JP5970523B2 - 水素貯蔵電池用正極材料及び正極 - Google Patents
水素貯蔵電池用正極材料及び正極 Download PDFInfo
- Publication number
- JP5970523B2 JP5970523B2 JP2014219113A JP2014219113A JP5970523B2 JP 5970523 B2 JP5970523 B2 JP 5970523B2 JP 2014219113 A JP2014219113 A JP 2014219113A JP 2014219113 A JP2014219113 A JP 2014219113A JP 5970523 B2 JP5970523 B2 JP 5970523B2
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- Prior art keywords
- positive electrode
- oxidized
- active material
- nickel
- capacity
- 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
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- 239000007774 positive electrode material Substances 0.000 title claims description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 33
- 239000001257 hydrogen Substances 0.000 title claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 32
- 238000003860 storage Methods 0.000 title claims description 16
- 239000002245 particle Substances 0.000 claims description 56
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- 239000011149 active material Substances 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 31
- 230000003647 oxidation Effects 0.000 claims description 31
- 238000007254 oxidation reaction Methods 0.000 claims description 31
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 49
- 210000004027 cell Anatomy 0.000 description 30
- 230000008569 process Effects 0.000 description 30
- 239000000654 additive Substances 0.000 description 20
- 239000003607 modifier Substances 0.000 description 17
- 239000007773 negative electrode material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- -1 nickel metal hydride Chemical class 0.000 description 8
- 230000002427 irreversible effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 6
- ZRUWFKRETRELPY-UHFFFAOYSA-N azane;nickel(2+) Chemical compound N.[Ni+2] ZRUWFKRETRELPY-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- 238000010943 off-gassing Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910019718 (Ni,Co,Zn)(OH)2 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
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- VUFYPLUHTVSSGR-UHFFFAOYSA-M hydroxy(oxo)nickel Chemical compound O[Ni]=O VUFYPLUHTVSSGR-UHFFFAOYSA-M 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 210000000352 storage cell Anatomy 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910018916 CoOOH Inorganic materials 0.000 description 2
- 229910003307 Ni-Cd Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000003172 battery degassing Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 210000003771 C cell Anatomy 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 229910006083 NiCoZn Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000002801 charged material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005323 electroforming Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 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
- 229910001453 nickel ion 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
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 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
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
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-
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- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- C01—INORGANIC CHEMISTRY
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Combustion & Propulsion (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、2001年6月29日出願の、開示内容が此処に引用して取り入れてある、米国仮出願特許番号第60/302131号に関し、その先出願日及び優先権の恩典を与えられるものである。
本発明は、再充電可能な水素貯蔵電池、並びにその製造方法に関する。より詳しくは、本発明は、活性水素貯蔵材料を有する負極、及びニッケル正極を具備する再充電可能な水素貯蔵電池に関する。
負極活物質 22g
負極エネルギー密度 315mAh/g
負極容量 6950mAh
正極活物質 19g
正極エネルギー密度 245mAh/g
正極容量 4655mAh
過剰負極容量(過充電及び過放電リザーブ容量の和) 2295mAh
正極活物質中に共析したCo2+(8%) 0.96g
ペースト中にCoOとして添加されたCo2+(6%) 0.90g
ペースト中に金属Coとして添加されたCo(5%) 0.95g
CoのCo3+への酸化により発生した予備充電の量* 845mAh
CoのCo3+への酸化により発生した予備充電の量** 1296mAh
正極の非可逆的酸化により発生した全予備充電 2141mAh
最大過充電リザーブ容量 154mAh
* 2Co+4H2O→2CoOOH+3H2(気体)
** 2CoO+2H2O→2CoOOH+H2(気体)
上に示したように、過充電リザーブ容量は、従来の電池においては単電池容量の僅か3%以下である。酸化による低減により、過充電状況の際に過充電リザーブ容量が皆無となる。
二つのC型単電池が調製され、一つは従来の水酸化ニッケルを有し(比較試料)、一つは事前酸化水酸化ニッケルを有していた。
・ 高濃度反応液の使用、それにより放出する流量を効果的に低減すること
・ 低いpHの使用、それにより機器の寿命及び工程管理の信頼性を拡大すること
・ 二つの反応装置を均衡させる必要性の消滅、それにより操作の容易性を向上すること
各成分の添加及び得られるスラリー(析出した事前酸化水酸化ニッケル材料を含有している)の取り出しは、スラリーが析出物の最大量と未反応成分の最小量とを含むように、相補的速度で注意深く制御されることが好ましい。スラリーは反応装置から取り出された後、濾過されて液体から析出物が分離される。液体は再利用され、析出物は処理されて、本発明の変性された事前酸化水酸化ニッケルを生成する。
・ (NiCo)(OH)2
・ (NiCoZn)(OH)2
・ (NiCoZnMgCa)(OH)2
・ (NiCoZnMnMgCa)(OH)2
・ (NiCoZnMgCaCuMn)(OH)2
変性剤の総量は、ニッケル材料の全金属化合物の20%未満を占めることが好ましい。Coは全金属組成に対して、好ましくは3から9原子%、より好ましくは4から8原子%、最も好ましくは5から7原子%存在する。Zn、Mg及びCaはそれぞれ2原子%未満であることが好ましい。事前酸化粒子は、事前酸化Coを含むことが好ましく、一つ以上のその他の事前酸化変性剤を含むことも可能である。
Claims (7)
- 水素貯蔵電池用の正極材料であって、
100%ではない第一の程度に部分的に酸化された活物質と、
前記第一の程度とは異なる100%ではない第二の程度に部分的に酸化された活物質と
からなり、
前記第二の程度に部分的に酸化された活物質が前記第一の程度に部分的に酸化された活物質を覆い包み、
前記第一の程度と前記第二の程度とにより2段階の酸化程度が形成される正極材料。 - 前記第一の程度に部分的に酸化された活物質と前記第二の程度に部分的に酸化された活物質とは同じ金属の化合物である、請求項1の正極材料。
- 前記第一の程度に部分的に酸化された活物質及び前記第二の程度に部分的に酸化された活物質は、水酸化ニッケル材料を含む、請求項1又は2の正極材料。
- 前記正極材料は複数の粒子からなる、請求項1から3のいずれか一項の正極材料。
- 各粒子は、前記第二の程度に部分的に酸化された活物質の表面を有する、請求項4の正極材料。
- 前記同じ金属は、ニッケル、コバルト又は亜鉛である、請求項2の正極材料。
- 請求項1から6のいずれか一項の正極材料を含む、焼結されていない正極。
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US30213101P | 2001-06-29 | 2001-06-29 | |
US60/302,131 | 2001-06-29 |
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JP2012090789A Division JP5663520B2 (ja) | 2001-06-29 | 2012-04-12 | 水素貯蔵電池、ニッケル正極、正極活物質、並びに製法 |
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JP2012090789A Expired - Lifetime JP5663520B2 (ja) | 2001-06-29 | 2012-04-12 | 水素貯蔵電池、ニッケル正極、正極活物質、並びに製法 |
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JP2012090789A Expired - Lifetime JP5663520B2 (ja) | 2001-06-29 | 2012-04-12 | 水素貯蔵電池、ニッケル正極、正極活物質、並びに製法 |
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US (2) | US6593024B2 (ja) |
EP (1) | EP1402593A4 (ja) |
JP (3) | JP5002113B2 (ja) |
CN (1) | CN100350667C (ja) |
MX (1) | MX241166B (ja) |
TW (1) | TW552738B (ja) |
WO (1) | WO2003003498A1 (ja) |
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EP1402593A1 (en) | 2004-03-31 |
MXPA03012054A (es) | 2004-03-26 |
JP5002113B2 (ja) | 2012-08-15 |
JP2004531872A (ja) | 2004-10-14 |
CN100350667C (zh) | 2007-11-21 |
US7396379B2 (en) | 2008-07-08 |
TW552738B (en) | 2003-09-11 |
CN1554133A (zh) | 2004-12-08 |
JP2012169281A (ja) | 2012-09-06 |
JP5663520B2 (ja) | 2015-02-04 |
MX241166B (es) | 2006-10-16 |
EP1402593A4 (en) | 2009-04-29 |
WO2003003498A1 (en) | 2003-01-09 |
US6593024B2 (en) | 2003-07-15 |
US20050002855A1 (en) | 2005-01-06 |
JP2015072912A (ja) | 2015-04-16 |
US20030054228A1 (en) | 2003-03-20 |
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