JP5205051B2 - ニッケル金属水素化物電池の設計 - Google Patents
ニッケル金属水素化物電池の設計 Download PDFInfo
- Publication number
- JP5205051B2 JP5205051B2 JP2007509476A JP2007509476A JP5205051B2 JP 5205051 B2 JP5205051 B2 JP 5205051B2 JP 2007509476 A JP2007509476 A JP 2007509476A JP 2007509476 A JP2007509476 A JP 2007509476A JP 5205051 B2 JP5205051 B2 JP 5205051B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- positive electrode
- active material
- metal hydride
- nickel
- 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.)
- Active
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 62
- 229910052759 nickel Inorganic materials 0.000 title claims description 37
- -1 Nickel metal hydride Chemical class 0.000 title claims description 33
- 229910052987 metal hydride Inorganic materials 0.000 title claims description 33
- 238000013461 design Methods 0.000 title description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 63
- 239000002245 particle Substances 0.000 claims description 59
- 239000000654 additive Substances 0.000 claims description 57
- 239000000463 material Substances 0.000 claims description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 44
- 239000010941 cobalt Substances 0.000 claims description 41
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 41
- 239000007773 negative electrode material Substances 0.000 claims description 39
- 230000000996 additive effect Effects 0.000 claims description 38
- 229910017052 cobalt Inorganic materials 0.000 claims description 38
- 239000007774 positive electrode material Substances 0.000 claims description 33
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 27
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 26
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000012670 alkaline solution Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 150000004681 metal hydrides Chemical class 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000006183 anode active material Substances 0.000 claims 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 1
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 1
- 239000011883 electrode binding agent Substances 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 229920002689 polyvinyl acetate Polymers 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 claims 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 description 36
- 238000000034 method Methods 0.000 description 33
- 239000001257 hydrogen Substances 0.000 description 30
- 229910052739 hydrogen Inorganic materials 0.000 description 30
- 239000008393 encapsulating agent Substances 0.000 description 29
- 239000010410 layer Substances 0.000 description 27
- 239000011149 active material Substances 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 23
- 238000003860 storage Methods 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 230000008569 process Effects 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000005755 formation reaction Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000003607 modifier Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910000943 NiAl Inorganic materials 0.000 description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- ZRUWFKRETRELPY-UHFFFAOYSA-N azane;nickel(2+) Chemical compound N.[Ni+2] ZRUWFKRETRELPY-UHFFFAOYSA-N 0.000 description 4
- 229910010277 boron hydride Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 4
- 229910018916 CoOOH Inorganic materials 0.000 description 3
- 229910003310 Ni-Al Inorganic materials 0.000 description 3
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 150000001869 cobalt compounds Chemical class 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229910003307 Ni-Cd Inorganic materials 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- 230000007246 mechanism Effects 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
- 235000011837 pasties Nutrition 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910005813 NiMH Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001447 compensatory effect Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000011262 electrochemically active material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013080 microcrystalline material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000652 nickel hydride Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/044—Activating, forming or electrochemical attack of the supporting material
- H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/242—Hydrogen storage electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/32—Nickel oxide or hydroxide electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/049—Manufacturing of an active layer by chemical means
- H01M4/0492—Chemical attack of the support material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Description
本発明は2004年4月23日に出願された米国仮出願第60/565,170号に関連し、その最初の出願日と優先権を主張するものであり、その開示を本明細書に引用する。
負極半電池における反応は可逆性である。放電すると、貯蔵水素が放出されて水分子を生成し、電導回路を通って電子を電池端子へ解放する。
Ni−MH電池用の正極活性材料としての水酸化ニッケルの使用は公知である。例えばオブシンスキー(Ovshinsky)ら、1996年6月4日発行、題名「アルカリ再充電可能電気化学電池用水酸化ニッケル増強正極材料」の米国特許第5,523,182号参照。その開示を本明細書に引用する。米国特許第5,523,182号では、オブシンスキーらは腐蝕生成物に対する抵抗性と電導率を増加するための水酸化ニッケル正極材料の粒子と、粒子上の実質的に連続で均一な封入剤層の前駆体被覆とを含有する正極材料を記載している。電極の加工中または充電中に酸化されると導電性の高い形に変換可能であり、次いで電極が放電するとその最初の形には戻らない材料から、被覆封入剤層が形成される。電気化学的に活性な水酸化物としては少なくとも水酸化ニッケルが含まれ、被覆封入剤層としては水酸化コバルトまたはオキシ水酸化コバルトが含まれる。
MH+1/4O2 → M+1/2H2O(負極)
しかしながら、電池を正極制御することのみによっては、過充電または過放電に由来する早期の故障を阻止しない。電池の早期故障を生じる他の機構がある。
水素ガスはNi−Al粉末と接触する金属水素化物負極材料中に吸着される。アルミニウムを溶解すると、金属水素化物材料に密着する表面積の大きいニッケル(ラネーニッケル)が後に残る。以下の表Iは、異なったレベルのNi−Al粉末を含む負極中で測定される予備電荷を示すが、予備荷電の割合は320mAh/gの負極容量に基づき計算され、電池は1.5の負極容量/正極容量(n/p)比を有する。室温で電極をKOH電解質中に浸した後20時間に測定を行った。
この反応は通常は触媒の存在下で進行し、金属水素化物合金がこの反応におけるよい触媒である。金属水素化物合金(M)がKBH4を含むアルカリ溶液中に存在すると、水素化硼素により放出された水素と反応し、結局の反応は以下の様に記される:
KBH4+2H2O+8M → 8MH+KBO2
ここでMHは金属水素化物である。化学的に生成される金属水素化物の量は水素化硼素水溶液の量と濃度、および反応時間に依存する。例えば、水素化硼素カリウムをAB5Mm負極と水素化ニッケル正極(AP50)を含むc−電池内に導入した。水素ガスが電池から出てくるのが見られ、負極の電位がHg/HgO参照電極に対して−0.885Vに増加し、この電極の荷電状態が増加していることを示している。予備電荷容量は全負極容量の12%であると測定された。
Claims (10)
- 負極活性材料を有する負極と、
前記負極と電気化学的に結合した正極と、
電解質と、を有し、
前記負極は予備電荷を有し、前記予備電荷の少なくとも一部は前記負極活性材料を化学的に還元することによって供給され、前記電解質は還元剤を有し、当該還元剤は、負極活性材料と反応して前記負極活性材料を化学的に還元するものであることを特徴とするニッケル金属水素化物電池。 - 前記正極が正極活性材料、前記負極において前記予備電荷を提供する少なくとも1つの正極添加剤および少なくとも1つの非酸化性バインダーを含むことを特徴とする請求項1に記載のニッケル金属水素化物電池。
- 前記負極が、(1)酸化により長サイクル寿命を提供し、(2)導電性を有する、酸化性添加剤を有し、前記添加剤が電池サイクルにより前記電解質中に溶出しても無害である成分を有することを特徴とする請求項1に記載のニッケル金属水素化物電池。
- 前記負極活性材料を水素ガスに晒すことによって、前記電解質と反応させて前記予備電荷を供給するNiAlが前記負極中に提供されることを特徴とする請求項1に記載のニッケル金属水素化物電池。
- 前記還元剤が水素化硼素ナトリウムおよび水素化硼素カリウムからなる群より選ばれることを特徴とする請求項4に記載のニッケル金属水素化物電池。
- 前記還元剤が亜燐酸ナトリウムおよび亜燐酸からなる群より選ばれることを特徴とする請求項1に記載のニッケル金属水素化物電池。
- 前記負活性材料がアルカリ溶液と反応する元素を有する合金を含み、前記化学的な還元反応が前記アルカリ溶液中で前記負活性材料をエッチングすることを特徴とする請求項1に記載のニッケル金属水素化物電池。
- 前記正極バインダーがカルボキシメチルセルロースおよび酢酸ポリビニールを含む群から選ばれることを特徴とする請求項2に記載のニッケル金属水素化物電池。
- 前記正極活性材料が、水酸化コバルト、オキシ水酸化コバルトおよびその組み合わせからなる群より選ばれるコバルト材料で封入された水酸化ニッケル粒子を含み、前記コバルト材料が導電性網状組織を形成することを特徴とする請求項2に記載のニッケル金属水素化物電池。
- 前記正極活性材料が前駆体被覆及び正極活性粒子を有し、前記前駆体被覆が前記正極の形成前に前記正極活性粒子を被覆封入することを特徴とする請求項2に記載のニッケル金属水素化物電池。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US56517004P | 2004-04-23 | 2004-04-23 | |
US60/565,170 | 2004-04-23 | ||
PCT/US2005/009613 WO2005109549A2 (en) | 2004-04-23 | 2005-03-22 | Nickel metal hydride battery design |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2007534133A JP2007534133A (ja) | 2007-11-22 |
JP5205051B2 true JP5205051B2 (ja) | 2013-06-05 |
Family
ID=35320916
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2007509476A Active JP5205051B2 (ja) | 2004-04-23 | 2005-03-22 | ニッケル金属水素化物電池の設計 |
Country Status (7)
Country | Link |
---|---|
US (1) | US7261970B2 (ja) |
EP (1) | EP1741154A2 (ja) |
JP (1) | JP5205051B2 (ja) |
CN (1) | CN100521309C (ja) |
CA (1) | CA2562708A1 (ja) |
MX (1) | MX290707B (ja) |
WO (1) | WO2005109549A2 (ja) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4305264B2 (ja) * | 2004-04-22 | 2009-07-29 | パナソニック株式会社 | アルカリ蓄電池用非焼結式正極およびアルカリ蓄電池 |
JP2007095544A (ja) * | 2005-09-29 | 2007-04-12 | Sanyo Electric Co Ltd | アルカリ二次電池用正極板およびアルカリ二次電池 |
US8012621B2 (en) * | 2007-11-26 | 2011-09-06 | Ceramatec, Inc. | Nickel-metal hydride battery using alkali ion conducting separator |
JP4985568B2 (ja) * | 2008-07-07 | 2012-07-25 | ソニー株式会社 | アルカリ電池 |
JP5013217B2 (ja) * | 2009-01-23 | 2012-08-29 | 株式会社豊田自動織機 | 非水系二次電池用活物質および非水系二次電池 |
US20110033769A1 (en) * | 2009-08-10 | 2011-02-10 | Kevin Huang | Electrical Storage Device Including Oxide-ion Battery Cell Bank and Module Configurations |
WO2012004943A1 (ja) * | 2010-07-07 | 2012-01-12 | パナソニック株式会社 | ニッケル水素蓄電池およびその製造方法 |
US20120129058A1 (en) | 2010-11-24 | 2012-05-24 | Litzinger Kevin P | Electrical Energy Storage Device |
US9054366B2 (en) | 2010-11-24 | 2015-06-09 | Siemens Aktiengesellschaft | Electrical energy storage device |
JP5744635B2 (ja) * | 2011-06-10 | 2015-07-08 | プライムアースEvエナジー株式会社 | アルカリ蓄電池及びアルカリ蓄電池の製造方法 |
CN103311516B (zh) * | 2013-07-02 | 2016-08-10 | 河南环宇电源股份有限公司 | 一种碱性电池用抗氧化剂及使用该抗氧化剂的碱性电池 |
CN106549189A (zh) * | 2015-09-22 | 2017-03-29 | 苏州宝时得电动工具有限公司 | 电池、电池组以及不间断电源 |
US20190097213A1 (en) * | 2017-09-28 | 2019-03-28 | Basf Corporation | Processes and compositions to improve high-temperature performance of nimh batteries |
US11611115B2 (en) | 2017-12-29 | 2023-03-21 | Form Energy, Inc. | Long life sealed alkaline secondary batteries |
CA3105128A1 (en) | 2018-07-27 | 2020-01-30 | Form Energy, Inc. | Negative electrodes for electrochemical cells |
CN109994716B (zh) * | 2018-11-07 | 2020-10-20 | 北京泰丰先行新能源科技有限公司 | 一种包覆型高镍三元前驱体及其制备方法 |
GB202002417D0 (en) * | 2020-02-21 | 2020-04-08 | Johnson Matthey Plc | Process |
JP7158550B1 (ja) | 2021-10-11 | 2022-10-21 | 新日本電工株式会社 | 水素吸蔵合金粉末、これを用いたニッケル水素二次電池用負極及びニッケル水素二次電池 |
CN114122569A (zh) * | 2021-11-25 | 2022-03-01 | 上海交通大学 | 同步处理废酸废碱并产电的氢化物/空气电池 |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3959018A (en) * | 1972-11-27 | 1976-05-25 | Communications Satellite Corporation | Low pressure nickel hydrogen cell |
DE2340869C3 (de) * | 1973-08-13 | 1985-02-07 | Varta Batterie Ag, 3000 Hannover | Positive, Nickelhydroxid als aktive Masse enthaltende Elektrode für alkalische Akkumulatoren |
NL7411045A (nl) * | 1974-08-19 | 1976-02-23 | Philips Nv | Herlaadbare electrochemische cel. |
US4049027A (en) * | 1976-08-26 | 1977-09-20 | Yardney Electric Corporation | Active material for pressed nickel electrodes |
FR2399484A1 (fr) * | 1977-08-02 | 1979-03-02 | Anvar | Nouveaux alliages a base de lanthane et de nickel, leur fabrication et leurs applications electrochimiques |
US4847174A (en) * | 1985-12-17 | 1989-07-11 | Combustion Engineering, Inc. | Thermally actuated hydrogen secondary battery |
US4935318A (en) * | 1987-03-25 | 1990-06-19 | Matsushita Electric Industrial Co., Ltd. | Sealed type nickel-hydride battery and production process thereof |
DE69014183T2 (de) * | 1989-09-18 | 1995-06-22 | Toshiba Battery | Nickel-Metallhydridsekundärzelle. |
US5536591A (en) * | 1990-04-26 | 1996-07-16 | Ovonic Battery Company, Inc. | Electrochemical hydrogen storage alloys for nickel metal hydride batteries |
JPH0447676A (ja) * | 1990-06-11 | 1992-02-17 | Matsushita Electric Ind Co Ltd | 密閉型蓄電池の製造法 |
US5348822A (en) * | 1992-11-12 | 1994-09-20 | Ovonic Battery Company, Inc. | Chemically and compositionally modified solid solution disordered multiphase nickel hydroxide positive electrode for alkaline rechargeable electrochemical cells |
US5344728A (en) * | 1992-11-12 | 1994-09-06 | Ovonic Battery Company, Inc. | Compositionally and structurally disordered multiphase nickel hydroxide positive electrode for alkaline rechargeable electrochemical cells |
US5523182A (en) * | 1992-11-12 | 1996-06-04 | Ovonic Battery Company, Inc. | Enhanced nickel hydroxide positive electrode materials for alkaline rechargeable electrochemical cells |
US5695530A (en) * | 1994-03-14 | 1997-12-09 | Hong; Kuochih | Method for making high charging efficiency and fast oxygen recombination rechargeable hydride batteries |
KR0148827B1 (ko) * | 1994-05-20 | 1998-10-15 | 전성원 | 알카리전지용 고밀도 수산화니켈의 제조방법 |
DE19545570A1 (de) * | 1995-12-07 | 1997-06-12 | Schuler Pressen Gmbh & Co | Transfereinrichtung für Mehrstationenpressen |
JP3390309B2 (ja) | 1996-09-27 | 2003-03-24 | 松下電器産業株式会社 | 密閉型アルカリ蓄電池 |
US6042753A (en) * | 1996-10-06 | 2000-03-28 | Matsushita Electric Industrial Co., Ltd. | Active materials for the positive electrode in alkaline storage batteries |
JP3387381B2 (ja) * | 1997-09-04 | 2003-03-17 | 松下電器産業株式会社 | アルカリ蓄電池 |
JP2001217000A (ja) * | 1999-02-26 | 2001-08-10 | Toshiba Battery Co Ltd | ニッケル・水素二次電池 |
FR2797526B1 (fr) * | 1999-08-09 | 2001-10-12 | Cit Alcatel | Accumulateur etanche nickel-metal hydrurable |
WO2002054526A1 (fr) * | 2000-12-27 | 2002-07-11 | Mitsubishi Chemical Corporation | Element secondaire au lithium |
MX241166B (es) * | 2001-06-29 | 2006-10-16 | Ovonic Battery Co | Bacteria de almacenamiento de hidrogeno; electrodo de niquel positivo; material activo de electrodo positivo y metodos para fabricarlos. |
-
2004
- 2004-07-08 US US10/887,434 patent/US7261970B2/en active Active
-
2005
- 2005-03-22 WO PCT/US2005/009613 patent/WO2005109549A2/en active Search and Examination
- 2005-03-22 CN CNB2005800201673A patent/CN100521309C/zh active Active
- 2005-03-22 CA CA002562708A patent/CA2562708A1/en not_active Abandoned
- 2005-03-22 JP JP2007509476A patent/JP5205051B2/ja active Active
- 2005-03-22 MX MXPA06012210 patent/MX290707B/es active IP Right Grant
- 2005-03-22 EP EP05726067A patent/EP1741154A2/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
CA2562708A1 (en) | 2005-11-17 |
CN1985389A (zh) | 2007-06-20 |
EP1741154A2 (en) | 2007-01-10 |
US20050238959A1 (en) | 2005-10-27 |
US7261970B2 (en) | 2007-08-28 |
JP2007534133A (ja) | 2007-11-22 |
CN100521309C (zh) | 2009-07-29 |
MXPA06012210A (es) | 2007-01-17 |
MX290707B (es) | 2011-10-04 |
WO2005109549A2 (en) | 2005-11-17 |
WO2005109549A3 (en) | 2006-10-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5205051B2 (ja) | ニッケル金属水素化物電池の設計 | |
JP5970523B2 (ja) | 水素貯蔵電池用正極材料及び正極 | |
US5506070A (en) | Metal hydride electrode, nickel electrode and nickel-hydrogen battery | |
JP3489960B2 (ja) | アルカリ蓄電池 | |
JP3246345B2 (ja) | アルカリ蓄電池用ニッケル正極とこれを用いたニッケル・水素蓄電池 | |
JP3191751B2 (ja) | アルカリ蓄電池及びその正極活物質の表面処理方法 | |
JP2012169281A5 (ja) | ||
JP3232990B2 (ja) | アルカリ蓄電池およびその製造方法 | |
JP2004531872A5 (ja) | ||
CN109830676A (zh) | 二次可充电镍氢电池用高容量且长寿命La-Mg-Ni型负极储氢材料及其制备方法 | |
JP4437338B2 (ja) | アルカリ蓄電池用正極 | |
JPH08264174A (ja) | 水素貯蔵合金陰極およびその製造方法 | |
JP3547920B2 (ja) | 水素吸蔵合金電極の製造方法 | |
JP3744642B2 (ja) | ニッケル−金属水素化物蓄電池及びその製造方法 | |
JP3516312B2 (ja) | 水素吸蔵合金電極の製造方法 | |
JPH097591A (ja) | 水素吸蔵合金及びその製造方法並びにそれを用いた水素吸蔵合金電極 | |
JP4366729B2 (ja) | アルカリ蓄電池用正極活物質 | |
JP2558624B2 (ja) | ニツケル−水素アルカリ蓄電池 | |
JPH06283170A (ja) | ニッケル−水素電池 | |
JP2857148B2 (ja) | 密閉形ニツケル−水素蓄電池の構成法 | |
JPH11224666A (ja) | アルカリ蓄電池とその製造方法 | |
JPH06318455A (ja) | ニッケル−水素電池 | |
JPH06215764A (ja) | 水素吸蔵電極の製造法およびその水素吸蔵電極を備えた金属酸化物−水素蓄電池 | |
JP2000188125A (ja) | 密閉形アルカリ蓄電池の製造方法 | |
JP2558624C (ja) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080306 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111115 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20120214 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20120221 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120509 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121127 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130110 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130205 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130218 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5205051 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160222 Year of fee payment: 3 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |