TWI502793B - Lithium composite oxide particle powder for nonaqueous electrolyte storage battery, method for producing the same, and nonaqueous electrolyte storage battery - Google Patents
Lithium composite oxide particle powder for nonaqueous electrolyte storage battery, method for producing the same, and nonaqueous electrolyte storage battery Download PDFInfo
- Publication number
- TWI502793B TWI502793B TW098130544A TW98130544A TWI502793B TW I502793 B TWI502793 B TW I502793B TW 098130544 A TW098130544 A TW 098130544A TW 98130544 A TW98130544 A TW 98130544A TW I502793 B TWI502793 B TW I502793B
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- Prior art keywords
- composite oxide
- particles
- core
- particle powder
- storage
- Prior art date
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- 239000002245 particle Substances 0.000 title claims description 336
- 239000002131 composite material Substances 0.000 title claims description 309
- 238000003860 storage Methods 0.000 title claims description 183
- 239000000843 powder Substances 0.000 title claims description 74
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 229910052744 lithium Inorganic materials 0.000 title claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 5
- 239000011572 manganese Substances 0.000 claims description 144
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 109
- 229910006465 Li—Ni—Mn Inorganic materials 0.000 claims description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 68
- 239000011163 secondary particle Substances 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 51
- 239000007774 positive electrode material Substances 0.000 claims description 38
- 230000020169 heat generation Effects 0.000 claims description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 229910017709 Ni Co Inorganic materials 0.000 claims description 22
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 22
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 229940044175 cobalt sulfate Drugs 0.000 claims description 20
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 20
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 20
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 20
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000007771 core particle Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims description 7
- 239000011246 composite particle Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000009775 high-speed stirring Methods 0.000 claims description 2
- 238000010303 mechanochemical reaction Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000011777 magnesium Substances 0.000 description 63
- 239000008151 electrolyte solution Substances 0.000 description 52
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 46
- 229910052748 manganese Inorganic materials 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 41
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 35
- 229910052808 lithium carbonate Inorganic materials 0.000 description 35
- 238000004455 differential thermal analysis Methods 0.000 description 32
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 32
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 22
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 229910005649 Li1.05Ni0.33Co0.33Mn0.33O2 Inorganic materials 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- 229940053662 nickel sulfate Drugs 0.000 description 18
- 239000010936 titanium Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229940099596 manganese sulfate Drugs 0.000 description 12
- 239000011702 manganese sulphate Substances 0.000 description 12
- 235000007079 manganese sulphate Nutrition 0.000 description 12
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 12
- 229910007966 Li-Co Inorganic materials 0.000 description 11
- 229910008295 Li—Co Inorganic materials 0.000 description 11
- 229910001386 lithium phosphate Inorganic materials 0.000 description 11
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 229910018657 Mn—Al Inorganic materials 0.000 description 6
- 229910017170 Ni0.80Co0.15Al0.05O2 Inorganic materials 0.000 description 6
- 229910018134 Al-Mg Inorganic materials 0.000 description 5
- 229910018467 Al—Mg Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910008080 Li-Ni-Co-Mn Inorganic materials 0.000 description 5
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 5
- 229910006461 Li—Ni—Co—Mn Inorganic materials 0.000 description 5
- 229910016365 Ni0.33Co0.33Mn0.33 Inorganic materials 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- 229940010048 aluminum sulfate Drugs 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 210000003746 feather Anatomy 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 229960003390 magnesium sulfate Drugs 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910008088 Li-Mn Inorganic materials 0.000 description 2
- 229910006327 Li—Mn Inorganic materials 0.000 description 2
- 229910016973 Ni0.84Co0.16(OH)2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000000504 luminescence detection Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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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
- H01M4/36—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
- C01G45/00—Compounds of manganese
- C01G45/12—Complex oxides containing manganese and at least one other metal element
- C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
- C01G45/1228—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Complex oxides containing cobalt and at least one other metal element
- C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
- C01G51/44—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element 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—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
-
- 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
-
- 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
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Description
本發明係提供一種在充電時熱安定性及高溫安定性均優良之高容量之Li-Ni複合氧化物粒子粉末。The present invention provides a high-capacity Li-Ni composite oxide particle powder excellent in thermal stability and high-temperature stability at the time of charging.
近年來，AV機器或電腦等之電子機器正朝向可攜帶化、無電線化在急速地進展中，此等之驅動用電源係高度要求為小型、輕量且具有高能量密度之蓄電池。此外，近年來基於對地球環境之考量，電動汽車、油電混合車正進行開發並已實用化，從而對於在大型用途上其保存特性優良之鋰離子蓄電池之要求越來越高。而在此種狀況下，該具有充放電容量大，且保存特性佳之優點的鋰離子蓄電池，則最受矚目。In recent years, electronic devices such as AV devices and computers are rapidly moving toward portability and non-wires. These driving power sources are required to be small, lightweight, and high-energy-density batteries. In addition, in recent years, electric vehicles and hybrid electric vehicles have been developed and put into practical use based on considerations of the global environment, and there is an increasing demand for lithium ion batteries having excellent storage characteristics for large-scale applications. Under such circumstances, the lithium ion secondary battery having the advantages of large charge and discharge capacity and excellent storage characteristics has been attracting attention.
傳統上，在具有4V級電壓之高能量型之鋰離子蓄電池上有用之正極活性物質，一般而言，已知有尖晶石型構造之LiMn2 O4 、曲折層狀構造之LiMnO2 、層狀岩鹽型構造之LiCoO2 、LiNiO2 等，其中，又以使用LiNiO2 之鋰離子蓄電池，其係具有高度之充放電容量之電池而受到注目。然而，此種材料，由於其充電時之熱安定性及充放電循環耐久性差之緣故，仍被要求須進一步改善其特性。Conventionally, a positive electrode active material useful in a high-energy type lithium ion secondary battery having a voltage of 4 V is generally known as a spinel structure LiMn 2 O 4 , a zigzag layered LiMnO 2 , and a layer. LiCoO 2 , LiNiO 2 , and the like having a salt-type structure, and a lithium ion secondary battery using LiNiO 2 , which is a battery having a high charge and discharge capacity, has been attracting attention. However, such materials are still required to further improve their characteristics due to their thermal stability during charging and poor durability of charge and discharge cycles.
亦即，LiNiO2 在將鋰去除時，Ni3+ 會變成Ni4+ 而產生楊-泰勒畸變，在將Li去除0.45之區域內會由六方晶變成單斜晶，進一步去除時，則會由單斜晶變成六方晶之結晶構造。因此，藉由重複充放電反應，結晶構造會變得不安定，循環特性變差，再因為與氧氣釋放之電解液的反應等產生，從而電池之熱安定性及保存特性變差者，即為其特徵所在。為解決此課題起見，有在LiNiO2 之Ni之一部中進行添加Co及Al之材料之研究，惟尚未得到可解決此等課題之材料，因此仍在追求結晶性更高之Li-Ni複合氧化物。That is, when LiNiO 2 is removed, Ni 3+ will change to Ni 4+ to produce Young-Taylor distortion, and in the region where Li is removed by 0.45, the hexagonal crystal will become monoclinic, and when it is further removed, it will be The monoclinic crystal becomes a crystal structure of hexagonal crystal. Therefore, by repeating the charge and discharge reaction, the crystal structure becomes unstable, the cycle characteristics are deteriorated, and the reaction with the oxygen-releasing electrolyte or the like causes the thermal stability and storage characteristics of the battery to deteriorate. Its characteristics. In order to solve this problem, there has been research on the addition of materials of Co and Al in one part of Ni of LiNiO 2 , but there is no material that can solve these problems, and therefore Li-Ni with higher crystallinity is still being pursued. Composite oxide.
此外，在Li-Ni複合氧化物之製造方法中，為得到高填充性且結晶構造安定之Li-Ni複合氧化物，必須使用物性、結晶性及雜質量均受控制之Ni複合氫氧化物粒子，再以未發生Ni2+ 混入於Li位置為條件而進行燒成。Further, in the method for producing a Li-Ni composite oxide, in order to obtain a Li-Ni composite oxide having a high filling property and a stable crystal structure, it is necessary to use Ni composite hydroxide particles in which physical properties, crystallinity, and impurity amount are controlled. Then, firing is performed under the condition that Ni 2+ is not mixed in the Li position.
亦即，非水電解質蓄電池用之正極活性物質，係要求為高填充性且結晶構造安定，又在充電狀態下具有優良熱安定性之Li-Ni複合氧化物。In other words, the positive electrode active material for a nonaqueous electrolyte secondary battery is required to have a high filling property and a stable crystal structure, and a Li-Ni composite oxide having excellent thermal stability in a charged state.
傳統上，為改善結晶構造之安定化、充放電循環特性等各種特性起見，對於LiNiO2 粉末進行了各種之改良。舉例而言，有在LiNiAlO2 表面上被覆Li-Ni-Co-Mn複合氧化物，以改良循環特性及熱安定性之技術(專利文獻1)；有材料之種類不同，惟將Li-Co複合氧化物與Li-Ni-Co-Mn複合氧化物加以混合，以改善Li-Co複合氧化物之充放電循環特性及熱安定性之技術(專利文獻2)；有在Li-Co複合氧化物上藉由使碳酸鋰、Ni(OH)2 、Co(OH)2 、碳酸錳產生懸浮，或將Li-Ni-Co-Mn複合氧化物以機械處理進行被覆，從而改善Li-Co複合氧化物之充放電循環特性及高溫特性之技術(專利文獻3及專利文獻4)；有將Li-Co複合氧化物、Li-Ni複合氧化物、Li-Mn複合氧化物以蕊粒子及被覆粒子而形成複合化粒子，以達成高填充性、高能量密度之技術(專利文獻5)；有藉由將Li-Co複合氧化物之表面以Li-Ni複合氧化物加以被覆，以抑制Co在電解液之溶離之技術(專利文獻6)等。Conventionally, various improvements have been made to the LiNiO 2 powder in order to improve various properties such as stability of the crystal structure and charge/discharge cycle characteristics. For example, there is a technique in which a Li-Ni-Co-Mn composite oxide is coated on the surface of LiNiAlO 2 to improve cycle characteristics and thermal stability (Patent Document 1); Li-Co composite is available depending on the type of material. A technique in which an oxide and a Li-Ni-Co-Mn composite oxide are mixed to improve charge and discharge cycle characteristics and thermal stability of a Li-Co composite oxide (Patent Document 2); and on a Li-Co composite oxide The Li-Co composite oxide is improved by suspending lithium carbonate, Ni(OH) 2 , Co(OH) 2 , or manganese carbonate, or coating the Li-Ni-Co-Mn composite oxide by mechanical treatment. A technique of charging and discharging cycle characteristics and high-temperature characteristics (Patent Document 3 and Patent Document 4); forming a composite of Li-Co composite oxide, Li-Ni composite oxide, and Li-Mn composite oxide with core particles and coated particles A technique for achieving high filling property and high energy density by a particle (Patent Document 5); coating a surface of a Li-Co composite oxide with a Li-Ni composite oxide to suppress dissolution of Co in an electrolytic solution Technology (Patent Document 6) and the like.
專利文獻1：特開2004-127694號公報Patent Document 1: JP-A-2004-127694
專利文獻2：特開2005-317499號公報Patent Document 2: JP-A-2005-317499
專利文獻3：特開2006-331943號公報Patent Document 3: JP-A-2006-331943
專利文獻4：特開2007-48711號公報Patent Document 4: JP-A-2007-48711
專利文獻5：特開平9-35715號公報Patent Document 5: Japanese Patent Publication No. 9-35715
專利文獻6：特開2000-195517號公報Patent Document 6: JP-A-2000-195517
關於非水電解質蓄電池用之正極活性物質，現在最需要者為：能兼顧改善了充電時之熱安定性以及高容量化及高溫安定性之Li-Ni複合氧化物，惟尚未獲得能滿足完全充分要求之材料。In the case of the positive electrode active material for a non-aqueous electrolyte battery, the Li-Ni composite oxide which improves the thermal stability during charging, high capacity, and high-temperature stability can be achieved, but it has not yet been fully satisfied. Required materials.
亦即，本發明者們，為達成上述目的，將具有正極及能將鋰金屬或鋰離子吸收釋放之材料所成之負極的非水電解質蓄電池中，前述正極之活性物質，係非水電解質蓄電池用Li-Ni複合氧化物粒子粉末，其特徵為在作為核之二次粒子之組成係Lix1 Ni1-y1-z1-w1 Coy1 Mnz1 M1w1 O2-v Kv (1<x1≦1.3，0≦y1≦0.33，0.2≦z1≦0.33，0≦w1<0.1，0≦v≦0.05，M1係選自Al、Mg之至少一種之金屬以及K係選自F-、PO4 3- 之至少一種陰離子)之Li-Ni-Mn複合氧化物中，於該二次粒子之粒子表面或表面附近，其係以組成為Lix2 Ni1-y2-22 Coy2 M2z2 O2 (0.98≦x2 ≦1.05，0.15≦y2≦0.2，0≦z2≦0.05，M2係選自Al、Mg、Zr、Ti之至少一種金屬)之Li-Ni複合氧化物加以被覆或使之存在之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末；該非水電解質蓄電池用Li-Ni複合氧化物粒子粉末之複合粒子之平均粒子徑係作為核之二次粒子之平均粒子徑之1.1倍以上，且相對於作為核之粒子之被覆粒子或在表面附近所存在之Li-Ni複合氧化物粒子之重量百分率係10%以上50%以下者(本發明1)。In other words, in order to achieve the above object, the present inventors have a nonaqueous electrolyte secondary battery in which a positive electrode and a negative electrode capable of absorbing and releasing lithium metal or lithium ions are used. A Li-Ni composite oxide particle powder characterized by a composition of a secondary particle as a core, Li x1 Ni 1-y1-z1-w1 Co y1 Mn z1 M1 w1 O 2-v K v (1<x1≦ 1.3,0≦y1≦0.33, 0.2≦z1≦0.33,0≦w1<0.1,0≦v≦0.05, M1 is a metal selected from at least one of Al and Mg, and K is selected from F-, PO 4 3- In the Li-Ni-Mn composite oxide of at least one of the anions, in the vicinity of the surface or surface of the particles of the secondary particles, the composition is Li x2 Ni 1-y2-22 Co y2 M2 z2 O 2 (0.98 ≦) a non-aqueous electrolyte in which a Li-Ni composite oxide of x 2 ≦ 1.05, 0.15 ≦ y2 ≦ 0.2, 0 ≦ z 2 ≦ 0.05, M 2 is at least one metal selected from the group consisting of Al, Mg, Zr, and Ti) Li-Ni composite oxide particle powder for battery; average particle diameter of composite particles of Li-Ni composite oxide particle powder for non-aqueous electrolyte storage battery as core 2 When the average particle diameter of the particles is 1.1 times or more, and the weight percentage of the coated particles as the particles of the core or the Li-Ni composite oxide particles present in the vicinity of the surface is 10% or more and 50% or less (Invention 1) .
此外，本發明係本發明1之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末，其中在將該Li-Ni複合氧化物作為正極活性物質而使用，且使用鋰金屬或可吸收釋放鋰離子之材料所成負極，所成之非水電解質蓄電池中，於4.3V充電狀態下，保存1週後殘存之放電容量相對於保存前之放電容量係95%以上者(本發明2)。Furthermore, the present invention relates to a Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery according to the present invention, wherein the Li-Ni composite oxide is used as a positive electrode active material, and lithium metal or absorbable lithium ion is used. In the non-aqueous electrolyte storage battery formed by the material, the discharge capacity remaining after storage for one week in the state of charge of 4.3 V is 95% or more with respect to the discharge capacity before storage (Invention 2).
此外，本發明係本發明1之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末，其中在將該Li-Ni複合氧化物作為正極活性物質而使用，且使用鋰金屬或可吸收釋放鋰離子之材料所成負極，所成之非水電解質蓄電池中，於4.3V充電狀態下，60℃下保存1週後在電解液中之錳離子之溶離量，將該Li-Ni複合氧化物改以作為核之Li-Ni-Mn複合氧化物，作為正極活性物質使用之情況相比時，係80%以下者(本發明3)。Furthermore, the present invention relates to a Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery according to the present invention, wherein the Li-Ni composite oxide is used as a positive electrode active material, and lithium metal or absorbable lithium ion is used. The material is a negative electrode, and the Li-Ni composite oxide is changed in the non-aqueous electrolyte storage battery by the amount of manganese ions dissolved in the electrolyte after storage at 60 ° C for one week in a charged state of 4.3 V. When the Li-Ni-Mn composite oxide as a core is used as a positive electrode active material, it is 80% or less (Invention 3).
此外，本發明係本發明1之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末，其中在將該Li-Ni複合氧化物作為正極活性物質而使用，且使用鋰金屬或可吸收釋放鋰離子之材料所成負極，所成之非水電解質蓄電池中，於4.3V至3.0V之範圍內，其0.2mA/cm2 之充放電速度下之放電容量，將該Li-Ni複合氧化物改以作為核之Li-Ni-Mn複合氧化物，作為正極活性物質使用之情況相比時，係3mAh/g以上而升高者(本發明4)。Furthermore, the present invention relates to a Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery according to the present invention, wherein the Li-Ni composite oxide is used as a positive electrode active material, and lithium metal or absorbable lithium ion is used. The material is a negative electrode, and the non-aqueous electrolyte battery is replaced by a discharge capacity at a charge and discharge rate of 0.2 mA/cm 2 in the range of 4.3 V to 3.0 V. When the Li-Ni-Mn composite oxide as a core is used as a positive electrode active material, it is increased by 3 mAh/g or more (Invention 4).
此外，本發明係本發明1之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末，其中在將該Li-Ni複合氧化物作為正極活性物質而使用，且使用鋰金屬或可吸收釋放鋰離子之材料所成負極，所成之非水電解質蓄電池中，以4.5V充電狀態之差示熱分析在200℃～310℃之範圍所示之產熱最大峰部，相較於將該Li-Ni複合氧化物改以作為核之Li-Ni-Mn複合氧化物，作為正極活性物質使用時，其溫度之降低係32℃以內者(本發明5)。Furthermore, the present invention relates to a Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery according to the present invention, wherein the Li-Ni composite oxide is used as a positive electrode active material, and lithium metal or absorbable lithium ion is used. In the non-aqueous electrolyte storage battery formed by the material, the maximum peak of heat generation shown in the range of 200 ° C to 310 ° C is shown by the difference of the state of charge of 4.5 V, compared to the Li-Ni. The composite oxide is changed to a Li-Ni-Mn composite oxide as a core, and when it is used as a positive electrode active material, the temperature is lowered within 32 ° C (Invention 5).
此外，本發明係本發明1～5之任一者中之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末之製造方法，於本發明1～5之任一者之Li-Ni複合氧化物粒子粉末之製造方法中，其特徵係在作為核之Li-Ni-Mn複合氧化物之二次粒子之表面或表面附近，將Li-Ni複合氧化物藉由濕式之化學性處理或乾式之機械性處理，或進一步在氧氣環境下施加700℃以上熱處理，而使其被覆或存在者(本發明6)。Furthermore, the present invention provides a method for producing a Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery according to any one of the present inventions 1 to 5, and a Li-Ni composite oxide according to any one of the present inventions 1 to 5. In the method for producing a particle powder, the Li-Ni composite oxide is chemically treated by a wet method or a dry type in the vicinity of a surface or a surface of a secondary particle of a Li-Ni-Mn composite oxide as a core. Mechanical treatment, or further application of heat treatment at 700 ° C or higher in an oxygen atmosphere, to coat or exist (Invention 6).
此外，本發明係本發明6之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末之製造方法，其中係將作為核之粒子於水中加以懸浮攪拌，再添加硫酸鎳、硫酸鈷混合液及鹼性溶液，同時控制其pH值在11.0以上，於得到以Ni-Co複合氫氧化物將表面被覆之中間體後，藉由將Li化合物及Al化合物混合而進行化學性處理，進一步在氧氣環境下，以700℃以上施加熱處理者(本發明7)。Further, the present invention is a method for producing a Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery according to the sixth aspect of the present invention, wherein the particles as a core are suspended and stirred in water, and then a mixture of nickel sulfate and cobalt sulfate and a base are added. The solution is simultaneously controlled to have a pH of 11.0 or more, and after obtaining an intermediate surface coated with Ni-Co composite hydroxide, chemical treatment is carried out by mixing the Li compound and the Al compound, further in an oxygen atmosphere. The heat treatment is applied at 700 ° C or higher (Invention 7).
此外，本發明係本發明6之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末之製造方法，其中係添加硫酸鎳、硫酸鈷混合液及鹼性溶液，同時控制其pH值，使其生成Ni-Co複合氫氧化物，再將其磨碎使得所得到之Ni-Co複合氫氧化物之平均粒子徑在2μm以下後，藉由作為核粒子之Li-Ni-Mn複合氧化物及高速攪拌混合機之機械化學反應使其存在於粒子表面，然後，藉由將Li化合物及Al化合物混合而進行乾式之機械性處理，進一步在氧氣環境下，以700℃以上施加熱處理者(本發明8)。Further, the present invention provides a method for producing a Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery according to the present invention, wherein a nickel sulfate, a cobalt sulfate mixed solution and an alkaline solution are added, and the pH thereof is controlled to generate After the Ni-Co composite hydroxide is ground, the average particle diameter of the obtained Ni-Co composite hydroxide is 2 μm or less, and the Li-Ni-Mn composite oxide as a core particle and high-speed stirring are used. The mechanochemical reaction of the mixer is carried out on the surface of the particles, and then a dry mechanical treatment is carried out by mixing the Li compound and the Al compound, and further heat treatment is applied at 700 ° C or higher in an oxygen atmosphere (Invention 8) .
此外，本發明係一種非水電解質蓄電池，其特徵係使用含有本發明1～5之任一者中之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末所成之正極活性物質的正極。Furthermore, the present invention is a non-aqueous electrolyte storage battery characterized by using a positive electrode active material comprising a positive electrode active material made of a non-aqueous electrolyte battery for Li-Ni composite oxide particles according to any one of the inventions 1 to 5.
本發明之Li-Ni複合氧化物粒子粉末，其在負極使用鋰金屬或可吸收釋放鋰離子之材料時，於4.3V充電狀態下，保存1週後之殘存放電容量相對於保存前之放電容量在95%以上，且保存1週後之電解液中之錳離子溶離量相對於作為核之Li-Ni-Mn複合氧化物之錳離子溶離量在80%以下之故，因此可提升鋰離子電池之高溫保存特性。The Li-Ni composite oxide particle powder of the present invention, when a lithium metal or a material capable of absorbing and releasing lithium ions is used in a negative electrode, is stored in a charged state of 4.3 V, and the storage capacity after storage for one week is relative to the discharge capacity before storage. In the case of 95% or more, the amount of dissolved manganese ions in the electrolytic solution after one week of storage is less than 80% of the amount of manganese ions dissolved in the Li-Ni-Mn composite oxide as a core, so that the lithium ion battery can be improved. High temperature storage characteristics.
此外，本發明之Li-Ni複合氧化物粒子粉末，在作為正極活性物質使用時，並將鋰金屬或可吸收釋放鋰離子之材料所成者作為負極而使用，所成之非水電解質蓄電池中，於4.3V至3.0V之範圍內，其以0.2mA/cm2 之充放電速度所進行之放電容量，相較於將該Li-Ni複合氧化物改以作為核之Li-Ni-Mn複合氧化物，作為正極活性物質使用而進行比較時，由於高達3mAh/g以上之故，因此可提升鋰離子電池之放電容量。Further, the Li-Ni composite oxide particle powder of the present invention is used as a negative electrode when a lithium metal or a material capable of absorbing and releasing lithium ions is used as a positive electrode active material, and is used in a nonaqueous electrolyte secondary battery. , in the range of 4.3V to 3.0V, the discharge capacity to charge and discharge rate 0.2mA / cm 2 of the PRC, compared to the Li-Ni composite oxide as a nucleus to change the Li-Ni-Mn complex When the oxide is used as a positive electrode active material for comparison, since it is as high as 3 mAh/g or more, the discharge capacity of the lithium ion battery can be improved.
進一步，本發明之Li-Ni複合氧化物粒子粉末，在作為正極活性物質使用時，並將鋰金屬或可吸收釋放鋰離子之材料所成者作為負極而使用，所成之非水電解質蓄電池中，以4.5V充電狀態之差示熱分析在200℃～310℃之範圍所示之產熱最大峰部，相較於將該Li-Ni複合氧化物改以作為核之Li-Ni-Mn複合氧化物，作為正極活性物質使用而進行比較時，其溫度之降低係32℃以內者，因此可維持鋰離子電池之熱安定性。Further, the Li-Ni composite oxide particle powder of the present invention is used as a negative electrode when a lithium metal or a material capable of absorbing and releasing lithium ions is used as a positive electrode active material, and is used in a nonaqueous electrolyte secondary battery. The maximum peak of heat generation shown in the range of 200 ° C to 310 ° C with a differential thermal analysis of 4.5 V state, compared to the Li-Ni-Mn composite of the Li-Ni composite oxide as a core When the oxide is used as a positive electrode active material for comparison, the temperature is lowered within 32 ° C, so that the thermal stability of the lithium ion battery can be maintained.
進一步，本發明之Li-Ni複合氧化物粒子粉末，其藉由在作為核之Li-Ni-Mn複合氧化物之二次粒子之粒子表面或表面附近，將Li-Ni複合氧化物以濕式之化學性處理或乾式之機械性處理，或進一步施加熱處理，可繼續維持充電時之安全性，而製造高溫保存特性及放電容量獲得提升之Li-Ni複合氧化物粒子粉末。Further, the Li-Ni composite oxide particle powder of the present invention has a Li-Ni composite oxide in a wet state by a particle surface or a surface of a secondary particle of a Li-Ni-Mn composite oxide as a core. The chemical treatment or the dry mechanical treatment or the further application of the heat treatment can continue to maintain the safety at the time of charging, and produce a Li-Ni composite oxide particle powder having improved high-temperature storage characteristics and discharge capacity.
因此，本發明之Li-Ni複合氧化物粒子粉末，其非常適合作為非水電解質蓄電池用之正極活性物質而使用。Therefore, the Li-Ni composite oxide particles of the present invention are very suitable for use as a positive electrode active material for a nonaqueous electrolyte secondary battery.
以下茲詳細地說明本發明之構成。The constitution of the present invention will be described in detail below.
首先，關於本發明之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末加以說明。First, the Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery of the present invention will be described.
本發明之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末，其係以具有特定組成之Li-Ni-Mn複合氧化物之二次粒子作為核，並在該二次粒子之粒子表面或粒子表面附近，使具有特定組成之Li-Ni複合氧化物粒子產生被覆或存在者。亦即，係將作為核之二次粒子之表面全體被覆於具有特定組成之Li-Ni複合氧化物粒子者，或在作為核之二次粒子之表面附近或粒子表面之一部上，使具有特定組成之Li-Ni複合氧化物粒子存在或產生被覆者。The Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery of the present invention is characterized in that a secondary particle of a Li-Ni-Mn composite oxide having a specific composition is used as a core, and a particle surface or a particle of the secondary particle is used. In the vicinity of the surface, a Li-Ni composite oxide particle having a specific composition is caused to be coated or present. That is, the entire surface of the secondary particles as the core is coated on the Li-Ni composite oxide particles having a specific composition, or on the surface of the secondary particles as the core or on one of the surface of the particles, so as to have The Li-Ni composite oxide particles of a specific composition are present or generate a coating.
作為核之Li-Ni-Mn複合氧化物之組成，係以Lix1 Ni1-y1-z1-w1 Coy1 Mnz1 M1w1 O2-v Kv (1＜x1≦1.3，0≦y1≦0.33，0.2≦z1≦0.33，0≦w1＜0.1，0≦v≦0.05，M1係選自Al、Mg之至少一種之金屬以及K係選自F- 、PO4 3- 之至少一種陰離子)為較佳。As a composition of the core Li-Ni-Mn composite oxide, Li x1 Ni 1-y1-z1-w1 Co y1 Mn z1 M1 w1 O 2-v K v (1<x1≦1.3,0≦y1≦0.33 , 0.2 ≦ z1 ≦ 0.33,0 ≦ w1 <0.1,0 ≦ v ≦ 0.05, M1 is selected from Al, Mg is at least one kind of metal selected from K and F -, PO 4 3- of at least one anionic) as compared with good.
組成範圍如在前述範圍外時，其欲得到Li-Ni-Mn複合氧化物之特徵之充電時熱安定性或高放電容量，就會變得困難。When the composition range is outside the above range, it is difficult to obtain thermal stability or high discharge capacity during charging which is characteristic of the Li-Ni-Mn composite oxide.
所被覆或存在之粒子粉末之組成，係以Lix2 Ni1-y2-z2 Coy2 M2z2 O2 (0.98≦x2≦1.05，0.15≦y2≦0.2，0≦z2≦0.05，M2係選自Al、Mg、Zr、Ti之至少一種金屬)為較佳。The composition of the coated or existing particle powder is Li x2 Ni 1-y2-z2 Co y2 M2 z2 O 2 (0.98≦x2≦1.05, 0.15≦y2≦0.2, 0≦z2≦0.05, M2 is selected from Al Preferably, at least one metal of Mg, Zr, and Ti).
組成範圍如在前述範圍外時，其欲得到高放電容量及高溫安定性，就會變得困難。When the composition range is outside the above range, it becomes difficult to obtain high discharge capacity and high temperature stability.
此外，藉由F- 、PO4 3- 之存在，由於作為核之粒子在充電時之熱安定性可以提高，因此Li-Ni複合氧化物粒子粉末在充電時之熱安定性就可以進一步獲得改善。K之組成(v)如在前述範圍外時，Li-Ni複合氧化物之放電容量就會降低。Further, by the presence of F - and PO 4 3- , since the thermal stability of the particles as the core during charging can be improved, the thermal stability of the Li-Ni composite oxide particles can be further improved upon charging. . When the composition (v) of K is outside the above range, the discharge capacity of the Li-Ni composite oxide is lowered.
在本發明中，相對於前述作為核之二次粒子之被覆或使其存在之Li-Ni複合氧化物，其重量百分率係滿足10%以上50%以下者。In the present invention, the weight percentage of the Li-Ni composite oxide which is coated or made of the secondary particles as the core is 10% or more and 50% or less.
重量百分率如未達10%時，在高溫保存時電解液中之錳會溶離，且在高溫保存特性變差時，高容量化還會變得困難。另一方面，重量百分率如超過50%時，將無法改善其在4.5V充電狀態下之熱安定性。When the weight percentage is less than 10%, the manganese in the electrolytic solution is dissolved at the time of high-temperature storage, and when the high-temperature storage characteristics are deteriorated, it becomes difficult to increase the capacity. On the other hand, if the weight percentage exceeds 50%, the thermal stability at a 4.5V state of charge cannot be improved.
為兼顧高溫保存特性及熱安定性之改善以及高容量化起見，其係以重量百分率儘可能接近50%者為較佳。使其被覆或存在之量，係以20%以上50%以下為較佳，並以25%～50%為最佳。In order to achieve both high-temperature storage characteristics and improvement in thermal stability and high capacity, it is preferred that the weight percentage is as close as possible to 50%. The amount to be coated or present is preferably 20% or more and 50% or less, and preferably 25% to 50%.
本發明之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末之平均粒子徑，相對於作為核之Li-Ni-Mn複合氧化物之平均粒子徑，係控制在1.1倍以上者。平均粒子徑之比如未達1.1倍時，將無使Li-Ni複合氧化物被覆或附著之效果。較佳之粒子徑比係1.2以上，最佳者則係1.3～2.0。The average particle diameter of the Li-Ni composite oxide particles for a non-aqueous electrolyte secondary battery of the present invention is controlled to be 1.1 times or more with respect to the average particle diameter of the Li-Ni-Mn composite oxide as a core. When the average particle diameter is less than 1.1 times, the effect of coating or adhering the Li-Ni composite oxide is not obtained. Preferably, the particle diameter ratio is 1.2 or more, and the most preferred one is 1.3 to 2.0.
此外，本發明之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末之平均粒子徑(以雷射繞射‧散射法進行測定)，係以3～20μm為較佳。平均粒子徑如在3μm以下時，在將Li-Ni複合氧化物作成電極漿料時之分散性會變差。如超過20μm時，由於電極之厚度變厚，速率特性變差，從而放電容量會降低。Further, the average particle diameter (measured by a laser diffraction/scattering method) of the Li-Ni composite oxide particles for a nonaqueous electrolyte secondary battery of the present invention is preferably 3 to 20 μm. When the average particle diameter is 3 μm or less, the dispersibility in the case where the Li—Ni composite oxide is used as the electrode slurry is deteriorated. When it exceeds 20 μm, since the thickness of the electrode becomes thick, the rate characteristics are deteriorated, and the discharge capacity is lowered.
以下所記載之實施型態，係使用本發明之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末作為正極活性物質而使用，且將鋰金屬或可吸收釋放鋰離子之材料所成者作為負極而使用，所成之非水電解質蓄電池中之態樣。In the embodiment described below, the Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery of the present invention is used as a positive electrode active material, and a lithium metal or a material capable of absorbing and releasing lithium ions is used as a negative electrode. And the use of the non-aqueous electrolyte battery in the form.
本發明之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末，在負極上將鋰金屬或可吸收釋放鋰離子之材料所成者作為負極而使用時，於4.3V充電狀態下，其保存1週後之殘存放電容量係以相對於保存前之放電容量能維持在95%以上者為較佳，並以接近於100%者為最佳。When the Li-Ni composite oxide particle powder for a non-aqueous electrolyte storage battery of the present invention is used as a negative electrode in a lithium metal or a material capable of absorbing and releasing lithium ions on the negative electrode, it is stored in a charged state of 4.3 V. The residual storage capacity after the week is preferably maintained at 95% or more with respect to the discharge capacity before storage, and is preferably as close as 100%.
本發明之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末，在負極上將鋰金屬或可吸收釋放鋰離子之材料所成者作為負極而使用時，於4.3V充電狀態下，其60℃下保存1週後在電解液中之錳離子之溶離量，相較於將該Li-Ni複合氧化物改以作為核之Li-Ni-Mn複合氧化物，作為正極活性物質使用而進行比較時，係以80%以下者為較佳。錳離子之溶離量如超過80%時，蓄電池之高溫保存時之殘存放電容量會降低。更佳之錳離子之溶離量係75%以下，最佳者則以接近於0%附近者為理想。When the Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery of the present invention is used as a negative electrode in a lithium metal or a material capable of absorbing and releasing lithium ions on a negative electrode, it is 60 ° C in a charged state of 4.3 V. The amount of dissolved manganese ions in the electrolytic solution after one week of storage is compared with the Li-Ni-Mn composite oxide in which the Li-Ni composite oxide is changed as a core, and used as a positive electrode active material for comparison. It is preferred that it is 80% or less. When the dissolved amount of manganese ions exceeds 80%, the storage capacity of the residual storage of the battery at a high temperature is lowered. More preferably, the dissolved amount of manganese ions is 75% or less, and the best one is preferably close to 0%.
本發明之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末，在負極上將鋰金屬或可吸收釋放鋰離子之材料所成者作為負極而使用時，於4.3V至3.0V之範圍內，其0.2mA/cm2 之充放電速度下之放電容量，相較於將該Li-Ni複合氧化物改以作為核之Li-Ni-Mn複合氧化物，作為正極活性物質使用而進行比較時，係3mAh/g以上而升高者為較佳，並以5mAh/g為更佳，且以越高可能者為最佳。The Li-Ni composite oxide particle powder for a non-aqueous electrolyte storage battery of the present invention is used in the range of 4.3 V to 3.0 V when a lithium metal or a material capable of absorbing and releasing lithium ions is used as a negative electrode on the negative electrode. When the discharge capacity at a charge/discharge rate of 0.2 mA/cm 2 is compared with the Li-Ni-Mn composite oxide in which the Li-Ni composite oxide is changed as a core, and used as a positive electrode active material for comparison, It is preferred that the increase is 3 mAh/g or more, and it is preferably 5 mAh/g, and the higher the possibility is the best.
本發明之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末，在負極上將鋰金屬或可吸收釋放鋰離子之材料所成者作為負極而使用時，相對於在表面附近所被覆或存在之Li-Ni複合氧化物，其以4.5V充電狀態之差示熱分析在200℃～310℃之範圍所示之產熱最大峰部，相較於將該Li-Ni複合氧化物改以作為核之Li-Ni-Mn複合氧化物，作為正極活性物質使用而進行比較時，其溫度之降低係32℃以內者為較佳，更佳者為20℃以內，最佳者則為無降低者。The Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery of the present invention is used as a negative electrode when a lithium metal or a material capable of absorbing and releasing lithium ions is used as a negative electrode, and is coated or present in the vicinity of the surface. Li-Ni composite oxide, which shows the maximum peak of heat generation in the range of 200 ° C to 310 ° C by differential thermal analysis at a charging state of 4.5 V, compared to the Li-Ni composite oxide as a core When the Li-Ni-Mn composite oxide is used as a positive electrode active material for comparison, the temperature is preferably lowered within 32 ° C, more preferably within 20 ° C, and most preferably no reduction.
在本發明中所謂之表面附近，係指將粒子假定為球狀且將粒子徑作成直徑時，由表面起算至相當於半徑(粒子徑之1/2)之25%左右之部分。In the vicinity of the surface in the present invention, when the particles are assumed to be spherical and the particle diameter is made to be a diameter, the surface is calculated from a surface to a portion corresponding to a radius (1/2 of the particle diameter) of about 25%.
接著，再就本發明之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末之製造方法加以說明。Next, a method of producing the Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery of the present invention will be described.
本發明之Li-Ni複合氧化物粒子粉末，係於作為核之Li-Ni-Mn複合氧化物二次粒子之粒子表面或表面附近，將使之被覆或存在之Li-Ni複合氧化物藉由濕式之化學性處理或乾式之機械性處理，再於作為核之二次粒子之粒子表面及/或表面附近使Li-Ni複合氧化物粒子產生存在者，並可視需要進而在氧氣環境下，一般為700℃以上，較佳為730℃以上，施加2小時以上之熱處理。The Li-Ni composite oxide particle powder of the present invention is a Li-Ni composite oxide which is coated or present in the vicinity of the surface or surface of the particle of the Li-Ni-Mn composite oxide secondary particle as a core. a wet chemical treatment or a dry mechanical treatment, in which the Li-Ni composite oxide particles are present in the vicinity of the surface and/or the surface of the particles as the secondary particles of the core, and optionally in an oxygen atmosphere, Generally, it is 700 ° C or more, preferably 730 ° C or more, and heat treatment is applied for 2 hours or more.
作為核之Li-Ni-Mn複合氧化物及使之被覆或存在之粒子之Li-Ni複合氧化物，可以通常之方法而得到，例如，可以固相法或濕式法與鋰鹽進行混合，並在空氣環境下以750℃～1000℃燒成而製得。The Li-Ni-Mn composite oxide as a core and the Li-Ni composite oxide of the particles coated or present may be obtained by a usual method, and for example, may be mixed with a lithium salt by a solid phase method or a wet method. It is prepared by firing at 750 ° C to 1000 ° C in an air atmosphere.
此外，如本發明中，使F- 或PO4 3- 存在時，在將為得到作為核之Li-Ni複合氧化物而使用之複合氫氧化物與鋰鹽，利用乾式或濕式進行混合時，可添加所定量之LiF或Li3 PO4 而得到。When time or PO 4 3- is present, in order to obtain the composite hydroxide with a lithium salt is used as the Li-Ni composite oxide core, the use of dry or wet mixing - Further, as the present invention, the F It can be obtained by adding a certain amount of LiF or Li 3 PO 4 .
作為核之二次粒子及使之被覆或存在之粒子之複合化方法，其並無特別之限制，可以濕式之化學性處理或乾式之機械性處理而進行。舉例而言，在濕式之化學性處理中，可將作為核之粒子懸浮於含有形成使之被覆或存在之粒子之元素的酸溶液中，再中和並進行熱處理之方法；或可於純水或有機溶劑中將使之被覆或存在之粒子進行懸浮後，再以熱處理將粒子進行複合化者。在機械性處理中，可將作為核之二次粒子及使之被覆或存在之粒子於所定之空隙間，一面施加壓縮裁斷力，一面進行粒子複合化。此外，亦可使用可在高速進行混合‧攪拌之裝置。在濕式之化學性處理或乾式之機械性處理中，一般係以氧氣環境下700～850℃，較佳係以720～820℃進行者為理想。The method of combining the secondary particles of the core and the particles coated or present is not particularly limited, and may be carried out by wet chemical treatment or dry mechanical treatment. For example, in a wet chemical treatment, a particle as a core may be suspended in an acid solution containing an element forming a particle to be coated or present, and then neutralized and heat-treated; or may be pure The particles which are coated or present in water or an organic solvent are suspended, and then the particles are composited by heat treatment. In the mechanical treatment, the secondary particles as the core and the particles coated or present may be subjected to particle compositing while applying a compressive cutting force between the predetermined spaces. In addition, it is also possible to use a device that can be mixed and stirred at a high speed. In the wet chemical treatment or the dry mechanical treatment, it is generally preferred to carry out the reaction at 700 to 850 ° C in an oxygen atmosphere, preferably at 720 to 820 ° C.
其次，茲就使用由本發明之非水電解質蓄電池用Li-Ni複合氧化物粒子粉末所成之正極活性物質的正極，加以說明。Next, the positive electrode of the positive electrode active material obtained from the Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery of the present invention will be described.
如使用本發明之正極活性物質製造正極時，其係依據一般方法，添加導電劑及結著劑並混合。導電劑較佳有乙炔碳黑、碳黑、石墨等，結著劑較佳有聚四氟乙烯、聚氟化亞乙烯等。When a positive electrode is produced by using the positive electrode active material of the present invention, a conductive agent and a binder are added and mixed according to a general method. The conductive agent is preferably acetylene black, carbon black, graphite or the like, and the binder is preferably polytetrafluoroethylene or polyvinylidene fluoride.
使用本發明之正極活性物質所製造之蓄電池，可由前述正極、負極及電解質所構成。The battery produced by using the positive electrode active material of the present invention may be composed of the above-mentioned positive electrode, negative electrode, and electrolyte.
負極活性物質，可使用鋰金屬、鋰/鋁合金、鋰/錫合金或石墨等。As the negative electrode active material, lithium metal, lithium/aluminum alloy, lithium/tin alloy, graphite or the like can be used.
此外，電解液之溶劑，除碳酸乙烯酯/碳酸二酯之組合外，並可使用包含碳酸丙烯酯、碳酸二甲酯等之碳酸酯類、或二甲氧基乙烷等之醚類中，至少一種之有機溶劑。Further, as the solvent of the electrolytic solution, in addition to the combination of the ethylene carbonate/carbonic acid diester, a carbonate containing propylene carbonate, dimethyl carbonate or the like, or an ether such as dimethoxyethane may be used. At least one organic solvent.
進一步，電解質，並可於上述溶劑中，在六氟化磷酸鋰以外，使用過氯酸鋰、四氟硼酸鋰等之鋰鹽之至少一種並加以溶解使用。Further, the electrolyte may be used by dissolving at least one of lithium salts such as lithium perchlorate or lithium tetrafluoroborate in addition to lithium hexafluorophosphate in the above solvent.
非水電解質蓄電池之熱安定性不足之原因，例如有氧脫離溫度過低。此種氧脫離之原因，例如有在充電狀態下由於構造上之不安定，使得氧氣從電極表面產生脫離。此外，高溫保存安定性不足之原因，例如有Co或Mn之溶離所導致者。The reason why the thermal stability of the nonaqueous electrolyte secondary battery is insufficient, for example, the aerobic desorption temperature is too low. The reason for such oxygen detachment is, for example, that in the state of charge, due to structural instability, oxygen is detached from the electrode surface. In addition, the reason for insufficient stability in high-temperature storage, for example, is caused by the dissolution of Co or Mn.
為抑制前述課題，非水電解質蓄電池用之正極活性物質，其表面改質就很重要，在先前技術(技術文獻1～4)中已進行過改善，例如專利文獻1中，其核粒子之組成係Li-Ni-Mn複合氧化物，惟在作為核之粒子之充放電效率變差之同時，其並無被覆狀態及被覆比例之記載，亦未考慮到被覆所致之熱安定性改善及高溫保存特性之改善。此外，專利文獻2中，其係藉由Li-Ni-Co-Mn複合氧化物混合於Li-Co複合氧化物以改善熱安定性，惟其並未考慮到Li-Ni-Mn複合氧化物之高溫保存特性之改善。此外，專利文獻3中，係藉由將Li-Ni-Co-Mn複合氧化物以表面被覆於Li-Co複合氧化物；專利文獻4中，係藉由在Co複合氧化物之表面形成由鋰、鎳、鈷、錳金屬所成之被覆層，從而改善高容量化及循環特性、高溫保存特性，惟其並未考慮到表面之Mn元素之溶離抑制及充電時之高溫保持特性之改善。專利文獻5中，係形成將Li-Co複合氧化物、Li-Ni複合氧化物、Li-Mn複合氧化物作為蕊粒子及被覆粒子所成之複合化粒子，並改善其填充性及能量密度，惟其除了蕊粒子及被覆粒子之組成之記載不明確以外，亦未考慮到高溫保存特性之改善。專利文獻6中，係藉由將Li-Co複合氧化物之表面以Li-Ni複合氧化物加以被覆，而抑制Co在電解液中之溶離，惟其係針對充電時欠缺熱安定性之Li-Co複合氧化物之Co溶離而加以抑制之技術，並未考慮到兼顧高溫保存特性之改善及熱安定性。In order to suppress the above-mentioned problem, the surface active material of the positive electrode active material for a non-aqueous electrolyte battery is important, and has been improved in the prior art (Technical Documents 1 to 4). For example, in Patent Document 1, the composition of the core particle It is a Li-Ni-Mn composite oxide, but the charge and discharge efficiency of the particles as a core is deteriorated, and there is no description of the coating state and the coating ratio, and the thermal stability improvement and high temperature due to coating are not considered. Save the improvement of features. Further, in Patent Document 2, the Li-Ni-Co-Mn composite oxide is mixed with the Li-Co composite oxide to improve thermal stability, but the high temperature of the Li-Ni-Mn composite oxide is not considered. Save the improvement of features. Further, in Patent Document 3, the Li-Ni-Co-Mn composite oxide is coated on the surface of the Li-Co composite oxide, and in Patent Document 4, lithium is formed on the surface of the Co composite oxide. A coating layer made of nickel, cobalt, or manganese metal improves the high capacity, cycle characteristics, and high temperature storage characteristics, but does not take into account the dissolution inhibition of the Mn element on the surface and the improvement of the high temperature retention characteristics during charging. In Patent Document 5, a composite particle composed of a Li—Co composite oxide, a Li—Ni composite oxide, and a Li—Mn composite oxide as core particles and coated particles is formed, and the filling property and energy density are improved. However, the description of the composition of the core particles and the coated particles is not clear, and the improvement of the high-temperature storage characteristics is not considered. In Patent Document 6, the surface of the Li-Co composite oxide is coated with a Li-Ni composite oxide to suppress the elution of Co in the electrolytic solution, but it is for Li-Co which lacks thermal stability during charging. The technique of suppressing the dissolution of Co by the composite oxide does not take into consideration the improvement of the high-temperature storage characteristics and the thermal stability.
因此，在本發明中，藉由：在作為核之二次粒子之組成係Lix1 Ni1-y1-z1-w1 Coy1 Mnz1 M1w1 O2-v Kv (1<x1≦1.3，0≦y1≦0.33，0.2≦z1≦0.33，0≦w1<0.1，0≦v≦0.05，M1係選自Al、Mg之至少一種之金屬以及K係選自F- 、PO4 3 -之至少一種陰離子)之Li-Ni-Mn複合氧化物中，於該二次粒子之粒子表面或表面附近，其係以組成為Lix2 Ni1-y2-z2 Coy2 M2z2 O2 (0.98≦x2≦1.05，0.15≦y2≦0.2，0≦z2≦0.05，M2係選自Al、Mg、Zr、Ti之至少一種金屬)之Li-Ni複合氧化物，使得所得到之複合粒子之粒子徑以作為核之粒子之粒子徑之1.1倍以上而被覆或存在，且在相對於核粒子之被覆粒子或在表面附近所存在之粒子之重量百分率係10%以上50%以下者，即可改善高溫保存時之殘存放電容量之降低及Mn溶離量，並改善其高溫保存特性。Therefore, in the present invention, by the composition of the secondary particles as the core, Li x1 Ni 1-y1-z1-w1 Co y1 Mn z1 M1 w1 O 2-v K v (1<x1≦1.3,0 ≦ y1 ≦ 0.33, 0.2 ≦ z1 ≦ 0.33, 0 ≦ w1 < 0.1, 0 ≦ v ≦ 0.05, M1 is a metal selected from at least one of Al and Mg, and K is selected from at least one of F - and PO 4 3 - The anion) Li-Ni-Mn composite oxide is composed of Li x2 Ni 1-y2-z2 Co y2 M2 z2 O 2 (0.98≦x2≦1.05) on the surface or near the surface of the particle of the secondary particle. , a Li-Ni composite oxide of 0.15 ≦ y2 ≦ 0.2, 0 ≦ z 2 ≦ 0.05, M 2 is at least one metal selected from the group consisting of Al, Mg, Zr, and Ti, so that the particle diameter of the obtained composite particles is used as a core When the particle diameter of the particles is 1.1 times or more, it is coated or present, and when the weight percentage of the particles present in the vicinity of the coated particles or in the vicinity of the surface is 10% or more and 50% or less, the residual at the time of high temperature storage can be improved. The discharge capacity is reduced and the Mn is dissolved, and the high temperature storage characteristics are improved.
此外，在本發明中，藉由使Li-Ni複合氧化物粒子粉末為前述構成者，相較於將該Li-Ni複合氧化物改以作為核之Li-Ni-Mn複合氧化物，作為正極活性物質使用而進行比較時，可高達3mAh/g以上之放電容量，並可達成電池之高容量化。Further, in the present invention, the Li-Ni composite oxide particles are the above-described constituents, and the Li-Ni composite oxide is changed to a Li-Ni-Mn composite oxide as a core, and is used as a positive electrode. When the active material is used for comparison, the discharge capacity can be as high as 3 mAh/g or more, and the capacity of the battery can be increased.
再者，本發明之Li-Ni複合氧化物粒子粉末，在作為核之Li-Ni-Mn複合氧化物二次粒子之粒子表面或表面附近，將Li-Ni複合氧化物藉由濕式之化學性處理或乾式之機械性處理，或進一步施加熱處理，其以4.5V充電狀態之差示熱分析在200℃～310℃之範圍所示之產熱最大峰部，相較於將該Li-Ni複合氧化物改以作為核之Li-Ni-Mn複合氧化物，作為正極活性物質使用而進行比較時，其溫度之降低可抑制在32℃以內，且可兼顧高容量化及充電時之安全性。Further, in the Li-Ni composite oxide particle powder of the present invention, the Li-Ni composite oxide is wet-processed in the vicinity of the surface or surface of the particle of the Li-Ni-Mn composite oxide secondary particle as a core. Sexual treatment or dry mechanical treatment, or further heat treatment, which shows the maximum peak of heat generation in the range of 200 ° C to 310 ° C in the difference of 4.5 V state of charge, compared to the Li-Ni When the composite oxide is changed to a Li-Ni-Mn composite oxide as a core, when the cathode active material is used as a positive electrode active material, the temperature can be lowered to 32 ° C or less, and the capacity can be increased and the safety during charging can be achieved. .
本發明之代表性實施型態，係如以下所示者。Representative embodiments of the invention are as follows.
Li-Ni複合氧化物之組成，係使用誘導電漿發光分光法ICP-7500[島津製作所(股)製]進行分析並確認。The composition of the Li-Ni composite oxide was analyzed and confirmed using an induced plasma luminescence spectrometry ICP-7500 [manufactured by Shimadzu Corporation).
平均粒子徑係使用雷射式粒度分布測定裝置LMS-30[SEISHIN(股)製]，並以濕式雷射法測定之體積基準之平均粒子徑。The average particle diameter is a laser particle size distribution measuring apparatus LMS-30 [manufactured by SEISHIN Co., Ltd.], and the average particle diameter of the volume basis measured by a wet laser method.
所被覆或存在之粒子之存在狀態，係使用附有能量分散型X射線分析裝置之掃描電子顯微鏡SEM-EPMA0[(股)日立高科技製]進行觀察。The state of existence of the coated or existing particles was observed using a scanning electron microscope SEM-EPMA0 [manufactured by Hitachi High-Tech Co., Ltd.] equipped with an energy dispersive X-ray analyzer.
使用Li-Ni複合氧化物粒子以鈕釦型電池進行初期充放電特性及高溫保存特性之評價。The initial charge and discharge characteristics and high-temperature storage characteristics of the Li-Ni composite oxide particles were evaluated using a button type battery.
首先，將正極活性物質之Li-Ni複合氧化物90重量%、導電材之乙炔碳黑3重量%、石墨KS-6之3重量%、及黏合劑之溶解於N-甲基吡咯烷酮之聚氟化亞乙烯4重量%加以混合後，塗佈於Al金屬箔並於150℃下乾燥。將該薄片打穿為16mmΦ 後，以1t/cm2 壓著，而作成電極厚度為50μm之物用於正極。負極則作成打穿為16mmΦ 之金屬鋰，電解液係使用溶解了1mol/l之LiPF6 之EC與DMC在體積比1：2進行混合之溶液，而作成CR2032型鈕釦型電池。為進行比較，將正極活性物質由上述Li-Ni複合氧化物改為作為核之Li-Ni-Mn複合氧化物，並作成鈕釦型電池。First, 90% by weight of the Li-Ni composite oxide of the positive electrode active material, 3% by weight of the acetylene black of the conductive material, 3% by weight of the graphite KS-6, and the polyfluoride of the binder dissolved in the N-methylpyrrolidone After mixing 4% by weight of vinylidene, it was applied to an Al metal foil and dried at 150 °C. After the sheet was punched through to 16 mm Φ , it was pressed at 1 t/cm 2 to prepare an electrode having an electrode thickness of 50 μm for the positive electrode. The negative electrode was made into a metal lithium which was punctured to 16 mm Φ , and the electrolyte was a solution in which a mixture of EC and DMC in which 1 mol/l of LiPF 6 was dissolved at a volume ratio of 1:2 was used to prepare a CR2032 type button type battery. For comparison, the positive electrode active material was changed from the above Li-Ni composite oxide to a Li-Ni-Mn composite oxide as a core, and a button type battery was fabricated.
初期充放電特性，係於室溫下充電至4.3V以0.2mA/cm2 進行後，放電至3.0V並以0.2mA/cm2 進行，再測定此時之初期充電容量、初期放電容量及初期效率。The initial charge and discharge characteristics were charged to 4.3 V at room temperature at 0.2 mA/cm 2 , and then discharged to 3.0 V at 0.2 mA/cm 2 , and then the initial charge capacity, initial discharge capacity, and initial stage were measured. effectiveness.
高溫保存特性，係與初期充放電特性評價同樣地進行，作成CR2032型鈕釦型電池，進行初期之充放電後，在第二次之充電達4.3V並以10小時充電完畢之情形下通電流，在該狀態下以60℃之恆溫槽中保存1週後，在室溫下就3.0V為止、0.2mA/cm2 進行放電時之殘存放電容量。The high-temperature storage characteristics were carried out in the same manner as the evaluation of the initial charge and discharge characteristics, and a CR2032 type button type battery was fabricated. After the initial charge and discharge, the current was charged at the second charge of 4.3 V and charged in 10 hours. In this state, the battery was stored in a thermostat at 60 ° C for one week, and then stored at a residual voltage of 3.0 mA/cm 2 at room temperature at room temperature.
高溫保存後之電解液之Mn溶離量，係與初期充放電特性評價同樣地進行，作成CR2032型鈕釦型電池，進行初期之充放電後，在第二次之充電達4.3V並以10小時充電完畢之情形下通電流，在該狀態下以60℃之恆溫槽中保存1週後，在該狀態下將鈕釦型電池分解並取出電解液，使用誘導電漿發光分光法ICP-7500[島津製作所(股)製]進行分析並確認。The amount of Mn dissolved in the electrolytic solution after high-temperature storage was carried out in the same manner as in the evaluation of the initial charge and discharge characteristics, and a CR2032 type button type battery was fabricated. After the initial charge and discharge, the second charge was 4.3 V for 10 hours. When the charging is completed, the current is passed, and after storing in a constant temperature bath of 60 ° C for one week in this state, the button type battery is decomposed and the electrolytic solution is taken out in this state, and the induced plasma luminescence spectroscopy ICP-7500 is used. The Shimadzu Corporation (stock system) is analyzed and confirmed.
Li-Ni複合氧化物粒子之安全性之評價，係與初期充放電特性評價同樣地進行，作成CR2032型鈕釦型電池，進行初期之充放電後，在第二次之充電達4.5V並以10小時充電完畢之情形下通電流，在該狀態下將鈕釦型電池分解並取出正極，在Al耐壓電池中，於電解液共存下加以密閉，再由室溫至400℃以5℃/min之掃描速度就差示熱分析進行測定。The evaluation of the safety of the Li-Ni composite oxide particles was carried out in the same manner as the evaluation of the initial charge and discharge characteristics, and a CR2032 type button type battery was fabricated. After the initial charge and discharge, the second charge was 4.5 V and the charge was When the charging is completed for 10 hours, the current is passed. In this state, the button type battery is decomposed and the positive electrode is taken out, and in the Al pressure resistant battery, it is sealed in the presence of the electrolyte, and then from room temperature to 400 ° C at 5 ° C / The scanning speed of min is measured by differential thermal analysis.
將2mol/l之硫酸鎳及硫酸鈷及硫酸錳混合而成Ni：Co：Mn=33：33：33之水溶液，以及5.0mol/l之氨水溶液，同時地供應於反應槽內。2 mol/l of nickel sulfate, cobalt sulfate and manganese sulfate were mixed to form an aqueous solution of Ni:Co:Mn=33:33:33, and an aqueous solution of 5.0 mol/l of ammonia was simultaneously supplied to the reaction tank.
反應槽以羽毛型攪拌機經常地加以攪拌，同時自動供給2mol/l之氫氧化鈉水溶液使其pH值=11.5±0.5。所生成之Ni-Co-Mn氫氧化物經溢流，以連結於溢流管之濃縮槽進行濃縮，再對反應槽進行循環，以40小時反應使反應槽及沈降槽中之Ni-Co-Mn氫氧化物濃度達到4mol/l為止。The reaction tank was frequently stirred with a feather mixer while automatically supplying a 2 mol/l aqueous sodium hydroxide solution to have a pH of 11.5 ± 0.5. The generated Ni-Co-Mn hydroxide is overflowed, concentrated in a concentration tank connected to the overflow pipe, and then the reaction tank is circulated, and the reaction tank and the Ni-Co- in the sedimentation tank are reacted for 40 hours. The Mn hydroxide concentration reached 4 mol/l.
反應後，將取出之懸浮液，使用壓濾機以相對於Ni-Co-Mn氫氧化物之重量為10倍之水進行水洗後，進行乾燥，而製得Ni：Co：Mn=33：33：33之平均二次粒子徑為9.5μm之Ni-Co-Mn氫氧化物粒子。Ni-Co-Mn氫氧化物粒子及碳酸鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合。After the reaction, the taken-out suspension was washed with water using a filter press at 10 times the weight of the Ni-Co-Mn hydroxide, and then dried to obtain Ni:Co:Mn=33:33. : Ni-Co-Mn hydroxide particles having an average secondary particle diameter of 9.5 μm of 33. Ni-Co-Mn hydroxide particles and lithium carbonate were mixed with a molar ratio of Li/(Ni + Co + Mn) = 1.05.
將此混合物在氧氣環境下，以925℃燒成4小時，再分解磨碎。所得到之燒成物之化學組成，依ICP分析之結果，係Li1.05 Ni0.33 Co0.33 Mn0.33 O2 。This mixture was fired at 925 ° C for 4 hours in an oxygen atmosphere, and then decomposed and ground. The chemical composition of the obtained fired product was Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 as a result of ICP analysis.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係291℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係156mAh/g，而在60℃下保存1週後之殘存放電容量係147mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係27ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a state of charge of 4.5 V, and the maximum peak temperature of the heat generation was 291 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 156 mAh/g, and the storage capacity after storage for one week at 60 ° C was 147 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 27 ppm.
除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與比較例1同樣地進行操作，而製得組成為Li1.05 Ni0.33 Co0.33 Mn0 .33 O1.95 F0.05 之Li-Ni-Mn複合氧化物。The operation was carried out in the same manner as in Comparative Example 1, except that the Ni-Co-Mn hydroxide particles, lithium carbonate and lithium fluoride were mixed with a molar ratio of Li/(Ni + Co + Mn) = 1.05. A Li-Ni-Mn composite oxide having a composition of Li 1.05 Ni 0.33 Co 0.33 Mn 0 . 33 O 1.95 F 0.05 was obtained.
該Li-Ni複合氧化物粒子粉末之放電容量係154mAh/g，而在60℃下保存1週後之殘存放電容量係143mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係26ppm。The discharge capacity of the Li-Ni composite oxide particles was 154 mAh/g, and the storage capacity after storage for one week at 60 ° C was 143 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 26 ppm.
除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及磷酸鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與比較例1同樣地進行操作，而製得組成為Li1.05 Ni0.33 Co0.33 Mn0.33 O1.95 (PO4 )0.05 之Li-Ni-Mn複合氧化物。The same operation as in Comparative Example 1 was carried out except that the Ni-Co-Mn hydroxide particles, lithium carbonate and lithium phosphate were mixed with a molar ratio of Li/(Ni + Co + Mn) = 1.05. A Li-Ni-Mn composite oxide having a composition of Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 1.95 (PO 4 ) 0.05 was obtained.
該Li-Ni複合氧化物粒子粉末之放電容量係153mAh/g，而在60℃下保存1週後之殘存放電容量係140mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係24ppm。The discharge capacity of the Li-Ni composite oxide particles was 153 mAh/g, and the storage capacity after storage for one week at 60 ° C was 140 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 24 ppm.
除了硫酸鎳及硫酸鈷及硫酸錳係混合成Ni：Co：Mn=50：20：30之水溶液，並將混合物在空氣環境下以950℃燒成4小時以外，其餘均與比較例1同樣地進行操作，而製得組成為Li1.05 Ni0.50 Co0.20 Mn0.30 O2 之Li-Ni-Mn複合氧化物。The same as in Comparative Example 1, except that nickel sulfate, cobalt sulfate, and manganese sulfate were mixed into an aqueous solution of Ni:Co:Mn=50:20:30, and the mixture was fired at 950 ° C for 4 hours in an air atmosphere. The operation was carried out to prepare a Li-Ni-Mn composite oxide having a composition of Li 1.05 Ni 0.50 Co 0.20 Mn 0.30 O 2 .
該Li-Ni複合氧化物粒子粉末之放電容量係167mAh/g，而在60℃下保存1週後之殘存放電容量係155mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係24ppm。The discharge capacity of the Li-Ni composite oxide particles was 167 mAh/g, and the storage capacity after storage for one week at 60 ° C was 155 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 24 ppm.
除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與比較例7同樣地進行操作，而製得組成為Li1.05 Ni0.50 Co0.20 Mn0.30 O1.95 F0.05 之Li-Ni-Mn複合氧化物。The same operation as in Comparative Example 7 except that the Ni-Co-Mn hydroxide particles, lithium carbonate, and lithium fluoride were mixed with a molar ratio of Li/(Ni + Co + Mn) = 1.05. A Li-Ni-Mn composite oxide having a composition of Li 1.05 Ni 0.50 Co 0.20 Mn 0.30 O 1.95 F 0.05 was obtained.
該Li-Ni複合氧化物粒子粉末之放電容量係165mAh/g，而在60℃下保存1週後之殘存放電容量係155mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係23ppm。The discharge capacity of the Li-Ni composite oxide particles was 165 mAh/g, and the residual storage capacity after storage for one week at 60 ° C was 155 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 23 ppm.
除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及磷酸鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與比較例7同樣地進行操作，而製得組成為Li1.05 Ni0.50 Co0.20 Mn0.30 O1.95 (PO4 )0.05 之Li-Ni-Mn複合氧化物。The same operation as in Comparative Example 7 was carried out except that the Ni-Co-Mn hydroxide particles, lithium carbonate and lithium phosphate were mixed with a molar ratio of Li/(Ni + Co + Mn) = 1.05. A Li-Ni-Mn composite oxide having a composition of Li 1.05 Ni 0.50 Co 0.20 Mn 0.30 O 1.95 (PO 4 ) 0.05 was obtained.
該Li-Ni複合氧化物粒子粉末之放電容量係163mAh/g，而在60℃下保存1週後之殘存放電容量係152mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係23ppm。The discharge capacity of the Li-Ni composite oxide particles was 163 mAh/g, and the storage capacity after storage for one week at 60 ° C was 152 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 23 ppm.
除了硫酸鎳及硫酸鈷及硫酸錳係混合成Ni：Co：Mn=60：20：20之水溶液，並將混合物在空氣環境下以830℃燒成4小時以外，其餘均與比較例1同樣地進行操作，而製得組成為Li1.05 Ni0.60 Co0.20 Mn0.20 O2 之Li-Ni-Mn複合氧化物。The same as in Comparative Example 1, except that nickel sulfate, cobalt sulfate, and manganese sulfate were mixed into an aqueous solution of Ni:Co:Mn=60:20:20, and the mixture was fired at 830 ° C for 4 hours in an air atmosphere. The operation was carried out to prepare a Li-Ni-Mn composite oxide having a composition of Li 1.05 Ni 0.60 Co 0.20 Mn 0.20 O 2 .
該Li-Ni複合氧化物粒子粉末之放電容量係174mAh/g，而在60℃下保存1週後之殘存放電容量係163mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係22ppm。The discharge capacity of the Li-Ni composite oxide particles was 174 mAh/g, and the storage capacity after storage for one week at 60 ° C was 163 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 22 ppm.
除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與比較例10同樣地進行操作，而製得組成為Li1.05 Ni0.60 Co0.20 Mn0.20 O1.95 F0.05 之Li-Ni-Mn複合氧化物。The same operation as in Comparative Example 10 except that the Ni-Co-Mn hydroxide particles, lithium carbonate, and lithium fluoride were mixed with a molar ratio of Li/(Ni + Co + Mn) = 1.05. A Li-Ni-Mn composite oxide having a composition of Li 1.05 Ni 0.60 Co 0.20 Mn 0.20 O 1.95 F 0.05 was obtained.
該Li-Ni複合氧化物粒子粉末之放電容量係172mAh/g，而在60℃下保存1週後之殘存放電容量係160mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係20ppm。The discharge capacity of the Li-Ni composite oxide particles was 172 mAh/g, and the storage capacity after storage for one week at 60 ° C was 160 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 20 ppm.
除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及磷酸鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與比較例10同樣地進行操作，而製得組成為Li1.05 Ni0.60 Co0.20 Mn0.20 O1.95 (PO4 )0.05 之Li-Ni-Mn複合氧化物。The same operation as in Comparative Example 10 was carried out, except that the Ni-Co-Mn hydroxide particles, lithium carbonate and lithium phosphate were mixed with a molar ratio of Li/(Ni + Co + Mn) = 1.05. A Li-Ni-Mn composite oxide having a composition of Li 1.05 Ni 0.60 Co 0.20 Mn 0.20 O 1.95 (PO 4 ) 0.05 was obtained.
該Li-Ni複合氧化物粒子粉末之放電容量係171mAh/g，而在60℃下保存1週後之殘存放電容量係158mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係21ppm。The discharge capacity of the Li-Ni composite oxide particles was 171 mAh/g, and the storage capacity after storage for one week at 60 ° C was 158 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 21 ppm.
除了硫酸鎳及硫酸鈷及硫酸錳及硫酸鋁係混合成Ni：Co：Mn：Al=33：24：33：9之水溶液，並將Ni-Co-Mn-Al氫氧化物粒子與碳酸鋰以莫爾比為Li/(Ni+Co+Mn+Al)=1.01而進行混合以外，其餘均與比較例1同樣地進行操作，而製得組成為Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.09 O2 之Li-Ni-Mn複合氧化物。In addition to nickel sulfate and cobalt sulfate, and manganese sulfate and aluminum sulfate, an aqueous solution of Ni:Co:Mn:Al=33:24:33:9 is mixed, and Ni-Co-Mn-Al hydroxide particles and lithium carbonate are used. The molar ratio of Li/(Ni+Co+Mn+Al)=1.01 was mixed, and the same operation as in Comparative Example 1 was carried out to obtain a composition of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.09 O 2 . Li-Ni-Mn composite oxide.
該Li-Ni複合氧化物粒子粉末之放電容量係152mAh/g，而在60℃下保存1週後之殘存放電容量係142mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係26ppm。The discharge capacity of the Li-Ni composite oxide particles was 152 mAh/g, and the storage capacity after storage for one week at 60 ° C was 142 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 26 ppm.
除了Ni-Co-Mn-Al氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn+Al)=1.01而進行混合以外，其餘均與比較例13同樣地進行操作，而製得組成為Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.09 O1.95 F0.05 之Li-Ni-Mn複合氧化物。Except that Ni-Co-Mn-Al hydroxide particles, lithium carbonate and lithium fluoride were mixed with a molar ratio of Li/(Ni + Co + Mn + Al) = 1.01, the others were compared with Comparative Example 13 The operation was carried out in the same manner, and a Li-Ni-Mn composite oxide having a composition of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.09 O 1.95 F 0.05 was obtained.
該Li-Ni複合氧化物粒子粉末之放電容量係150mAh/g，而在60℃下保存1週後之殘存放電容量係140mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係25ppm。The discharge capacity of the Li-Ni composite oxide particles was 150 mAh/g, and the storage capacity after storage for one week at 60 ° C was 140 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 25 ppm.
除了Ni-Co-Mn-Al氫氧化物粒子及碳酸鋰及磷酸鋰，係以莫爾比為Li/(Ni+Co+Mn+Al)=1.01而進行混合以外，其餘均與比較例13同樣地進行操作，而製得組成為Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.09 O1.95 (PO4 )0.05 之Li-Ni-Mn複合氧化物。The same conditions as in Comparative Example 13 except that the Ni-Co-Mn-Al hydroxide particles, lithium carbonate and lithium phosphate were mixed with a molar ratio of Li/(Ni + Co + Mn + Al) = 1.01. The operation was carried out to obtain a Li-Ni-Mn composite oxide having a composition of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.09 O 1.95 (PO 4 ) 0.05 .
該Li-Ni複合氧化物粒子粉末之放電容量係149mAh/g，而在60℃下保存1週後之殘存放電容量係138mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係24ppm。The discharge capacity of the Li-Ni composite oxide particles was 149 mAh/g, and the storage capacity after storage for one week at 60 ° C was 138 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 24 ppm.
除了硫酸鎳及硫酸鈷及硫酸錳及硫酸鎂係混合成Ni：Co：Mn：Mg=33：24：33：9之水溶液，並將Ni-Co-Mn-Mg氫氧化物粒子與碳酸鋰以莫爾比為Li/(Ni+Co+Mn+Mg)=1.01而進行混合以外，其餘均與比較例1同樣地進行操作，而製得組成為Li1.01 Ni0.33 Co0.24 Mn0.33 Mg0.09 O2 之Li-Ni-Mn複合氧化物。In addition to nickel sulfate and cobalt sulfate, and manganese sulfate and magnesium sulfate, an aqueous solution of Ni:Co:Mn:Mg=33:24:33:9 is mixed, and Ni-Co-Mn-Mg hydroxide particles and lithium carbonate are used. The mixture was operated in the same manner as in Comparative Example 1 except that the molar ratio was Li/(Ni + Co + Mn + Mg) = 1.01, and the composition was Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Mg 0.09 O 2 . Li-Ni-Mn composite oxide.
該Li-Ni複合氧化物粒子粉末之放電容量係148mAh/g，而在60℃下保存1週後之殘存放電容量係135mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係25ppm。The discharge capacity of the Li-Ni composite oxide particles was 148 mAh/g, and the storage capacity after storage for one week at 60 ° C was 135 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 25 ppm.
除了Ni-Co-Mn-Mg氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn+Mg)=1.01而進行混合以外，其餘均與比較例16同樣地進行操作，而製得組成為Li1.01 Ni0.33 Co0.24 Mn0.33 Mg0.09 O1.95 F0.05 之Li-Ni-Mn複合氧化物。Except that Ni-Co-Mn-Mg hydroxide particles, lithium carbonate and lithium fluoride were mixed with a molar ratio of Li/(Ni+Co+Mn+Mg)=1.01, the same as Comparative Example 16 The Li-Ni-Mn composite oxide having a composition of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Mg 0.09 O 1.95 F 0.05 was obtained in the same manner.
該Li-Ni複合氧化物粒子粉末之放電容量係147mAh/g，而在60℃下保存1週後之殘存放電容量係136mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係24ppm。The discharge capacity of the Li-Ni composite oxide particles was 147 mAh/g, and the storage capacity after storage for one week at 60 ° C was 136 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 24 ppm.
除了Ni-Co-Mn-Mg氫氧化物粒子及碳酸鋰及磷酸鋰，係以莫爾比為Li/(Ni+Co+Mn+Mg)=1.01而進行混合以外，其餘均與比較例16同樣地進行操作，而製得組成為Li1.01 Ni0.33 Co0.24 Mn0.33 Mg0.09 O1.95 (PO4 )0.05 之Li-Ni-Mn複合氧化物。The same conditions as in Comparative Example 16 except that the Ni-Co-Mn-Mg hydroxide particles, lithium carbonate and lithium phosphate were mixed with a molar ratio of Li/(Ni + Co + Mn + Mg) = 1.01. The operation was carried out to obtain a Li-Ni-Mn composite oxide having a composition of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Mg 0.09 O 1.95 (PO 4 ) 0.05 .
該Li-Ni複合氧化物粒子粉末之放電容量係146mAh/g，而在60℃下保存1週後之殘存放電容量係135mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係23ppm。The discharge capacity of the Li-Ni composite oxide particles was 146 mAh/g, and the storage capacity after storage for one week at 60 ° C was 135 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 23 ppm.
除了硫酸鎳及硫酸鈷及硫酸錳及硫酸鋁及硫酸鎂係混合成Ni：Co：Mn：Al：Mg=33：24：33：5：4之水溶液，並將Ni-Co-Mn-Al-Mg氫氧化物粒子與碳酸鋰以莫爾比為Li/(Ni+Co+Mn+Al+Mg)=1.01而進行混合以外，其餘均與比較例1同樣地進行操作，而製得組成為Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.05 Mg0.04 O2 之Li-Ni-Mn複合氧化物。In addition to nickel sulfate and cobalt sulfate and manganese sulfate, and aluminum sulfate and magnesium sulfate are mixed into an aqueous solution of Ni:Co:Mn:Al:Mg=33:24:33:5:4, and Ni-Co-Mn-Al- The Mg hydroxide particles and lithium carbonate were mixed in the same manner as in Comparative Example 1 except that the molar ratio was Li/(Ni + Co + Mn + Al + Mg) = 1.01, and the composition was Li. 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.05 Mg 0.04 O 2 Li-Ni-Mn composite oxide.
該Li-Ni複合氧化物粒子粉末之放電容量係147mAh/g，而在60℃下保存1週後之殘存放電容量係135mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係24ppm。The discharge capacity of the Li-Ni composite oxide particles was 147 mAh/g, and the storage capacity after storage for one week at 60 ° C was 135 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 24 ppm.
除了Ni-Co-Mn-Al-Mg氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn+Al+Mg)=1.01而進行混合以外，其餘均與比較例19同樣地進行操作，而製得組成為Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.05 Mg0.04 O1.95 F0.05 之Li-Ni-Mn複合氧化物。Except Ni-Co-Mn-Al-Mg hydroxide particles, lithium carbonate and lithium fluoride, the molar ratio is Li/(Ni+Co+Mn+Al+Mg)=1.01, and the others are mixed. The operation was carried out in the same manner as in Comparative Example 19 to obtain a Li-Ni-Mn composite oxide having a composition of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.05 Mg 0.04 O 1.95 F 0.05 .
該Li-Ni複合氧化物粒子粉末之放電容量係145mAh/g，而在60℃下保存1週後之殘存放電容量係133mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係22ppm。The discharge capacity of the Li-Ni composite oxide particles was 145 mAh/g, and the storage capacity after storage for one week at 60 ° C was 133 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 22 ppm.
除了Ni-Co-Mn-Al-Mg氫氧化物粒子及碳酸鋰及磷酸鋰，係以莫爾比為Li/(Ni+Co+Mn+Al+Mg)=1.01而進行混合以外，其餘均與比較例19同樣地進行操作，而製得組成為Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.05 Mg0.04 O1.95 (PO4 )0.05 之Li-Ni-Mn複合氧化物。Except for Ni-Co-Mn-Al-Mg hydroxide particles, lithium carbonate and lithium phosphate, the molar ratio is Li/(Ni+Co+Mn+Al+Mg)=1.01, and the others are mixed. Comparative Example 19 was operated in the same manner to obtain a Li-Ni-Mn composite oxide having a composition of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.05 Mg 0.04 O 1.95 (PO 4 ) 0.05 .
該Li-Ni複合氧化物粒子粉末之放電容量係143mAh/g，而在60℃下保存1週後之殘存放電容量係132mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係23ppm。The discharge capacity of the Li-Ni composite oxide particles was 143 mAh/g, and the storage capacity after storage for one week at 60 ° C was 132 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 23 ppm.
將2mol/l之硫酸鎳及硫酸鈷及硫酸錳混合而成Ni：Co：Mn=33：33：33之水溶液，以及5.0mol/l之氨水溶液，同時地供應於反應槽內。2 mol/l of nickel sulfate, cobalt sulfate and manganese sulfate were mixed to form an aqueous solution of Ni:Co:Mn=33:33:33, and an aqueous solution of 5.0 mol/l of ammonia was simultaneously supplied to the reaction tank.
反應槽以羽毛型攪拌機經常地加以攪拌，同時自動供給2mol/l之氫氧化鈉水溶液使其pH值=11.5±0.5。所生成之Ni-Co-Mn氫氧化物經溢流，以連結於溢流管之濃縮槽進行濃縮，再對反應槽進行循環，以40小時反應使反應槽及沈降槽中之Ni-Co-Mn氫氧化物濃度達到4mol/l為止。The reaction tank was frequently stirred with a feather mixer while automatically supplying a 2 mol/l aqueous sodium hydroxide solution to have a pH of 11.5 ± 0.5. The generated Ni-Co-Mn hydroxide is overflowed, concentrated in a concentration tank connected to the overflow pipe, and then the reaction tank is circulated, and the reaction tank and the Ni-Co- in the sedimentation tank are reacted for 40 hours. The Mn hydroxide concentration reached 4 mol/l.
反應後，將取出之懸浮液，使用壓濾機以相對於Ni-Co-Mn氫氧化物之重量為10倍之水進行水洗後，進行乾燥，而製得Ni：Co：Mn=33：33：33之平均二次粒子徑為9.5μm之Ni-Co-Mn氫氧化物粒子。Ni-Co-Mn氫氧化物粒子及碳酸鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合。After the reaction, the taken-out suspension was washed with water using a filter press at 10 times the weight of the Ni-Co-Mn hydroxide, and then dried to obtain Ni:Co:Mn=33:33. : Ni-Co-Mn hydroxide particles having an average secondary particle diameter of 9.5 μm of 33. Ni-Co-Mn hydroxide particles and lithium carbonate were mixed with a molar ratio of Li/(Ni + Co + Mn) = 1.05.
將此混合物在氧氣環境下，以925℃燒成4小時，再分解磨碎。所得到之燒成物之化學組成，依ICP分析之結果，係Li1.05 Ni0.33 Co0.33 Mn0.33 O2 ，其平均粒子徑係9.6μm。將該Li-Ni-Mn複合氧化物當成作為核之二次粒子粉末而使用。This mixture was fired at 925 ° C for 4 hours in an oxygen atmosphere, and then decomposed and ground. The chemical composition of the obtained fired product was Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 as a result of ICP analysis, and the average particle diameter was 9.6 μm. This Li-Ni-Mn composite oxide was used as a secondary particle powder as a core.
將該二次粒子粉末300g懸浮於水中，再將2mol/l之硫酸鎳及硫酸鈷已混合成Ni：Co=84：16之混合水溶液，以及5.0mol/l氨水溶液，同時供應於反應槽內。300 g of the secondary particle powder was suspended in water, and 2 mol/l of nickel sulfate and cobalt sulfate were mixed to form a mixed aqueous solution of Ni:Co=84:16, and a 5.0 mol/l aqueous ammonia solution, and supplied to the reaction tank. .
反應槽以羽毛型攪拌機經常地加以攪拌，同時自動供給2mol/l之氫氧化鈉水溶液使其pH值=11.5±0.5。所生成之Ni-Co氫氧化物，相對於Li1.05 Ni0.33 Co0.33 Mn0.33 O2 ，係成為重量百分率為10wt%者。The reaction tank was frequently stirred with a feather mixer while automatically supplying a 2 mol/l aqueous sodium hydroxide solution to have a pH of 11.5 ± 0.5. The Ni-Co hydroxide produced was found to have a weight percentage of 10% by weight based on Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 .
將該懸浮液，使用壓濾機以相對於Li-Ni-Mn氫氧化物之重量為10倍之水進行水洗後，進行乾燥，而製得以Ni-Co氫氧化物加以被覆之Li1.05 Ni0.33 Co0.33 Mn0.33 O2 中間體。The suspension was washed with water using a filter press at 10 times the weight of the Li-Ni-Mn hydroxide, and then dried to obtain Li 1.05 Ni 0.33 coated with Ni-Co hydroxide. Co 0.33 Mn 0.33 O 2 intermediate.
將經Ni-Co氫氧化物被覆之Li1.05 Ni0.33 Co0.33 Mn0.33 O2 中間體，以及事先以磨碎機進行過粒度調整之氫氧化鋰及氫氧化鋁，以莫爾比為Li/(表面之Ni+Co+Al)=0.98而進行混合。Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 intermediate coated with Ni-Co hydroxide, and lithium hydroxide and aluminum hydroxide previously subjected to particle size adjustment by an attritor, with a molar ratio of Li/( The surface was mixed with Ni+Co+Al)=0.98.
將此混合物在氧氣環境下，以750℃燒成10小時，而製得在作為核之Li1.05 Ni0.33 Co0.33 Mn0.33 O2 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.05 O2 以10重量%加以被覆之平均粒子徑為10.6μm之Li-Ni複合氧化物粒子粉末。The mixture was fired at 750 ° C for 10 hours in an oxygen atmosphere to obtain Li 0.98 Ni 0.80 Co 0.15 Al on the surface of particles of secondary particles of Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 as a core. A Li-Ni composite oxide particle powder having an average particle diameter of 10.6 μm coated with 0.05 O 2 at 10% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係290℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係160mAh/g，而在60℃下保存1週後之殘存放電容量係155mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係21ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis in a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 290 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 160 mAh/g, and the storage capacity after storage for one week at 60 ° C was 155 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 21 ppm.
除了用以被覆之Ni-Co氫氧化物相對於Li1.05 Ni0.33 Co0.33 Mn0.33 O2 ，以重量百分率計，係成為30wt%以外，其餘均與實施例1相同地進行操作，而製得在作為核之Li1.05 Ni0.33 Co0.33 Mn0.33 O2 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.05 O2 以30重量%加以被覆之平均粒子徑為11.0μm之Li-Ni複合氧化物粒子粉末。The same procedure as in Example 1 was carried out except that the Ni-Co hydroxide to be coated was used in the same manner as in Example 1 except that Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 was used in an amount of 30% by weight. On the surface of the particles of the secondary particles of Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 as a core, Li-Ni was coated with Li 0.98 Ni 0.80 Co 0.15 Al 0.05 O 2 at 30% by weight and having an average particle diameter of 11.0 μm. Composite oxide particle powder.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係281℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係167mAh/g，而在60℃下保存1週後之殘存放電容量係161mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係19ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 281 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 167 mAh/g, and the residual storage capacity after storage for one week at 60 ° C was 161 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 19 ppm.
除了用以被覆之Ni-Co氫氧化物相對於Li1.05 Ni0.33 Co0.33 Mn0.33 O2 ，以重量百分率計，係成為50wt%以外，其餘均與實施例1相同地進行操作，而製得在作為核之Li1.05 Ni0.33 Co0.33 Mn0.33 O2 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.05 O2 以50重量%加以被覆之平均粒子徑為13.0μm之Li-Ni複合氧化物粒子粉末。The same procedure as in Example 1 was carried out except that the Ni-Co hydroxide to be coated was used in the same manner as in Example 1 except that Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 was used in an amount of 50% by weight. On the surface of the particles of the secondary particles of Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 as a core, there is Li 0.98 Ni 0.80 Co 0.15 Al 0.05 O 2 coated with 50% by weight of Li-Ni having an average particle diameter of 13.0 μm. Composite oxide particle powder.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係259℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係176mAh/g，而在60℃下保存1週後之殘存放電容量係170mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係18ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a state of charge of 4.5 V, and the maximum peak temperature of the heat generation was 259 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 176 mAh/g, and the residual storage capacity after storage for one week at 60 ° C was 170 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 18 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與實施例3同樣地進行操作，而製得在作為核之Li1.05 Ni0.33 Co0.33 Mn0.33 O1.95 F0.05 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.05 O2 以50重量%加以被覆之平均粒子徑為13.5μm之Li-Ni複合氧化物粒子粉末。In the production of the Li-Ni-Mn composite oxide, in addition to the Ni-Co-Mn hydroxide particles, lithium carbonate and lithium fluoride, the molar ratio is Li/(Ni+Co+Mn)=1.05. Except for the mixing, the same operation as in Example 3 was carried out to obtain Li 0.98 Ni 0.80 Co 0.15 Al on the surface of the particles of the secondary particles of Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 1.95 F 0.05 as the core. A Li-Ni composite oxide particle powder having an average particle diameter of 13.5 μm coated with 0.05 O 2 at 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係292℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係158mAh/g，而在60℃下保存1週後之殘存放電容量係150mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係18ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a charging state of 4.5 V, and the maximum peak temperature of the heat generation was 292 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 158 mAh/g, and the storage capacity after storage for one week at 60 ° C was 150 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 18 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與實施例3同樣地進行操作，而製得在作為核之Li1.05 Ni0.33 Co0.33 Mn0.33 O1.95 (PO4 )0.05 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.05 O2 以50重量%加以被覆之平均粒子徑為13.2μm之Li-Ni複合氧化物粒子粉末。In the production of the Li-Ni-Mn composite oxide, in addition to the Ni-Co-Mn hydroxide particles, lithium carbonate and lithium fluoride, the molar ratio is Li/(Ni+Co+Mn)=1.05. Except for the mixing, the same operation as in Example 3 was carried out, and on the surface of the particles of the secondary particles of Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 1.95 (PO 4 ) 0.05 as a core, Li 0.98 Ni 0.80 was obtained. Co 0.15 Al 0.05 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.2 μm coated at 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係295℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係157mAh/g，而在60℃下保存1週後之殘存放電容量係151mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係15ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis in a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 295 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 157 mAh/g, and the storage capacity after storage for one week at 60 ° C was 151 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 15 ppm.
與實施例1同樣地進行操作，而製得核之組成為Li1.05 Ni0.33 Co0.33 Mn0.33 O2 之平均粒子徑為9.6μm之Li-Ni-Mn複合氧化物。In the same manner as in Example 1, a Li-Ni-Mn composite oxide having a core composition of Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 and having an average particle diameter of 9.6 μm was obtained.
將2mol/l之硫酸鎳及硫酸鈷混合而成Ni：Co=84：16之水溶液，以及5.0mol/l之氨水溶液，同時地供應於反應槽內。2 mol/l of nickel sulfate and cobalt sulfate were mixed to form an aqueous solution of Ni:Co=84:16, and an aqueous solution of 5.0 mol/l of ammonia was simultaneously supplied to the reaction tank.
反應槽以羽毛型攪拌機經常地加以攪拌，同時自動供給2mol/l之氫氧化鈉水溶液使其pH值=11.5±0.5。所生成之Ni-Co氫氧化物經溢流，以連結於溢流管之濃縮槽進行濃縮，再對反應槽進行循環，以40小時反應使反應槽及沈降槽中之Ni-Co氫氧化物濃度達到4mol/l為止。The reaction tank was frequently stirred with a feather mixer while automatically supplying a 2 mol/l aqueous sodium hydroxide solution to have a pH of 11.5 ± 0.5. The generated Ni-Co hydroxide is overflowed, concentrated in a concentration tank connected to the overflow pipe, and then the reaction tank is circulated to react the Ni-Co hydroxide in the reaction tank and the sedimentation tank for 40 hours. The concentration reached 4 mol/l.
將該懸浮液使用壓濾機以相對於Ni-Co氫氧化物之重量為10倍之水進行水洗後，進行乾燥，並以氣流粉碎機進行粉碎，而製得平均粒子徑為1.8μm之Ni：Co=84：16之Ni-Co氫氧化物粒子。The suspension was washed with water 10 times the weight of the Ni-Co hydroxide by a filter press, dried, and pulverized by a jet mill to obtain Ni having an average particle diameter of 1.8 μm. : Co = 84: 16 Ni-Co hydroxide particles.
在此，對於作為核之Li1.05 Ni0.33 Co0.33 Mn0.33 O2 ，進一步混合平均粒子徑為1.8μm之Ni0.84 Co0.16 (OH)2 使其重量百分率成為50%，再使用機械性磨碎機進行30分鐘之機械性處理，而製得以Ni-Co氫氧化物加以被覆之Li1.05 Ni0.33 Co0.33 Mn0.33 O2 中間體。Here, for Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 as a core, Ni 0.84 Co 0.16 (OH) 2 having an average particle diameter of 1.8 μm was further mixed to have a weight percentage of 50%, and a mechanical grinder was used. A mechanical treatment of 30 minutes was carried out to prepare a Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 intermediate coated with Ni-Co hydroxide.
將經Ni-Co氫氧化物被覆之Li1.05 Ni0.33 Co0.33 Mn0.33 O2 中間體，以及事先以磨碎機進行過粒度調整之氫氧化鋰及氫氧化鋁，以莫爾比為Li/(表面之Ni+Co+Al)=0.98而進行混合。Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 intermediate coated with Ni-Co hydroxide, and lithium hydroxide and aluminum hydroxide previously subjected to particle size adjustment by an attritor, with a molar ratio of Li/( The surface was mixed with Ni+Co+Al)=0.98.
將此混合物在氧氣環境下，以750℃燒成10小時，而製得在作為核之Li1.05 Ni0.33 Co0.33 Mn0.33 O2 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.05 O2 以50重量%加以被覆之平均粒子徑為13.1μm之Li-Ni複合氧化物粒子粉末。The mixture was fired at 750 ° C for 10 hours in an oxygen atmosphere to obtain Li 0.98 Ni 0.80 Co 0.15 Al on the surface of particles of secondary particles of Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 as a core. A Li-Ni composite oxide particle powder having an average particle diameter of 13.1 μm coated with 0.05 O 2 at 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係298℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係159mAh/g，而在60℃下保存1週後之殘存放電容量係154mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係17ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a state of charge of 4.5 V, and the maximum peak temperature of the heat generation was 298 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 159 mAh/g, and the storage capacity after storage for one week at 60 ° C was 154 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 17 ppm.
除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與實施例6同樣地進行操作，而製得在作為核之Li1.05 Ni0.33 Co0.33 Mn0.33 O1.95 F0.05 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.05 O2 以50重量%加以被覆之平均粒子徑為13.0μm之Li-Ni複合氧化物粒子粉末。The operation was carried out in the same manner as in Example 6 except that the Ni-Co-Mn hydroxide particles, lithium carbonate and lithium fluoride were mixed with a molar ratio of Li/(Ni + Co + Mn) = 1.05. On the surface of the particles of the secondary particles of Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 1.95 F 0.05 as the core, the average particle diameter of Li 0.98 Ni 0.80 Co 0.15 Al 0.05 O 2 coated at 50% by weight was obtained. It is a Li-Ni composite oxide particle powder of 13.0 μm.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係290℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係158mAh/g，而在60℃下保存1週後之殘存放電容量係151mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係14ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis in a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 290 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 158 mAh/g, and the storage capacity after storage for one week at 60 ° C was 151 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 14 ppm.
除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與實施例6同樣地進行操作，而製得在作為核之Li1.05 Ni0.33 Co0.33 Mn0.33 O1.95 (PO4 )0.05 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.05 O2 以50重量%加以被覆之平均粒子徑為13.3μm之Li-Ni複合氧化物粒子粉末。The operation was carried out in the same manner as in Example 6 except that the Ni-Co-Mn hydroxide particles, lithium carbonate and lithium fluoride were mixed with a molar ratio of Li/(Ni + Co + Mn) = 1.05. On the surface of the particles of the secondary particles of Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 1.95 (PO 4 ) 0.05 as a core, Li 0.98 Ni 0.80 Co 0.15 Al 0.05 O 2 was coated at 50% by weight. A Li-Ni composite oxide particle powder having an average particle diameter of 13.3 μm.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係295℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係157mAh/g，而在60℃下保存1週後之殘存放電容量係152mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係16ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis in a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 295 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 157 mAh/g, and the storage capacity after storage for one week at 60 ° C was 152 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 16 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了將2mol/l之硫酸鎳及硫酸鈷及硫酸錳混合而成Ni：Co：Mn=50：20：30之水溶液，並將此混合物在氧氣環境下，以950℃燒成4小時；以及將經Ni-Co氫氧化物被覆之Li1.05 Ni0.50 Co0.20 Mn0.30 O2 中間體，及事先以磨碎機進行過粒度調整之氫氧化鋰及氫氧化鋁，以莫爾比為Li/(表面之Ni+Co+Al+Mg)=0.98而進行混合以外，其餘均與實施例3同樣地進行操作，而製得在作為核之Li1.05 Ni0.50 Co0.20 Mn0.30 O2 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.04 Mg0.01 O2 以50重量%加以被覆之平均粒子徑為13.4μm之Li-Ni複合氧化物粒子粉末。In the manufacture of the Li-Ni-Mn composite oxide, in addition to 2 mol/l of nickel sulfate and cobalt sulfate and manganese sulfate, an aqueous solution of Ni:Co:Mn=50:20:30 is prepared, and the mixture is in oxygen. In the environment, firing at 950 ° C for 4 hours; and Li 1.05 Ni 0.50 Co 0.20 Mn 0.30 O 2 intermediate coated with Ni-Co hydroxide, and lithium hydroxide previously subjected to particle size adjustment by a grinder The aluminum hydroxide was mixed in the same manner as in Example 3 except that the molar ratio was Li/(Ni+Co+Al+Mg on the surface)=0.98, and Li 1.05 Ni as a core was obtained. On the surface of the particles of the secondary particles of 0.50 Co 0.20 Mn 0.30 O 2 , Li-Ni composite oxide particles having an average particle diameter of 13.4 μm coated with Li 0.98 Ni 0.80 Co 0.15 Al 0.04 Mg 0.01 O 2 at 50% by weight powder.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係285℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係171mAh/g，而在60℃下保存1週後之殘存放電容量係166mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係17ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 285 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 171 mAh/g, and the residual storage capacity after storage for one week at 60 ° C was 166 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 17 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與實施例9同樣地進行操作，而製得在作為核之Li1.05 Ni0.50 Co0.20 Mn0.30 O1.95 F0.05 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.04 Mg0.01 O2 以50重量%加以被覆之平均粒子徑為13.3μm之Li-Ni複合氧化物粒子粉末。In the production of the Li-Ni-Mn composite oxide, in addition to the Ni-Co-Mn hydroxide particles, lithium carbonate and lithium fluoride, the molar ratio is Li/(Ni+Co+Mn)=1.05. Except for the mixing, the same operation as in Example 9 was carried out to obtain Li 0.98 Ni 0.80 Co 0.15 Al on the surface of the particles of the secondary particles of Li 1.05 Ni 0.50 Co 0.20 Mn 0.30 O 1.95 F 0.05 as the core. 0.04 Mg 0.01 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.3 μm coated at 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係287℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係169mAh/g，而在60℃下保存1週後之殘存放電容量係163mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係15ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 287 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 169 mAh/g, and the storage capacity after storage for one week at 60 ° C was 163 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 15 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及磷酸鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與實施例9同樣地進行操作，而製得在作為核之Li1.05 Ni0.50 Co0.20 Mn0.30 O1.95 (PO4 )0.05 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.04 Mg0.01 O2 以50重量%加以被覆之平均粒子徑為13.4μm之Li-Ni複合氧化物粒子粉末。In the production of the Li-Ni-Mn composite oxide, in addition to the Ni-Co-Mn hydroxide particles, lithium carbonate and lithium phosphate, the molar ratio is Li/(Ni+Co+Mn)=1.05. The operation was carried out in the same manner as in Example 9 except that Li 0.98 Ni 0.80 Co was obtained on the surface of the particles of the secondary particles of Li 1.05 Ni 0.50 Co 0.20 Mn 0.30 O 1.95 (PO 4 ) 0.05 which is a core. 0.15 Al 0.04 Mg 0.01 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.4 μm coated with 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係285℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係167mAh/g，而在60℃下保存1週後之殘存放電容量係161mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係18ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 285 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 167 mAh/g, and the residual storage capacity after storage for one week at 60 ° C was 161 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 18 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了將2mol/l之硫酸鎳及硫酸鈷及硫酸錳混合而成Ni：Co：Mn=60：20：20之水溶液，並將此混合物在氧氣環境下，以830℃燒成4小時；以及將經Ni-Co氫氧化物被覆之Li1.05 Ni0.60 Co0.20 Mn0.20 O2 中間體，及事先以磨碎機進行過粒度調整之氫氧化鋰及氫氧化鎂及氧化鋯，以莫爾比為Li/(表面之Ni+Co+Al+Mg+Zr)=0.98而進行混合以外，其餘均與實施例3同樣地進行操作，而製得在作為核之Li1.05 Ni0.60 Co0.20 Mn0.20 O2 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.03 Mg0.01 Zr0.01 O2 以50重量%加以被覆之平均粒子徑為13.6μm之Li-Ni複合氧化物粒子粉末。In the manufacture of the Li-Ni-Mn composite oxide, in addition to 2 mol/l of nickel sulfate and cobalt sulfate and manganese sulfate, an aqueous solution of Ni:Co:Mn=60:20:20 is prepared, and the mixture is in oxygen. In the environment, firing at 830 ° C for 4 hours; and Li 1.05 Ni 0.60 Co 0.20 Mn 0.20 O 2 intermediate coated with Ni-Co hydroxide, and lithium hydroxide previously subjected to particle size adjustment by a grinder Magnesium hydroxide and zirconium oxide were mixed in the same manner as in Example 3 except that the molar ratio was Li/(Ni+Co+Al+Mg+Zr on the surface)=0.98, and the same was obtained. On the surface of the particles of the secondary particles of Li 1.05 Ni 0.60 Co 0.20 Mn 0.20 O 2 , there is Li 0.98 Ni 0.80 Co 0.15 Al 0.03 Mg 0.01 Zr 0.01 O 2 The average particle diameter coated with 50% by weight is 13.6 μm. Li-Ni composite oxide particle powder.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係278℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係184mAh/g，而在60℃下保存1週後之殘存放電容量係177mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係17ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a state of charge of 4.5 V, and the maximum peak temperature of the heat generation was 278 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 184 mAh/g, and the residual storage capacity after storage for one week at 60 ° C was 177 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 17 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與實施例12同樣地進行操作，而製得在作為核之Li1.05 Ni0.60 Co0.20 Mn0.20 O1.95 F0.05 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.03 Mg0.01 Zr0.01 O2 以50重量%加以被覆之平均粒子徑為13.7μm之Li-Ni複合氧化物粒子粉末。In the production of the Li-Ni-Mn composite oxide, in addition to the Ni-Co-Mn hydroxide particles, lithium carbonate and lithium fluoride, the molar ratio is Li/(Ni+Co+Mn)=1.05. Except for the mixing, the same operation as in Example 12 was carried out, and Li 0.98 Ni 0.80 Co 0.15 Al was obtained on the surface of the particles of the secondary particles of Li 1.05 Ni 0.60 Co 0.20 Mn 0.20 O 1.95 F 0.05 which is a core. 0.03 Mg 0.01 Zr 0.01 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.7 μm coated with 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係279℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係183mAh/g，而在60℃下保存1週後之殘存放電容量係175mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係15ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a charging state of 4.5 V, and the maximum peak temperature of the heat generation was 279 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 183 mAh/g, and the storage capacity after storage for one week at 60 ° C was 175 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 15 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了Ni-Co-Mn氫氧化物粒子及碳酸鋰及磷酸鋰，係以莫爾比為Li/(Ni+Co+Mn)=1.05而進行混合以外，其餘均與實施例12同樣地進行操作，而製得在作為核之Li1.05 Ni0.60 Co0.20 Mn0.20 O1.95 (PO4 )0.05 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.03 Mg0.01 Zr0.01 O2 以50重量%加以被覆之平均粒子徑為13.8μm之Li-Ni複合氧化物粒子粉末。In the production of the Li-Ni-Mn composite oxide, in addition to the Ni-Co-Mn hydroxide particles, lithium carbonate and lithium phosphate, the molar ratio is Li/(Ni+Co+Mn)=1.05. The operation was carried out in the same manner as in Example 12 except that on the surface of the particles of the secondary particles of Li 1.05 Ni 0.60 Co 0.20 Mn 0.20 O 1.95 (PO 4 ) 0.05 as a core, Li 0.98 Ni 0.80 Co was obtained. 0.15 Al 0.03 Mg 0.01 Zr 0.01 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.8 μm coated at 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係274℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係181mAh/g，而在60℃下保存1週後之殘存放電容量係175mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係16ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a charging state of 4.5 V, and the maximum peak temperature of the heat generation was 274 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 181 mAh/g, and the residual storage capacity after storage for one week at 60 ° C was 175 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 16 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了將2mol/l之硫酸鎳及硫酸鈷及硫酸錳及硫酸鋁混合而成Ni：Co：Mn：Al=33：24：33：9之水溶液，將Ni-Co-Mn-Al氫氧化物粒子及碳酸鋰以莫爾比為Li/(Ni+Co+Mn+Al)=1.01而進行混合，並將2mol/l之硫酸鎳及硫酸鈷混合而成Ni：Co=79：21之水溶液，以及將經Ni：Co=79：21之Ni-Co氫氧化物被覆之Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.09 O2 中間體，及事先以磨碎機進行過粒度調整之氫氧化鋰及氫氧化鋁及氫氧化鎂及氧化鋯及氧化鈦，以莫爾比為Li/(表面之Ni+Co+Al+Mg+Zr+Ti)=1.05而進行混合以外，其餘均與實施例3同樣地進行操作，而製得在作為核之Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.09 O2 之二次粒子之粒子表面上，有Li1.05 Ni0.75 Co0.20 Al0.02 Mg0.01 Zr0.01 Ti0.01 O2 以50重量%加以被覆之平均粒子徑為13.0μm之Li-Ni複合氧化物粒子粉末。In the production of Li-Ni-Mn composite oxide, an aqueous solution of Ni:Co:Mn:Al=33:24:33:9 is prepared by mixing 2 mol/l of nickel sulfate and cobalt sulfate, and manganese sulfate and aluminum sulfate. Mixing Ni-Co-Mn-Al hydroxide particles and lithium carbonate with a molar ratio of Li/(Ni+Co+Mn+Al)=1.01, and mixing 2 mol/l of nickel sulfate and cobalt sulfate An aqueous solution of Ni:Co=79:21, and a Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.09 O 2 intermediate coated with a Ni:Co=79:21 Ni-Co hydroxide, and previously ground The crusher is subjected to particle size adjustment of lithium hydroxide and aluminum hydroxide and magnesium hydroxide and zirconia and titanium oxide, and the molar ratio is Li/(surface Ni+Co+Al+Mg+Zr+Ti)=1.05 Except for the mixing, the same operation as in Example 3 was carried out, and on the surface of the particles of the secondary particles of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.09 O 2 as a core, Li 1.05 Ni 0.75 Co 0.20 was obtained. Al 0.02 Mg 0.01 Zr 0.01 Ti 0.01 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.0 μm coated with 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係300℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係165mAh/g，而在60℃下保存1週後之殘存放電容量係159mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係19ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis in a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 300 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 165 mAh/g, and the storage capacity after storage for one week at 60 ° C was 159 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 19 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了Ni-Co-Mn-Al氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn+Al)=1.01而進行混合以外，其餘均與實施例15同樣地進行操作，而製得在作為核之Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.09 O1.95 F0.05 之二次粒子之粒子表面上，有Li1.05 Ni0.75 Co0.20 Al0.02 Mg0.01 Zr0.01 Ti0.01 O2 以50重量%加以被覆之平均粒子徑為13.2μm之Li-Ni複合氧化物粒子粉末。In the production of Li-Ni-Mn composite oxide, in addition to Ni-Co-Mn-Al hydroxide particles and lithium carbonate and lithium fluoride, the molar ratio is Li/(Ni+Co+Mn+Al). The same procedure as in Example 15 was carried out except that the mixture was mixed at 1.01 , and Li on the surface of the particles of the secondary particles of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.09 O 1.95 F 0.05 as a core was obtained. 1.05 Ni 0.75 Co 0.20 Al 0.02 Mg 0.01 Zr 0.01 Ti 0.01 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.2 μm coated at 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係295℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係163mAh/g，而在60℃下保存1週後之殘存放電容量係157mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係15ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis in a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 295 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 163 mAh/g, and the storage capacity after storage for one week at 60 ° C was 157 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 15 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了Ni-Co-Mn-Al氫氧化物粒子及碳酸鋰及磷酸鋰，係以莫爾比為Li/(Ni+Co+Mn+Al)=1.01而進行混合以外，其餘均與實施例15同樣地進行操作，而製得在作為核之Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.09 O1.95 (PO4 )0.05 之二次粒子之粒子表面上，有Li1.05 Ni0.75 Co0.20 Al0.02 Mg0.01 Zr0.01 Ti0.01 O2 以50重量%加以被覆之平均粒子徑為13.3μm之Li-Ni複合氧化物粒子粉末。In the production of Li-Ni-Mn composite oxide, in addition to Ni-Co-Mn-Al hydroxide particles and lithium carbonate and lithium phosphate, the molar ratio is Li/(Ni+Co+Mn+Al)= The same procedure as in Example 15 was carried out except that mixing was carried out at 1.01, and on the surface of the particles of the secondary particles of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.09 O 1.95 (PO 4 ) 0.05 as a core, Li 1.05 Ni 0.75 Co 0.20 Al 0.02 Mg 0.01 Zr 0.01 Ti 0.01 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.3 μm coated with 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係290℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係162mAh/g，而在60℃下保存1週後之殘存放電容量係157mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係15ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis in a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 290 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 162 mAh/g, and the residual storage capacity after storage for one week at 60 ° C was 157 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 15 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了將2mol/l之硫酸鎳及硫酸鈷及硫酸錳及硫酸鋁混合而成Ni：Co：Mn：Mg=33：24：33：9之水溶液，將Ni-Co-Mn-Mg氫氧化物粒子及碳酸鋰以莫爾比為Li/(Ni+Co+Mn+Mg)=1.01而進行混合，並將2mol/l之硫酸鎳及硫酸鈷混合而成Ni：Co=79：21之水溶液，以及將經Ni：Co=79：21之Ni-Co氫氧化物被覆之Li1.01 Ni0.33 Co0.24 Mn0.33 Mg0.09 O2 中間體，及事先以磨碎機進行過粒度調整之氫氧化鋰及氫氧化鋁及氫氧化鎂及氧化鋯及氧化鈦，以莫爾比為Li/(表面之Ni+Co+Al+Mg+Zr+Ti)=1.05而進行混合以外，其餘均與實施例3同樣地進行操作，而製得在作為核之Li1.01 Ni0.33 Co0.24 Mn0.33 Mg0.09 O2 之二次粒子之粒子表面上，有Li1.05 Ni0.75 Co0.20 Al0.02 Mg0.01 Zr0.01 Ti0.01 O2 以50重量%加以被覆之平均粒子徑為13.1μm之Li-Ni複合氧化物粒子粉末。In the manufacture of Li-Ni-Mn composite oxide, an aqueous solution of Ni:Co:Mn:Mg=33:24:33:9 is prepared by mixing 2 mol/l of nickel sulfate and cobalt sulfate, and manganese sulfate and aluminum sulfate. Mixing Ni-Co-Mn-Mg hydroxide particles and lithium carbonate with a molar ratio of Li/(Ni+Co+Mn+Mg)=1.01, and mixing 2 mol/l of nickel sulfate and cobalt sulfate An aqueous solution of Ni:Co=79:21, and a Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Mg 0.09 O 2 intermediate coated with a Ni:Co=79:21 Ni-Co hydroxide, and previously ground The crusher is subjected to particle size adjustment of lithium hydroxide and aluminum hydroxide and magnesium hydroxide and zirconia and titanium oxide, and the molar ratio is Li/(surface Ni+Co+Al+Mg+Zr+Ti)=1.05 The same procedure as in Example 3 was carried out except that the mixing was carried out, and Li 1.05 Ni 0.75 Co 0.20 was obtained on the surface of the particles of the secondary particles of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Mg 0.09 O 2 as the core. Al 0.02 Mg 0.01 Zr 0.01 Ti 0.01 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.1 μm coated at 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係292℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係163mAh/g，而在60℃下保存1週後之殘存放電容量係156mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係17ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a charging state of 4.5 V, and the maximum peak temperature of the heat generation was 292 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 163 mAh/g, and the storage capacity after storage for one week at 60 ° C was 156 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 17 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了Ni-Co-Mn-Mg氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn+Mg)=1.01而進行混合以外，其餘均與實施例18同樣地進行操作，而製得在作為核之Li1.01 Ni0.33 Co0.24 Mn0.33 Mg0.09 O1.95 F0.05 之二次粒子之粒子表面上，有Li1.05 Ni0.75 Co0.20 Al0.02 Mg0.01 Zr0.01 Ti0.01 O2 以50重量%加以被覆之平均粒子徑為13.0μm之Li-Ni複合氧化物粒子粉末。In the production of Li-Ni-Mn composite oxide, in addition to Ni-Co-Mn-Mg hydroxide particles and lithium carbonate and lithium fluoride, the molar ratio is Li/(Ni+Co+Mn+Mg) The same procedure as in Example 18 was carried out except that the mixture was mixed at 1.01 , and Li on the surface of the particles of the secondary particles of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Mg 0.09 O 1.95 F 0.05 as a core was obtained. 1.05 Ni 0.75 Co 0.20 Al 0.02 Mg 0.01 Zr 0.01 Ti 0.01 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.0 μm coated with 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係294℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係162mAh/g，而在60℃下保存1週後之殘存放電容量係156mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係18ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a state of charge of 4.5 V, and the maximum peak temperature of the heat generation was 294 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 162 mAh/g, and the residual storage capacity after storage for one week at 60 ° C was 156 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 18 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了Ni-Co-Mn-Mg氫氧化物粒子及碳酸鋰及磷酸鋰，係以莫爾比為Li/(Ni+Co+Mn+Mg)=1.01而進行混合以外，其餘均與實施例18同樣地進行操作，而製得在作為核之Li1.01 Ni0.33 Co0.24 Mn0.33 Mg0.09 O1.95 (PO4 )0.05 之二次粒子之粒子表面上，有Li1.05 Ni0.75 Co0.20 Al0.02 Mg0.01 Zr0.01 Ti0.01 O2 以50重量%加以被覆之平均粒子徑為13.4μm之Li-Ni複合氧化物粒子粉末。In the production of Li-Ni-Mn composite oxide, in addition to Ni-Co-Mn-Mg hydroxide particles and lithium carbonate and lithium phosphate, the molar ratio is Li/(Ni+Co+Mn+Mg)= The same procedure as in Example 18 was carried out except that mixing was carried out at 1.01, and on the surface of the particles of the secondary particles of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Mg 0.09 O 1.95 (PO 4 ) 0.05 as a core, Li 1.05 Ni 0.75 Co 0.20 Al 0.02 Mg 0.01 Zr 0.01 Ti 0.01 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.4 μm coated with 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係305℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係160mAh/g，而在60℃下保存1週後之殘存放電容量係155mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係17ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a state of charge of 4.5 V, and the maximum peak temperature of the heat generation was 305 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 160 mAh/g, and the storage capacity after storage for one week at 60 ° C was 155 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 17 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了將2mol/l之硫酸鎳及硫酸鈷及硫酸錳及硫酸鋁及硫酸鎂混合而成Ni：Co：Mn：Al：Mg=33：24：33：5：4之水溶液，將Ni-Co-Mn-Al-Mg氫氧化物粒子及碳酸鋰以莫爾比為Li/(Ni+Co+Mn+Al+Mg)=1.01而進行混合以外，其餘均與實施例3同樣地進行操作，而製得在作為核之Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.05 Mg0.04 O2 之二次粒子之粒子表面上，有Li1.05 Ni0.75 Co0.20 Al0.02 Mg0.01 Zr0.01 Ti0.01 O2 以50重量%加以被覆之平均粒子徑為13.3μm之Li-Ni複合氧化物粒子粉末。In the manufacture of Li-Ni-Mn composite oxide, Ni:Co:Mn:Al:Mg=33:24 is obtained by mixing 2 mol/l of nickel sulfate and cobalt sulfate and manganese sulfate, and aluminum sulfate and magnesium sulfate. An aqueous solution of 33:5:4 is prepared by mixing Ni-Co-Mn-Al-Mg hydroxide particles and lithium carbonate with a molar ratio of Li/(Ni+Co+Mn+Al+Mg)=1.01. The rest were operated in the same manner as in Example 3, and Li 1.05 Ni 0.75 Co 0.20 Al 0.02 was obtained on the surface of the particles of the secondary particles of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.05 Mg 0.04 O 2 as the core. Mg 0.01 Zr 0.01 Ti 0.01 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.3 μm coated with 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係306℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係164mAh/g，而在60℃下保存1週後之殘存放電容量係159mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係16ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a state of charge of 4.5 V, and the maximum peak temperature of the heat generation was 306 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 164 mAh/g, and the storage capacity after storage for one week at 60 ° C was 159 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 16 ppm.
在Li-Ni-Mn複合氧化物之製造中，除了Ni-Co-Mn-Al-Mg氫氧化物粒子及碳酸鋰及氟化鋰，係以莫爾比為Li/(Ni+Co+Mn+Al+Mg)=1.01而進行混合以外，其餘均與實施例21同樣地進行操作，而製得在作為核之Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.05 Mg0.04 O1.95 F0.05 之二次粒子之粒子表面上，有Li1.05 Ni0.75 Co0.20 Al0.02 Mg0.01 Zr0.01 Ti0.01 O2 以50重量%加以被覆之平均粒子徑為13.2μm之Li-Ni複合氧化物粒子粉末。In the manufacture of Li-Ni-Mn composite oxide, in addition to Ni-Co-Mn-Al-Mg hydroxide particles and lithium carbonate and lithium fluoride, the molar ratio is Li/(Ni+Co+Mn+ The same procedure as in Example 21 was carried out except that Al+Mg) was 1.01, and the secondary particles of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.05 Mg 0.04 O 1.95 F 0.05 as a core were obtained. On the surface of the particles, there were Li 1.05 Ni 0.75 Co 0.20 Al 0.02 Mg 0.01 Zr 0.01 Ti 0.01 O 2 Li-Ni composite oxide particles powder coated with 50% by weight and having an average particle diameter of 13.2 μm.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係305℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係163mAh/g，而在60℃下保存1週後之殘存放電容量係158mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係17ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a state of charge of 4.5 V, and the maximum peak temperature of the heat generation was 305 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 163 mAh/g, and the storage capacity after storage for one week at 60 ° C was 158 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 17 ppm.
除了Ni-Co-Mn-Al-Mg氫氧化物粒子及碳酸鋰及磷酸鋰，係以莫爾比為Li/(Ni+Co+Mn+Al+Mg)=1.01而進行混合以外，其餘均與實施例21同樣地進行操作，而製得在作為核之Li1.01 Ni0.33 Co0.24 Mn0.33 Al0.05 Mg0.04 O1.95 (PO4 )0.05 之二次粒子之粒子表面上，有Li1.05 Ni0.75 Co0.20 Al0.02 Mg0.01 Zr0.01 Ti0.01 O2 以50重量%加以被覆之平均粒子徑為13.1μm之Li-Ni複合氧化物粒子粉末。Except for Ni-Co-Mn-Al-Mg hydroxide particles, lithium carbonate and lithium phosphate, the molar ratio is Li/(Ni+Co+Mn+Al+Mg)=1.01, and the others are mixed. In the same manner as in Example 21, Li 1.05 Ni 0.75 Co 0.20 was obtained on the surface of the particles of the secondary particles of Li 1.01 Ni 0.33 Co 0.24 Mn 0.33 Al 0.05 Mg 0.04 O 1.95 (PO 4 ) 0.05 as a core. Al 0.02 Mg 0.01 Zr 0.01 Ti 0.01 O 2 Li-Ni composite oxide particle powder having an average particle diameter of 13.1 μm coated at 50% by weight.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係303℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係161mAh/g，而在60℃下保存1週後之殘存放電容量係157mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係16ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis in a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 303 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 161 mAh/g, and the storage capacity after storage for one week at 60 ° C was 157 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 16 ppm.
除了所被覆之Ni-Co氫氧化物，相對於Li1.05 Ni0.33 Co0.33 Mn0.33 O2 ，以重量百分率計，係成為5wt%以外，其餘均與實施例1同樣地進行操作，而製得在作為核之Li1.05 Ni0.33 Co0.33 Mn0.33 O2 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.05 O2 以5重量%加以被覆之平均粒子徑為9.8μm之Li-Ni複合氧化物粒子粉末。The same procedure as in Example 1 was carried out except that the Ni-Co hydroxide coated was operated in the same manner as in Example 1 except that Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 was used in an amount of 5 wt% by weight. On the surface of the particles of the secondary particles of Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 as a core, Li-Ni was coated with Li 0.98 Ni 0.80 Co 0.15 Al 0.05 O 2 at 5% by weight and having an average particle diameter of 9.8 μm. Composite oxide particle powder.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係290℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係157mAh/g，而在60℃下保存1週後之殘存放電容量係153mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係25ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis in a charged state of 4.5 V, and the maximum peak temperature of the heat generation was 290 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 157 mAh/g, and the storage capacity after storage for one week at 60 ° C was 153 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 25 ppm.
除了所被覆之Ni-Co氫氧化物，相對於Li1.05 Ni0.33 Co0.33 Mn0.33 O2 ，以重量百分率計，係成為60wt%以外，其餘均與實施例1同樣地進行操作，而製得在作為核之Li1.05 Ni0.33 Co0.33 Mn0.33 O2 之二次粒子之粒子表面上，有Li0.98 Ni0.80 Co0.15 Al0.05 O2 以60重量%加以被覆之平均粒子徑為13.5μm之Li-Ni複合氧化物粒子粉末。The same procedure as in Example 1 was carried out except that the Ni-Co hydroxide coated was operated in the same manner as in Example 1 except that Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 was 60 wt% by weight. On the surface of the particles of the secondary particles of Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 as a core, there is Li 0.98 Ni 0.80 Co 0.15 Al 0.05 O 2 coated with 60% by weight of Li-Ni having an average particle diameter of 13.5 μm. Composite oxide particle powder.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係253℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係178mAh/g，而在60℃下保存1週後之殘存放電容量係170mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係12ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a charging state of 4.5 V, and the maximum peak temperature of the heat generation was 253 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 178 mAh/g, and the residual storage capacity after storage for one week at 60 ° C was 170 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high temperature storage was 12 ppm.
除了對於作為核之Li1.05 Ni0.33 Co0.33 Mn0.33 O2 ，係混合平均粒子徑5.0μm之Ni0.84 Co0.16 (OH)2 使其成為重量百分率50%，並使用機械性磨碎機進行30分鐘之機械性處理外，其餘均與實施例6同樣地進行操作，而製得平均粒子徑為7.3μm之Li-Ni複合氧化物粒子粉末。Except for Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O 2 as a core, Ni 0.84 Co 0.16 (OH) 2 having an average particle diameter of 5.0 μm was mixed to a weight percentage of 50%, and a mechanical grinder was used for 30 minutes. In the same manner as in Example 6, except that the mechanical treatment was carried out, Li-Ni composite oxide particles having an average particle diameter of 7.3 μm were obtained.
該Li-Ni複合氧化物粒子粉末在4.5V充電狀態下進行差示熱分析之結果，其發熱最大峰部溫度係279℃。此外，該Li-Ni複合氧化物粒子粉末之放電容量係157mAh/g，而在60℃下保存1週後之殘存放電容量係148mAh/g。進一步，高溫保存後之電解液中之錳溶離量，係24ppm。The Li-Ni composite oxide particles were subjected to differential thermal analysis at a charging state of 4.5 V, and the maximum peak temperature of the heat generation was 279 °C. Further, the discharge capacity of the Li-Ni composite oxide particles was 157 mAh/g, and the residual storage capacity after storage for one week at 60 ° C was 148 mAh/g. Further, the amount of manganese dissolved in the electrolytic solution after high-temperature storage was 24 ppm.
在實施例1～23及比較例1～21所得到之Li-Ni複合氧化物之作為核之粒子之組成、在表面或表面附近所被覆或使之存在之粒子之組成、所被覆或使之存在之粒子之重量百分率、平均粒子徑、初期放電容量、高溫保存後之殘存容量率、Mn溶離量、Mn溶離率、最大發熱峰部溫度，均如表1～表4所示者。The composition of the particles of the core of the Li-Ni composite oxide obtained in Examples 1 to 23 and Comparative Examples 1 to 21, the composition of the particles coated or present on or near the surface, coated or made The weight percentage, average particle diameter, initial discharge capacity, residual capacity ratio after high temperature storage, Mn elution amount, Mn elution rate, and maximum heat peak temperature of the particles present are as shown in Tables 1 to 4.
在實施例1～23所得到之Li-Ni複合氧化物粒子粉末，不論何者，其最大發熱峰部，相對於作為核之最大發熱峰部，峰部溫度之降低均在32℃以內，故係充電時具有優良之熱安定性之正極材料。In any of the Li-Ni composite oxide particles obtained in Examples 1 to 23, the maximum exothermic peak portion has a peak temperature decrease of 32 ° C or less with respect to the maximum exothermic peak as the core. A positive electrode material with excellent thermal stability during charging.
又除了高溫保存後之放電容量殘存率係95%以上外，其高溫保存後之Mn溶離率相對於作為核之Li-Ni-Mn複合氧化物係在80%以下，故係具有優良之高溫保存特性之正極材料。In addition, the residual capacity of the discharge capacity after high-temperature storage is 95% or more, and the Mn dissolution rate after high-temperature storage is 80% or less with respect to the Li-Ni-Mn composite oxide as the core, so that it has excellent high-temperature storage. The positive electrode material of the characteristic.
關於實施例1及實施例3所得到之Li-Ni複合氧化物粒子，其斷面狀態之觀察結果係如圖1及圖2所示者。The observation results of the cross-sectional state of the Li-Ni composite oxide particles obtained in Example 1 and Example 3 are as shown in Figs. 1 and 2 .
根據圖1及圖2，可知實施例1及實施例3所得到之Li-Ni複合氧化物粒子，其粒子表面之Al金屬之濃度變高，且Mn金屬之濃度變低，而在作為核之Li-Ni-Mn複合氧化物之二次粒子之粒子表面上，有本發明1記載之Li-Ni複合氧化物被覆者。1 and 2, it is understood that the Li-Ni composite oxide particles obtained in Examples 1 and 3 have a high concentration of Al metal on the surface of the particles, and the concentration of the Mn metal is low, and is used as a core. On the surface of the particles of the secondary particles of the Li-Ni-Mn composite oxide, there is a coating of the Li-Ni composite oxide according to the first aspect of the invention.
使用實施例1、實施例3、比較例1所得到之Li-Ni複合氧化物粒子粉末，所進行之鈕釦型電池安全性評價之差示熱分析結果，係如圖3所示者。The results of the differential thermal analysis using the Li-Ni composite oxide particle powder obtained in Example 1, Example 3, and Comparative Example 1 for the safety evaluation of the button type battery were as shown in FIG.
根據圖3，可知實施例1及實施例3所得到之Li-Ni複合氧化物粒子，其在作為核之粒子之表面或表面附近，有本發明1～5記載之Li-Ni複合氧化物粒子存在，且對於核粒子之被覆粒子或在表面附近存在之粒子之重量百分率為10%以上50%以下，就可以將最大發熱峰部溫度之降低抑制在32℃以內。According to FIG. 3, the Li-Ni composite oxide particles obtained in Examples 1 and 3 have the Li-Ni composite oxide particles of the first to fifth embodiments in the vicinity of the surface or the surface of the particles as the core. When the weight percentage of the coated particles of the core particles or the particles present in the vicinity of the surface is 10% or more and 50% or less, the decrease in the maximum heat peak temperature can be suppressed to 32 ° C or less.
根據以上之結果，確認本發明之Li-Ni複合氧化物粒子粉末，其作為具有優良之充電時之熱安定性及高溫安定性之高容量非水電解液電池用活性物質，係相當有效的。From the above results, it was confirmed that the Li-Ni composite oxide particles of the present invention are effective as high-capacity non-aqueous electrolyte battery active materials having excellent thermal stability during charging and high-temperature stability.
本發明藉由使用：一種非水電解質蓄電池用Li-Ni複合氧化物粒子粉末，其特徵為在作為核之二次粒子之組成係Lix1 Ni1-y1-z1-w1 Coy1 Mnz1 M1w1 O2-v Kv (1＜x1≦1.3，0≦y1≦0.33，0.2≦z1≦0.33，0≦w1＜0.1，0≦v≦0.05，M1係選自Al、Mg之至少一種之金屬以及K係選自F- 、PO4 3- 之至少一種陰離子)之Li-Ni-Mn複合氧化物中，於該二次粒子之粒子表面或表面附近，其係以組成為Lix2 Ni1-y2-z2 Coy2 M2z2 O2 (0.98≦x2≦1.05，0.15≦y2≦0.2，0≦z2≦0.05，M2係選自Al、Mg、Zr、Ti之至少一種金屬)之Li-Ni複合氧化物加以被覆或使之存在之Li-Ni複合氧化物，使所得到之複合粒子之粒子徑係作為核之粒子之粒子徑之1.1倍以上，且相對於核粒子之被覆粒子或在表面附近所存在之粒子之重量百分率係10%以上50%以下者；即可得到一種充放電容量大，且充電時之熱安定性及高溫安定性皆優良之非水電解液電池。The present invention employs: a Li-Ni composite oxide particle powder for a nonaqueous electrolyte secondary battery, characterized in that it is a constituent of a secondary particle as a core, Li x1 Ni 1-y1-z1-w1 Co y1 Mn z1 M1 w1 O 2-v K v (1<x1≦1.3,0≦y1≦0.33, 0.2≦z1≦0.33, 0≦w1<0.1,0≦v≦0.05, M1 is a metal selected from at least one of Al and Mg, and K is a Li-Ni-Mn composite oxide selected from the group consisting of at least one anion of F - and PO 4 3- ), and is composed of Li x2 Ni 1-y2 near the surface or surface of the particle of the secondary particle. -z2 Co y2 M2 z2 O 2 (0.98≦x2≦1.05, 0.15≦y2≦0.2,0≦z2≦0.05, M2 is a metal selected from at least one of Al, Mg, Zr, Ti) Li-Ni composite oxide The Li-Ni composite oxide to be coated or formed is such that the particle diameter of the obtained composite particles is 1.1 times or more the particle diameter of the particles of the core, and is present in the coated particles with respect to the core particles or in the vicinity of the surface. The weight percentage of the particles is 10% or more and 50% or less; a non-aqueous electrolyte having a large charge and discharge capacity and excellent thermal stability and high temperature stability during charging can be obtained. battery.
圖1：觀察實施例1所得到之Li-Ni複合氧化物粒子粉末之橫斷面狀態，而顯示各元素之存在狀態之照片(EPMA)。Fig. 1: The cross-sectional state of the Li-Ni composite oxide particle powder obtained in Example 1 was observed, and a photograph (EPMA) showing the state of existence of each element was shown.
圖2：觀察實施例3所得到之Li-Ni複合氧化物粒子粉末之橫斷面狀態，而顯示各元素之存在狀態之照片(EPMA)。Fig. 2: A cross-sectional state of the Li-Ni composite oxide particles obtained in Example 3 was observed, and a photograph (EPMA) showing the state of existence of each element was shown.
圖3：使用實施例1、實施例3、比較例1所得到之Li-Ni複合氧化物粒子粉末，並以鈕釦型電池之安全性評價所進行之差示熱分析結果。Fig. 3 shows the results of differential thermal analysis performed using the Li-Ni composite oxide particle powders obtained in Example 1, Example 3, and Comparative Example 1 and evaluated by the safety of a button type battery.
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| JP2010092848A (en) | 2010-04-22 |
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