxide / hydrogen storage battery is considered to be a promising battery system. Nickel oxide and manganese oxide are suitable as metal oxides in consideration of economical efficiency. Among them, although some trial production of nickel-hydrogen storage batteries using nickel oxide has been reported, The capacity is defined as 10 Ah to 100 Ah) and a large capacity battery (hereinafter, the capacity is 100 Ah)
Defined above. Regarding (2), at present, there are few proposals for specific battery configurations.
【００１６】そこで、金属酸化物・水素蓄電池を代表す
る電池系としてニッケル・水素蓄電池を取り上げ、この
電池における小型電池での特徴を踏まえて中・大容量電
池化を図るには、多くの技術課題があり、これを以下に
説明する。In view of this, nickel-hydrogen storage batteries are taken as a battery system representative of metal oxide-hydrogen storage batteries, and there are many technical issues in achieving medium- to large-capacity batteries based on the characteristics of small batteries. This will be described below.
【００１７】１．高エネルギー密度化と高信頼性につい
て。
とくに、移動用の電源に用いる場合は、小型の電池の場
合と異なり重量あたりのエネルギー密度（Ｗｈ／ｋｇ）
を大きくすることが重視される。したがって、軽量かつ
高容量密度の電極を組み合わせて使用することが重要で
ある。しかし、中・大容量電池では、放熱性が劣ること
による温度上昇や使用中の高温雰囲気における温度上昇
により、従来の正極をそのまま採用したのでは、充電受
入れ性が低下して所望のエネルギー密度が得られない。
また、信頼性の高い寿命電池にするには正負極材料の脱
落を防止する電極構造の改善が、小型電池における以上
に必要である。1. High energy density and high reliability. In particular, when used as a mobile power supply, unlike a small battery, the energy density per weight (Wh / kg)
It is important to increase the size. Therefore, it is important to use a combination of lightweight and high capacity density electrodes. However, in the case of medium- and large-capacity batteries, if the conventional positive electrode is used as it is due to the temperature rise due to poor heat dissipation and the temperature rise in a high-temperature atmosphere during use, the charge acceptability decreases and the desired energy density decreases. I can't get it.
Further, in order to obtain a highly reliable life battery, it is necessary to improve the electrode structure for preventing the positive and negative electrode materials from falling off more than in a small battery.
【００１８】２．密閉電池の構造について。
小型電池と異なり、中・大容量密閉電池の場合は容量が
大きいため円筒形状を採用するのは製法上困難である。
このため、角型形状を採用するのがよいが、角型形状で
は一般に電槽の耐圧強度が著しく減少する。そこで、通
常の電池の使用で最も電池内圧が上昇する充電末期にお
いても、電池内圧は従来よりも低くすることが必要であ
る。また、極柱などのシーリングに耐久性をもたせる構
造を採用する必要がある。2. About the structure of the sealed battery. Unlike small batteries, medium- and large-capacity sealed batteries have large capacities, so it is difficult to adopt a cylindrical shape due to the manufacturing method.
For this reason, it is preferable to adopt a square shape, but in general, the pressure resistance of the battery case is significantly reduced. Therefore, it is necessary to lower the battery internal pressure even at the end of charging, when the battery internal pressure rises most when using a normal battery. In addition, it is necessary to adopt a structure that provides durability to the ceiling such as a pole.
【００１９】３．低自己放電について。
この電池系は、ニッケル・カドミウム電池と比べても自
己放電が極めて大きいと言われている。移動用の電源な
どのように高温で使用されたり放置される機会が多い用
途の場合、自己放電の大きい電池では容量の減少が著し
く、実使用に支障を来たすことがある。従って自己放電
を低くすることが必要である。3. About low self-discharge. It is said that this battery system has an extremely large self-discharge as compared with a nickel-cadmium battery. In an application such as a power supply for transportation which is frequently used or left at high temperatures, a battery having a large self-discharge has a remarkable decrease in capacity, which may hinder actual use. Therefore, it is necessary to reduce self-discharge.
【００２０】４．安全性の確保について。
一般に、電池の中・大容量化に伴い正負極の短絡時に発
熱したり電池内に発生する酸素や水素ガスによる爆発の
危険性が増加する。従って短絡が起きにくくかつ短絡し
ても発火には至らない電池構造や、酸素や水素ガスに火
種が触れない電池構造にし、安全性の高い電池を開発す
る必要がある。4. About ensuring safety. In general, as the capacity of a battery increases, the risk of explosion due to heat generation or oxygen or hydrogen gas generated in the battery increases when the positive and negative electrodes are short-circuited. Therefore, it is necessary to develop a highly safe battery by using a battery structure in which a short circuit does not easily occur and a fire does not occur even if a short circuit occurs, or a battery structure in which a fire does not come into contact with oxygen or hydrogen gas.
【００２１】このように、水素吸蔵合金を用いたニッケ
ル・水素蓄電池を小型容量から中大型容量にわたって巾
広く実用化するためには多くの解決すべき技術課題があ
る。As described above, there are many technical problems to be solved in order to put a nickel-hydrogen storage battery using a hydrogen storage alloy into practical use from a small capacity to a medium to large capacity.
【００２２】本発明はこのような課題を解決することを
目的とするもので、高温から低温までの広い温度範囲で
高エネルギー密度（とくにＷｈ／ｋｇ）と高信頼性を有
し、強度面および内部ガスの発生についても安全性に優
れ、自己放電が低い密閉式金属酸化物・水素蓄電池を提
供することである。An object of the present invention is to solve such a problem, and has a high energy density (especially Wh / kg) and high reliability in a wide temperature range from a high temperature to a low temperature. It is an object of the present invention to provide a sealed metal oxide / hydrogen storage battery that is excellent in the generation of internal gas and has low self-discharge.
【００２３】[0023]
【課題を解決するための手段】本発明は前記する諸課題
を解決するために、まず重量当たりのエネルギー密度
（Ｗｈ／ｋｇ）を高める構成として、正極および負極と
も高エネルギー密度かつ軽量化手段として、正極ならび
に負極、ともにその活物質を三次元構造の電極基体に保
持させた。In order to solve the above-mentioned problems, the present invention has a structure in which the energy density per weight (Wh / kg) is increased. The active material of each of the positive electrode and the negative electrode was held on an electrode substrate having a three-dimensional structure.
【００２４】また、電池の高温化を少なくするために、
Ｃｏ、Ｃｄ、Ｃａ、Ａｇ、Ｍｎ、Ｚｎ、Ｓｒ、Ｖ、Ｂ
ａ、Ｓｂ、Ｙ、希土類金属からなる群のうちから選ばれ
た金属を固溶体として、または上記金属の酸化物を添加
剤として、正極活物質に加えたものである。ここでの希
土類金属とは、当業者周知のＬａ、Ｃｅ、Ｐｒ、Ｎｄ、
Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔ
ｍ、Ｙｂ、Ｌｕを指す。Also, in order to reduce the temperature of the battery,
Co, Cd, Ca, Ag, Mn, Zn, Sr, V, B
Metals selected from the group consisting of a, Sb, Y, and rare earth metals are added to the positive electrode active material as a solid solution or an oxide of the above metal as an additive. Here, the rare earth metals are La, Ce, Pr, Nd, and
Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, T
m, Yb, and Lu.
【００２５】さらに、本発明は負極となる水素吸蔵合金
の一例として使用されるＭｍＮｉα（４．５≦α≦５．
５）ではＭｍ中のＬａ量、Ｎｉと置換するＭｎやＣｏ量
を、またＺｒＮｉβ（１．９≦β≦２．４）ではＺｒや
Ｎｉと置換するＴｉやＶ量を増加することとしたもので
ある。Further, the present invention relates to MmNiα (4.5 ≦ α ≦ 5.m) which is used as an example of a hydrogen storage alloy serving as a negative electrode.
In 5), the amount of La in Mm and the amount of Mn and Co replacing Ni are increased, and in ZrNiβ (1.9 ≦ β ≦ 2.4), the amount of Ti and V replacing Zr and Ni are increased. It is.
【００２６】アルカリ電解液については、本発明はＮａ
ＯＨやＬｉＯＨの量について、ＮａＯＨは３．５モル／
リットルを上限とし、ＬｉＯＨは１．５モル／リットル
を上限として添加することとしたものである。With regard to the alkaline electrolyte, the present invention
Regarding the amount of OH and LiOH, NaOH is 3.5 mol /
Liter is the upper limit, and LiOH is added at the upper limit of 1.5 mol / liter.
【００２７】さらに、本発明は正負極間に介在されるセ
パレータとしてポリオレフィン系樹脂例えばポリプロピ
レン系樹脂を使用し、とくにポリプロピレンのスルフォ
ン化セパレータとしたものである。Further, the present invention uses a polyolefin-based resin such as a polypropylene-based resin as a separator interposed between the positive and negative electrodes, and in particular, a sulfonated separator of polypropylene.
【００２８】また、本発明は電池蓋または電槽などの外
装体に安全弁を設けることとし、その安全弁の作動圧力
は、内外圧力差を２ないし５ｋｇ／ｃｍ2の範囲とした
ものである。Further, in the present invention, a safety valve is provided on an exterior body such as a battery lid or a battery case, and the operating pressure of the safety valve is such that the pressure difference between inside and outside is in a range of 2 to 5 kg / cm 2 .
【００２９】[0029]
【発明の実施の形態】本発明は前記する構成であり、ま
ず正負極をそれぞれその活物質を三次元構造の電極基体
に保持させたため、二次元構造の電極基体と異なり、そ
れ自体軽量かつ高保持性をもち、活物質の高い充填密度
と軽量化が図れる。例えば正極中の活物質である金属酸
化物はニッケル酸化物、マンガン酸化物、これら両者の
混合物および両者の固溶体からなる群のうちからの何れ
かを主材料とすることが好ましく、その際の金属酸化物
粉末の充填密度は、ニッケル酸化物とマンガン酸化物と
が一電子反応時に平均５８０ｍＡｈ／ｃｍ3以上が好ま
しい。また、電極中にＣｏ、Ｃｄ、Ｃａ、Ａｇ、Ｍｎ、
Ｚｎ、Ｓｒ、Ｖ、Ｂａ、Ｓｂ、Ｙ、希土類金属などのい
ずれかの固溶体、または上記金属の酸化物を添加剤とし
て加えることにより、正極活物質の酸素ガス発生過電圧
を高めて、充電末期における酸素発生を遅らすものであ
る。従って充電末期における正極から発生する酸素ガス
が電池内の水素ガスまたは負極の水素と反応して発熱量
が急増して電池を高温化することを低減して、正極の充
電受入れ性の低下による電池容量の減少を少なくするこ
とができる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention has the above-mentioned structure. First, the positive electrode and the negative electrode have their active materials held on an electrode substrate having a three-dimensional structure. It has good retentivity and can achieve high packing density and light weight of the active material. For example, it is preferable that the metal oxide as the active material in the positive electrode be a main material selected from the group consisting of nickel oxide, manganese oxide, a mixture of these two and a solid solution of both, and the metal The packing density of the oxide powder is preferably 580 mAh / cm 3 or more on average when nickel oxide and manganese oxide undergo one-electron reaction. In addition, Co, Cd, Ca, Ag, Mn,
By adding any solid solution such as Zn, Sr, V, Ba, Sb, Y, or rare earth metal, or an oxide of the above metal as an additive, the oxygen gas generation overpotential of the positive electrode active material is increased, and at the end of charging. It delays oxygen generation. Therefore, the oxygen gas generated from the positive electrode at the end of charging reacts with the hydrogen gas in the battery or the hydrogen of the negative electrode to reduce the heat generation and increase the temperature of the battery. The decrease in capacity can be reduced.
【００３０】さらに負極となる水素吸蔵合金として使用
されるＭｍＮｉα（４．５≦α≦５．５）ではＭｍ中の
Ｌａ量、Ｎｉと置換するＭｎやＣｏ量を、またＺｒＮｉ
β（１．９≦β≦２．４）ではＺｒやＮｉと置換するＴ
ｉやＶ量を増加したことにより、水素平衡圧を低減し、
電池内圧を高めることを低減することができ、電槽など
の電池構成物の保護、安全性を高めることができる。In the case of MmNiα (4.5 ≦ α ≦ 5.5) used as a hydrogen storage alloy serving as a negative electrode, the amount of La in Mm, the amount of Mn and Co replacing Ni, and the amount of ZrNi
For β (1.9 ≦ β ≦ 2.4), T to replace with Zr or Ni
By increasing i and V amount, hydrogen equilibrium pressure is reduced,
The increase in battery internal pressure can be reduced, and protection and safety of battery components such as a battery case can be improved.
【００３１】つぎに、電解液は２０℃での比重が１．１
５ないし１．３５のＫＯＨ主体の水溶液を用いる。さら
に、好ましくは、ＮａＯＨやＬｉＯＨの量として、Ｎａ
ＯＨは３．５モル／リットル、ＬｉＯＨは１．５モル／
リットルを上限として添加することにより、電池の利用
率を向上し、かつ高率放電特性の低下をきたさないもの
である。Next, the electrolyte has a specific gravity at 20 ° C. of 1.1.
A KOH-based aqueous solution of 5 to 1.35 is used. Further, preferably, as the amount of NaOH or LiOH,
OH is 3.5 mol / l, LiOH is 1.5 mol / l
By adding liters as the upper limit, the utilization rate of the battery is improved and the high-rate discharge characteristics are not reduced.
【００３２】また、セパレータについては親水処理され
たポリオレフィン系のものを用いる。特にポリプロピレ
ン系の不織布または織布である樹脂セパレータとしたこ
とにより、電池容量を従来のポリアミド系セパレータに
比較して長期間維持することができるものである。As the separator, a hydrophilic polyolefin-based separator is used. Particularly, by using a resin separator made of a polypropylene-based nonwoven fabric or a woven fabric, the battery capacity can be maintained for a long time as compared with a conventional polyamide-based separator.
【００３３】また、電池蓋または電槽に安全弁を設け、
その安全弁の作動圧力を電池の内外圧力差が２ないし５
ｋｇ／ｃｍ2の範囲とすることにより、電槽の耐圧性に
より電槽を破壊するようなことがないものである。Also, a safety valve is provided on the battery lid or battery case,
The operating pressure of the safety valve is set so that the pressure difference between the inside and outside of the battery is 2 to 5
By setting the pressure in the range of kg / cm 2 , the container is not broken by the pressure resistance of the container.
【００３４】[0034]
【実施例】以下、本発明の実施例を説明する。Embodiments of the present invention will be described below.
【００３５】（実施例１）濃度０．６モル／リットルの
硫酸ニッケル（ＮｉＳＯ4）水溶液に、Ｎｉに対する金
属量換算で０．５重量％になるように硫酸コバルトを添
加した混合溶液と濃度０.6５モル／リットルの水酸化ナ
トリウム（ＮａＯＨ）水溶液を準備する。前者の混合溶
液を円筒形の容器にいれ充分攪拌しながら、中心部の下
方から後者を、中心部の上方から前者を少しずつ加えｐ
Ｈを１１．３の一定値にする。なお、液温度は３５℃付
近に保つ。Ｃｏを固溶するＮｉ（ＯＨ）2の粒子径を平
均２０μｍ程度まで成長させた後連続して取り出して、
正極用の主活物質とする。これに平均粒子径５μｍのコ
バルト（Ｃｏ）粉末、純度９９．５％以上の水酸化カル
シウム（Ｃａ（ＯＨ）2）粉末および純度９９．５％以
上のグラファイト粉末をそれぞれ前記のＮｉ（ＯＨ）2
に対し５重量％、２重量％および３重量％加え、均一な
混合粉末にする。この混合粉末と水とのペーストを、厚
さ１．６ｍｍ、多孔度９５％の電極基体となる発泡ニッ
ケル基板に充填し、乾燥後、加圧成形して厚さ０．９ｍ
ｍ、Ｎｉ（ＯＨ）2の充填密度約６００ｍＡｈ／ｃｃの
ニッケル正極板を得る。これを６０×７０ｍｍに切断
し、理論容量２．３Ａｈのニッケル正極とする。その概
略断面図を図１に示した。図中の１１は活物質と添加剤
の混合物、１２は発泡ニッケル、１３は空間であり、２
は正極を示す。この電極基体について以下に説明する。(Example 1) A mixed solution obtained by adding cobalt sulfate to an aqueous solution of nickel sulfate (NiSO 4 ) having a concentration of 0.6 mol / liter so as to be 0.5% by weight in terms of a metal amount with respect to Ni, and a concentration of 0% Prepare an aqueous solution of sodium hydroxide (NaOH) at .65 mol / liter. The former mixed solution is placed in a cylindrical container and sufficiently stirred, and the latter is added little by little from below the center and the former is added little by little from above the center to p.
Let H be a constant value of 11.3. The liquid temperature is kept at around 35 ° C. After growing the average particle diameter of Ni (OH) 2 which dissolves Co to about 20 μm on average, it is taken out continuously,
The main active material for the positive electrode. Cobalt (Co) powder having an average particle diameter of 5 μm, calcium hydroxide (Ca (OH) 2 ) powder having a purity of 99.5% or more, and graphite powder having a purity of 99.5% or more were each added to the above-mentioned Ni (OH) 2.
, 5%, 2% and 3% by weight to obtain a uniform mixed powder. A paste of this mixed powder and water is filled into a foamed nickel substrate serving as an electrode substrate having a thickness of 1.6 mm and a porosity of 95%, dried, and then pressed and molded to a thickness of 0.9 m.
Thus, a nickel positive plate having a packing density of about 600 mAh / cc of Ni (OH) 2 is obtained. This is cut into 60 × 70 mm to obtain a nickel positive electrode having a theoretical capacity of 2.3 Ah. FIG. 1 shows a schematic sectional view thereof. In the figure, 11 is a mixture of an active material and an additive, 12 is nickel foam, 13 is a space,
Indicates a positive electrode. This electrode base will be described below.
【００３６】すなわち、正極に用いるニッケル酸化物は
結着性および導電性の両方に乏しいため、二次元の芯材
に塗着する構成法は採用しがたい。このため、正極とし
ては活物質の保持性と電子伝導度に優れた三次元の金属
基板を使用するのが適切である。この基板の中では、従
来の焼結基板に替えて高多孔度で軽量のスポンジ状ニッ
ケルまたはニッケル繊維のフェルトを基板に使用して電
極の高容量密度化と軽量化を図ることが好ましい。たと
えば、焼結基板（多孔度が７７ないし８０％である。）
に替えてスポンジ状ニッケル（多孔度が９３ないし９５
％である。）を用いた発泡メタル式ニッケル正極では、
活物質の理論充填量と使用材料の軽減から前者より容量
が約３０％高く重量が約２０％軽減できる。ところが、
このような孔径の大きい三次元の網状基板に充填した活
物質の利用率は低いので、コバルトやカドミウムを水酸
化ニッケルの内部に固溶させたり、さらにコバルトやそ
の酸化物の粉末を添加剤に、ニッケル、グラファイトな
どの粉末を導電材として添加することが有効である。そ
の場合のコバルト、ニッケル、グラファイトのうち一種
以上の添加量は正極活物質に対して０．１〜１０．０重
量％であることが好ましい。That is, since the nickel oxide used for the positive electrode is poor in both the binding property and the conductivity, it is difficult to adopt a constitution method in which the nickel oxide is coated on a two-dimensional core material. For this reason, it is appropriate to use a three-dimensional metal substrate having excellent active material retention and electron conductivity as the positive electrode. Among these substrates, it is preferable to use high-porosity, lightweight sponge-like nickel or nickel fiber felt for the substrate in place of the conventional sintered substrate to achieve high capacity density and lightweight electrodes. For example, a sintered substrate (porosity is 77 to 80%)
Replaced with sponge-like nickel (porosity 93-95
%. ) Using a foamed metal nickel positive electrode
The capacity can be reduced by about 30% and the weight can be reduced by about 20% from the former because of the theoretical filling amount of the active material and the reduction of the materials used. However,
Since the utilization rate of the active material filled in such a three-dimensional net-like substrate having a large pore size is low, cobalt or cadmium can be solid-dissolved in nickel hydroxide, or powder of cobalt or its oxide can be used as an additive. It is effective to add a powder such as nickel, graphite or the like as a conductive material. In this case, the addition amount of one or more of cobalt, nickel, and graphite is preferably 0.1 to 10.0% by weight based on the positive electrode active material.
【００３７】負極としては、高容量で堅牢な水素吸蔵合
金を上記と同様に軽い基板に充填した電極や、この場合
は水素吸蔵合金が電子伝導度に優れることから、電極基
体に結着剤などと共に塗着した塗着式電極が採用でき
る。ただし、後者の場合は結着剤量が多すぎると電極反
応を阻害するので、できるだけ少量で結着性の優れた材
料を選択する必要がある。また、電極基体は穴あき板も
しくはエキスパンデッドメタルが好ましく、さらに穴あ
き板もしくはエキスパンデッドメタルはその大部分の表
面がニッケルであることが好ましい。結着剤としては、
ポリテトラフルオロエチレンやポリスチロールの他に、
電解液で膨潤するポリビニールアルコール、カルボキシ
メチルセルロース、メチルセルロースやポリスチロール
などを適量、場合によっては組み合わせて使用すること
が良い。これらの量は、水素吸蔵合金粉末に対して１な
いし５重量％の範囲が好ましく５重量％を越えると電極
反応が著しく低下した。As the negative electrode, an electrode obtained by filling a light-weight substrate with a high-capacity and durable hydrogen-absorbing alloy in the same manner as described above, and in this case, since the hydrogen-absorbing alloy has excellent electron conductivity, a binder such as a binder A coated electrode coated together with the above can be used. However, in the latter case, if the amount of the binder is too large, the electrode reaction is hindered. Therefore, it is necessary to select a material that is as small as possible and has excellent binding properties. The electrode substrate is preferably a perforated plate or expanded metal, and more preferably, the surface of most of the perforated plate or expanded metal is nickel. As a binder,
In addition to polytetrafluoroethylene and polystyrene,
It is preferable to use polyvinyl alcohol, carboxymethylcellulose, methylcellulose, polystyrene or the like which swells in the electrolytic solution in an appropriate amount, and in some cases, in combination. These amounts are preferably in the range of 1 to 5% by weight with respect to the hydrogen storage alloy powder, and when it exceeds 5% by weight, the electrode reaction was remarkably reduced.
【００３８】次に、固溶体形成物について述べる。前記
にＣｏの例を示したが、Ｃｏの代りにＣｄ、Ｚｎ、Ｃ
ａ、Ａｇ、Ｍｎ、Ｓｒ、Ｖ、Ｂａ、Ｓｂ、Ｙ、希土類金
属の塩を単独もしくは混合して用いても良い。これらの
うちでは、Ｃｄが高温充電受入れ性においてＣｏより若
干優れていたが、常温での活物質利用率に関しては逆に
劣るためＣｏ固溶体を代表例とした。Next, the solid solution formed product will be described. Although the example of Co is shown above, Cd, Zn, C
a, Ag, Mn, Sr, V, Ba, Sb, Y, and salts of rare earth metals may be used alone or in combination. Among these, Cd was slightly superior to Co in high-temperature charge acceptability, but was inferior in active material utilization at room temperature, so Co solid solution was used as a representative example.
【００３９】また、導電剤としてグラファイト粉末を示
したが、粒子径の小さいニッケル（Ｎｉ）粉末でも良
い。しかし、重量当たりの高エネルギー密度をとくに目
的にする場合は、若干軽量化が可能となるグラファイト
粉末を実施例の代表例とした。粉末添加剤の代表例とし
て、ＣｏとＣａ（ＯＨ）2（記号ｇ）を示したが、Ｃ
ｏ、Ｃｄ、Ｍｎ、Ａｇ、Ｚｎ、Ｓｒ、Ｖ、Ｂａ、Ｓｂ、
Ｙ、希土類金属の酸化物でも高温充電受入れ性の改善に
効果を有している。Although graphite powder is used as the conductive agent, nickel (Ni) powder having a small particle size may be used. However, in the case where a high energy density per weight is particularly intended, a graphite powder capable of slightly reducing the weight was used as a representative example of the examples. Co and Ca (OH) 2 (symbol g) are shown as typical examples of the powder additive.
o, Cd, Mn, Ag, Zn, Sr, V, Ba, Sb,
Y and rare earth metal oxides also have an effect on improving high-temperature charge acceptability.
【００４０】これらのうち、ＣｏとＣａ（ＯＨ）2の添
加が最も優れた組合せの一つであった。比較として、Ｃ
ｏが５重量％とＣｄＯが３重量％およびＣｏが５重量
％、Ｃａ（ＯＨ）2が１重量％とＺｎＯが２重量％を添
加した同様な構造の２例をそれぞれ（ｆ）および（ｈ）
のニッケル正極とし、またグラファイト以外なにも添加
しない同様な構成のニッケル正極（ｄ）およびグラファ
イトにＣｏのみを加えたニッケル正極（ｅ）を作製し
た。また、汎用ではあるが、充填密度約４００ｍＡｈ／
ｃｃの同サイズの焼結式ニッケル正極（ｎ）も準備し
た。Of these, the addition of Co and Ca (OH) 2 was one of the most excellent combinations. For comparison, C
(f) and (h) show two examples of the same structure in which o was added by 5% by weight, CdO was 3% by weight, Co was 5% by weight, Ca (OH) 2 was 1% by weight, and ZnO was 2% by weight. )
A nickel positive electrode (d) having the same configuration as that described above except that graphite was not added and a nickel positive electrode (e) obtained by adding only Co to graphite were produced. Although it is a general purpose, the packing density is about 400 mAh /
A sintered nickel positive electrode (n) of the same size of cc was also prepared.
【００４１】セリウムが４８重量％、ランタンが２８重
量％を含むミッシュメタル（Ｍｍ）、ニッケル、コバル
ト、マンガン、アルミニウムを所定の割合で混合し、高
周波溶解炉にて溶解した約１５００℃の溶湯を水冷中の
銅容器（空間部の厚さは薄い）に一気に流しこんで得ら
れる組成ＭｍＮｉ3.8Ｃｏ0.5Ｍｎ0.4Ａｌ0.3の合金を一
例として作製した。この合金のインゴットを機械的に粉
砕した後、８０℃、７．２モル／リットルのＫＯＨ水溶
液中に３０分間攪拌しながら浸漬し、ついで水洗し、乾
燥して平均粒子径約２０μｍの粉末とした。この粉末と
水とのペーストを、厚さ１．０ｍｍ、多孔度９３％の発
泡ニッケル基板に充填し、乾燥後、加圧成形して厚さ
０．６ｍｍ、充填密度約１２８０ｍＡｈ／ｃｃの負極板
を得る。これを６０×７０ｍｍに切断し、理論容量３．
２Ａｈの水素吸蔵合金負極とする。Misch metal (Mm) containing 48% by weight of cerium and 28% by weight of lanthanum, nickel, cobalt, manganese, and aluminum were mixed at a predetermined ratio, and the molten metal at about 1500 ° C. was melted in a high-frequency melting furnace. copper container (space thickness is thin) at once flowed elaborate in composition obtained MmNi 3.8 Co 0.5 Mn 0.4 Al 0.3 alloy in a water-cooled to produce as an example. After mechanically grinding the ingot of this alloy, it was immersed in a KOH aqueous solution of 7.2 mol / l at 80 ° C. for 30 minutes with stirring, then washed with water and dried to obtain a powder having an average particle diameter of about 20 μm. . A paste of this powder and water is filled into a foamed nickel substrate having a thickness of 1.0 mm and a porosity of 93%, dried, and then press-molded to form a negative electrode plate having a thickness of 0.6 mm and a packing density of about 1280 mAh / cc. Get. This was cut into 60 × 70 mm, and the theoretical capacity was 3.
A 2 Ah hydrogen storage alloy negative electrode is used.
【００４２】ここで示した合金例の他には、ＺｒＭｎ
0.6Ｖ0.1Ｎｉ1.3Ｔｉ0.2などの合金が水素吸蔵量が多
く、平衡圧力も低いので高エネルギー密度合金として優
れている。しかし、いずれの場合も溶湯を通常のアルミ
ナ容器で冷却しただけでは、水素濃度が高いとき、つま
り吸蔵量が大きくなったときの水素平衡圧力の上昇が著
しく、この電池で好ましい１ｋｇ／ｃｍ2を越える場合
があった。これらの６０℃におけるＰＣＴ曲線図を図２
に示した。両合金とも、徐冷（ａ、ｂ）の場合より急冷
（ａ−１、ｂ−１）による水素平衡圧力低減の効果は明
らかであり、後者を用いた電池では充電末期における低
い電池内圧が期待できる。以下に水素吸蔵合金について
説明する。In addition to the alloy examples shown here, ZrMn
Alloys such as 0.6 V 0.1 Ni 1.3 Ti 0.2 are excellent as high energy density alloys because of their high hydrogen storage capacity and low equilibrium pressure. However, only cooling the molten metal in a conventional alumina vessel either case, when the hydrogen concentration is high, i.e. increase of the hydrogen equilibrium pressure when the storage amount is increased significantly, the preferred 1 kg / cm 2 in this cell Sometimes exceeded. The PCT curve at 60 ° C. is shown in FIG.
It was shown to. In both alloys, the effect of hydrogen equilibrium pressure reduction by rapid cooling (a-1, b-1) is clearer than that of slow cooling (a, b), and a lower internal pressure at the end of charging is expected for batteries using the latter. it can. Hereinafter, the hydrogen storage alloy will be described.
【００４３】水素吸蔵合金はＣａＣｕ5系やＭｇＣｕ2系
のいずれの結晶系の合金でも、適切な充放電効率と耐酸
化性（堅牢さ）を有していれば良い。さらに堅牢にする
には、合金粉末にアルカリ処理を施して、予め溶出しや
すい元素を表面から除去することにより表面層に多数の
凹凸を設けたり表面層をＮｉの量を多くしたり、また、
触媒性や耐電解液性の導電性を有する材料で被覆して合
金母体の酸化を防ぐことも大切である。そして耐電解液
性を有する導電性材料として炭素粉末が好ましい。The hydrogen storage alloy, whether it is a CaCu 5 -based or MgCu 2 -based crystal-based alloy, may have appropriate charge / discharge efficiency and oxidation resistance (robustness). In order to make it more robust, the alloy powder is subjected to an alkali treatment, and elements that are easily eluted are removed from the surface in advance, thereby providing many irregularities on the surface layer or increasing the amount of Ni in the surface layer,
It is also important to coat with a conductive material having catalytic properties and electrolyte resistance to prevent oxidation of the alloy matrix. Further, carbon powder is preferable as the conductive material having an electrolytic solution resistance.
【００４４】なお、ＣａＣｕ5型結晶構造はＡＢα系合
金（４．５≦α≦５．５）であり、同構造式のＡは、希
土類金属か、それらの混合物であるミッシュメタルか、
もしくはその一部がＣａ、Ｍｇ、Ｖ、ＴｉおよびＺｒの
群から選ばれた一種以上の金属で原子量０．１ないし
０．３相当置換されたものであり、ＢはＮｉが主体でそ
の一部にＣｏ、Ａｌ、Ｍｎ、Ｃｕ、Ｆｅ、Ｖ、Ｃｒ、Ｓ
ｉの群から選ばれた一種以上の金属で、合計した原子量
が０．５ないし２．０相当含まれている。またＭｇＣｕ
2系（Ｃ１５型ラーベル結晶構造のＡＢβ系）結晶合金
（１．９≦β＜２．４）は、その構造式中ＡはＺｒが主
体であり、その一部がＴｉ、Ｖ、希土類金属およびＣａ
の群から選ばれた一種以上の金属で原子量０．１ないし
０．４相当置換されたものであり、ＢはＮｉが主体であ
って、その一部にＣｏ、Ａｌ、Ｍｎ、Ｃｕ、Ｆｅ、Ｖ、
Ｃｒの群から選ばれた一種以上の金属で原子量０．３な
いし１．２相当含まれたものである。そして上記におい
て水素吸蔵合金の粉末に触媒性や導伝性を与える材料と
しては、微粉末状のＮｉ、Ｃｕ、Ｃｏ、Ａｇ、Ｃｒ、Ｓ
ｎおよび白金属金属の群から選ばれた金属が使用できる
ものであり、これらは水素吸蔵合金粉末とは金属同志の
一部が溶融し合っていることが好ましい。The CaCu 5 type crystal structure is an ABα-based alloy (4.5 ≦ α ≦ 5.5), and A in the structural formula is a rare earth metal, a misch metal which is a mixture thereof,
Alternatively, a part thereof is substituted by one or more metals selected from the group consisting of Ca, Mg, V, Ti, and Zr corresponding to an atomic weight of 0.1 to 0.3, and B is mainly composed of Ni and a part thereof. Co, Al, Mn, Cu, Fe, V, Cr, S
One or more metals selected from the group i, and the total atomic weight is equivalent to 0.5 to 2.0. MgCu
In the 2 system (ABβ system having a C15 type Rabel crystal structure) crystal alloy (1.9 ≦ β <2.4), A in the structural formula is mainly Zr, and a part thereof is Ti, V, rare earth metal and Ca
Are substituted by one or more metals selected from the group consisting of: corresponding to an atomic weight of 0.1 to 0.4, B is mainly composed of Ni, and a part thereof is Co, Al, Mn, Cu, Fe, V,
At least one metal selected from the group consisting of Cr and having an atomic weight of 0.3 to 1.2. In the above, as a material for imparting catalytic property or conductivity to the powder of the hydrogen storage alloy, Ni, Cu, Co, Ag, Cr, S
A metal selected from the group consisting of n and a white metal can be used, and it is preferable that a part of the metal is fused with the hydrogen storage alloy powder.
【００４５】このような電極同志を組み合わせること
で、活物質の高い充填密度と軽量化が図れる。By combining such electrodes, a high packing density and a light weight of the active material can be achieved.
【００４６】しかし、中・大容量電池でしかも多くの電
極を重ねて使用する場合には放熱性が劣るので、とくに
電極群が高温になりやすい。そのため、金属板を電極群
中のセパレータ間に挿入し極柱を通して熱を外部に逃が
す工夫も有効であった。この場合、挿入する金属板は少
なくとも表面がニッケルで覆われた金属板が好ましく、
さらにその金属板は穴あき板もしくはエキスパンデッド
メタルであることが好ましい。しかし金属板を挿入して
も充電末期における電極群の温度上昇が著しい。この理
由は、充電末期に正極から発生する酸素ガスが電池内の
水素ガスまたは負極の水素と反応して発熱量が急増する
ことによる。この高温化の傾向は、ニッケル、カドミウ
ム電池よりニッケル、水素（Ｎｉ・ＭＨ）蓄電池の方が
大きい。この結果、ニッケル・水素蓄電池では正極の充
電受入れ性が著しく低下して電池容量が減少する。当
然、高温雰囲気下での充電時には、さらに顕著になる。
そこで、正極活物質の酸素ガス発生過電圧を高めて、で
きるだけ充電が終了に近づくまで酸素発生を遅らすこと
が必要である。この改善には、前記固溶体形成物（Ｃ
ｏ、Ｃｄ）の他にＣａ、Ａｇ、Ｍｎ、Ｚｎ、Ｓｒ、Ｖ、
Ｂａ、Ｓｂ、Ｙ、希土類金属の固溶体が酸素ガス発生過
電圧の向上に有効であった。高エネルギー密度を維持す
るには、少量の使用材料で効果的にすることが重要であ
る。少量でも充電効率の向上に有効なＣｏは、０．０５
ないし３．０重量％で良く、また、Ｃｄ、上記のＣａか
ら希土類金属までの元素は５重量％以下加えることが適
切である。同様な目的で、正極への粉末添加剤として
は、前記添加剤（Ｃｏ、Ｃｏ酸化物）の他にＣａ、Ｓ
ｒ、Ｂａ、Ｓｂ、Ｙ、Ｚｎ、希土類金属のそれぞれの酸
化物が効果的なことを見出した。活物質の充填密度を大
きく低下させないためには、それぞれの添加量は０．１
ないし５重量％以下が適当である。固溶体、粉末添加剤
を組み合わせると、さらに効果的である。表１に正極１
３枚（３０Ａｈ）負極１４枚（４５Ａｈ）で構成された
３０Ａｈの密閉電池での雰囲気温度４５℃および６０℃
における利用率を示した。However, when a medium / large capacity battery is used with a large number of electrodes stacked on top of each other, the heat dissipation is inferior. Therefore, it has been effective to insert a metal plate between the separators in the electrode group and release heat to the outside through the poles. In this case, the metal plate to be inserted is preferably a metal plate at least the surface of which is covered with nickel,
Further, the metal plate is preferably a perforated plate or an expanded metal. However, even when a metal plate is inserted, the temperature of the electrode group significantly increases at the end of charging. The reason for this is that oxygen gas generated from the positive electrode at the end of charging reacts with hydrogen gas in the battery or hydrogen of the negative electrode, resulting in a rapid increase in heat generation. This tendency to increase the temperature is greater in nickel and hydrogen (Ni.MH) storage batteries than in nickel and cadmium batteries. As a result, in the nickel-metal hydride storage battery, the charge acceptability of the positive electrode is significantly reduced, and the battery capacity is reduced. Naturally, it becomes more remarkable when charging in a high-temperature atmosphere.
Therefore, it is necessary to increase the oxygen gas generation overvoltage of the positive electrode active material and delay the generation of oxygen until the charging approaches the end as much as possible. To improve this, the solid solution forming product (C
o, Cd) besides Ca, Ag, Mn, Zn, Sr, V,
The solid solution of Ba, Sb, Y and rare earth metal was effective in improving the oxygen gas generation overvoltage. In order to maintain a high energy density, it is important to be effective with small amounts of materials used. Co effective for improving charging efficiency even in a small amount is 0.05
To 3.0% by weight, and it is appropriate to add 5% by weight or less of Cd and the above-mentioned elements from Ca to the rare earth metal. For the same purpose, powder additives to the positive electrode include Ca, S in addition to the additives (Co and Co oxides).
It has been found that each oxide of r, Ba, Sb, Y, Zn and rare earth metal is effective. In order not to significantly reduce the packing density of the active material, the amount of each additive is 0.1%.
To 5% by weight or less is appropriate. It is more effective to combine a solid solution and a powder additive. Table 1 shows positive electrode 1
Atmosphere temperature of 45 ° C and 60 ° C in a 30Ah sealed battery composed of three sheets (30Ah) and 14 negative electrodes (45Ah)
The utilization rate was shown.
【００４７】[0047]
【表１】 [Table 1]
【００４８】正極活物質へのいずれの固溶体形成物も粉
末添加剤も添加量は３重量％とし、導電材としてグラフ
ァイトを３重量％加えた。充電は、３Ａで１２時間、放
電は９Ａで終止電圧を１．０Ｖとした各々５セルの結果
である。いずれの固溶体も粉末添加剤も高温での利用率
を高める効果が認められた。前記（表１）にはＹ2Ｏ3を
単独で用いる場合を示したが、２種以上の粉末添加剤を
加える場合のそれぞれの添加量の比率は、添加量総量が
３重量％となるように、Ｙ2Ｏ3と希土類金属の酸化物を
併用することができ、例えば、Ｙ2Ｏ3：Ｃｅ（ＯＨ）3
が１：１やＹ2Ｏ 3：Ｃｅ（ＯＨ）3が１：２など適宜選
択できる。Any solid solution formed on the positive electrode active material is powdered.
The additive amount of the powder additive is 3% by weight,
3% by weight was added. Charging is 12 hours at 3A
The current was 9 A and the final voltage was 1.0 V. Results for 5 cells each
It is. Utilization of both solid solutions and powder additives at high temperatures
The effect of increasing was recognized. In the above (Table 1), YTwoOThreeTo
The case where it is used alone is shown, but two or more kinds of powder additives are used.
When adding, the ratio of each addition amount is
Y to be 3% by weight.TwoOThreeAnd oxides of rare earth metals
Can be used together, for example, YTwoOThree: Ce (OH)Three
Is 1: 1 or YTwoO Three: Ce (OH)Three1: 2 etc.
You can choose.
【００４９】また、充電末期の高温の問題は、水素吸蔵
合金にも及ぶ。すなわち、高温になるにつれて水素平衡
圧力が上昇して電池内圧を高めることである。中・大容
量電池においては、常識的な厚さの樹脂電槽や金属電槽
を使用するかぎり耐圧強度は大きくない。１．５ないし
３ｍｍ厚の樹脂電槽の場合、補強しても外部との圧力差
が５ｋｇ／ｃｍ2以上になると変形が著しく、場合によ
っては破壊に至った。従って、電池内圧（外部との圧力
差）は最大５ｋｇ／ｃｍ2以下の好ましくは２ｋｇ／ｃ
ｍ2程度に留める必要がある。すなわち、温度上昇によ
る水素平衡圧力の上昇と充電末期以降の発生ガスに起因
する電池内圧の上昇はそれぞれ１ｋｇ／ｃｍ2の増加
（合計２ｋｇ／ｃｍ2）に留めるのが適切である。The problem of high temperature at the end of charging extends to hydrogen storage alloys. That is, as the temperature becomes higher, the hydrogen equilibrium pressure increases and the internal pressure of the battery increases. In medium- and large-capacity batteries, the pressure resistance is not large as long as a resin container or metal container having a common sense thickness is used. In the case of a resin container having a thickness of 1.5 to 3 mm, even if it was reinforced, when the pressure difference from the outside became 5 kg / cm 2 or more, the deformation was significant, and in some cases, it was broken. Therefore, the internal pressure of the battery (the pressure difference from the outside) is at most 5 kg / cm 2 or less, preferably 2 kg / cm 2.
it is necessary to keep to about m 2. That is, it is appropriate that the increase in the hydrogen equilibrium pressure due to the temperature increase and the increase in the battery internal pressure due to the generated gas after the end of charging are each increased by 1 kg / cm 2 (total 2 kg / cm 2 ).
【００５０】水素平衡圧の低減には、合金の組成を改良
する方法と製法を工夫する方法が考えられる。前者に関
しては、ＭｍＮｉα（４．５≦α≦５．５）ではＭｍ中
のＬａ量、Ｎｉと置換するＭｎやＣｏ量を増加させるこ
と、ＺｒＮｉβ（１．９≦β≦２．４）ではＺｒやＮｉ
と置換するＴｉやＶ量の増加が有効である。ＭｍＮｉα
の例を表２に示す。To reduce the hydrogen equilibrium pressure, a method of improving the composition of the alloy and a method of devising a manufacturing method are conceivable. Regarding the former, it is necessary to increase the amount of La in Mm, the amount of Mn or Co replacing Ni, in MmNiα (4.5 ≦ α ≦ 5.5), and to increase the amount of Zr in ZrNiβ (1.9 ≦ β ≦ 2.4). And Ni
It is effective to increase the amount of Ti or V to be replaced. MmNiα
Is shown in Table 2.
【００５１】[0051]
【表２】 [Table 2]
【００５２】ＭｍＮｉαにおけるＭｍ中のＬａ量は合金
の耐酸化性の低下を考慮すると５５重量％以下が、Ｎｉ
と置換する元素の合計はエネルギー密度の低下を考慮す
ると合計置換原子量２．０以下が好ましい。一方のＺｒ
ＮｉβにおけるＴｉ量は、結晶性の低下を考慮して原子
量０．４以下に、Ｖ量は同様の理由で０．４以下で他の
置換元素との合計では１．２以下が適量である。The amount of La in Mm in MmNiα is 55% by weight or less in consideration of the decrease in the oxidation resistance of the alloy.
The total number of substituted atoms is preferably 2.0 or less in consideration of a decrease in energy density. One Zr
The appropriate amount of Ti in Niβ is 0.4 or less in terms of atomic weight in consideration of a decrease in crystallinity, and V is 0.4 or less for the same reason and 1.2 or less in total with other substitution elements.
【００５３】製法の改良は水素平衡圧力の低減に極めて
有効であった。いずれの合金においても組成の均一化を
図ると、図２のａ−１とｂ−１に示すようにＰＣＴ曲線
のプラトー領域が平坦になり、充電末期の水素を吸収し
た状態の平衡圧力がとくに低い。この組成の均一化に
は、合金の溶湯を冷却性に優れた容器に一気に流しこん
で急冷するような方法が適切であった。The improvement in the production method was extremely effective in reducing the hydrogen equilibrium pressure. In any alloy, when the composition is made uniform, the plateau region of the PCT curve becomes flat as shown in a-1 and b-1 in FIG. 2, and the equilibrium pressure in the state of absorbing hydrogen at the end of charging is particularly low. . In order to make the composition uniform, a method in which a molten metal of the alloy was poured into a container having excellent cooling properties at once and cooled rapidly was appropriate.
【００５４】また、表面付近がポリエチレンで被覆され
たポリプロピレン製の繊維を熱溶着し一体化した、目付
重量が７５ｇ／ｍ2、厚さ約０．１５ｍｍの不織布を準
備する。これを１００℃、９５％の濃度酸中に５分間浸
漬してスルフォン化した後、順次低濃度の硫酸に浸漬し
最後に水洗し、ついで乾燥したセパレータで、前記の正
極、負極をそれぞれ熱溶着により袋状に包む。電極リー
ドを配した上方は一部のみ溶着するに留めた。これを図
１に図示する。図中の３は電極リード、４はセパレー
タ、４−１はその溶着部を示す。ここでセパレータにつ
いて以下に示す。A non-woven fabric having a basis weight of 75 g / m 2 and a thickness of about 0.15 mm is prepared by heat-welding polypropylene fibers whose surfaces are coated with polyethylene. This was sulfonated by immersion in an acid of 100% and 95% concentration for 5 minutes, then sequentially immersed in low-concentration sulfuric acid, finally washed with water, and then heat-welded with a dried separator using a separator. And wrap it in a bag. Only a part of the upper part where the electrode lead was disposed was welded. This is illustrated in FIG. In the figure, 3 is an electrode lead, 4 is a separator, and 4-1 is a welded portion thereof. Here, the separator is described below.
【００５５】すなわち、自己放電の低減には、中・大容
量の電池においても、ポリアミド系に替えてポリオレフ
ィン系中のポリプロピレン系のセパレータを使用するこ
とが効果的である。このセパレータをスルフォン化して
使用した前記と同様な構成の容量３０Ａｈの電池を、完
全充電した後４５℃で保存したときの容量変化を図６中
のｇに示す。比較として、従来のポリアミド系の６ナイ
ロンを用いた電池の場合をｇ−１に示す。後者は２週間
で容量を無くしたのに対し、前者は４週間後にも５５％
の容量を維持した。そして図７に示すように従来のセパ
レータを使用したものは充放電サイクルが少ないことが
判る。That is, in order to reduce the self-discharge, it is effective to use a polypropylene-based separator in a polyolefin-based battery instead of a polyamide-based battery even in a medium- and large-capacity battery. The g in FIG. 6 shows a change in capacity when a battery having a capacity of 30 Ah having the same configuration as that used in this separator and sulfonated was fully charged and stored at 45 ° C. For comparison, g-1 shows the case of a battery using a conventional polyamide 6 nylon. The latter lost capacity in two weeks, whereas the former lost 55% after four weeks
Of volume was maintained. As shown in FIG. 7, it can be seen that the one using the conventional separator has few charge / discharge cycles.
【００５６】しかし、電極サイズが増大するにつれ充放
電中に活物質等の脱落が生じやすく、長期の苛酷な使用
に耐えられないと共に微小短絡による自己放電の増加の
原因となる。このため、正極および負極をセパレータに
より袋状に包むことが最も確実である。図１（Ｄ）、
（Ｅ）に袋状に包んだ電極の概略図を示す。ここでは、
上部の一部に未シール部を残したが、電解液の注液時に
おけるガス抜きに有効なためである。また、繊維に方向
性がある場合は、それを上下方向にすることがさらにこ
の目的に好ましい。However, as the electrode size increases, the active material or the like tends to fall off during charge / discharge, so that it cannot withstand severe long-term use and causes an increase in self-discharge due to a minute short circuit. For this reason, it is most certain that the positive electrode and the negative electrode are wrapped in a bag shape by the separator. FIG. 1 (D),
(E) shows a schematic view of the electrode wrapped in a bag. here,
This is because an unsealed portion is left in a part of the upper portion, which is effective for venting gas when the electrolyte is injected. In addition, when the fiber has directionality, it is more preferable that the fiber be oriented vertically.
【００５７】セパレータに包まれた正極１３枚と負極１
４枚を交互に組み合わせて容量３０Ａｈの密閉形ニッケ
ル・水素蓄電池の発電要素を構成し、金属性補助板を介
してそれぞれのリードを極柱と溶接した極板群を、約２
ｍｍの肉圧のポリプロピレン製電槽に挿入する。所定の
蓋体を電槽と溶着した後、５モル／リットルのＫＯＨと
２モル／リットルのＮａＯＨ水溶液に１モルのＬｉＯＨ
を溶解した電解液を６０ｃｃ注液し、ついで安全弁体を
差し込んで注液口を塞ぎ、密閉形ニッケル・水素蓄電池
を作製した。ここで電解液について以下に述べる。Thirteen positive electrodes and negative electrode 1 wrapped in a separator
The four plates are alternately combined to form a power generating element of a sealed nickel-metal hydride storage battery having a capacity of 30 Ah, and an electrode plate group in which each lead is welded to a pole through a metal auxiliary plate is about 2 pieces.
into a polypropylene container with a wall thickness of 1 mm. After welding a predetermined lid with a battery case, 1 mol of LiOH was added to 5 mol / l of KOH and 2 mol / l of NaOH aqueous solution.
Then, 60 cc of an electrolytic solution in which was dissolved was injected, and then a safety valve was inserted to close the injection port, thereby producing a sealed nickel-metal hydride storage battery. Here, the electrolyte is described below.
【００５８】すなわち、電解液は、高温時の正極の充電
効率と電池内圧に関係する。適量のＮａＯＨやＬｉＯＨ
の添加が前者に極めて有効である。図３に、ＫＯＨとＮ
ａＯＨのモル数を一定（７モル／リットル）にしたとき
の、４５℃雰囲気下での前記と同様の容量３０Ａｈの電
池の利用率の一例を示した。ＮａＯＨ量の増加につれて
利用率が向上するが、多すぎると高率放電特性の低下を
きたすので３．５モル／リットル以下が適切である。Ｌ
ｉＯＨの添加は上記の混合組成においても一様に効果的
であり、１．５モル／リットル以下が適切であった。電
解液量は充電末期以降に発生する酸素と水素ガスの消去
能に関係し、前記の３０Ａｈ電池では正極容量１Ａｈ当
たり２．８ｃｃ以下がガスの消去、つまり内圧低減に有
効であった。しかし、１．３ｃｃ以下では電極反応に支
障をきたすので、１．３ないし２．８ｃｃが適量であ
る。That is, the electrolytic solution relates to the charging efficiency of the positive electrode at a high temperature and the internal pressure of the battery. Appropriate amount of NaOH or LiOH
Is extremely effective for the former. FIG. 3 shows KOH and N
An example of the utilization rate of a battery having a capacity of 30 Ah in an atmosphere of 45 ° C. when the number of moles of aOH is constant (7 mol / liter) is shown. The utilization rate increases as the amount of NaOH increases, but if it is too large, the high-rate discharge characteristics deteriorate. Therefore, the use rate of 3.5 mol / liter or less is appropriate. L
The addition of iOH was uniformly effective even in the above mixed composition, and 1.5 mol / liter or less was appropriate. The amount of the electrolytic solution is related to the elimination ability of oxygen and hydrogen gas generated after the last stage of charging. In the above-mentioned 30 Ah battery, 2.8 cc or less per 1 Ah of the positive electrode capacity was effective for erasing the gas, that is, for reducing the internal pressure. However, when the amount is less than 1.3 cc, the electrode reaction is hindered. Therefore, an appropriate amount is 1.3 to 2.8 cc.
【００５９】図中の１、２は負極と正極、３は電極リー
ド、５は電解液、６は極柱、７は空間、９は電槽、１０
は安全弁体をしめす。なお、８はセパレータを複数枚重
ねた多孔体で電極間のスパークが空間７の酸素、水素ガ
スに引火するのを防ぐ目的である。ここでは８にセパレ
ータを用いたが、スポンジ状合成樹脂、合成樹脂製織布
または合成樹脂製不織布であることが好ましい。また、
極柱６と電槽９との間のシールは、石油ピッチを両者に
塗布した後電槽の上下両側からＯリングで押圧し、その
Ｏリングは平ワッシャー状の樹脂で固定した。上記Ｏリ
ングはエチレン・プロピレン共重合体、ネオプレン、フ
ッソ樹脂のいずれかからなることが好ましい。In the figure, 1 and 2 are a negative electrode and a positive electrode, 3 is an electrode lead, 5 is an electrolytic solution, 6 is a pole, 7 is a space, 9 is a container, 10
Shows the safety valve body. Reference numeral 8 denotes a porous body in which a plurality of separators are stacked to prevent sparks between the electrodes from igniting oxygen and hydrogen gas in the space 7. Here, although the separator is used for 8, it is preferable to use a sponge-like synthetic resin, a synthetic resin woven fabric, or a synthetic resin nonwoven fabric. Also,
The seal between the pole 6 and the battery case 9 was obtained by applying a petroleum pitch to both of them, and then pressing the O-rings from above and below both sides of the battery case, and the O-ring was fixed with a flat washer-like resin. The O-ring is preferably made of any one of ethylene / propylene copolymer, neoprene, and fluorine resin.
【００６０】安全弁体１０の作動圧力は、スプリングの
位置を調整して２．０ないし２．５ｋｇ／ｃｍ2 とし
た。その安全弁体の概略断面図を図１（Ｆ）に示す。１
０ａはポリプロピレン製の枠本体、１４はステンレス製
のスプリング、１５はエチレン・プロピレン共重合体製
のゴム栓、１５−１はスプリングとの固定部、１６はス
プリングの位置を自由に変えることができるポリプロピ
レン製のボルト、１７は通気孔である。ここで安全弁に
ついて以下に述べる。The operating pressure of the safety valve body 10 was adjusted to 2.0 to 2.5 kg / cm 2 by adjusting the position of the spring. FIG. 1F shows a schematic sectional view of the safety valve element. 1
0a is a frame body made of polypropylene, 14 is a spring made of stainless steel, 15 is a rubber stopper made of ethylene-propylene copolymer, 15-1 is a fixing portion with the spring, and 16 can freely change the position of the spring. A polypropylene bolt 17 is a ventilation hole. Here, the safety valve will be described below.
【００６１】すなわち、これまでは、広い温度範囲でも
高エネルギー密度を有し、長寿命かつ低自己放電で、完
全充電まで低い電池内圧を保つ中・大容量電池の発電要
素構造を記載してきた。しかし、実用電池として評価に
供するには信頼性の高い安全弁や安全性を考慮した電池
構成の採用が必要である。That is, a power generation element structure of a medium / large capacity battery which has a high energy density even in a wide temperature range, has a long life, low self-discharge, and maintains a low battery internal pressure until complete charging has been described. However, in order to be evaluated as a practical battery, it is necessary to employ a highly reliable safety valve and a battery configuration in consideration of safety.
【００６２】安全弁はその作動圧力が温度変化に影響さ
れないためには、金属性のスプリングを用いてゴムの押
圧を調整する構造が適切であった。作動圧力は、電槽の
耐圧性を考慮して圧力差２ないし５ｋｇ／ｃｍ2の範囲
が好ましい。In order for the operating pressure of the safety valve to be unaffected by a change in temperature, a structure in which rubber pressure is adjusted using a metal spring is appropriate. The working pressure is preferably in the range of 2 to 5 kg / cm 2 in consideration of the pressure resistance of the battery case.
【００６３】前記の（ｄ）、（ｆ）、（ｇ）、（ｈ）、
（ｎ）をそれぞれの正極に使用した３０Ａｈの電池（た
だし、ｎの焼結式の場合は充填密度が小さいので２２Ａ
ｈ）５セルづつを試作し、２０℃の雰囲気で充放電した
ときのエネルギー密度とサイクルの関係を図４に示す。
ここで図中の曲線は、エネルギー密度の上下１セルを除
いた３セルの平均値を示す。充電は０．２Ｃで６時間、
放電は０．５Ｃで１．０Ｖまでとした。この結果、
（ｆ）は７１Ｗｈ／ｋｇ、（ｇ）、（ｈ）は７２Ｗｈ／
ｋｇのエネルギー密度を１０００サイクルまで維持し
た。これに対し（ｄ）は、エネルギー密度が６５Ｗｈ／
ｋｇと低く、５００サイクル以後はその低下が著しかっ
た。（ｎ）は、エネルギー密度は５２ないし５３Ｗｈ／
ｋｇと低いがサイクルによる容量低下はほとんど無かっ
た。（ｄ）、（ｆ）、（ｇ）、（ｈ）のエネルギー密度
の違いは、正極の酸素発生過電圧に起因した充電受入れ
性によると考えられる。これは、（ｄ）が充電電圧が早
く立ち上がるが、立ち上がった電圧が低いこと、および
これに応じて電池温度が早く上昇することから裏づけら
れる。また、（ｄ）の容量劣化は、過充電量が増加する
ことによる高温のため安全弁が作動したことに起因する
と考えられる。（ｎ）のエネルギー密度が低いのは正極
の充填密度の違いにより、容量低下が少ないのは、正極
に対する負極の容量が大きすぎるために温度が上昇して
も水素平衡圧の上昇が小さいことによると考えられる。
図５には、雰囲気温度４５℃における同様な試験結果を
示す。ただし、充電電気量は、初期容量の１２０％に留
めるように充電時間をそれぞれ調節した。この結果から
明らかなように、２０℃での傾向が、さらに大きくなっ
ていることがわかる。これらの結果から、本発明の正極
を用いたニッケル・水素蓄電池は、エネルギー密度が広
い雰囲気温度範囲で大きく、サイクル寿命も１０００サ
イクル以上を示した。The above (d), (f), (g), (h),
A battery of 30 Ah using (n) for each positive electrode (however, in the case of the sintering method of n, 22 A
h) FIG. 4 shows the relationship between the energy density and the cycle when charge / discharge was performed in an atmosphere of 20 ° C. by trial production of 5 cells each.
Here, the curve in the figure indicates the average value of three cells excluding one cell above and below the energy density. Charging at 0.2C for 6 hours,
Discharge was performed at 0.5 C up to 1.0 V. As a result,
(F) is 71 Wh / kg, (g) and (h) are 72 Wh / kg.
The energy density of kg was maintained up to 1000 cycles. On the other hand, (d) shows that the energy density is 65 Wh /
kg, and the decrease was remarkable after 500 cycles. (N) indicates that the energy density is 52 to 53 Wh /
kg, but there was almost no capacity reduction due to the cycle. The difference in energy density between (d), (f), (g), and (h) is considered to be due to the charge acceptability due to the oxygen overvoltage of the positive electrode. This is supported by the fact that in (d), the charging voltage rises quickly, but the voltage that has risen is low, and the battery temperature rises accordingly. The capacity deterioration in (d) is considered to be caused by the operation of the safety valve due to the high temperature caused by the increase in the overcharge amount. The reason why the energy density of (n) is low is that the capacity decrease is small due to the difference in the packing density of the positive electrode, and the increase in hydrogen equilibrium pressure is small even when the temperature rises because the capacity of the negative electrode with respect to the positive electrode is too large. it is conceivable that.
FIG. 5 shows a similar test result at an ambient temperature of 45 ° C. However, the charging time was adjusted so that the amount of charged electricity was kept at 120% of the initial capacity. As is clear from the results, the tendency at 20 ° C. is further increased. From these results, the nickel-hydrogen storage battery using the positive electrode of the present invention exhibited a large energy density in a wide ambient temperature range and a cycle life of 1000 cycles or more.
【００６４】（実施例２）実施例１と同様にして得られ
た正極板と負極板をそれぞれ長さ１４．４ｍｍ、幅１０
ｍｍに切断し、ニッケル極１３枚と水素吸蔵合金負極１
４枚を組み合わせて１００Ａｈのニッケル・水素蓄電池
を作製した。その他の構成材料と構造は実施例１と同様
にした。ただし、電解液量は２１０ｃｃ／セルとした。
この電池５セルにおける実施例１と同様な充放電試験の
結果、２０℃のエネルギー密度は７８Ｗｈ／ｋｇ、４５
℃でのそれは６０Ｗｈ／ｋｇを示し、サイクルによる劣
化も少なくとも５００サイクルまではほとんど認められ
なかった。１００Ａｈの大容量電池においても、本発明
の電池は優れた特性と信頼性を示すことがわかった。Example 2 A positive electrode plate and a negative electrode plate obtained in the same manner as in Example 1 were each 14.4 mm long and 10 mm wide.
mm, 13 nickel electrodes and hydrogen storage alloy negative electrode 1
The four batteries were combined to produce a 100 Ah nickel-metal hydride storage battery. The other constituent materials and structures were the same as in Example 1. However, the amount of the electrolyte was 210 cc / cell.
As a result of the same charge / discharge test as in Example 1 for the five cells of this battery, the energy density at 20 ° C. was 78 Wh / kg, 45
At 60 ° C., it showed 60 Wh / kg, and almost no deterioration due to cycling was observed until at least 500 cycles. It was found that the battery of the present invention exhibited excellent characteristics and reliability even in a large capacity battery of 100 Ah.
【００６５】（実施例３）実施例１と同様な要領で、硫
酸ニッケルと硫酸コバルトの混合水溶液と濃度０．６モ
ル／リットルの硫酸マンガンを等量づつ加えＮａＯＨに
よりｐＨ１１．５に調整しながら、ニッケルとマンガン
の原子量比がほぼ１：１の共晶酸化物粉末を準備する。
粒子径は、同様に平均２０μｍになるように液中での滞
留時間を調整した。この粉末を用いて実施例１と同様な
方法で３０Ａｈの電池を３セル試作し、同様に充放電を
行った。その結果、電圧は約５０ｍＶ低下したが、３セ
ルとも５００サイクル経過してもわずかな容量減少で留
まった。実施例１のニッケル・水素蓄電池に対しては、
特に特性上優ることはないが、材料の安価はＭｎが使用
できることに大きな意味があると考えられる。(Example 3) In the same manner as in Example 1, while adding an equal amount of a mixed aqueous solution of nickel sulfate and cobalt sulfate and manganese sulfate having a concentration of 0.6 mol / L, the pH was adjusted to 11.5 with NaOH. A eutectic oxide powder having an atomic ratio of nickel to manganese of about 1: 1 is prepared.
Similarly, the residence time in the liquid was adjusted so that the particle diameter became 20 μm on average. Using this powder, three 30-Ah batteries were prototyped in the same manner as in Example 1, and charged and discharged in the same manner. As a result, the voltage was reduced by about 50 mV, but the capacity of each cell remained small even after 500 cycles. For the nickel-metal hydride storage battery of the first embodiment,
Although it is not particularly superior in characteristics, it is considered that the inexpensive material has great significance in that Mn can be used.
【００６６】なお、Ｍｎの比率をさらに高めることも可
能であるが、その際はｐＨ値も上げて酸化物を析出させ
ることが大切である。Although it is possible to further increase the ratio of Mn, it is important to increase the pH value to precipitate oxides.
【００６７】[0067]
【発明の効果】以上のように本発明によれば、広い温度
幅で高エネルギー密度を有し、自己放電の小さい、高信
頼性の密閉形ニッケル・水素蓄電池を提供することがで
きる。As described above, according to the present invention, it is possible to provide a highly reliable sealed nickel-metal hydride battery having high energy density over a wide temperature range, low self-discharge, and high reliability.
【図１】（Ａ）本発明の一実施例における正極の概略断
面図
（Ｂ）同単電池の内部正面図
（Ｃ）同側断面図
（Ｄ）同電極をセパレータにより袋状に包んだ正面図
（Ｅ）同側断面図
（Ｆ）同安全弁体の拡大断面図1A is a schematic cross-sectional view of a positive electrode according to an embodiment of the present invention, FIG. 1B is an internal front view of the same cell, FIG. 1C is a cross-sectional side view of the same cell, and FIG. (E) Same side sectional view (F) Enlarged sectional view of the same safety valve element
【図２】本発明の実施例１における負極用の、低い水素
平衡圧力を有する水素吸蔵合金のＰＣＴ曲線を示す図FIG. 2 is a diagram showing a PCT curve of a hydrogen storage alloy having a low hydrogen equilibrium pressure for a negative electrode in Example 1 of the present invention.
【図３】同電池の４５℃における利用率と電解液中のＮ
ａＯＨ量の関係を示す図FIG. 3 shows the utilization factor of the same battery at 45 ° C. and N in an electrolytic solution.
Diagram showing the relationship between aOH amounts
【図４】同電池の２０℃におけるエネルギー密度と充放
電サイクルの関係を示す図FIG. 4 is a diagram showing the relationship between the energy density at 20 ° C. and the charge / discharge cycle of the battery.
【図５】同電池の４５℃におけるエネルギー密度と充放
電サイクルの関係を示す図FIG. 5 is a diagram showing a relationship between an energy density at 45 ° C. and a charge / discharge cycle of the battery.
【図６】同電池のセパレータ種類と自己放電の関係を示
す図FIG. 6 is a diagram showing the relationship between the type of separator and self-discharge of the battery.
【図７】同電池のセパレータの構成法と充放電サイクル
寿命の関係を示す図FIG. 7 is a diagram showing a relationship between a configuration method of a separator of the battery and a charge / discharge cycle life.
１ 負極 ２ 正極 ３ 電極リード ４ セパレータ １０ 安全弁体 1 negative electrode 2 Positive electrode 3 Electrode lead 4 separator 10 Safety valve body
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｈ０１Ｍ 4/62 Ｈ０１Ｍ 4/62 Ｃ 10/30 10/30 Ｚ (72)発明者 豊口 吉徳 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 松田 宏夢 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 平４−66636（ＪＰ，Ａ) 特開 昭48−48931（ＪＰ，Ａ) 特開 昭62−222566（ＪＰ，Ａ) 実開 昭52−123626（ＪＰ，Ｕ) 特許3042043（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/00 - 4/62 H01M 10/00 - 10/34 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI H01M 4/62 H01M 4/62 C 10/30 10/30 Z (72) Inventor Yoshinori Toyoguchi 1006 Kadoma, Kazuma, Kadoma, Osaka Matsushita (72) Inventor Hiromu Matsuda Inventor Hiromu Matsuda 1006 Kadoma, Kadoma, Osaka Pref. Matsushita Electric Industrial Co., Ltd. (56) References JP-A-4-66636 (JP, A) 48931 (JP, A) JP-A-62-222566 (JP, A) JP-A 52-123626 (JP, U) Patent 3042043 (JP, B2) (58) Fields investigated (Int. Cl. 7 , DB name ) H01M 4/00-4/62 H01M 10/00-10/34
Claims (3)
を有する負極、セパレータ、アルカリ電解液、および安
全弁を備えた蓋部と電槽を有する密閉式金属酸化物・水
素蓄電池であり、前記正極はイットリウム酸化物、希土
類金属（Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍを除く）の酸化
物からなる群のいずれか１種以上をそれぞれ０．１〜５
重量％含み、金属酸化物の結晶中にはＣｏが金属酸化物
に対して０．０５〜３．０重量％固溶されている密閉式
金属酸化物・水素蓄電池。1. A sealed metal oxide / hydrogen storage battery having a positive electrode having a metal oxide, a negative electrode having a hydrogen storage alloy, a separator, an alkaline electrolyte, a lid provided with a safety valve, and a battery case. Represents at least one member selected from the group consisting of oxides of yttrium oxide and rare earth metals (excluding La, Ce, Pr, Nd, and Sm) in the range of 0.1 to 5 respectively.
Wt% wherein, sealed metal oxide-hydrogen storage battery Co is dissolved 0.05 to 3.0 wt% relative to the metal oxide crystal of the metal oxide.
構造のＡＢα系合金（４．５≦α≦５．５）であり、前
記構造式Ａはミッシュメタルであり、Ｂは、Ｎｉが主体
でその一部にＣｏ、Ａｌ、Ｍｎ、Ｃｕ、Ｆｅ、Ｖ、Ｃ
ｒ、Ｓｉの群から選ばれた一種以上の金属を含むもので
あり、前記ミッシュメタル中のＬａ量が２８〜５５重量
％である請求項１に記載の密閉式金属酸化物・水素蓄電
池。2. The hydrogen storage alloy is an ABα-based alloy having a CaCu 5- type crystal structure (4.5 ≦ α ≦ 5.5). The structural formula A is a misch metal. Co, Al, Mn, Cu, Fe, V, C
r, it is intended to include one or more metals selected from the group consisting of Si, sealed metal oxide-hydrogen storage battery according to claim 1 La content in the misch metal is a 2 8-55 wt%.
を有する負極、セパレータ、アルカリ電解液、および安
全弁を備えた蓋部と電槽を有し、前記蓋部および電槽が
合成樹脂製であり、両者は熱溶着または接着剤により一
体化されている請求項１または２に記載の密閉式金属酸
化物・水素蓄電池。3. A lid having a positive electrode having a metal oxide, a negative electrode having a hydrogen storage alloy, a separator, an alkaline electrolyte, and a safety valve, and a battery case, wherein the cover portion and the battery case are made of synthetic resin. 3. The sealed metal oxide / hydrogen storage battery according to claim 1, wherein both are integrated by heat welding or an adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003005713A JP3536850B2 (en) | 2003-01-14 | 2003-01-14 | Sealed metal oxide / hydrogen storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003005713A JP3536850B2 (en) | 2003-01-14 | 2003-01-14 | Sealed metal oxide / hydrogen storage battery |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24840092A Division JP3438142B2 (en) | 1992-09-18 | 1992-09-18 | Medium / large capacity sealed metal oxide / hydrogen storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003229122A JP2003229122A (en) | 2003-08-15 |
| JP3536850B2 true JP3536850B2 (en) | 2004-06-14 |
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| JP4240078B2 (en) * | 2006-07-19 | 2009-03-18 | トヨタ自動車株式会社 | Lithium secondary battery |
| US9859531B2 (en) * | 2015-02-06 | 2018-01-02 | Ovonic Battery Company, Inc. | Alkaline and non-aqueous proton-conducting pouch-cell batteries |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3042043B2 (en) | 1991-07-18 | 2000-05-15 | 松下電器産業株式会社 | Nickel positive electrode for alkaline storage battery and nickel-hydrogen storage battery using the same |
-
2003
- 2003-01-14 JP JP2003005713A patent/JP3536850B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3042043B2 (en) | 1991-07-18 | 2000-05-15 | 松下電器産業株式会社 | Nickel positive electrode for alkaline storage battery and nickel-hydrogen storage battery using the same |
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|---|---|
| JP2003229122A (en) | 2003-08-15 |
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