WO1998006670A1 - Oxyde composite de lithium/nickel/cobalt, procede pour sa preparation, et materiau actif de cathode pour batterie rechargeable - Google Patents
Oxyde composite de lithium/nickel/cobalt, procede pour sa preparation, et materiau actif de cathode pour batterie rechargeable Download PDFInfo
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- WO1998006670A1 WO1998006670A1 PCT/JP1997/002803 JP9702803W WO9806670A1 WO 1998006670 A1 WO1998006670 A1 WO 1998006670A1 JP 9702803 W JP9702803 W JP 9702803W WO 9806670 A1 WO9806670 A1 WO 9806670A1
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- Prior art keywords
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- general formula
- composite oxide
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- aqueous medium
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000006182 cathode active material Substances 0.000 title abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 45
- 229910052744 lithium Inorganic materials 0.000 title description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 7
- 229910052759 nickel Inorganic materials 0.000 title description 4
- 229910017052 cobalt Inorganic materials 0.000 title description 2
- 239000010941 cobalt Substances 0.000 title description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 2
- 229910052796 boron Inorganic materials 0.000 claims abstract description 24
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 239000011164 primary particle Substances 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 27
- -1 basic metal salt Chemical class 0.000 claims description 26
- 229910052728 basic metal Inorganic materials 0.000 claims description 24
- 238000010304 firing Methods 0.000 claims description 23
- 150000002642 lithium compounds Chemical class 0.000 claims description 19
- 239000007774 positive electrode material Substances 0.000 claims description 17
- 150000001450 anions Chemical class 0.000 claims description 15
- 239000012736 aqueous medium Substances 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- 239000011163 secondary particle Substances 0.000 claims description 14
- 238000000465 moulding Methods 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 150000001639 boron compounds Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 1
- 230000001568 sexual effect Effects 0.000 claims 1
- 229910003005 LiNiO2 Inorganic materials 0.000 abstract 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 239000007864 aqueous solution Substances 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 43
- 238000000034 method Methods 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 28
- 238000012360 testing method Methods 0.000 description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 22
- 239000001301 oxygen Substances 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 22
- 239000000047 product Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 238000001694 spray drying Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000000634 powder X-ray diffraction Methods 0.000 description 16
- 239000011572 manganese Substances 0.000 description 15
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 14
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 12
- 239000004327 boric acid Substances 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 11
- 239000004570 mortar (masonry) Substances 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000006104 solid solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 101100194322 Caenorhabditis elegans rei-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- 108010014173 Factor X Proteins 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- VLDIHELOHZKRMB-UHFFFAOYSA-N O[N+]([O-])=O.O[N+]([O-])=O.O[N+]([O-])=O Chemical compound O[N+]([O-])=O.O[N+]([O-])=O.O[N+]([O-])=O VLDIHELOHZKRMB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- KPSZQYZCNSCYGG-UHFFFAOYSA-N [B].[B] Chemical compound [B].[B] KPSZQYZCNSCYGG-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DBDNZCBRIPTLJF-UHFFFAOYSA-N boron(1-) monohydride Chemical compound [BH-] DBDNZCBRIPTLJF-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- 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
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- 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
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 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
- C01P2006/12—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
-
- 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
Definitions
- the present invention relates to a lithium nickel cobalt composite oxide having a stable structure, a high purity, a high degree of crystallinity, a high battery capacity, and a small decrease in capacity due to an increase in the number of charge / discharge cycles. It relates to the positive electrode active material for secondary batteries.
- Conventional technology relates to a lithium nickel cobalt composite oxide having a stable structure, a high purity, a high degree of crystallinity, a high battery capacity, and a small decrease in capacity due to an increase in the number of charge / discharge cycles.
- Conventional technology Conventional technology
- Li N i ⁇ 2 is expected to have higher electric capacity than Li Co C 2 .
- Li N i 0 2 or this has also been made an attempt to'll control the physical properties of the shape and size of particles, etc. Although solid solution with other components, satisfactory outcomes can not be obtained.
- JP-A-5-151998 discloses that the particle size distribution can be improved by specifying a 10% cumulative diameter of 3 to 15, a 50% cumulative diameter of 8 to 35, and a 90% cumulative diameter of 30 to 80.
- pulverizing the positive electrode active material to adjust the particle distribution to such a size is not a very difficult and practical method.
- L i N i 0 2 is L i component (L i ⁇ _H, L i 2 C 0 3, L i N_ ⁇ 3, etc.) and, N i components (hydroxide, carbonate etc.) and dry
- N i components hydrooxide, carbonate etc.
- An object of the present invention is to improve the above-mentioned disadvantages of the conventional LiNiO 2 and its composite oxide.
- An object of the present invention is to provide a novel lithium nickel cobalt composite oxide having a small structure and a stable structure.
- the present inventor has conducted intensive studies to solve the above-described problems, and as a result, has the following general formula (I) created by a method via a wet method described below.
- the first feature is the composition represented by the general formula (I). While maintaining the high battery capacity of Li Ni 2 , it has improved its cycle characteristics (deterioration of the discharge capacity due to an increase in the number of cycles) and its stability at high temperatures. It minimized the use of slag and realized economic efficiency.
- the second feature is the high crystallinity and high purity in X-ray diffraction. That is, the diffraction peak ratio at the (003) plane and the (104) plane at the Miller index hk 1 of the X-ray diffraction is (003) / (104) force ⁇ 1.2 or more, and the diffraction peak ratio at the (006) plane and the (101) plane Diffraction peak ratio (006) Z (101) is 0.13 or less, (NiCo3 + ) is 99% or more of all (Ni + Co), BET specific surface area is 0.1 ⁇ 2 rrf Zg, average Secondary particle diameter D is 5 to 100, 10% of the particle size distribution is 0.5D or more, 90% is 2D or less, and spherical secondary particles with irregularities on the surface observed with a scanning electron microscope (SEM).
- the primary particle size of the spherical secondary particles is within the range of 0.2 to 30 as observed by SEM, and the average particle size of the major axis is 0.3 to 30
- the lithium-nickel-cobalt composite oxide of the present invention is a high-purity composite oxide despite at least one solid solution selected from the group consisting of A, Fe, Mn, and B being dissolved. Can be.
- Co and A £ and / or B can be used together to efficiently reduce the distance between layers, so that the structural instability of N 1 due to the entrance and exit of lithium ions should be eliminated.
- the most important feature of the present invention is that lithium nickel oxide is selected from the group consisting of C0 and A, Fe, Mn and B. The at least one selected is to form a solid solution in a small amount and uniformly.
- the primary particles have a major particle size of 0.2 to 30 /, preferably 1 to 20 ⁇ as observed by SEM, and an average major particle size of 0.3 to 30.
- the average particle diameter D of the spherical secondary particles formed into a spherical shape by the spray-drying and baking method is 5 to 300, preferably 5 to 100, more preferably 5 to 20, and 10% of the particle size distribution is 0.5 D.
- 90% of the particles have a uniform particle size of 2D or less, and as seen from SEM observation, are spherical secondary particles with uneven surfaces. Particles.
- the particle diameter ratio (major axis Z minor axis) of the spherical secondary particles observed by SEM is usually the largest even if a small particle diameter ratio may be contained when unframed after firing. In the range of 1.5 or less and 1.2 or less in average, more than 90% of the particles are spherical and uniformly distributed in 1.3 or less.
- the spherical product of the present invention preferably obtained by a spray-drying / firing step, is not only suitable for close-packing, but also when used for batteries, for example, in the form of an electrolyte, a conductive material. It can be seen that the contact area with the agent etc. increases, which is also advantageous from the entrance and exit of lithium ions with the outside.c
- the particle size of the spherical secondary particles can be set as desired from 5 to 100. When used, those having an average particle size of about 5 to 30 are desirable from the viewpoint of processability.
- the BET specific surface area is 0.1 to 2 nf / g or less, and when used as a battery material, the viscosity of the electrolyte does not increase, so that the dielectric constant does not decrease.
- the above spray (or frozen) dried product can be more easily obtained by press molding.
- These large primary particles retain the physical properties of high purity and high crystallinity, have excellent high-temperature stability, etc., and are especially expected to be used under severe conditions. It is suitably used as a positive electrode active material of.
- the bulk density increases due to press molding, and this high bulk density is a plus for improving the battery capacity.
- M represents at least one member selected from the group consisting of A £, Fe and Mn).
- An amount of lithium compound corresponding to the number of moles of Li atoms represented by y is added to the basic metal salt represented by in an aqueous medium, and the resulting slurry is sprayed or freeze-dried, and then oxidized. It can be manufactured by firing at about 600 ° C under 900 ° C for about 4 hours or more.
- M represents a combination of B and at least one of A, Fe and Mn).
- a water-soluble lithium compound and a basic metal salt represented by the above general formula ( ⁇ ), ( ⁇ ) or (IV) (hereinafter, these basic metal salts are collectively referred to simply as “basic metal salt”) Used is one containing anions that evaporate during firing Is done.
- lithium compound for example, L i OH, L i N0 3, L i 2 C 0; or Ru can select one or more from among such hydrates thereof.
- boric acid As the boron compound, boric acid, lithium tetraborate and the like can be preferably used.
- the basic metal salt Ru and A n for example, N_ ⁇ 3 2 -, C one, B r - CHa COO-, C 0 3 2 -, S 0 - selected child from Anion represented by like Can be.
- Li0H is used as a lithium compound
- boric acid is used as a boron compound
- anion is used as a basic metal salt. Is particularly preferable from the viewpoint of battery characteristics.
- a basic salt having a specific composition which is a fine particle having a primary particle size of 0.1 or less as measured by a Scherrer method, is preferred.
- the fine particles preferably have a BET specific surface area of lOnfZg or more, preferably 40 nf / g or more, and more preferably lOOnZg or more.
- BET specific surface area When measuring the BET specific surface area by drying a basic metal salt in an aqueous solution, primary particles, which are fine particles, are agglomerated during drying, and the BET specific surface area of the aggregate is measured. In other words, if the cohesion is strong, the value will be small without nitrogen gas entering. Therefore, the specific surface area of the basic metal salt that actually reacts with the lithium compound in the aqueous solution shows a larger value, and is set to 10 nf or more from the above-mentioned actual condition having a highly reactive surface.
- the basic metal salt of this specific composition has a layered structure, and if the chemical composition and the crystal structure are such that M is at least one of A, Fe and Mn, Hydroxide of N i. -X C o, if M is B, hydroxide of N i, -x C ⁇ ⁇ 1 , ⁇ is ⁇ and at least one of A £ Fe and ⁇ ⁇ for the Nii-, it is those close to the hydroxides of C 0 ⁇ ⁇ ⁇ ⁇ 3, moreover surface microcrystals rich in activity.
- Basic metal salt used here N ii C 0 xl M x2 salt, N i> - relative x C o xl salt or N io xl N x3 salt, about 0.7 0.95 equivalents, preferably about 0.8 0.95 equivalents It can be produced by adding and reacting under a reaction condition of about 80 ° C or less.
- alkali used here include hydroxides of alkali metals such as sodium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide, amines and the like. It is more preferable that this basic metal salt be aged at 20 70 ° C for 0.1 10 hours after the synthesis.
- Drying of the slurry obtained by such a reaction is preferably carried out by spraying. Alternatively, freeze-drying is preferred.
- the spray drying method that can be dried instantaneously and can obtain spheroids is spherical granulation and uniformity of the composition. (The drying method that requires a long drying time transfers lithium to the surface, resulting in an uneven composition. ) It is more suitable.
- the calcination is performed in a temperature range of 600 to 800 ° C, preferably 700 to 750 ° C, and is performed in an oxidizing atmosphere (under oxygen flow) for about 4 hours or more. Preferably 4 to 72 hours-more preferably about 4 to 20 hours. If the calcination time is 72 hours or more, not only will the cost be increased, but also the volatilization of lithium, the trivalent ratio of (N i + C o) will be rather low, resulting in poor purity.
- the second production method is a press molding method that is effective in increasing the primary particles and further increasing the bulk density.
- the primary particles By baking the dried product obtained by the spray drying method or the freeze drying method and then firing, the primary particles can be set freely within the range of 1 to 30 ⁇ , the bulk density is high, and the crystallinity and purity are high. A composite oxide can be obtained.
- Spherical products which are spray-dried products, are powders with excellent fluidity, moldability, and filling properties, and are good materials that can be directly subjected to press molding according to ordinary methods.
- the molding pressure varies depending on the press machine, the charged amount, and the like, and is not particularly limited, but is preferably about 500 to 3000 kgZcnf.
- the press molding machine can be suitably used, such as a tableting machine, a pre-packet machine, and a roller compactor, but is not particularly limited as long as it can be pressed.
- the density of the pressed product is preferably 1 to 4 g / cc, preferably about 2 to 3 g / cc.
- Press molding is extremely useful in that it reduces the intermolecular travel distance and promotes crystal growth during firing. Therefore, the material used for press molding Does not necessarily have to be a spray-dried spherical product, and a freeze-dried product can also be used.
- the calcination temperature is usually 600 to 900 ° C., preferably 700 to 800 ° C., in an oxygen stream for at least 4 hours, preferably 10 to 72 hours.
- a method of performing two firings of pre-firing and post-firing may be used.
- the slurry obtained by the above-mentioned manufacturing method is sprayed or freeze-dried, and is directly baked in an oxidizing atmosphere at about 600 to 900 ° C for 0.5 hours or more (preferably 0.5 to 4 hours).
- the obtained pre-baked product is pulverized, if necessary, pressed, and further post-baked in an oxidizing atmosphere at about 600 to 900 ° C for about 1 hour or more (preferably 4 to 48 hours). It is a manufacturing method. Using this method, the total time required for firing can be reduced.
- the composite oxide represented by the above general formula (I) of the present invention thus obtained has a high capacity of 160 to 180 mAhZ even after the 100th charge / discharge cycle, as will be apparent from Examples described later. Thus, it can be effectively used as a positive electrode active material of a secondary battery having improved high temperature cyclability (stability).
- FIG. 1 is a powder X-ray diffraction diagram of the composite oxide obtained in Examples 1 to 4 and Comparative Examples 1 and 2.
- FIG. 2 is an SEM photograph (X 1500 magnification) showing the primary particles of the composite oxide obtained in Example 1.
- FIG. 3 is an SEM photograph (X 1500 magnification) showing the primary particles of the composite oxide obtained in Example 4.
- FIG. 4 is a powder X-ray diffraction diagram of the composite oxide obtained in Example 5.
- FIG. 5 is a powder X-ray diffraction diagram of the composite oxide obtained in Example 6.
- FIG. 6 is a powder X-ray diffraction diagram of the composite oxide obtained in Example 7.
- FIG. 7 is an SEM photograph (X30,000) showing the primary particles of the composite oxide obtained in Example 5.
- FIG. 8 is a SEM photograph (X3000 magnification) showing the primary particles of the composite oxide obtained in Example 6.
- FIG. 9 is an SEM photograph (X 10,000 magnification) showing the primary particles of the composite oxide obtained in Example 7.
- FIG. 10 is a powder X-ray diffraction diagram of the composite oxide obtained in Example 8.
- FIG. 11 is a powder X-ray diffraction diagram of the composite oxide obtained in Example 9.
- FIG. 12 is a powder X-ray diffraction diagram of the composite oxide obtained in Example 10.
- FIG. 13 is a powder X-ray diffraction diagram of the composite oxide obtained in Example 11.
- Figure 14 is an SEM photograph showing the primary particles of the composite oxide obtained in Example 8.
- FIG. 15 is an SEM photograph showing primary particles of the composite oxide obtained in Example 10.
- FIG. 16 is an SEM photograph showing primary particles of the composite oxide obtained in Example 11.
- a 2.0 M mixed aqueous solution of nickel nitrate and cobalt nitrate was prepared so that the molar ratio of Ni: C0 was 80:19. While stirring, add this mixed aqueous solution to the reaction tank. A 1.0 M aqueous sodium hydroxide solution was added using a metering pump, and a continuous reaction was performed while adjusting the liquid volume of the aqueous sodium hydroxide solution so as to maintain a pH of 8.0 at a reaction temperature of 25 ° C. . Residence time was 10 minutes on average. The reaction product that overflowed from the reaction tank in a continuous reaction was received and stored in a container, and the reaction was terminated when the required amount was collected.
- TF-630 tubular furnace
- the calcined product had a chemical composition of LiNioComBoOa.
- a mixed aqueous solution of 2.0 M nickel nitrate and cobalt nitrate was prepared so that the molar ratio of Ni: C0 was 80: 19.5.
- This mixed aqueous solution and a 1.0 M aqueous sodium hydroxide solution were added simultaneously to obtain a reaction pH of 8.0 according to Example 1, and a continuous reaction was performed at a reaction temperature of 25 ° C and a residence time of 10 minutes. .
- the resulting reaction product is filtered, washed with water (The composition although dry part, 1 ⁇ .. 8 (:. 0 ..
- the chemical composition of the fired product is Li Ni. 8 . C o. i e5 B. . . 5 0 was 2.
- Example 3 The chemical composition of the fired product is Li Ni. 8 . C o. i e5 B. . . 5 0 was 2.
- a mixed aqueous solution of 2.0 M nickel nitrate and cobalt nitrate was prepared so that the molar ratio of Ni: C0 was 80:18.
- This mixed aqueous solution and a 1.0 M sodium hydroxide aqueous solution were simultaneously added to obtain a reaction pH of 8.0 according to Example 1, and a continuous reaction was performed at a reaction temperature of 25 ° C and a residence time of 10 minutes. went.
- the resulting reaction product is filtered, washed with water (The composition although dry part, ⁇ ⁇ . 8 C oo 18 (OH) 1 .7 9 (N0 3) o IT ⁇ 0.
- the chemical composition of the fired product is Li Ni. 8 . C o. 18 B. .. It was 2 ⁇ 2.
- a mixed aqueous solution of 2.0 M niger nitrate and cobalt nitrate was prepared so that the molar ratio of Ni: C0 was 80:15.
- This mixed aqueous solution and a 1.0 M sodium hydroxide aqueous solution were simultaneously added to obtain a reaction pH of 8.0 according to Example 1, and a continuous reaction was performed at a reaction temperature of 25 ° C and a residence time of 10 minutes. Was done.
- the resulting reaction product is filtered, washed with water (The composition but dried partially, N i. 8 C ⁇ .
- the chemical composition of the fired product is Li Ni. 8 . C o. 5 B. . 5 was ⁇ 2.
- a mixed aqueous solution of 2.0 M niger nitrate and cobalt nitrate was prepared so that the molar ratio of Ni: Co was 80:10.
- This mixed aqueous solution and a 1.0 M aqueous sodium hydroxide solution were simultaneously added to obtain a reaction pH of 8.0 according to Example 1, and a continuous reaction was performed at a reaction temperature of 25 ° (with a residence time of 10 minutes).
- the obtained reaction product was filtered and washed with water (the composition of a partially dried product was Ni.
- the chemical composition of the fired product was LiNio ⁇ CoQjoBoC.
- This mixed aqueous solution and a 1.0 M aqueous sodium hydroxide solution were simultaneously added to obtain a reaction pH of 8.0 according to Example 1, and a continuous reaction was performed at a reaction temperature of 25 ° C and a residence time of 10 minutes. Obtained anti Filtered response product, washed with water (The composition but dried partially, N ". C o.
- the chemical composition of the burned material was L i N i C oo. 0 2.
- FIG. 1 shows powder X-ray diffraction diagrams of the composite oxides obtained in Examples 1 to 4 and Comparative Examples 1 and 2. As is clear from the figure, no peaks of by-products were observed in any of the production methods, and it was found that they had a layered structure in which the solid solution was uniformly dissolved.
- Table 1 shows the crystal particle diameters of the basic metal salts obtained by the continuous reactions of Examples 1 to 4 and Examples 5 to 12 described later, which were determined by X-ray diffraction. In each case, the value was 0.1 or less, indicating that a basic metal salt having a fine primary particle diameter was generated.
- Table 2 shows the physical properties such as (006) / (101), the average diameter of the secondary particles measured by a laser microtrack, and the major diameter of the primary particles obtained from SEM photograph observation.
- the trivalent ratio of (N i + Co) was measured in accordance with Test Example 2, and the BET specific surface area was measured in accordance with Test Example 3.
- Table 3 shows that the composite oxides of Examples 1 to 4 containing boron exhibited improved cycle characteristics as compared with Comparative Example 2 containing no boron, and further contained 0.05 to 2 mol% of boron. In the composite oxides of Examples 1 to 3, improvement in the initial discharge capacity is also observed.
- the mixed aqueous solution and 1.0 m 01 / i sodium hydroxide solution were continuously added under the conditions of PH 8.0, reaction temperature 25 ° C, and strong stirring, and the resulting reaction solution was filtered. , washed with water, by suspending in water, N io so C oQ. ' o a io (OH) i ( N_ ⁇ 3). . I got a slurry.
- the mixed aqueous solution and a 1.0 mol sodium hydroxide solution were continuously added under conditions of pH 8.0, a reaction temperature of 25 ° C, and strong stirring, and the obtained reaction solution was filtered. After washing with water, suspend by water. 8 . C o. Fifteen . 05 (Rei_1 1. 7 (1 ⁇ ⁇ 3) from 0. 35 to obtain a slurry scratch.
- An amount of 3.0 mo 1 lithium hydroxide aqueous solution was added dropwise to react, followed by lyophilization and drying. It was molded at a pressure of t / cnf to form a pellet with a thickness of 014 and a thickness of two.
- the (N i + Co) trivalent ratio of these composite oxides, the BET specific surface area, and the peak intensity ratio obtained from powder X-ray diffraction (003) / (104), (006) / (101) The physical properties such as bulk density and bulk density are shown in Table 4, and SEM photographs showing the primary particles of the composite oxide are shown in Fig. 7 (X30,000) for Example 5 and in Fig. 8 (X30,000) for Example 6.
- Example 7 is shown in FIG. 9 ( ⁇ 10000 times). The unit of each line shown below the photo is 1.
- the trivalent ratio of (N i + Co) was measured in accordance with Test Example 2, and the BET specific surface area was measured in accordance with Test Example 3.
- a mixed solution of 2.0 m 0 1 Z £ of niger nitrate, cobalt nitrate, and aluminum nitrate was prepared at a molar ratio of N i: C o: A of 790 : 165 : 25.
- the mixed aqueous solution and a 1.0 m 0/1 sodium hydroxide solution were simultaneously added at a reaction temperature of 25 ° C. under vigorous stirring so that the pH became 10.0, and a continuous reaction was performed.
- the resulting reaction product is filtered, washed with water (The composition but dried partially, N i 5 A ⁇ 0 25 (OH) N 0 3 "C oo.”.) - 0.
- the resulting dried gel is placed in an alumina bottle, baked at 750 ° C for 10 hours in a tubular furnace (TF-630, manufactured by Yamada Denki) under an oxygen flow, crushed in a mortar, and liNi. . 7 9 . C o. 165 A. 025 B. .. 2 . 0 obtained was a two-powder.
- TF-630 manufactured by Yamada Denki
- the mixed aqueous solution and 1.0 m 01 / sodium hydroxide solution were reacted simultaneously at a reaction temperature of 25 ° C under strong stirring so that the pH became 9.75.
- the reaction was performed. ..
- the resulting reaction product is filtered, washed with water (The composition but dried partially, N i 0 79 C O0 14 A ⁇ 0. D 5 (OH) l 86 (NO3) 01 5 -
- the obtained dry gel was put in an alumina boat, under an oxygen flow was calcined between hours 775 ° C 10 in a tubular furnace (Yamada electrical steel TF- 630 type), pulverized in a mortar, Li Ni 0 n 0 to obtain a C o 14 o a £ o 50 B 0 2 0 2 powder.
- a mixed solution of 2.0 mo1 / / Nigel nitrate, cobalt nitrate, and aluminum nitrate was prepared so that the molar ratio of Ni: C0: A was 790: 90: 100.
- the mixed aqueous solution was reacted with a sodium hydroxide solution of 1.0 mol / H at a reaction temperature of 25 ° C under strong stirring to achieve a pH of 9.5, and a continuous reaction was performed. .
- the resulting reaction product is filtered, washed with water (The composition but dried partially, was N io C oo.
- a mixed aqueous solution of 2.0 mo ⁇ £ of Niger nitrate and cobalt nitrate, aluminum nitrate, and iron nitrate was prepared at a molar ratio of Ni: Co: A ⁇ : Fe of 800: 100: 50 : 50.
- This mixed aqueous solution and 1.0 ml of sodium hydroxide solution were added simultaneously at a reaction temperature of 25 ° C. under strong stirring so that the reaction pH became 9.5, and a continuous sulfur reaction was performed.
- the resulting reaction product is filtered, washed with water (The composition but dried partially, Ni 0 8 C o A 5 F e 0 5 ( ⁇ _H)! N0 3).
- the mixed aqueous solution and a sodium hydroxide solution of 1.0 m 01 / p were added simultaneously at a reaction temperature of 25 ° C. under vigorous stirring so that the reaction pH became 9.0, and a continuous reaction was carried out.
- the obtained reaction product was filtered, washed with water, and suspended in water to form a slurry.
- Table 5 shows the physical properties such as (006) / (101). Further, SEM photographs showing the primary particles of the composite oxide are shown in FIG. 14 (X 1500 times) for Example 8, FIG. 15 (X 1500 times) for Example 10, and FIG. 16 (X 1500 times) for Example 11. 1500 times). The unit of each line shown below the photo is 10.
- Table 6 shows that when the Ai content of the lithium nickel cobalt composite oxide increases and the C0 content decreases, the initial discharge capacity tends to decrease as compared with Comparative Example 2 in Table 3. Improvement of cycle characteristics is recognized by addition of boron. Furthermore, it can be seen that the addition of Fe has a greater tendency to lower the initial discharge capacity than the addition of A. However, those of the present invention are superior in both the initial discharge capacity and the cycle characteristics as compared with Comparative Examples 4 and 5 according to the dry method.
- Table 7 shows the results of a test performed on the thermal stability of the composite oxide obtained according to the present invention in accordance with Test Example 5.
- the lithium-nickel-cobalt composite oxide of the present invention is a positive electrode active material for a secondary battery that satisfies battery performance.
- Test example 1 is a positive electrode active material for a secondary battery that satisfies battery performance.
- This method is based on the following formula (1), assuming that the crystal has no distortion and the crystallite size is uniform, and that the spread of the diffraction line is based only on the crystallite size. .
- D h is the size of the crystallite in the direction perpendicular to the (hk 1) plane
- s is the wavelength of the X-ray
- ⁇ is the diffraction line width
- ⁇ is the number of turns.
- K and k are constants.
- the trivalent ratio of (N i + C 0) is the percentage of the ratio of trivalent (N i + C 0) to all (N i + C o) and is measured by redox titration. I do. Dissolve 0.2 g of the sample in 0.25M FeS0 * -3.6N sulfuric acid solution, add concentrated phosphoric acid, and titrate with 0.1N potassium permanganate. Perform a blank test in the same manner, and determine the percentage of (N i + C 0) of trivalent in the sample from the following formula. In the formula, f is the factor X of a 0.1 N permanganate ream solution, X. Is the blank test titer, X is the titer (), m is the sample volume (g), A is the Ni content (%), and B is the Co content (%).
- the sample was heated and degassed under the flow of a gas mixture of 30% nitrogen and 70% helium. It is measured by the continuous flow method.
- Lithium nickel composite oxide was mixed in a mixing ratio of 88% by weight, acetylene black as a conductive agent 6.0% by weight, and tetrafluoroethylen as a binder 6.0% by weight, and then compression molded on a stainless steel mesh To obtain a pellet with a diameter of 18 mm, and dried at 200 ° C for 2 hours or more to obtain a positive electrode material.
- a rolled lithium metal sheet pressed on a stainless steel substrate is used, and as the diaphragm, a porous polypropylene membrane (Cell Guard 2502) and a glass filter paper are used.
- a battery is prepared by the method shown in Test Example 3 and charged to 4.4 V at a constant current density of 0.4 mA / cnf. After charging, disassemble the battery, take out the positive electrode, wash the positive electrode with electrolyte, and dry it in a vacuum. The dried positive electrode material is measured with a differential thermal analyzer under a nitrogen flow at a heating rate of 2 ° C Z minutes, and the exothermic peak temperature accompanying oxygen desorption is measured.
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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US09/242,308 US6395250B2 (en) | 1996-08-12 | 1997-08-11 | Lithium/nickel/cobalt composite oxide, process for preparing the same, and cathode active material for rechargeable battery |
CA002263320A CA2263320C (en) | 1996-08-12 | 1997-08-11 | A lithium nickel cobalt complex oxide, a process for preparing the same and a positive electrode active material for a secondary battery |
EP97934763A EP0918041B1 (en) | 1996-08-12 | 1997-08-11 | Lithium/nickel/cobalt composite oxide, process for preparing the same, and cathode active material for rechargeable battery |
JP50959598A JP4131521B2 (ja) | 1996-08-12 | 1997-08-11 | リチウムニッケルコバルト複合酸化物、その製法及び二次電池用正極活物質 |
DE69740063T DE69740063D1 (de) | 1996-08-12 | 1997-08-11 | Lithium/nickel/kobalt verbundoxid, verfahren zur herstellung und kathode-aktives material für wiederaufladbare batterie |
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JP8/231396 | 1996-08-12 | ||
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JP8/355120 | 1996-12-20 |
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US (1) | US6395250B2 (ja) |
EP (2) | EP0918041B1 (ja) |
JP (1) | JP4131521B2 (ja) |
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CA (1) | CA2263320C (ja) |
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Also Published As
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EP2058281A3 (en) | 2009-12-23 |
CA2263320C (en) | 2006-08-08 |
DE69740063D1 (de) | 2011-01-05 |
CN1232438A (zh) | 1999-10-20 |
JP4131521B2 (ja) | 2008-08-13 |
EP0918041A4 (en) | 2006-05-17 |
US6395250B2 (en) | 2002-05-28 |
CN1155525C (zh) | 2004-06-30 |
EP0918041B1 (en) | 2010-11-24 |
EP2058281A2 (en) | 2009-05-13 |
TW363940B (en) | 1999-07-11 |
EP2058281B1 (en) | 2012-09-19 |
KR100490708B1 (ko) | 2005-05-24 |
EP0918041A1 (en) | 1999-05-26 |
CA2263320A1 (en) | 1998-02-19 |
KR20000029966A (ko) | 2000-05-25 |
US20010010807A1 (en) | 2001-08-02 |
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