CN100438152C - Active mixed nickel hydroxide cathode material for alkaline storage batteries and process for its production - Google Patents
Active mixed nickel hydroxide cathode material for alkaline storage batteries and process for its production Download PDFInfo
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- CN100438152C CN100438152C CNB038231123A CN03823112A CN100438152C CN 100438152 C CN100438152 C CN 100438152C CN B038231123 A CNB038231123 A CN B038231123A CN 03823112 A CN03823112 A CN 03823112A CN 100438152 C CN100438152 C CN 100438152C
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000010406 cathode material Substances 0.000 title claims description 30
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title abstract description 17
- 238000003860 storage Methods 0.000 title description 13
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000009826 distribution Methods 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 29
- 230000002902 bimodal effect Effects 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 162
- 229910052759 nickel Inorganic materials 0.000 claims description 79
- 239000002245 particle Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 26
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052725 zinc Inorganic materials 0.000 claims description 22
- 239000011701 zinc Substances 0.000 claims description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- 239000000376 reactant Substances 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 150000002815 nickel Chemical class 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 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 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000009938 salting Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- -1 nickelous cation Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 230000000750 progressive effect Effects 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000005304 joining Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims 2
- 238000001556 precipitation Methods 0.000 abstract description 8
- 239000006182 cathode active material Substances 0.000 abstract 1
- 238000010908 decantation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 238000002474 experimental method Methods 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 15
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 239000008139 complexing agent Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 5
- 150000004679 hydroxides Chemical class 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 150000004692 metal hydroxides Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- YWMAPNNZOCSAPF-UHFFFAOYSA-N Nickel(1+) Chemical compound [Ni+] YWMAPNNZOCSAPF-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004452 microanalysis Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940006444 nickel cation Drugs 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 230000003534 oscillatory effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000006101 laboratory sample Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/32—Nickel oxide or hydroxide electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/53—Particles with a specific particle size distribution bimodal size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel 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
- H01M10/34—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to cathode active material based on mixed nickel hydroxide which is used for alkaline batteries and has a special bimodal particle-size distribution providing said material with high-performance characteristics. The inventive material based on mixed nickel hydroxide is produced by means of a very advantageous continuous precipitation process in a closed flow reactor which is provided with an integrated decantation area.
Description
The present invention relates to a kind of active nickel mixed hydroxide cathode material that is used for alkaline battery and preparation method thereof, more definite theory the present invention relates to a kind of main grain group of institute's definition amount and size and nickel mixed hydroxide material and a kind of method for preparing bimodal nickel mixed hydroxide with one-step method of secondary grain group of containing.
Prior art
Mainly contain nickel hydroxide and in nickel-cadmium (Ni-Cd) storage battery and nickel-metal hydrides (NiMH) storage battery, be used as positive electrode as the nickel mixed hydroxide electrode of active material.Because to the requirement that storage battery improves constantly especially for the capacity increase of the storage battery in movably electrical equipment or the automobile, this just needs to improve the energy density of used storage battery.The energy density of this storage battery is mainly relevant with the quality that is used to prepare the used nickel mixed hydroxide material of positive electrode.It is particularly advantageous having high electrochemical storage capacity and high stamped density.
For there is the whole bag of tricks in the characteristic of improving the nickel mixed hydroxide cathode material, it all forms relevant with preparation methods with material.
EP 0353837 B1 has described a kind of being used for by combination nickel (II) salting liquid, ammonium source and hydroxide source to prepare the method for nickel mixed hydroxide.When preparation was included in the nickel electrode of the nickel hydroxide powder that contains the zinc that is solid solution or magnesium in its nickel hydroxide crystal, zinc or magnesium existed with 3-10 weight % or 1-3 weight %, and the pore radius in the powder is not more than 3nm, and pore volume is less than 0.05cm
3/ g.The preparation of material realizes by the nickel hydroxide crystal that precipitation from the sulfate that is added with ammonium sulfate is water-soluble contains a small amount of zinc or magnesium, adds NaOH or potassium hydroxide in view of the above so that the pH value is 11-13.
The method that can contain the ball-shape nickel hydroxide particle of cobalt or cadmium from JP 3252318 known a kind of preparations.Add continuously to reactor for this reason:
A) nickel salt aqueous solution or contain the aqueous solution of nickel salt, cobalt salt and cadmium salt,
B) alkali metal hydroxide aqueous solution,
C) ammonium ion is given body,
To prepare nickel hydroxide particle or to contain cobalt or the nickel hydroxide particle of cadmium.This reaction is that 9-12 and the continuous product of discharging quicken by keeping temperature to be 20-80 ℃ with the pH value.This method is suitable for obtaining completely specified granularity by regulating some condition.For the desired particle size that reaches in cathode material distributes, two kinds of mixed hydroxides that narrower particle size distribution is respectively arranged that will under different condition, prepare in another procedure of processing with given mixed.Particularly can find out, not reach the best distribution of the different size particles of this mixed hydroxides by mixing thereafter from figure.
Used reactive hydrogen nickel oxide powder also is described among the EP 0523284B1 when the positive nickel electrode of preparation.Before this positive electrode of preparation, the mixture that this powder is made up of spherical and subsphaeroidal particle and aspherical particle, this particle comprises at least a nickel hydroxide powder that is selected from the element of cadmium, calcium, zinc, magnesium, iron, cobalt, manganese, cobalt oxide, zinc oxide and cadmium oxide that contains 1-7 weight %.This powder is that the aqueous solution by nickel salt and at least a selected element obtains, and wherein pH value in reaction is adjusted to 11.3 ± 0.2, with adjustment to 30-40 ℃.
EP 0658514 B1 has described that a kind of to be used for preparing continuously general formula be M
(x)(OH)
xThe method of metal hydroxides of slightly solubility, wherein M=Co, Zn, Ni or Cu, x is the valence state of metal.In first step, the metal hydroxides of the anodic oxidation gained by metal resolves into general formula with complexing agent L in the presence of alkali metal salt AY be ML
nY
mMetallic complex salt, alkali hydroxide soln time resolves into slightly solubility metal hydroxides, complexing agent and alkali metal salt in pH＞7, at this moment complexing agent L and alkali metal salt AY turn back to first step, and the alkali hydroxide soln that the decomposition of this metallic complex salt is used in first step formation carries out
People such as Scherzberg are at Chemie Ingenieur Technik
70Reported preparation in 12/1998, the 1530-1535 page or leaf, it is characterized in that the particle size distribution of arrowband about unimodal oxygen oxide such as magnesium hydroxide and nickel hydroxide.Can prepare spherical metal hydroxide with its described equipment with narrow particle size distribution.
The purpose of this invention is to provide a kind of high nickel mixed hydroxide of electrochemistry durability that under sufficiently high stamped density, has high electrochemical storage capacity, little self discharge and high BET surface area.
Summary of the invention
This purpose is to realize by the bimodal size distribution that the nickel mixed hydroxide cathode material that makes plan of the present invention be used for alkaline battery has based on quality, wherein main grain group's the intermediate value based on the particle size distribution of quality is 5 μ m-25 μ m, secondary grain group is 0.3 μ m-3 μ m based on the intermediate value of the particle size distribution of quality, and main grain group's mass content is 70-96%.
It is found that nickel mixed hydroxide cathode material of the present invention even also demonstrate enough big stamped density when arranging (101 reflections of measuring in here with X-ray diffraction and 102 half widths that reflect are as measuring) at high crystal dislocation.
The too high degree of order of crystal causes the electrochemical properties of non-the best, as the memory capacity that reduces.But the increase that dislocation is arranged in the crystal also causes the deterioration of mechanical property (to reduce to 1.5g/m as stamped density so far
3Below), the difference filterability and particle size distribution have bigger width.It is characterized by the nickel mixed hydroxide cathode material that contains two kinds of promptly main grain groups of definite grain group and secondary grain group by preparation, can overcome above-mentioned shortcoming.
Promptly this purpose realizes by making precipitated product, and this product is become with pair grain group by the main grain group with particle size distribution relevant with quality, promptly is also referred to as the nickel mixed hydroxide of bimodal distribution.Can make main grain group's span keep narrow thus.Importantly, with main grain faciation ratio, secondary grain group's average grain diameter is so little, so that should pair grain group be filled in main grain group's the cavity when closely knit filling for distribution.Can compensate or alleviate the decline of the stamped density that causes by reducing the degree of order thus.Compare with suitable Unimodal Distribution, when bimodal distribution, can reach higher space compactedness.In addition, obtain the more contact points between each particle, this helps the durability of storage medium and big BET surface.
Obtained by the granularity based on the nickel mixed hydroxide of the present invention of volume based on the intermediate value of the particle size distribution of quality, this granularity is by the laser particle assay determination, and described the nickel mixed hydroxide of the present invention of different experiments time in Fig. 4,5 and 6.Following relation of plane will be converted into the particle size distribution based on quality based on the particle size distribution of volume:
m
i＝
ρi ρV
i
M wherein
iThe mass fraction of=particle size fraction i, ρ
iThe grain density of=particle size fraction i, ρ=nickel mixed hydroxide pure density, V
iThe volume fraction of=particle size fraction i.According to disperseing the micro-analysis of X-ray can be by ρ in the experiment of scanning electron microscopy with based on energy
i=ρ=3.56g/cm
3Derive with the incoherent material of granularity and form and density of material, make that be identical based on the particle size distribution of the nickel mixed hydroxide of the present invention of quality with particle size distribution based on volume.
In a preferred embodiment of the invention, the main grain group's of particle intermediate value is 6-12 μ m, and secondary grain group's intermediate value is 0.3-1.5 μ m.In another embodiment, main grain group's mass fraction is that 70-95 weight % is particularly preferred.
Term hybrid hydroxide means usually and contains different cationic hydroxide.The term hybrid nickel hydroxide means a kind of like this mixed hydroxides hereinafter, and promptly its mainly nickeliferous (II) ion is a cation, is used for particularly more a spot of other cation of electrical characteristics of ectocrine physical chemistry characteristic but in addition also contain.
Nickel mixed hydroxide cathode material of the present invention preferably has such composition, promptly is selected from least a component of magnesium, calcium, zinc, cobalt, aluminium, manganese, iron, chromium, rare earth element except that nickel cation in addition.
In addition, this mixed hydroxides can contain monovalence or dianion, particularly is selected from the anion of chloride ion, nitrate ion, sulfate ion.The same with other divalence and the Tricationic that exist with the subordinate amount, these anion can embed in the nickel hydroxide crystal structure.
The nickel content of nickel mixed hydroxide cathode material is preferably 40-60 weight %, more preferably 55-59 weight % by dry weight basis.The specific area of mixed oxide of the present invention is 10-100m by the BET pH-value determination pH
2/ g is preferably 15-40m
2/ g.
By having the performance that specific bimodal size distribution realizes improved nickel mixed hydroxide cathode material.
Compare with the identical pure density and the powder of form with having corresponding unimodal distribution of particles, the powder with bimodal size distribution demonstrates higher packed density under suitable sphere diameter ratio.Also increased the number of sites that contacts of the internal surface area of material and per unit volume in addition.Although the material of this precipitation has quite low density, also reached 1.8g/cm
3-2.0g/cm
3Stamped density.The electrochemical storage capacity is increased to more than the 260mAh/g.This precipitation of material is fast, have good filterability and washability and the BET surface area that is significantly increased is 20m
2/ g-40m
2/ g.Its circular aggregation by unbodied spherical host grain constitutes, and this host grain itself is made of the big crystal grain of the 100-200nm that embeds the shape arrangement.But the favourable electrochemical properties of other of material of the present invention is also obtained by above-mentioned bimodal distribution as the durability that increases.
The key that is suitable for effect of the present invention is grain group's suitable ball warp ratio and the appropriate mass ratio between the grain group, and this is to establish as yet in the prior art.For example main grain group and secondary grain group's distribution of particles percentage D based on quality
90%And D
10%Between span should make it can be not overlapping.At this moment the given x value of this percentage, this distribution summation can obtain this corresponding percentage of total distributed divided by this parameter x.
The preparation of nickel mixed hydroxide cathode material of the present invention can be as described in detail below the depositing technology that passes through in having the loop reactor of incorporate settling section carry out.Can make the selection of the mean residence time of solid in reactor irrelevant with the time of staying of reaction solution basically by incorporate settling section.
Can successfully prepare the unexpected part with cathode material of bimodal size distribution of the present invention in having the loop reactor of incorporate settling section is, the feature of the known gained of depositing technology thus material normally very homogeneous unimodal, be particle size distribution (people (1998) Scherzberg such as Scherzberg, the H. of special arrowband sometimes; Kahle, K.;
K.; K.; Chemie Ingenieur Technik
7012/1998, the 1530-1535 page or leaf).The mass distribution width of the particle mean size of particle and particle diameter is relevant with a series of physics and chemical characteristic, and specific to material and method.The nickel hydroxide that the method for describing with people such as Scherzberg prepares has the radial growth structure and the arrowband particle size distribution of particle.Because selected condition, the material of precipitation grows into spheric granules with very fine and close form.It is tending towards rapid subsidence, has favourable filtering feature and also can very well wash.The BET surface area of this material is at stamped density＞2.1g/cm
3Shi Tongchang is about 10m
2/ g.But the electrochemical storage capability value of this material is 220mAh/g-240mAh/g, is starkly lower than other known materials.
The unexpected discovery when nickel mixed hydroxide precipitates, when suitably regulating parameter, can temporarily stablize a kind of state, second group appears under this state, it has obviously less average grain diameter and the constant in time approximately amount ratio of main grain group than coarse grain, and it accounts for about 5-30% of gross mass.It is found that these ratios are to the advantageous feature particular importance of material just.
Occur so-called oscillatory occurences during parameter regulation of the present invention in said process, promptly at this moment particle mean size at first constantly increases and crystallization nucleus number constantly reduces, and second group of small particle diameter forms up to having obviously more.Then this group not only all constantly increases on the amount ratio but also on particle diameter.Discharge material requested in the determined period of experiment.
A kind of possible method that is used for preparing the nickel mixed hydroxide cathode material of the present invention that can not prepare with the known so far precipitation method is on purpose to cause the oscillatory occurences that relates to granularity at reactor by regulating parameter.Find that the sediment of being made up of the thinnest host grain with the coarse grain agglomerate that is caused mutually by other generation synchronized mixes takes place in settling step thus, and produce the material with bimodal distribution of the present invention.
Another kind of be, except that continuous logistics, also increase the number of host grain by unexpected adding slaine with initiation voluntarily with regular time intervals with the get everything ready method of bimodal size distribution of the settling step interlock system of continuity method.Form the second product grain group who has than small particle diameter by the number that increases the crystallization nucleus.
Therefore the feature that is used to prepare the method for required nickel mixed hydroxide cathode material of the present invention is usually, exists by nickel mixed hydroxide, for example by alkali metal ion, nickel (II) ion, ammonia, OH in having the loop reactor of integrated settling section
-Ion and at least a magnesium that particularly is selected from, calcium, zinc, cobalt, aluminium, manganese, iron, chromium, the divalence of rare earth element or the component of Tricationic and at least a chloride ion that particularly is selected from, nitrate anion, the aqueous solution that the monovalence of sulfate radical or the component of dianion are formed, the reactant mixture of forming, and add and contain the particularly aforementioned cationic nickel of other metal ion (II) salting liquid, ammonia spirit and alkali hydroxide soln to be forming mixed oxide, with the graininess nickel mixed hydroxide cathode material that forms as solid with the liquid parts of the reactant mixture solid/liquid separation of discharging and lead.In this process, can under substantially invariable pH value, substantially side by side alternately add nickel (II) salting liquid and alkali hydroxide soln, or except that continuously and add nickel salt solution and the alkali hydroxide soln substantially simultaneously, by every 0.5-5 hour the nickel salt solution that has rule the time interval to measure to add 0.5-15 volume % and alkali hydroxide soln in batches in reactant mixture, at this moment can not cause pH value to continue change.
The nickel cation that added nickel (II) salting liquid preferably contains 80-125g/l is selected from the cation of magnesium, calcium, zinc, cobalt, aluminium, manganese, iron, chromium, rare earth element with one or more, and its amount respectively is 0.1-20g/l.
Ammonia spirit preferably contains the ammonia of 1-25 weight %.
Alkali hydroxide soln can be made up of NaOH, KOH and/or the LiOH aqueous solution, preferably only by the NaOH solution composition.The alkali metal hydroxide total content is counted 10-30 weight % by the gross mass of solution, preferred about 20 weight %.
Advantageously, when this method of enforcement, is that 50-60g/l, nickel (II) ion concentration are that the total concentration of 0.1-100mg/l, magnesium, calcium, zinc, cobalt, aluminium and manganese is 0.1-100mg/l with the concentration adjustment of this reactant mixture in reaction solution to the total concentration of sodium, potassium and lithium, at this moment has OH
-, chloride ion, nitrate anion and/or sulfate radical be as counter ion.
Solids content in the reactant mixture should be adjusted to 220g/l-400g/l, preferred 300g/l-380g/l.
The product suspended substance that is flowed out by the mixed zone of loop reactor is transformed into no solid solution and contains the solid that the 0.05-0.35 weight portion adheres to solution through known solid/liquid separation method such as vacuum band filter.
In clarification equipment thereafter, collect and return this reactor with the solid particle that circular response solution in the reactor flows out.
The temperature of reactant mixture should constantly remain on 20-80 ℃ in time, and preferred 30-60 ℃, more preferably in ± 1 ℃ interval.
According to reaction temperature, the pH value of this reaction solution is 9.8-13.7, preferred 11.6-12.9, and its tolerance in time should constant remaining on ± 0.05.
Alkali hydroxide soln can be the 0.9-1.3 mol ratio by the cation total amount to nickel (II) salting liquid, preferably is the metering of 1.05-1.10 mol ratio and adds reactor.This alkali hydroxide soln is preferably directly joining in the reactor at liquid surface under the liquid surface or directly.
This nickel (II) salting liquid preferably under liquid surface, is more preferably introduced in the reactor in fluid dynamic loop district.
Ammonia spirit especially preferably directly adds at liquid surface under liquid surface or directly, preferably adds in the porch near nickel (II) salting liquid.
Find, as every 1m
3Reactor volume is produced 7-30kg/h, the nickel mixed hydroxide of preferred 18-25kg/h and when to keep than output in time be constant, and this is very favorable to product.
The reactor volume of particularly suitable is 1 liter-100m
3In a particularly preferred embodiment of the present invention, this loop reactor comprises the dihedral vane blender, the 6-dihedral vane blender that preferably has axially vertical shaft, its stirring vane has 15 °-85 °, preferred 30 °-60 ° constant or progressive inclination angle, stirring intensity is 150W/m
3-320W/m
3, preferred 290W/m
3-300W/m
3, and in conduit, produce different flow velocitys and in reactant mixture, produce shearing force.
Prepare of the combination of the particularly preferred process of nickel mixed hydroxide cathode material of the present invention, and comprise based on adaptive mutually chemistry, physics and mechanical factor:
Guarantee that specific energy is input as 150W/m
3-320W/m
3, preferred 290W/m
3,
Guarantee every m
3The ratio output of reactor volume is 7kg/h-30kg/h, preferred 15kg/h-25kg/h,
The adjusting solids content reaches by the strong confounding of precipitation reactor counts 220kg/m
3-400kg/m
3, preferred 300kg/m
3-380kg/m
3,
Regulate excessive the reaching of constant precipitation reagent and count every m by hydroxide ion
3Solution 0kg-10kg, preferred 1.5kg-6.3kg,
The temperature of regulating the product suspended substance is 20 ℃-90 ℃,
Upper area in loop stream is imported required logistics in the strong difference that mixes reaction zone,
Application has 15 °-85 °, the dihedral vane blender at preferred 30 °-60 ° constant or progressive inclination angle, and it guarantees different flow velocitys to occur and shearing force occurs in conduit in suspended substance, to influence the formation of particle by required mode.
Use described equipment and prepare the reactant mixture of nickel mixed hydroxide material of the present invention with continuity method by nickel mixed hydroxide that has prepared and alkali metal ion, nickel (II) ion, ammonia, alkali hydroxide soln and at least a being selected from as magnesium, calcium, zinc, cobalt, aluminium, manganese, iron, chromium, rare earth is particularly including the divalence of lanthanide series or the component and at least a being selected from as chloride ion of Tricationic, nitrate anion, the aqueous solution that the monovalence of sulfate radical or the component of dianion are formed is formed.In this reactant mixture, add nickel (II) salting liquid, ammonia spirit and the alkali hydroxide soln that contains other metal ion.This reaction solution contains the alkali metal ion of 50-60g/l, the nickel of 0.1-100mg/l (II) ion, the cation of 0.1-100mg/l and the anion of 0.1-200g/l.This nickel (II) salting liquid contains the nickel of 80-125g/l, for example magnesium, calcium, zinc, cobalt, aluminium, manganese, iron, chromium, the divalence of rare earth or the monovalence or the dianion of Tricationic and for example chloride ion, nitrate anion, sulfate radical of 0.1-20g/l.This alkali hydroxide soln contains NaOH, KOH, at least a component among the LiOH of 10-30 quality % and also contains NH when needing
3Ammonia spirit contains the ammonia of 1-25 quality %.
To the present invention be described in detail in detail with drawings and Examples below.Wherein:
Fig. 1 illustrates the process equipment figure that is used to prepare the nickel mixed hydroxide cathode material;
Fig. 2 illustrates and is used to prepare the used loop reactor figure of nickel hydroxide material of the present invention;
Fig. 3 illustrates the UV spectrogram of reaction solution;
Fig. 4 illustrates the particle size distribution figure after 24 hours;
Fig. 5 illustrates the particle size distribution figure after 46 hours;
Fig. 6 illustrates the particle size distribution figure after 78 hours.
As shown in Figure 1, in basin 1 doped nickel solution, in basin 2 alkali hydroxide soln, in basin 3 ammonia solution.These solution are sent into by basin in the loop reactor 6 of heating and thermal insulation through pipeline 13,14 and 15 with pump 4 and 5.Overflow 16 through reactor 6 is heated the reaction solution importing of low-solid content in the also adiabatic clarifier 7.The underflow available pump 11 of this clarifier 7 turns back in the reactor 6 through return line 18.The reaction solution of unnecessary low-solid content can be collected in the basin 8 through the overflow 17 of clarifier 7.The heat cycles that is used for clarifier 7 and loop reactor 6 has the heating tank 10 of band pump.From the beginning the precipitated product of reactor 6 through reactor underflow 19 be by mesh the sieve 12 of 0.063mm removing presumable oversized particles, and arrive solid/liquid separation apparatus as product suspended substance 19.The adjusting of this technology realizes by adjuster 9.
Fig. 2 illustrates the loop reactor with integrated settling section of the particularly suitable that is used to prepare nickel mixed hydroxide material of the present invention.Hydrostatic column 21 has container bottom 22 for example flat or taper.Be fixed with one or more wall stream deflection plates 23 in the inboard of container 21; For example can stagger 4 wall stream deflection plates 23 are installed by per 90 ° of angles.This loop reactor can be equipped with overflow launder 24, collects the reaction solution of unnecessary low-solid content therein, and for example is sent to clarifier 7 through taphole 30.The solid particle that is entrained with the reaction solution that comes autoreactor can be collected in thereafter the clarifier 7, and turns back to reactor.In container 21, annular separating plate 25 and ring duct 26 roughly are installed with one heart with the cylinder axis of loop reactor.The blender 28 that drives through axle 27 is arranged in conduit 26, make suspended substance and the precipitated product in loop reactor formed by reaction solution keep motion state thus.This blender for example can be the dihedral vane blender 28 of band vertical axial shaft 27, and this paddle has 15 °-85 °, preferred 30 °-60 ° constant or progressive inclination angle.But also can in conduit 26, conveying screw rod be installed.The crystal of multiviscosisty or other precipitated product can be by being drawn off by loop reactor in the outlet 29 of the crystal of bottom and subsequently after filtration.
Fig. 3 illustrates the typical UV spectrum as the reaction solution that is used to prepare the nickel mixed hydroxide material with bimodal size distribution in the methods of the invention.Detectable thus go out the order of magnitude be 1mg/l-100mg/l be nickel (II) ion that complexing is connected with ammonia.Be the also available UV spectrometry monitoring of remaining nickel content that complexing connects in this reaction solution, can be when needing by intervening the adjusting of pH value or adding NH
3Proofread and correct.
Fig. 4-6 illustrates the particle size distribution of different experiments time among the embodiment 1.The laser particle assay determination of this particle size distribution.The feature of this method of measurement be its result based on volume, and estimation theory is based on ideal ball.Laboratory sample is by passing through slurried preparation the in deionized water through growth and dry nickel mixed hydroxide cathode material.Gained based on the particle size distribution of volume and based on the particle size distribution of quality owing to be the result that scanning electron microscope analysis and energy disperse the micro-analysis of X-ray, so can think consistent.
Embodiment
Embodiment loop reactor with Fig. 2 in the equipment of Fig. 1 carries out.In used loop reactor,, select the time of staying of solid in reactor under the situation that can have nothing to do substantially in the time of staying by incorporate settling section with solution as described.To a) contain the Ni saline solution of other additive from different containers, b) alkali hydroxide soln, c) ammoniacal liquor is under the liquid level or be metered into the zones of different of loop reactor on the liquid level.The metering of raw material is carried out under temperature through regulating and pH value.The product suspended matter that employing has the vertical axial shaft and the 6-dihedral vane blender of the mixing arm of installation remains in the loop reactor between 15 °-85 ° is motion state.Product is drawn off by the reactor mixed zone, and the gained suspended matter after filtration subsequently.The solid matter of discharging with solution stream in reactor overflow enters clarifier, and turns back to reactor again by it.The solution of overflow is collected in the basin with filtrate in clarifier.
Mastersizer (laser particle analyzer) with Malvern company measures distribution of particles.
The time of staying of solution increase solid can be brought up to solid content greater than 350g/l relatively.The high grain density of suspended matter and cause having the product of high stamped density through the input of the high-energy of blender, this product is suitable as the active material of storage battery.The mechanical stress of solid produces and has the secondary grain group that average grain diameter is the product of 0.5-1 μ m in the mixed zone of reactor.Main grain group's intermediate value is 6-12 μ m.In this way the nickel mixed hydroxide that obtains bimodal distribution under the additional blend step can not had.
Embodiment 1
Embodiment 1 describes continuous preparation technology
Nickel/zinc the sulfate liquor that will contain 115g/l nickel and 8.7g/l zinc with measuring pump joins the strong confounding of the loop reactor with incorporate settling section and 400 heave shallow lake capacity.As complexing agent with the ammonia spirit of 25% concentration in next-door neighbour's sulfate liquor porch with 0.7 mole of NH
3: the ratio of 1 mole of nickel adds in the reactor.With the sodium hydrate aqueous solution of 20% concentration with 1.1 moles of NaOH: the ratio of 1 mole of nickel directly is added to the loop stream zone of mixed zone in the reactor.Being 20-90 ℃ in the reaction solution temperature is to form nickel mixed hydroxide of the present invention under 12.6 conditions with the pH value.Density of solid in the reactor rose to 350g/l in 19 hours.Can draw off crystal afterwards, it draws off reactor with the amount of 9.5kg per hour.Than output is about 2kg/ (hm
3).
This is measured after the different reaction time with the following properties of the nickel mixed hydroxide material of drying through washing.
| Reaction time | Main grain group's intermediate value D 50 | Secondary grain group's intermediate value D 50 | Mass distribution | BET | Stamped density |
| h | μm | μm | Main grain group: secondary grain group | m 2/g | g/ |
| 24 | 9.6 | 0.53 | 88∶12 | 43.6 | 1.7 |
| 46 | 7.8 | 0.55 | 87∶13 | 34.2 | 1.8 |
| 62 | 8.6 | 0.63 | 89∶11 | 32.2 | 1.9 |
| 78 | 8.9 | 0.60 | 88∶12 | 26.0 | 1.9 |
Particle size distribution after 24 hours reaction time and the visible Fig. 4 of its ratio in cumulative volume, the particle size distribution after 46 hours and the visible Fig. 5 of its ratio in cumulative volume, the particle size distribution after 78 hours and the visible Fig. 6 of its ratio in cumulative volume.
Nickel/zinc the sulfate liquor that will contain 115g/l nickel and 8.7g/l zinc with measuring pump joins the strong confounding of the loop reactor with incorporate settling section and 22 heave shallow lake capacity.As complexing agent with the ammonia spirit of 25% concentration in next-door neighbour's sulfate liquor porch with 0.7 mole of NH
3: the ratio of 1 mole of nickel adds in the reactor.With the sodium hydrate aqueous solution of 20% concentration with 1.07 moles of NaOH: the ratio of 1 mole of nickel directly is added to the loop stream zone of mixed zone in the reactor.The reaction medium temperature is 60 ℃, is 20kg/hm than output
3Obtaining having the particle mean size of leading the grain group is the nickel mixed hydroxide of 13-15 μ m.Secondary grain group's percentage mass fraction is 0-4%.After the experiment in 52 hours, each is reinforced and per hour 16% NaOH solution is reinforced by in the reaction medium that is added in batches in the reactor with 4% nickel/zinc sulfate liquor per hour simultaneously by per 2 hours frequency.In the 76th experiment hour, the intermediate value that obtains having main grain group is that 12.0 μ m and secondary grain group's intermediate value is 0.8 μ m and main grain group and secondary grain group's mass distribution ratio is 95%: 5% a nickel mixed hydroxide.
This following properties through the washing and the nickel mixed hydroxide material of drying is measured at different experimental period points.
| The experiment hour | Stamped density | BET | Main grain group intermediate value D 50％ | Secondary grain group intermediate value D 50％ | Distribute |
| h | g/cm 3 | m 2/g | μm | μm | Main grain group: |
| 16 | 2.0 | 12.6 | 13.1 | - | 100∶0 |
| 48 | 2.0 | 11.3 | 15.8 | 1.5 | 96∶4 |
| 76 | 1.9 | 16.6 | 12.0 | 0.8 | 95∶5 |
| 90 | 2.0 | 17.4 | 10.8 | 0.8 | 94∶6 |
Embodiment 3
The preparation technology that embodiment 3 describes is interrupted after the intermediate preparation of bimodal nickel mixed hydroxide, and empties reactor and then restart this process.
Nickel/zinc the sulfate liquor that will contain 115g/l nickel and 8.7g/l zinc with measuring pump joins the strong confounding of the loop reactor with incorporate settling section and 22 heave shallow lake capacity.As complexing agent with the ammonia spirit of 25% concentration in next-door neighbour's sulfate liquor porch with 0.7 mole of NH
3: the ratio of 1 mole of nickel adds in the reactor.With the sodium hydrate aqueous solution of 20% concentration with 1.3 moles of NaOH: the ratio of 1 mole of nickel directly is added to the loop stream zone of mixed zone in the reactor.The reaction medium temperature is 40 ℃, is 20kg/hm than production capacity
3From the 16th experiment hour from reactor with 60 liters/1m per hour
3Reactor volume draws off the product suspended matter, so that the solid content in the volume of mixed zone hour rises to 450g/l suspended matter volume through 55 experiments.Periodic particle size distribution below under constant maintenance experiment condition, occurring.Obtain having monomodal grit distribution and particle mean size is the product of 5.8 μ m in when beginning experiment (the 7th experiment hour).At the maximum solids content time point of the 55th experiment hour, the intermediate value that bimodal distribution and its main grain group occur having be 7.8mm and secondary grain group's intermediate value be 0.7 and main grain group be 96: 4 product to secondary grain group's mass distribution ratio.After 78 experiments hour, obtain the Unimodal Distribution product that intermediate value is 4.5 μ m, and intermediate value of its main grain group that gets back to be 5.4 μ m and secondary grain group's intermediate value be 0.7 μ m and main grain group are 90: 10 bimodal distribution product to secondary grain group's mass distribution ratio after 93 experiments hour.
This following properties through the washing and the nickel mixed hydroxide material of drying is measured by different reaction time points.
| The experiment hour | Stamped density | BET | Main grain group intermediate value D 50％ | Secondary grain group intermediate value D 50％ | Distribute |
| h | g/cm 3 | m 2/g | μm | μm | Main grain group: |
| 7 | 1.4 | 33.7 | 5.8 | - | 100∶0 |
| 55 | 2.0 | 18.9 | 7.8 | 0.7 | 96∶4 |
| 78 | 1.5 | 16.6 | 4.5 | - | 100∶0 |
| 93 | 1.8 | 29.1 | 5.4 | 0.7 | 90∶10 |
Claims (36)
1. nickel mixed hydroxide cathode material that is used for alkaline battery with bimodal size distribution, it is characterized in that, the main grain group's who is drawn by the laser particle analysis the intermediate value based on the particle size distribution of quality is 5 μ m-25 μ m, the secondary grain group's who draws by the laser particle analysis the intermediate value based on the particle size distribution of quality is 0.3 μ m-3 μ m, and main grain group's mass fraction is 70-96 weight %.
2. the nickel mixed hydroxide cathode material of claim 1 is characterized in that, the main grain group intermediate value of particle is 6-12 μ m, and secondary grain group's intermediate value is 0.3-1.5 μ m.
3. the nickel mixed hydroxide cathode material of claim 1 is characterized in that, main grain group and secondary grain group's the percentage D based on the distribution of particles of quality
90%And D
10%Between the span non-overlapping.
4. the nickel mixed hydroxide cathode material of claim 1 is characterized in that, it contains nickelous cation and at least a component that is selected from magnesium, calcium, zinc, cobalt, aluminium, manganese, iron, chromium, rare earth element.
5. the nickel mixed hydroxide cathode material of claim 1 is characterized in that, contains the monovalence or the dianion that are selected from chloride ion, nitrate ion, sulfate ion in nickel mixed hydroxide.
6. the nickel mixed hydroxide cathode material of claim 1 is characterized in that, nickel content is counted 40-60 weight % by dry material.
7. the nickel mixed hydroxide cathode material of claim 8 is characterized in that, described nickel content is 55-59 weight %.
8. the nickel mixed hydroxide cathode material of claim 1 is characterized in that, its specific area is 10-100m
2/ g.
9. the nickel mixed hydroxide cathode material of claim 8 is characterized in that, its specific area is 15-40m
2/ g.
10. a method for preparing the nickel mixed hydroxide cathode material of one of claim 1-9 is characterized in that, exists by nickel mixed hydroxide, by alkali metal ion, bivalent nickel ion, ammonia, OH in having the loop reactor of integrated settling section
-Ion and at least a component that is selected from magnesium, calcium, zinc, cobalt, aluminium, manganese, iron, chromium, rare earth element and at least a be selected from chloride ion, nitrate ion, sulfate ion the aqueous solution formed of component, the reactant mixture of forming, add contain other metal ion that is selected from magnesium, calcium, zinc, cobalt, aluminium, manganese, iron, chromium, rare earth element divalent nickel salt solution, ammonia spirit and alkali hydroxide soln to form mixed oxide, the graininess nickel mixed hydroxide cathode material that forms discharged with reactant mixture as solid and after filtration.
11. the method for claim 10 is characterized in that, described divalent nickel salt solution and alkali hydroxide soln add under substantially invariable pH value substantially simultaneously.
12. the method for claim 10, it is characterized in that, except that continuously and add nickel salt solution and the alkali hydroxide soln substantially simultaneously, add nickel salt solution that volume fraction is 0.5-15 volume % and alkali hydroxide soln in reactant mixture by measure in batches, at this moment can not continue to change change pH values every 0.5-5 hour the regular time interval.
13. the method for claim 10 is characterized in that, the nickel that added divalent nickel salt solution contains 80-125g/l is selected from the cation of magnesium, calcium, zinc, cobalt, aluminium, manganese, iron, chromium, rare earth element with one or more, and its amount respectively is 0.1-20g/l.
14. the method for claim 10 is characterized in that, ammonia spirit contains the ammonia of 1-25 weight %.
15. the method for claim 10 is characterized in that, alkali hydroxide soln is made up of NaOH, KOH and/or the LiOH aqueous solution, and the alkali metal hydroxide total content is counted 10-30 weight % by the gross mass of solution.
16. the method for claim 15 is characterized in that, described alkali hydroxide soln is by the NaOH solution composition.
17. the method for claim 10, it is characterized in that, when this method of enforcement, the concentration of reactant mixture in reaction solution should be adjusted to and count 50-60g/l, bivalent nickel ion concentration with the total concentration of sodium, potassium and lithium is that the total concentration of 0.1-100mg/l, magnesium, calcium, zinc, cobalt, aluminium, manganese, iron, chromium, rare earth element is 0.1-100mg/l, wherein has OH
-, chloride ion, nitrate anion and/or sulfate radical be as counter ion.
18. the method for claim 10 is characterized in that, the solids content in the reactant mixture is adjusted to 220g/l-400g/l.
19. the method for claim 18 is characterized in that, described solids content is 300g/l-380g/l.
20. the method for claim 10 is characterized in that, collects and return this reactor by reactor with the solid particle that reaction solution flows out in clarification equipment thereafter.
21. the method for claim 10 is characterized in that, the temperature of reactant mixture is 20-80 ℃.
22. the method for claim 21 is characterized in that, described temperature is constant in time to remain on ± 1 ℃ of interval in.
23. the method for claim 21 is characterized in that, described temperature is 30-60 ℃.
24. the method for claim 10 is characterized in that, according to reaction temperature, the pH value of described reaction solution is 9.8-13.7, and its tolerance in time should constant remaining on ± 0.05.
25. the method for claim 10 is characterized in that, the pH value of described reaction solution is 11.6-12.9.
26. the method for claim 10 is characterized in that, described alkali hydroxide soln can be the metering of 0.9-1.3 mol ratio by the cationic total amount to divalent nickel salt solution and add reactor.
27. the method for claim 26 is characterized in that, described mol ratio is 1.05-1.10.
28. the method for claim 10 is characterized in that, described alkali hydroxide soln is directly joining in the reactor at liquid surface under the liquid surface or directly.
29. the method for claim 10 is characterized in that, described divalent nickel salt solution is introduced in the reactor under liquid surface.
30. the method for claim 29 is characterized in that, described salting liquid is introduced into goes forward side by side into fluid power loop district.
31. the method for claim 10 is characterized in that, ammonia spirit is directly under liquid surface or directly at liquid surface place adding reactor.
32. the method for claim 31 is characterized in that, described solution adds in the porch of tight nearly divalent nickel salt solution.
33. the method for claim 10 is characterized in that, reactive applications dihedral vane blender carries out, and the stirring vane of this blender has 15 °-85 ° constant or progressive inclination angle, and stirring intensity is 150W/m
3-320W/m
3, and in conduit, produce different flow velocitys and in reactant mixture, produce shearing force.
34. the method for claim 33 is characterized in that, described dihedral vane blender is the 6-dihedral vane blender with vertical axial shaft.
35. the method for claim 33 is characterized in that, described inclination angle is 30 °-60 °.
36. the method for claim 33 is characterized in that, stirring intensity is 290W/m
3-300W/m
3
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10245467.1 | 2002-09-28 | ||
| DE10245467A DE10245467A1 (en) | 2002-09-28 | 2002-09-28 | Active nickel mixed hydroxide cathode material for alkaline batteries and process for its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1685541A CN1685541A (en) | 2005-10-19 |
| CN100438152C true CN100438152C (en) | 2008-11-26 |
Family
ID=31984243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038231123A Expired - Fee Related CN100438152C (en) | 2002-09-28 | 2003-09-26 | Active mixed nickel hydroxide cathode material for alkaline storage batteries and process for its production |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1543573A2 (en) |
| JP (1) | JP2006515950A (en) |
| KR (1) | KR20050073456A (en) |
| CN (1) | CN100438152C (en) |
| AU (1) | AU2003280296A1 (en) |
| DE (1) | DE10245467A1 (en) |
| WO (1) | WO2004032260A2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006265086A (en) * | 2005-02-24 | 2006-10-05 | Toyota Motor Corp | Method and apparatus for manufacturing nickel hydroxide particles |
| DE102006062762A1 (en) * | 2006-03-31 | 2008-01-31 | H.C. Starck Gmbh | Process for the preparation of pulverulent Ni, Co mixed hydroxides and their use |
| DE102006049107A1 (en) | 2006-10-13 | 2008-04-17 | H.C. Starck Gmbh | Powdery compounds, processes for their preparation and their use in electrochemical applications |
| DE102007039471A1 (en) * | 2007-08-21 | 2009-02-26 | H.C. Starck Gmbh | Powdered compounds, process for their preparation and their use in lithium secondary batteries |
| DE102007049108A1 (en) * | 2007-10-12 | 2009-04-16 | H.C. Starck Gmbh | Powdered compounds, process for their preparation and their use in batteries |
| JP5614334B2 (en) * | 2010-03-02 | 2014-10-29 | 住友金属鉱山株式会社 | Nickel-cobalt composite hydroxide, method for producing the same, and positive electrode active material for non-aqueous electrolyte secondary battery obtained using the composite hydroxide |
| US10059602B2 (en) | 2013-05-08 | 2018-08-28 | Basf Se | Process for producing suspensions |
| WO2017033895A1 (en) * | 2015-08-24 | 2017-03-02 | 住友金属鉱山株式会社 | Manganese nickel composite hydroxide and method for producing same, lithium manganese nickel composite oxide and method for producing same, and nonaqueous electrolyte secondary battery |
| DE102015115691B4 (en) * | 2015-09-17 | 2020-10-01 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Gemeinnützige Stiftung | Lithium-nickel-manganese-based transition metal oxide particles, their production and their use as electrode material |
| KR102115685B1 (en) | 2015-09-30 | 2020-05-27 | 유미코아 | Precursor for lithium transition metal oxide cathode materials for rechargeable batteries |
| US11305243B2 (en) | 2016-06-14 | 2022-04-19 | Sumitomo Metal Mining Co., Ltd. | Chemical reaction device and particle production method using chemical reaction device |
| KR102555562B1 (en) * | 2020-06-15 | 2023-07-17 | 주식회사 엘 앤 에프 | Apparatus for Manufacturing Multi-component Metal Hydroxide |
| CN114171727A (en) * | 2021-10-27 | 2022-03-11 | 深圳市豪鹏科技股份有限公司 | Positive electrode material, positive electrode slurry, positive plate and nickel-metal hydride battery |
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| JPH1025117A (en) * | 1996-07-09 | 1998-01-27 | Japan Metals & Chem Co Ltd | Production of nickel hydroxide |
| JP2002093417A (en) * | 2000-09-11 | 2002-03-29 | Mitsubishi Cable Ind Ltd | Li-co base composite oxide, and positive plate and lithium ion secondary battery using the same |
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2002
- 2002-09-28 DE DE10245467A patent/DE10245467A1/en not_active Withdrawn
-
2003
- 2003-09-26 EP EP03770891A patent/EP1543573A2/en not_active Withdrawn
- 2003-09-26 KR KR1020057004929A patent/KR20050073456A/en not_active Application Discontinuation
- 2003-09-26 WO PCT/DE2003/003219 patent/WO2004032260A2/en active Application Filing
- 2003-09-26 JP JP2004540514A patent/JP2006515950A/en active Pending
- 2003-09-26 AU AU2003280296A patent/AU2003280296A1/en not_active Abandoned
- 2003-09-26 CN CNB038231123A patent/CN100438152C/en not_active Expired - Fee Related
Patent Citations (4)
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|---|---|---|---|---|
| US5498403A (en) * | 1994-05-20 | 1996-03-12 | Hyundai Motor Company | Method for preparing high density nickel hydroxide used for alkali rechargeable batteries |
| JPH1025117A (en) * | 1996-07-09 | 1998-01-27 | Japan Metals & Chem Co Ltd | Production of nickel hydroxide |
| CN1370331A (en) * | 1999-06-21 | 2002-09-18 | 株式会社东芝 | Active material for anode of secondary cell and its making and non-aqueous electrolyte secondary cell, and recycled electronic functional material and method for recycling such material |
| JP2002093417A (en) * | 2000-09-11 | 2002-03-29 | Mitsubishi Cable Ind Ltd | Li-co base composite oxide, and positive plate and lithium ion secondary battery using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003280296A1 (en) | 2004-04-23 |
| WO2004032260A2 (en) | 2004-04-15 |
| CN1685541A (en) | 2005-10-19 |
| JP2006515950A (en) | 2006-06-08 |
| EP1543573A2 (en) | 2005-06-22 |
| DE10245467A1 (en) | 2004-04-08 |
| WO2004032260A3 (en) | 2005-02-03 |
| KR20050073456A (en) | 2005-07-13 |
| AU2003280296A8 (en) | 2004-04-23 |
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