JP2021057226A - Positive electrode active material for nonaqueous electrolyte secondary battery and manufacturing method thereof - Google Patents
Positive electrode active material for nonaqueous electrolyte secondary battery and manufacturing method thereof Download PDFInfo
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- JP2021057226A JP2021057226A JP2019180060A JP2019180060A JP2021057226A JP 2021057226 A JP2021057226 A JP 2021057226A JP 2019180060 A JP2019180060 A JP 2019180060A JP 2019180060 A JP2019180060 A JP 2019180060A JP 2021057226 A JP2021057226 A JP 2021057226A
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- strontium
- cobalt
- positive electrode
- lithium
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 64
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 74
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 58
- 239000010941 cobalt Substances 0.000 claims abstract description 58
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 58
- -1 lithium transition metal Chemical class 0.000 claims abstract description 40
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 39
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 39
- 239000002905 metal composite material Substances 0.000 claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 150000003438 strontium compounds Chemical class 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 18
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 10
- 150000002739 metals Chemical class 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 32
- 229910001427 strontium ion Inorganic materials 0.000 claims description 19
- 150000001869 cobalt compounds Chemical class 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 9
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052765 Lutetium Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052789 astatine Inorganic materials 0.000 claims 2
- 239000000243 solution Substances 0.000 description 35
- 238000000034 method Methods 0.000 description 23
- 229910001631 strontium chloride Inorganic materials 0.000 description 14
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910000018 strontium carbonate Inorganic materials 0.000 description 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 159000000008 strontium salts Chemical class 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 3
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 2
- FXWRHZACHXRMCI-UHFFFAOYSA-L strontium;diformate Chemical compound [Sr+2].[O-]C=O.[O-]C=O FXWRHZACHXRMCI-UHFFFAOYSA-L 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Images
Classifications
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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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本開示は、非水系電解質二次電池用正極活物質及びその製造方法に関する。 The present disclosure relates to a positive electrode active material for a non-aqueous electrolyte secondary battery and a method for producing the same.
電気自動車等の大型動力機器用途の非水系電解質二次電池用電極活物質には、高いエネルギー密度が求められている。これに関連して、特許文献１には、ニッケルを必須とするリチウム遷移金属複合酸化物を特定の方法で水洗し、炭酸リチウム等ガス発生の元となる物質を除去する技術が記載されている。また、特許文献２には、コバルト酸リチウムのリチウム層と遷移金属層の一部を異種元素で置換する技術が記載され、熱安定性とサイクル特性が向上するとされている。
High energy densities are required for electrode active materials for non-aqueous electrolyte secondary batteries used in large power equipment such as electric vehicles. In connection with this,
本開示に係る一態様は、エネルギー密度の高い非水系電解質二次電池用正極活物質の製造方法を提供することを目的とする。 One aspect of the present disclosure is to provide a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery having a high energy density.
第１の態様は、コバルト及びストロンチウムを含み、コバルトのモル数に対するストロンチウムのモル数の比が０．０００１より大きく、０．０００５未満である第１複合物を準備することと、第１複合物とリチウム化合物とを混合して、リチウム混合物を得ることと、リチウム混合物を熱処理して、層状構造を有しコバルトを含むリチウム遷移金属複合酸化物とストロンチウム化合物とを含む第２複合物を得ることと、を含む非水系電解質二次電池用正極活物質の製造方法である。リチウム遷移金属複合酸化物は、リチウム以外の金属の総モル数に対するコバルトのモル数の比が０．９以上である組成を有する。 The first aspect comprises preparing a first compound comprising cobalt and strontium, wherein the ratio of the number of moles of strontium to the number of moles of cobalt is greater than 0.0001 and less than 0.0005. And a lithium compound are mixed to obtain a lithium mixture, and the lithium mixture is heat-treated to obtain a second complex containing a lithium transition metal composite oxide having a layered structure and containing cobalt and a strontium compound. It is a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery including. The lithium transition metal composite oxide has a composition in which the ratio of the number of moles of cobalt to the total number of moles of metals other than lithium is 0.9 or more.
第２の態様は、コバルトを含み、層状構造を有するリチウム遷移金属複合酸化物と、ストロンチウム化合物とを含む非水系電解質二次電池用正極活物質である。リチウム遷移金属複合酸化物におけるリチウム以外の金属の総モル数に対するコバルトのモル数の比が０．９以上である。非水系電解質二次電池用正極活物質は、リチウム遷移金属複合酸化物に含まれるコバルトのモル数に対する、ストロンチウム化合物に含まれるストロンチウムのモル数の比が０．０００１より大きく、０．０００５未満である。 A second aspect is a positive electrode active material for a non-aqueous electrolyte secondary battery containing cobalt, a lithium transition metal composite oxide having a layered structure, and a strontium compound. The ratio of the number of moles of cobalt to the total number of moles of metals other than lithium in the lithium transition metal composite oxide is 0.9 or more. In the positive electrode active material for a non-aqueous electrolyte secondary battery, the ratio of the number of moles of strontium contained in the strontium compound to the number of moles of cobalt contained in the lithium transition metal composite oxide is larger than 0.0001 and less than 0.0005. is there.
本開示に係る一態様によれば、エネルギー密度の高い非水系電解質二次電池用正極活物質の製造方法を提供することができる。 According to one aspect of the present disclosure, it is possible to provide a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery having a high energy density.
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。また組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。以下、本発明の実施形態を詳細に説明する。ただし、以下に示す実施形態は、本発明の技術思想を具体化するための、非水系電解質二次電池用正極活物質及びその製造方法を例示するものであって、本発明は、以下に示す非水系電解質二次電池用正極活物質及びその製造方法に限定されない。 In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. .. Further, the content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. Hereinafter, embodiments of the present invention will be described in detail. However, the embodiments shown below exemplify a positive electrode active material for a non-aqueous electrolyte secondary battery and a method for producing the same, in order to embody the technical idea of the present invention, and the present invention is shown below. It is not limited to the positive electrode active material for a non-aqueous electrolyte secondary battery and the method for producing the same.
非水系電解質二次電池用正極活物質の製造方法
非水系電解質二次電池用正極活物質（以下、単に正極活物質ともいう）の製造方法は、コバルト及びストロンチウムを含み、コバルトのモル数に対するストロンチウムのモル数の比が０．０００１より大きく、０．０００５未満である第１複合物を準備する準備工程と、第１複合物とリチウム化合物とを混合して、リチウム混合物を得る混合工程と、リチウム混合物を熱処理して、層状構造を有しコバルトを含むリチウム遷移金属複合酸化物とストロンチウム化合物とを含む第２複合物を得る熱処理工程と、を含む。そしてリチウム遷移金属複合酸化物は、リチウム以外の金属の総モル数に対するコバルトのモル数の比が０．９以上である組成を有する。
Method for producing positive electrode active material for non-aqueous electrolyte secondary battery The method for producing positive electrode active material for non-aqueous electrolyte secondary battery (hereinafter, also simply referred to as positive electrode active material) contains cobalt and strontium, and strontium with respect to the number of moles of cobalt. A preparatory step of preparing a first complex having a molar ratio of more than 0.0001 and less than 0.0005, and a mixing step of mixing the first complex and a lithium compound to obtain a lithium mixture. The process comprises a heat treatment step of heat-treating the lithium mixture to obtain a second composite containing a lithium transition metal composite oxide having a layered structure and containing cobalt and a strontium compound. The lithium transition metal composite oxide has a composition in which the ratio of the number of moles of cobalt to the total number of moles of metals other than lithium is 0.9 or more.
コバルトとストロンチウムを上述したモル数の比にて含む第１複合物を、リチウム化合物と共に熱処理することで、コバルトを含むリチウム遷移金属複合酸化物とストロンチウム化合物とを含む第２複合物として正極活物質が得られる。得られる正極活物質は、粒子の内部が緻密化する。また、正極を形成する際に高密度の正極活物質層を形成することができ、高いエネルギー密度を達成することができる。 By heat-treating the first complex containing cobalt and strontium in the above-mentioned molar ratio together with the lithium compound, the positive electrode active material is used as the second complex containing the lithium transition metal composite oxide containing cobalt and the strontium compound. Is obtained. In the obtained positive electrode active material, the inside of the particles is densified. Further, when forming the positive electrode, a high-density positive electrode active material layer can be formed, and a high energy density can be achieved.
準備工程
準備工程では、コバルト及びストロンチウムを含み、コバルトのモル数に対するストロンチウムのモル数の比が０．０００１より大きく、０．０００５未満である第１複合物を準備する。第１複合物に含まれるコバルト元素の総モル数に対するストロンチウム元素の総モル数の比であるモル数の比（Ｓｒ／Ｃｏ）は、例えば０．０００１より大きく、０．０００５未満であり、好ましくは０．０００１５以上０．０００５未満であり、より好ましくは、０．０００２以上０．０００４５以下である。
Preparation Step In the preparation step, a first composite containing cobalt and strontium and having a ratio of the number of moles of strontium to the number of moles of cobalt greater than 0.0001 and less than 0.0005 is prepared. The ratio of the number of moles (Sr / Co), which is the ratio of the total number of moles of the strontium element to the total number of moles of the cobalt element contained in the first composite, is, for example, larger than 0.0001 and less than 0.0005, preferably less than 0.0005. Is 0.00015 or more and less than 0.0005, and more preferably 0.0002 or more and 0.00045 or less.
第１複合物は例えば、コバルト化合物とストロンチウム化合物とを含んで構成される。第１複合物を構成するコバルト化合物としては例えば、酸化コバルト（ＩＩ）、四酸化三コバルト、水酸化コバルト、炭酸コバルト、塩化コバルト、硝酸コバルト等を挙げることができ、これらからなる群から選択される少なくとも１種が好ましい。また第１複合物を構成するストロンチウム化合物としては例えば、酸化ストロンチウム（ＩＩ）、水酸化ストロンチウム、炭酸ストロンチウム、塩化ストロンチウム、硫酸ストロンチウム等を挙げることができ、これらからなる群から選択される少なくとも１種が好ましく、中でも塩化ストロンチウムが好ましい。第１複合物がコバルト化合物とストロンチウム化合物とを含む場合、第１複合物はコバルト化合物の表面にストロンチウム化合物が付着したものであってよく、コバルト化合物の内部にストロンチウム化合物が存在する状態のものであってよい。また、コバルト化合物とストロンチウム化合物とが略均一に混合したものであってよい。 The first complex is composed of, for example, a cobalt compound and a strontium compound. Examples of the cobalt compound constituting the first complex include cobalt oxide (II), tricobalt tetraoxide, cobalt hydroxide, cobalt carbonate, cobalt chloride, cobalt nitrate and the like, and are selected from the group consisting of these. At least one type is preferable. Examples of the strontium compound constituting the first complex include strontium oxide (II), strontium hydroxide, strontium carbonate, strontium chloride, strontium sulfate, and the like, and at least one selected from the group consisting of these. Is preferable, and strontium chloride is particularly preferable. When the first complex contains a cobalt compound and a strontium compound, the first complex may be one in which the strontium compound is attached to the surface of the cobalt compound, and the strontium compound is present inside the cobalt compound. It may be there. Further, the cobalt compound and the strontium compound may be mixed substantially uniformly.
第１複合物は例えば、酸素を含むコバルト化合物と、ストロンチウムイオンを含む溶液とを接触させて付着物を得ることを含む方法で準備してよい。酸素を含むコバルト化合物と、ストロンチウムイオンを含む溶液とを接触させる方法としては、例えば、固体状の酸素を含むコバルト化合物とストロンチウムイオンを含む溶液とを混合する方法があり、他にも酸素を含むコバルト化合物を溶解又は分散させた液媒体と、ストロンチウムイオンを含む溶液とを混合する方法、酸素を含むコバルト化合物を溶解又は分散させた液媒体にストロンチウム化合物又はストロンチウム塩を溶解する方法、等を挙げることができる。 The first complex may be prepared, for example, by a method comprising contacting a cobalt compound containing oxygen with a solution containing strontium ions to obtain deposits. As a method of contacting a cobalt compound containing oxygen with a solution containing strontium ions, for example, there is a method of mixing a cobalt compound containing solid oxygen and a solution containing strontium ions, and another method containing oxygen. A method of mixing a liquid medium in which a cobalt compound is dissolved or dispersed and a solution containing strontium ions, a method of dissolving a strontium compound or a strontium salt in a liquid medium in which a cobalt compound containing oxygen is dissolved or dispersed, and the like are mentioned. be able to.
酸素を含むコバルト化合物としては、水酸化コバルト、酸化コバルト、四酸化三コバルト等を挙げることができ、これらからなる群から選択される少なくとも１種が好ましい。ストロンチウムイオンを含む溶液は、例えば、ストロンチウム化合物又はストロンチウム塩を液媒体に溶解することで調製することができる。ストロンチウム化合物又はストロンチウム塩としては、ギ酸ストロンチウム、酢酸ストロンチウム、塩化ストロンチウム、硝酸ストロンチウム、硫酸ストロンチウム等を挙げることができ、これらからなる群から選択される少なくとも１種が好ましく、中でも塩化ストロンチウムが好ましい。液媒体は例えば、水を含んでいてよい。ストロンチウムイオンを含む溶液の濃度はストロンチウムイオンのモル濃度として、塩化ストロンチウムを用いる場合、例えば、０．０１モル／Ｌ以上３．０モル／Ｌ以下であり、好ましくは０．１モル／Ｌ以上２．０モル／Ｌ以下である。 Examples of the cobalt compound containing oxygen include cobalt hydroxide, cobalt oxide, tricobalt tetraoxide, and the like, and at least one selected from the group consisting of these is preferable. A solution containing strontium ions can be prepared, for example, by dissolving a strontium compound or a strontium salt in a liquid medium. Examples of the strontium compound or strontium salt include strontium formate, strontium acetate, strontium chloride, strontium nitrate, strontium sulfate, and the like, and at least one selected from the group consisting of these is preferable, and strontium chloride is particularly preferable. The liquid medium may contain, for example, water. When strontium chloride is used as the molar concentration of strontium ions, the concentration of the solution containing strontium ions is, for example, 0.01 mol / L or more and 3.0 mol / L or less, preferably 0.1 mol / L or more 2 It is 0.0 mol / L or less.
酸素を含むコバルト化合物と、ストロンチウムイオンを含む溶液との接触は、酸素を含むコバルト化合物に含まれるコバルトの総モル数に対するストロンチウムイオンを含む溶液に含まれるストロンチウムの総モル数の比が、所定の比率、例えば０．０００１より大きく、０．０００５未満であり、エネルギー密度の点から好ましくは０．０００１５以上０．０００５未満であり、より好ましくは、０．０００２以上０．０００４５以下となるようにして行えばよい。 In the contact between the oxygen-containing cobalt compound and the solution containing strontium ions, the ratio of the total number of moles of strontium contained in the solution containing strontium ions to the total number of moles of cobalt contained in the oxygen-containing cobalt compound is predetermined. The ratio is, for example, greater than 0.0001 and less than 0.0005, preferably 0.00015 or more and less than 0.0005, and more preferably 0.0002 or more and 0.00045 or less in terms of energy density. You can do it.
接触の温度は例えば、２０℃以上８０℃以下であり、好ましくは４０℃以上６０℃以下である。接触時間は例えば、５分以上３６０分以下であり、好ましくは３０分以上１８０分以下である。接触の雰囲気は例えば、大気雰囲気であってよい。接触により得られる付着物に対しては、濾別、水洗、乾燥等の精製処理をさらに行ってもよい。 The contact temperature is, for example, 20 ° C. or higher and 80 ° C. or lower, preferably 40 ° C. or higher and 60 ° C. or lower. The contact time is, for example, 5 minutes or more and 360 minutes or less, preferably 30 minutes or more and 180 minutes or less. The atmosphere of contact may be, for example, an atmospheric atmosphere. The deposits obtained by contact may be further refined by filtration, washing with water, drying or the like.
第１複合物は、酸素を含むコバルト化合物と、ストロンチウムイオンを含む溶液との接触により得られる付着物であってよいし、付着物を熱処理して得られるものであってよい。付着物を熱処理して第１複合物を得る場合、熱処理の温度としては例えば、１００℃以上４００℃以下であり、好ましくは３００℃以上３５０℃以下である。熱処理時間は例えば、２時間以上３０時間以下であり、好ましくは１０時間以上２０時間以下である。熱処理の雰囲気は例えば、大気雰囲気であってよい。熱処理は、例えばボックス炉、ロータリーキルン炉、プッシャー炉、ローラーハースキルン炉等を用いて行うことができる。 The first complex may be a deposit obtained by contacting a cobalt compound containing oxygen with a solution containing strontium ions, or may be a deposit obtained by heat-treating the deposit. When the deposit is heat-treated to obtain the first composite, the temperature of the heat treatment is, for example, 100 ° C. or higher and 400 ° C. or lower, preferably 300 ° C. or higher and 350 ° C. or lower. The heat treatment time is, for example, 2 hours or more and 30 hours or less, preferably 10 hours or more and 20 hours or less. The atmosphere of the heat treatment may be, for example, an atmospheric atmosphere. The heat treatment can be performed using, for example, a box furnace, a rotary kiln furnace, a pusher furnace, a roller harsquill furnace, or the like.
また例えば、第１複合物は、コバルトイオンを含む溶液（以下、コバルト溶液ともいう）と、ストロンチウムイオンを含む溶液（以下、ストロンチウム溶液ともいう）とから沈殿物を得ることを含む方法で準備してよい。得られる沈殿物は、コバルト元素とストロンチウム元素と含んでいてよく、さらに酸素元素を含んでいてよい。 Further, for example, the first complex is prepared by a method including obtaining a precipitate from a solution containing cobalt ions (hereinafter, also referred to as a cobalt solution) and a solution containing strontium ions (hereinafter, also referred to as a strontium solution). It's okay. The obtained precipitate may contain a cobalt element and a strontium element, and may further contain an oxygen element.
コバルト溶液と、ストロンチウム溶液とから沈殿物を得る方法としては、コバルト溶液とストロンチウム溶液とを混合して、コバルトイオンとストロンチウムイオンを含む溶液を得て、必要に応じてｐＨを調整する方法、コバルトイオンとストロンチウムイオンを含む溶液から溶媒の少なくとも一部を除去する方法等が挙げられる。コバルト溶液とストロンチウム溶液との混合は、これらを直接混合してよく、これらを別々に適当な液媒体に添加して混合してもよい。また、コバルト溶液とストロンチウム溶液との混合では、必要に応じて混合液を撹拌してよい。 As a method of obtaining a precipitate from a cobalt solution and a strontium solution, a method of mixing a cobalt solution and a strontium solution to obtain a solution containing cobalt ions and strontium ions, and adjusting the pH as necessary, cobalt Examples thereof include a method of removing at least a part of the solvent from a solution containing ions and strontium ions. The cobalt solution and the strontium solution may be mixed directly, or they may be separately added to a suitable liquid medium and mixed. Further, in the mixing of the cobalt solution and the strontium solution, the mixed solution may be stirred if necessary.
コバルト溶液とストロンチウム溶液との混合時にｐＨを調整する場合、ｐＨは例えば、７以上１１以下に維持してよく、好ましくは８以上１０以下に維持してよい。コバルトイオンとストロンチウムイオンを含む溶液のｐＨを調整して沈殿物を得る場合、ｐＨは例えば、７以上１１以下にしてよく、好ましくは８以上１０以下としてよい。ｐＨの調整には、酸性溶液及びアルカリ性溶液を用いることができる。酸性溶液としては例えば、塩酸、硝酸、硫酸等の無機酸の水溶液が挙げられる。アルカリ性溶液としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム等のアルカリ金属水酸化物の水溶液を挙げることができる。 When adjusting the pH at the time of mixing the cobalt solution and the strontium solution, the pH may be maintained, for example, 7 or more and 11 or less, preferably 8 or more and 10 or less. When the pH of the solution containing cobalt ions and strontium ions is adjusted to obtain a precipitate, the pH may be, for example, 7 or more and 11 or less, preferably 8 or more and 10 or less. An acidic solution and an alkaline solution can be used for adjusting the pH. Examples of the acidic solution include an aqueous solution of an inorganic acid such as hydrochloric acid, nitric acid, and sulfuric acid. Examples of the alkaline solution include an aqueous solution of an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, and lithium hydroxide.
コバルトイオンを含む溶液は、コバルト化合物又はコバルト塩を液媒体に溶解することで調製することができる。また、ストロンチウムイオンを含む溶液は、例えば、ストロンチウム化合物又はストロンチウム塩を液媒体に溶解することで調製することができる。コバルト化合物又はコバルト塩としては、硫酸コバルト、塩化コバルト、硝酸コバルト等を挙げることができる。ストロンチウム化合物又はストロンチウム塩としては、ギ酸ストロンチウム、酢酸ストロンチウム、塩化ストロンチウム、硝酸ストロンチウム、硫酸ストロンチウム等を挙げることができる。液媒体は例えば、水を含んでいてよい。コバルトイオンを含む溶液の濃度はコバルトイオンのモル濃度として、例えば、塩化ストロンチウムを用いる場合、例えば、０．０１モル／Ｌ以上３．０モル／Ｌ以下であり、好ましくは０．１モル／Ｌ以上２．０モル／Ｌ以下である。 A solution containing cobalt ions can be prepared by dissolving a cobalt compound or a cobalt salt in a liquid medium. In addition, a solution containing strontium ions can be prepared, for example, by dissolving a strontium compound or a strontium salt in a liquid medium. Examples of the cobalt compound or cobalt salt include cobalt sulfate, cobalt chloride, and cobalt nitrate. Examples of the strontium compound or strontium salt include strontium formate, strontium acetate, strontium chloride, strontium nitrate, and strontium sulfate. The liquid medium may contain, for example, water. The concentration of the solution containing cobalt ions is, for example, 0.01 mol / L or more and 3.0 mol / L or less, preferably 0.1 mol / L when strontium chloride is used as the molar concentration of cobalt ions. More than 2.0 mol / L or less.
コバルトイオンを含む溶液と、ストロンチウムイオンを含む溶液との混合は、コバルトイオンを含む溶液に含まれるコバルトの総モル数に対するストロンチウムイオンを含む溶液に含まれるストロンチウムの総モル数の比が、所定の比率、例えば、０．０００１より大きく、０．０００５未満、好ましくは０．０００１５以上０．０００５未満であり、より好ましくは０．０００２以上０．０００４５以下となるようにして行えばよい。 In the mixing of the solution containing cobalt ions and the solution containing strontium ions, the ratio of the total number of moles of strontium contained in the solution containing strontium ions to the total number of moles of cobalt contained in the solution containing cobalt ions is predetermined. The ratio may be larger than 0.0001, less than 0.0005, preferably 0.00015 or more and less than 0.0005, and more preferably 0.0002 or more and 0.00045 or less.
沈殿物を得る時の温度は例えば、２０℃以上８０℃以下であり、好ましくは４０℃以上６０℃以下である。沈殿物を得る時の雰囲気は例えば、大気雰囲気であってよい。得られる沈殿物に対しては、濾別、水洗、乾燥等の精製処理をさらに行ってもよい。 The temperature at which the precipitate is obtained is, for example, 20 ° C. or higher and 80 ° C. or lower, preferably 40 ° C. or higher and 60 ° C. or lower. The atmosphere at which the precipitate is obtained may be, for example, an atmospheric atmosphere. The obtained precipitate may be further purified by filtration, washing with water, drying or the like.
第１複合物は、コバルト溶液とストロンチウム溶液とから得られる沈殿物であってよいし、沈殿物を熱処理して得られるものであってよい。沈殿物を熱処理して第１複合物を得る場合、熱処理の温度としては例えば、１００℃以上４００℃以下であり、好ましくは３００℃以上３５０℃以下である。熱処理時間は例えば、２時間以上３０時間以下であり、好ましくは１０時間以上２０時間以下である。熱処理の雰囲気は例えば、大気雰囲気であってよい。熱処理は、例えばボックス炉、ロータリーキルン炉、プッシャー炉、ローラーハースキルン炉等を用いて行うことができる。 The first complex may be a precipitate obtained from a cobalt solution and a strontium solution, or may be obtained by heat-treating the precipitate. When the precipitate is heat-treated to obtain the first composite, the temperature of the heat treatment is, for example, 100 ° C. or higher and 400 ° C. or lower, preferably 300 ° C. or higher and 350 ° C. or lower. The heat treatment time is, for example, 2 hours or more and 30 hours or less, preferably 10 hours or more and 20 hours or less. The atmosphere of the heat treatment may be, for example, an atmospheric atmosphere. The heat treatment can be performed using, for example, a box furnace, a rotary kiln furnace, a pusher furnace, a roller harsquill furnace, or the like.
混合工程
混合工程では、第１複合物とリチウム化合物とを混合してリチウム混合物を得る。第１複合物と混合するリチウム化合物としては、例えば、水酸化リチウム、炭酸リチウム、酸化リチウム等を挙げることができ、これらからなる群から選択される少なくとも１種が好ましい。混合工程で用いるリチウム化合物の粒径は、体積基準による累積粒度分布の５０％平均粒径として例えば、０．１μｍ以上１００μｍ以下であり、第１複合物との混合性の点から２μｍ以上２０μｍ以下が好ましい。
Mixing Step In the mixing step, the first composite and the lithium compound are mixed to obtain a lithium mixture. Examples of the lithium compound to be mixed with the first complex include lithium hydroxide, lithium carbonate, lithium oxide and the like, and at least one selected from the group consisting of these is preferable. The particle size of the lithium compound used in the mixing step is, for example, 0.1 μm or more and 100 μm or less as a 50% average particle size of the cumulative particle size distribution based on the volume, and 2 μm or more and 20 μm or less from the viewpoint of mixing with the first composite. Is preferable.
リチウム混合物における第１複合物に含まれるコバルトの総モル数に対するリチウムの総モル数の比は例えば、０．９５以上１．５以下であり、好ましくは０．９９以上１．０２以下である。第１複合物とリチウム化合物との混合は、例えば、高速せん断ミキサー等を用いて行うことができる。 The ratio of the total number of moles of lithium to the total number of moles of cobalt contained in the first complex in the lithium mixture is, for example, 0.95 or more and 1.5 or less, preferably 0.99 or more and 1.02 or less. The mixing of the first composite and the lithium compound can be performed using, for example, a high-speed shear mixer or the like.
リチウム混合物は、コバルト、ストロンチウム及びリチウム以外の他の金属元素Ｍをさらに含んでいてよい。他の金属元素Ｍとしては、ニッケル（Ｎｉ）、マンガン（Ｍｎ）、アルミニウム（Ａｌ）、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）、ニオブ（Ｎｂ）、タリウム（Ｔａ）、クロム（Ｃｒ）、モリブデン（Ｍｏ）、鉄（Ｆｅ）、銅（Ｃｕ）、ケイ素（Ｓｉ）、スズ（Ｓｎ）、ビスマス（Ｂｉ）、ガリウム（Ｇａ）、イットリウム（Ｙ）、サマリウム（Ｓｍ）、エルビウム（Ｅｒ）、セリウム（Ｃｅ）、ネオジム（Ｎｄ）、ランタン（Ｌａ）、カドミウム（Ｃｄ）、ルテチウム（Ｌｕ）等が挙げられ、これらからなる群から選択される少なくとも１種が好ましい。リチウム混合物が、他の金属元素Ｍを含む場合、他の金属元素の単体又は金属化合物を第１複合物及びリチウム化合物と共に混合することで、リチウム混合物を得ることができる。他の金属元素Ｍを含む金属化合物としては、酸化物、水酸化物、塩化物、窒化物、炭酸塩、硫酸塩、硝酸塩、酢酸塩、蓚酸塩等を挙げることができる。 The lithium mixture may further contain a metal element M other than cobalt, strontium and lithium. Other metal elements M include nickel (Ni), manganese (Mn), aluminum (Al), magnesium (Mg), calcium (Ca), titanium (Ti), zirconium (Zr), niobium (Nb), and cerium ( Ta), chromium (Cr), molybdenum (Mo), iron (Fe), copper (Cu), silicon (Si), tin (Sn), bismuth (Bi), gallium (Ga), ittrium (Y), cerium (Y) Sm), erbium (Er), cerium (Ce), neodymium (Nd), lantern (La), cadmium (Cd), lutetium (Lu) and the like, and at least one selected from the group consisting of these is preferable. .. When the lithium mixture contains another metal element M, a lithium mixture can be obtained by mixing a simple substance or a metal compound of the other metal element together with the first complex and the lithium compound. Examples of the metal compound containing the other metal element M include oxides, hydroxides, chlorides, nitrides, carbonates, sulfates, nitrates, acetates, oxalates and the like.
リチウム混合物が、他の金属元素Ｍを含む場合、第１複合物に含まれるコバルト元素の総モル数に対する他の金属元素Ｍの総モル数の比は例えば、０．０１５以上０．１以下であり、好ましくは０．０２５以上０．０５以下である。 When the lithium mixture contains another metal element M, the ratio of the total number of moles of the other metal element M to the total number of moles of the cobalt element contained in the first composite is, for example, 0.015 or more and 0.1 or less. Yes, preferably 0.025 or more and 0.05 or less.
熱処理工程
熱処理工程では、リチウム混合物を熱処理して、リチウム遷移金属複合酸化物とストロンチウム化合物とを含む第２複合物を得る。第２複合物を構成するリチウム遷移金属複合酸化物は、層状構造を有し、リチウム以外の金属の総モル数に対するコバルトのモル数の比が例えば０．９以上である。
Heat Treatment Step In the heat treatment step, the lithium mixture is heat-treated to obtain a second composite containing a lithium transition metal composite oxide and a strontium compound. The lithium transition metal composite oxide constituting the second composite has a layered structure, and the ratio of the number of moles of cobalt to the total number of moles of metals other than lithium is, for example, 0.9 or more.
リチウム混合物の熱処理温度は例えば、５５０℃以上１２００℃以下であり、好ましくは６００℃以上１１５０℃以下、より好ましくは７００℃以上１１００℃以下である。混合物の熱処理は、単一の温度で行ってもよいが、均一に合成を行う観点から複数の温度で行ってもよい。複数の温度で熱処理する場合、例えば、第一温度を所定時間で保持した後、さらに昇温し、第二温度を所定時間で保持することが望ましい。第一温度は、例えば５５０℃以上９５０℃以下であり、好ましくは６５０℃以上７５０℃以下である。また第二温度は、例えば９５０℃以上１１００℃以下であり、好ましくは１０００℃以上１１００℃以下である。また第一温度と第二温度との差は、例えば３０℃以上であり、好ましくは２００℃以上であり、また例えば１０００℃以下であり、好ましくは５００℃以下である。 The heat treatment temperature of the lithium mixture is, for example, 550 ° C. or higher and 1200 ° C. or lower, preferably 600 ° C. or higher and 1150 ° C. or lower, and more preferably 700 ° C. or higher and 1100 ° C. or lower. The heat treatment of the mixture may be carried out at a single temperature, or may be carried out at a plurality of temperatures from the viewpoint of uniform synthesis. In the case of heat treatment at a plurality of temperatures, for example, it is desirable to hold the first temperature for a predetermined time, then raise the temperature further, and hold the second temperature for a predetermined time. The first temperature is, for example, 550 ° C. or higher and 950 ° C. or lower, preferably 650 ° C. or higher and 750 ° C. or lower. The second temperature is, for example, 950 ° C. or higher and 1100 ° C. or lower, preferably 1000 ° C. or higher and 1100 ° C. or lower. The difference between the first temperature and the second temperature is, for example, 30 ° C. or higher, preferably 200 ° C. or higher, and for example, 1000 ° C. or lower, preferably 500 ° C. or lower.
単一の温度で熱処理する場合の熱処理時間は例えば、１時間以上２０時間以下であり、５時間以上１０時間以下が好ましい。また、複数の温度で熱処理する場合、第一温度での熱処理時間は、例えば１時間以上２０時間以下であり、５時間以上１０時間以下が好ましい。第二温度での熱処理時間は、例えば１時間以上２０時間以下であり、２時間以上１０時間以下が好ましい。第一温度での熱処理時間と第二温度での熱処理時間とは同じであっても、異なっていてもよい。異なる場合、例えば第一温度の熱処理時間を第二温度での熱処理時間よりも長くすることができる。具体的には例えば、第二温度での熱処理時間を第一温度での熱処理時間の１．０５倍から２倍とすることができ、１．１倍から１．５倍であることが好ましい。ここで第一熱処理及び第二熱処理は連続して行ってもよく、それぞれ独立して行ってもよい。第一熱処理及び第二熱処理を連続して行う場合、第一温度から第二温度への昇温速度は例えば、５℃／分とすることができる。 The heat treatment time in the case of heat treatment at a single temperature is, for example, 1 hour or more and 20 hours or less, preferably 5 hours or more and 10 hours or less. When heat treatment is performed at a plurality of temperatures, the heat treatment time at the first temperature is, for example, 1 hour or more and 20 hours or less, preferably 5 hours or more and 10 hours or less. The heat treatment time at the second temperature is, for example, 1 hour or more and 20 hours or less, preferably 2 hours or more and 10 hours or less. The heat treatment time at the first temperature and the heat treatment time at the second temperature may be the same or different. If they are different, for example, the heat treatment time at the first temperature can be longer than the heat treatment time at the second temperature. Specifically, for example, the heat treatment time at the second temperature can be 1.05 to 2 times the heat treatment time at the first temperature, preferably 1.1 to 1.5 times. Here, the first heat treatment and the second heat treatment may be performed continuously or independently. When the first heat treatment and the second heat treatment are continuously performed, the rate of temperature rise from the first temperature to the second temperature can be, for example, 5 ° C./min.
熱処理の雰囲気は、大気中であっても、酸素を含む雰囲気であってもよい。熱処理は、例えばボックス炉やロータリーキルン炉、プッシャー炉、ローラーハースキルン炉等を用いて行うことができる。 The atmosphere of the heat treatment may be the atmosphere or an atmosphere containing oxygen. The heat treatment can be performed using, for example, a box furnace, a rotary kiln furnace, a pusher furnace, a roller harsquill furnace, or the like.
熱処理物には、必要に応じて分散処理が行われる。強い剪断力や衝撃を伴う粉砕処理ではなく、分散処理によって焼結した熱処理物の解離を行うことで粒度分布が狭く、粒度の揃った第２複合物が得られる。分散処理は乾式で行っても、湿式で行ってもよく、乾式で行うことが好ましい。分散処理は例えば、ボールミル、ジェットミル等を用いて行うことができる。 The heat-treated product is subjected to a dispersion treatment as needed. By dissociating the heat-treated product sintered by the dispersion treatment instead of the crushing treatment accompanied by a strong shearing force or impact, a second composite having a narrow particle size distribution and a uniform particle size can be obtained. The dispersion treatment may be performed by a dry method or a wet method, and is preferably performed by a dry method. The dispersion treatment can be performed using, for example, a ball mill, a jet mill, or the like.
第２複合物を構成するリチウム遷移金属複合酸化物は、リチウム以外の金属の総モル数に対するコバルトのモル数の比が例えば０．９以上であり、好ましくは０．９５以上である。リチウム遷移金属複合酸化物は、例えば、下記式（１）で表される組成を有していてよい。
ＬｉｐＣｏ（１−ｘ−ｙ）ＳｒｘＭｙＯ２ （１）
式（１）中、Ｍは、Ｎｉ、Ｍｎ、Ａｌ、Ｍｇ、Ｃａ、Ｔｉ、Ｚｒ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｆｅ、Ｃｕ、Ｓｉ、Ｓｎ、Ｂｉ、Ｇａ、Ｙ、Ｓｍ、Ｅｒ、Ｃｅ、Ｎｄ、Ｌａ、Ｃｄ及びＬｕからなる群より選択される少なくとも１種であって、０．９≦ｐ≦１．２、０≦ｘ＜０．０００５、０≦ｙ≦０．１、ｘ＋ｙ≦０．１を満たす。
In the lithium transition metal composite oxide constituting the second composite, the ratio of the number of moles of cobalt to the total number of moles of metals other than lithium is, for example, 0.9 or more, preferably 0.95 or more. The lithium transition metal composite oxide may have, for example, a composition represented by the following formula (1).
Li p Co (1-x- y) Sr x M y O 2 (1)
In formula (1), M is Ni, Mn, Al, Mg, Ca, Ti, Zr, Nb, Ta, Cr, Mo, Fe, Cu, Si, Sn, Bi, Ga, Y, Sm, Er, Ce. , Nd, La, Cd and Lu, at least one selected from the group consisting of 0.9 ≦ p ≦ 1.2, 0 ≦ x <0.0005, 0 ≦ y ≦ 0.1, x + y ≦ Satisfy 0.1.
第２複合物を構成するストロンチウム化合物としては例えば、酸化ストロンチウム（ＩＩ）、水酸化ストロンチウム、炭酸ストロンチウム、塩化ストロンチウム、硝酸ストロンチウム、硫酸ストロンチウム等を挙げることができ、これらからなる群から選択される少なくとも１種が好ましく、中でも炭酸ストロンチウムが好ましい。ストロンチウム化合物は、リチウム遷移金属複合酸化物の表面に存在していてよく、リチウム遷移金属複合酸化物の内部に存在していてよい。 Examples of the strontium compound constituting the second complex include strontium oxide (II), strontium hydroxide, strontium carbonate, strontium chloride, strontium nitrate, strontium sulfate, and the like, and at least selected from the group consisting of these. One type is preferable, and strontium carbonate is particularly preferable. The strontium compound may be present on the surface of the lithium transition metal composite oxide and may be present inside the lithium transition metal composite oxide.
非水電解質二次電池用正極活物質
非水電解質二次電池用正極活物質（以下、単に正極活物質ともいう）は、コバルトを含むリチウム遷移金属複合酸化物と、ストロンチウム化合物とを含む。正極活物質においては、リチウム遷移金属複合酸化物に含まれるコバルト元素の総モル数に対する、ストロンチウム化合物に含まれるストロンチウム元素の総モル数の比が０．０００１より大きく、０．０００５未満であり、好ましくは０．０００１５以上０．０００５未満であり、より好ましくは、０．０００２以上０．０００４５以下である。また、正極活物質を構成するリチウム遷移金属複合酸化物は、層状構造を有し、その組成がリチウム以外の金属の総モル数に対するコバルトのモル数の比が０．９以上である。
Positive electrode active material for non-aqueous electrolyte secondary battery The positive electrode active material for non-aqueous electrolyte secondary battery (hereinafter, also simply referred to as positive electrode active material) contains a lithium transition metal composite oxide containing cobalt and a strontium compound. In the positive electrode active material, the ratio of the total number of moles of the strontium element contained in the strontium compound to the total number of moles of the cobalt element contained in the lithium transition metal composite oxide is larger than 0.0001 and less than 0.0005. It is preferably 0.00015 or more and less than 0.0005, and more preferably 0.0002 or more and 0.00045 or less. Further, the lithium transition metal composite oxide constituting the positive electrode active material has a layered structure, and the ratio of the number of moles of cobalt to the total number of moles of metals other than lithium is 0.9 or more.
正極活物質が、コバルトを含むリチウム遷移金属複合酸化物と、ストロンチウム化合物とを含んで構成されることとで、リチウム遷移金属複合酸化物の内部密度が高くなり、また正極を構成する場合に正極活物質層の密度が向上する。これによりエネルギー密度の高い正極を構成することができる。 When the positive electrode active material is composed of a lithium transition metal composite oxide containing cobalt and a strontium compound, the internal density of the lithium transition metal composite oxide is increased, and the positive electrode is formed when the positive electrode is formed. The density of the active material layer is improved. This makes it possible to form a positive electrode having a high energy density.
正極活物質を構成するリチウム遷移金属複合酸化物は、リチウム以外の金属の総モル数に対するコバルトのモル数の比が例えば０．９以上であり、好ましくは０．９５以上である。リチウム遷移金属複合酸化物は、コバルト及びリチウム以外の他の金属元素Ｍをさらに含んでいてよい。他の金属元素Ｍとしては、Ｎｉ、Ｍｎ、Ａｌ、Ｍｇ、Ｃａ、Ｔｉ、Ｚｒ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｆｅ，Ｃｕ、Ｓｉ、Ｓｎ、Ｂｉ、Ｇａ、Ｙ、Ｓｍ、Ｅｒ、Ｃｅ、Ｎｄ、Ｌａ、Ｃｄ、Ｌｕ等が挙げられ、これらからなる群から選択される少なくとも１種が好ましい。リチウム遷移金属複合酸化物が他の金属元素Ｍを含む場合、コバルト元素の総モル数に対する他の金属元素Ｍの総モル数の比は例えば、０．０１５以上０．１以下であり、好ましくは０．０２５以上０．０５以下である。リチウム遷移金属複合酸化物は、例えば、下記式（１）で表される組成を有していてよい。
ＬｉｐＣｏ（１−ｘ−ｙ）ＳｒｘＭｙＯ２ （１）
式（２）中、Ｍは、Ｎｉ、Ｍｎ、Ａｌ、Ｍｇ、Ｃａ、Ｔｉ、Ｚｒ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｆｅ，Ｃｕ、Ｓｉ、Ｓｎ、Ｂｉ、Ｇａ、Ｙ、Ｓｍ、Ｅｒ、Ｃｅ、Ｎｄ、Ｌａ、Ｃｄ及びＬｕからなる群より選択される少なくとも１種であって、０．９≦ｐ≦１．２、０≦ｘ＜０．０００５、０≦ｙ≦０．１、ｘ＋ｙ≦０．１を満たす。
In the lithium transition metal composite oxide constituting the positive electrode active material, the ratio of the number of moles of cobalt to the total number of moles of metals other than lithium is, for example, 0.9 or more, preferably 0.95 or more. The lithium transition metal composite oxide may further contain cobalt and other metal elements M other than lithium. Other metal elements M include Ni, Mn, Al, Mg, Ca, Ti, Zr, Nb, Ta, Cr, Mo, Fe, Cu, Si, Sn, Bi, Ga, Y, Sm, Er, Ce, Examples thereof include Nd, La, Cd, Lu and the like, and at least one selected from the group consisting of these is preferable. When the lithium transition metal composite oxide contains another metal element M, the ratio of the total number of moles of the other metal element M to the total number of moles of the cobalt element is, for example, 0.015 or more and 0.1 or less, preferably 0.15 or more. It is 0.025 or more and 0.05 or less. The lithium transition metal composite oxide may have, for example, a composition represented by the following formula (1).
Li p Co (1-x- y) Sr x M y O 2 (1)
In formula (2), M is Ni, Mn, Al, Mg, Ca, Ti, Zr, Nb, Ta, Cr, Mo, Fe, Cu, Si, Sn, Bi, Ga, Y, Sm, Er, Ce. , Nd, La, Cd and Lu, at least one selected from the group consisting of 0.9 ≦ p ≦ 1.2, 0 ≦ x <0.0005, 0 ≦ y ≦ 0.1, x + y ≦ Satisfy 0.1.
正極活物質を構成するストロンチウム化合物としては、例えば、酸化ストロンチウム（ＩＩ）、水酸化ストロンチウム、炭酸ストロンチウム、塩化ストロンチウム、硝酸ストロンチウム、硫酸ストロンチウム等を挙げることができ、これらからなる群から選択される少なくとも１種が好ましく、中でも、炭酸ストロンチウムが好ましい。ストロンチウム化合物は、少なくとも一部がリチウム遷移金属複合酸化物の表面に存在していてよく、少なくとも一部がリチウム遷移金属複合酸化物の内部に存在していてよく、リチウム遷移金属複合酸化物の表面及び内部に、略均一に分布していてよい。 Examples of the strontium compound constituting the positive electrode active material include strontium oxide (II), strontium hydroxide, strontium carbonate, strontium chloride, strontium nitrate, strontium sulfate, and the like, and at least selected from the group consisting of these. One type is preferable, and among them, strontium carbonate is preferable. The strontium compound may be present at least in part on the surface of the lithium transition metal composite oxide, at least in part inside the lithium transition metal composite oxide, and on the surface of the lithium transition metal composite oxide. And inside, it may be distributed substantially uniformly.
正極活物質の５０％粒径Ｄ５０は、例えば１μｍ以上５０μｍ以下であってよく、錠剤密度の観点から１．５μｍ以上が好ましく、３μｍ以上がより好ましく、２０μｍ以上がさらに好ましく、また、４５μｍ以下が好ましく、４０μｍ以下がより好ましい。５０％粒径Ｄ５０は、レーザー回折式粒径分布測定装置を用いて、湿式条件で測定される体積基準の累積粒度分布において、小径側からの累積５０％に対応する粒径として求められる。 50% particle diameter D 50 of the positive electrode active material, for example, may be at 1μm or more 50μm or less, in view preferably not less than 1.5μm from the tablet density, more preferably at least 3 [mu] m, more preferably not less than 20 [mu] m, also, 45 [mu] m or less Is preferable, and 40 μm or less is more preferable. The 50% particle size D 50 is determined as a particle size corresponding to the cumulative 50% from the small diameter side in the volume-based cumulative particle size distribution measured under wet conditions using a laser diffraction type particle size distribution measuring device.
非水系電解質二次電池用電極
非水系電解質二次電池用電極は、集電体と、集電体上に配置され、前記製造方法で製造される非水系電解質二次電池用正極活物質を含む正極活物質層とを備える。係る電極を備える非水系電解質二次電池は、高い耐久性と高い出力特性とを達成することができる。
Electrodes for non-aqueous electrolyte secondary batteries Electrodes for non-aqueous electrolyte secondary batteries include a current collector and a positive electrode active material for non-aqueous electrolyte secondary batteries that is arranged on the current collector and is manufactured by the above manufacturing method. It includes a positive electrode active material layer. A non-aqueous electrolyte secondary battery provided with such an electrode can achieve high durability and high output characteristics.
集電体の材質としては例えば、アルミニウム、ニッケル、ステンレス等が挙げられる。正極活物質層は、上記の正極活物質、導電材、結着剤等を溶媒と共に混合して得られる正極合剤を集電体上に塗布し、乾燥処理、加圧処理等を行うことで形成することができる。導電材としては例えば、天然黒鉛、人造黒鉛、アセチレンブラック等が挙げられる。結着剤としては例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリアミドアクリル樹脂等が挙げられる。 Examples of the material of the current collector include aluminum, nickel, stainless steel and the like. The positive electrode active material layer is formed by applying a positive electrode mixture obtained by mixing the above positive electrode active material, a conductive material, a binder, etc. together with a solvent onto a current collector, and performing a drying treatment, a pressure treatment, or the like. Can be formed. Examples of the conductive material include natural graphite, artificial graphite, acetylene black and the like. Examples of the binder include polyvinylidene fluoride, polytetrafluoroethylene, and polyamide acrylic resin.
非水系電解質二次電池
非水系電解質二次電池は、上記非水系電解質二次電池用電極を備える。非水系電解質二次電池は、非水系電解質二次電池用電極に加えて、非水系二次電池用負極、非水系電解質、セパレータ等を備えて構成される。非水系電解液二次電池における、負極、非水系電解質、セパレータ等については例えば、特開２００２−０７５３６７号公報、特開２０１１−１４６３９０号公報、特開２００６−１２４３３号公報（これらは、その開示内容全体が参照により本明細書に組み込まれる）等に記載された、非水系電解質二次電池用のためのものを適宜用いることができる。
Non-aqueous electrolyte secondary battery The non-aqueous electrolyte secondary battery includes the electrode for the non-aqueous electrolyte secondary battery. The non-aqueous electrolyte secondary battery includes an electrode for a non-aqueous electrolyte secondary battery, a negative electrode for a non-aqueous secondary battery, a non-aqueous electrolyte, a separator, and the like. Regarding the negative electrode, the non-aqueous electrolyte, the separator and the like in the non-aqueous electrolyte secondary battery, for example, JP-A-2002-075367, JP-A-2011-146390, JP-A-2006-12433 (these are disclosure thereof). Those for non-aqueous electrolyte secondary batteries described in (the entire contents thereof are incorporated in the present specification by reference) and the like can be appropriately used.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
（実施例１）
正極活物質前駆体の調製
撹拌している純水中に、６０℃、回転数６５０ｒｐｍで撹拌しながら、硫酸コバルト水溶液及び塩化ストロンチウム水溶液を滴下した。このとき塩化ストロンチウム水溶液は、コバルトの総モル数に対するストロンチウムの総モル数の比が０．０００２５となるように滴下した。同時にｐＨ＝８．０となるように７．９モル／Ｌの水酸化ナトリウム水溶液を滴下した。硫酸コバルト水溶液及びストロンチウム水溶液の滴下が終了した後、水酸化ナトリウム水溶液のみをｐＨが９．４以上９．８以下になるまで滴下しつづけ、コバルトとストロンチウムを含む沈殿物を得た。得られた沈殿物をろ過、水洗後、３３０℃で１７時間熱処理し、コバルト及びストロンチウムを含む複合酸化物として、第１複合物を得た。
(Example 1)
Preparation of Positive Electrode Active Material Precursor A cobalt sulfate aqueous solution and a strontium chloride aqueous solution were added dropwise to the stirring pure water at 60 ° C. and a rotation speed of 650 rpm. At this time, the aqueous solution of strontium chloride was added dropwise so that the ratio of the total number of moles of strontium to the total number of moles of cobalt was 0.00025. At the same time, a 7.9 mol / L sodium hydroxide aqueous solution was added dropwise so that the pH was 8.0. After the dropping of the cobalt sulfate aqueous solution and the strontium aqueous solution was completed, only the sodium hydroxide aqueous solution was continuously added dropwise until the pH became 9.4 or more and 9.8 or less to obtain a precipitate containing cobalt and strontium. The obtained precipitate was filtered, washed with water, and then heat-treated at 330 ° C. for 17 hours to obtain a first composite as a composite oxide containing cobalt and strontium.
正極活物質の調製
コバルト及びストロンチウムを含む複合酸化物に含まれるコバルトに対して、リチウムのモル数の比が１．０１倍になるように炭酸リチウムを秤量し、複合酸化物及び炭酸リチウムを乾式混合してリチウム混合物を得た。得られたリチウム混合物を大気雰囲気中、７００℃で５時間熱処理した後、連続して１０８０℃で５時間、熱処理した。その後、分散処理をしてリチウム遷移金属複合酸化物とストロンチウム化合物を含む第２複合物として、正極活物質を得た。
Preparation of positive electrode active material Lithium carbonate is weighed so that the ratio of the number of moles of lithium to cobalt contained in the composite oxide containing cobalt and strontium is 1.01 times, and the composite oxide and lithium carbonate are dried. Mixing gave a lithium mixture. The obtained lithium mixture was heat-treated at 700 ° C. for 5 hours in an air atmosphere, and then continuously heat-treated at 1080 ° C. for 5 hours. Then, the dispersion treatment was carried out to obtain a positive electrode active material as a second composite containing a lithium transition metal composite oxide and a strontium compound.
（比較例１）
正極活物質前駆体の調製において、コバルトの総モル数に対するストロンチウムの総モル数の比が０．０００１になるように塩化ストロンチウム水溶液の量を変更した以外は、実施例１と同様の方法で、正極活物質を得た。
(Comparative Example 1)
In the preparation of the positive electrode active material precursor, the method was the same as in Example 1 except that the amount of the strontium chloride aqueous solution was changed so that the ratio of the total number of moles of strontium to the total number of moles of cobalt was 0.0001. A positive electrode active material was obtained.
（比較例２）
正極活物質前駆体の調製において、コバルトの総モル数に対するストロンチウムの総モル数の比が０．０００５になるように塩化ストロンチウムを水溶液の量を変更した以外は、実施例１と同様の方法で、正極活物質を得た。
(Comparative Example 2)
In the preparation of the positive electrode active material precursor, the same method as in Example 1 was used except that the amount of the aqueous solution of strontium chloride was changed so that the ratio of the total number of moles of strontium to the total number of moles of cobalt was 0.0005. , A positive electrode active material was obtained.
（比較例３）
正極活物質前駆体の調製
実施例１の正極活物質前駆体の調製において、塩化ストロンチウム水溶液を用いなかったこと以外は、実施例１と同様にしてコバルト酸化物を含む正極活物質前駆体を得た。
(Comparative Example 3)
Preparation of Positive Electrode Active Material Precursor A positive electrode active material precursor containing cobalt oxide was obtained in the same manner as in Example 1 except that an aqueous solution of strontium chloride was not used in the preparation of the positive electrode active material precursor of Example 1. It was.
正極活物質の調製
コバルト酸化物に含まれるコバルトの総モル数に対するストロンチウムの総モル数の比が０．０００５になるように炭酸ストロンチウムを秤量し、リチウムの総モル数の比が１．０１倍になるように炭酸リチウムを秤量した。前述のコバルト酸化物を含む正極活物質前駆体、炭酸ストロンチウム及び炭酸リチウムを乾式混合してリチウム混合物を得た。得られたリチウム混合物を大気雰囲気中、７００℃で５時間、次いで１０８０℃で５時間、熱処理した。その後、分散処理をして正極活物質を得た。
Preparation of positive electrode active material Strontium carbonate was weighed so that the ratio of the total number of moles of strontium to the total number of moles of cobalt contained in the cobalt oxide was 0.0005, and the ratio of the total number of moles of lithium was 1.01 times. Lithium carbonate was weighed so as to be. The above-mentioned positive electrode active material precursor containing cobalt oxide, strontium carbonate and lithium carbonate were dry-mixed to obtain a lithium mixture. The resulting lithium mixture was heat treated in an air atmosphere at 700 ° C. for 5 hours and then at 1080 ° C. for 5 hours. Then, the dispersion treatment was carried out to obtain a positive electrode active material.
（比較例４）
比較例３の正極活物質の調製において、炭酸ストロンチウムを添加しなかったこと以外は、比較例３と同様にして正極活物質を得た。
(Comparative Example 4)
A positive electrode active material was obtained in the same manner as in Comparative Example 3 except that strontium carbonate was not added in the preparation of the positive electrode active material of Comparative Example 3.
（断面ＳＥＭ−ＥＤＸの撮影）
上記で得られた正極活物質をエポキシ樹脂に分散させて固化した後、クロスセクションポリッシャにて二次粒子の断面出しを行って測定用断面サンプルを得た。得られたサンプルについて、走査透過型電子顕微鏡（ＳＥＭ；ＪＥＯＬ社製）／エネルギー分散型Ｘ線分析装置（ＥＤＸ；ＯＸＦＯＲＤ社製）にてＳＥＭ−ＥＤＸ像（加速電圧１０ｋＶ）を測定した。
(Cross section SEM-EDX photography)
The positive electrode active material obtained above was dispersed in an epoxy resin and solidified, and then the secondary particles were cross-sectioned with a cross-section polisher to obtain a cross-section sample for measurement. The obtained sample was measured with a scanning transmission electron microscope (SEM; manufactured by JEOL) / energy dispersive X-ray analyzer (EDX; manufactured by OXFORD) for an SEM-EDX image (acceleration voltage of 10 kV).
実施例１で得られた正極活物質のＳＥＭ−ＥＤＸ像を図１に示す。図１中の白色領域（例えば、符号１で示される）からは、ストロンチウムが検出され、それ以外の領域からはストロンチウムは検出されなかった。比較例３で得られた正極活物質のＳＥＭ−ＥＤＸ像を図２に示す。図２中の白色領域（例えば、符号２で示される）の位置からはストロンチウムが検出され、それ以外の領域からはストロンチウムは検出されなかった。比較例４で得られた正極活物質のＳＥＭ−ＥＤＸ像を図３に示す。図３のＳＥＭ−ＥＤＸ像からはストロンチウムは検出されなかった。 The SEM-EDX image of the positive electrode active material obtained in Example 1 is shown in FIG. Strontium was detected in the white region (for example, indicated by reference numeral 1) in FIG. 1, and strontium was not detected in the other regions. The SEM-EDX image of the positive electrode active material obtained in Comparative Example 3 is shown in FIG. Strontium was detected from the position of the white region (for example, indicated by reference numeral 2) in FIG. 2, and strontium was not detected from the other regions. The SEM-EDX image of the positive electrode active material obtained in Comparative Example 4 is shown in FIG. No strontium was detected in the SEM-EDX image of FIG.
（エネルギー密度の評価）
上記で得られた正極活物質９９質量部、ＰＶＤＦ（ポリフッ化ビニリデン）１．０質量部を、ジルコニアボール入スイングロールミキサーを用いて混合した後、３．０ｇ秤量し、圧力６５ｋＮで２０秒間加圧してペレットを作製し、ペレットの密度を測定した。得られた密度に、コバルト酸リチウムの理論容量である２７２ｍＡｈ／ｇを掛けた数値をエネルギー密度とした。結果を表１に示す。
(Evaluation of energy density)
After mixing 99 parts by mass of the positive electrode active material and 1.0 part by mass of PVDF (polyvinylidene fluoride) obtained above using a swing roll mixer containing zirconia balls, 3.0 g is weighed and added at a pressure of 65 kN for 20 seconds. Pellets were prepared by pressing and the density of the pellets was measured. The value obtained by multiplying the obtained density by 272 mAh / g, which is the theoretical capacity of lithium cobalt oxide, was taken as the energy density. The results are shown in Table 1.
（サイクル特性の評価）
正極の作製
上記で得られた正極活物質９６質量部、アセチレンブラック１．５質量部、及びＰＶＤＦ（ポリフッ化ビニリデン）２．５質量部を、Ｎ−メチル−２−ピロリドン（ＮＭＰ）に分散させて正極スラリーを調製した。得られた正極スラリーをアルミニウム箔に塗布し、乾燥後ロールプレス機で圧縮成形し、所定サイズに裁断して正極板を得た。
(Evaluation of cycle characteristics)
Preparation of Positive Electrode 96 parts by mass of the positive electrode active material obtained above, 1.5 parts by mass of acetylene black, and 2.5 parts by mass of PVDF (polyvinylidene fluoride) were dispersed in N-methyl-2-pyrrolidone (NMP). Prepared a positive electrode slurry. The obtained positive electrode slurry was applied to an aluminum foil, dried, compression-molded with a roll press, and cut into a predetermined size to obtain a positive electrode plate.
負極の作製
人造黒鉛９５．０質量部、カルボキシメチルセルロース（ＣＭＣ）１．５質量部、気相炭素繊維（ＶＧＣＦ）２．５質量部、及びスチレンブタジエンゴム（ＳＢＲ）１．０質量部を水に分散させて負極スラリーを調製した。得られた負極スラリーを銅箔に塗布し、乾燥後ロールプレス機で圧縮成形し、所定サイズに裁断して負極板を得た。
Preparation of negative electrode 95.0 parts by mass of artificial graphite, 1.5 parts by mass of carboxymethyl cellulose (CMC), 2.5 parts by mass of vapor phase carbon fiber (VGCF), and 1.0 part by mass of styrene butadiene rubber (SBR) in water. Negative electrode slurry was prepared by dispersion. The obtained negative electrode slurry was applied to a copper foil, dried, compression-molded with a roll press, and cut into a predetermined size to obtain a negative electrode plate.
評価用二次電池の組み立て
正極板のアルミニウム箔と負極板の銅箔に、それぞれリード電極を取り付けたのち１２０℃で真空乾燥を行った。次いで、正極と負極との間にセルロースからなるセパレータを配し、袋状のラミネートパックにそれらを収納した。収納後６０℃で真空乾燥して各部材に吸着した水分を除去した。真空乾燥後、ラミネートパック内に、ポリマー系非水電解液を注入、封止して、ラミネートタイプの評価用二次電池を得た。なお、ポリマー系非水電解液は、ポリマー系非水電解液は、エチレンカーボネート（ＥＣ）とプロピレンカーボネート（ＰＣ）とを体積比率を１：１に混合して、六フッ化リン酸リチウム（ＬｉＰＦ６）を濃度が１ｍｏｌ／ｌになるように溶解したものを用いた。
Assembly of secondary battery for evaluation After attaching lead electrodes to the aluminum foil of the positive electrode plate and the copper foil of the negative electrode plate, vacuum drying was performed at 120 ° C. Next, a separator made of cellulose was arranged between the positive electrode and the negative electrode, and they were stored in a bag-shaped laminate pack. After storage, it was vacuum dried at 60 ° C. to remove the moisture adsorbed on each member. After vacuum drying, a polymer-based non-aqueous electrolytic solution was injected into the laminate pack and sealed to obtain a laminate type secondary battery for evaluation. The polymer-based non-aqueous electrolyte solution is a polymer-based non-aqueous electrolyte solution in which ethylene carbonate (EC) and propylene carbonate (PC) are mixed at a volume ratio of 1: 1 to form lithium hexafluorophosphate (LiPF). 6 ) was dissolved so as to have a concentration of 1 mol / l.
サイクル評価
得られた評価用二次電池を２５℃で、低レートでのエージングした後、温度４５℃、定電流２．０Ｃ（１Ｃ＝１８０ｍＡｈ設定）で定電圧４．４５Ｖ、終止電圧２．７５Ｖで１００サイクル充放電を行った。１００サイクル目の放電容量と１サイクル目の放電容量から、下式にてサイクル容量維持率を算出した。結果を表１に示す。
（１００サイクル目の放電容量）／（１サイクル目の放電容量）×１００
Cycle evaluation After aging the obtained secondary battery for evaluation at a low rate at 25 ° C, the constant voltage is 4.45V and the final voltage is 2.75V at a temperature of 45 ° C and a constant current of 2.0C (1C = 180mAh setting). The battery was charged and discharged for 100 cycles. From the discharge capacity of the 100th cycle and the discharge capacity of the 1st cycle, the cycle capacity retention rate was calculated by the following formula. The results are shown in Table 1.
(Discharge capacity in the 100th cycle) / (Discharge capacity in the 1st cycle) x 100
表１より、実施例１で得られた正極活物質は、比較例１から４で得られた正極活物質に対して高いエネルギー密度を持つ事を確認できた。また、実施例１で得られた正極活物質は、比較例２及び３で得られた正極活物質より高いサイクル容量維持率を持つことが確認できた。 From Table 1, it was confirmed that the positive electrode active material obtained in Example 1 had a higher energy density than the positive electrode active material obtained in Comparative Examples 1 to 4. Further, it was confirmed that the positive electrode active material obtained in Example 1 had a higher cycle capacity retention rate than the positive electrode active material obtained in Comparative Examples 2 and 3.
Claims (8)
前記第１複合物とリチウム化合物とを混合して、リチウム混合物を得ることと、
前記リチウム混合物を熱処理して、層状構造を有しコバルトを含むリチウム遷移金属複合酸化物とストロンチウム化合物とを含む第２複合物を得ることと、を含み、
前記リチウム遷移金属複合酸化物は、リチウム以外の金属の総モル数に対するコバルトのモル数の比が０．９以上である非水系電解質二次電池用正極活物質の製造方法。 To prepare a first complex containing cobalt and strontium, where the ratio of the number of moles of strontium to the number of moles of cobalt is greater than 0.0001 and less than 0.0005.
Mixing the first complex with a lithium compound to obtain a lithium mixture,
The lithium mixture is heat-treated to obtain a second composite containing a lithium transition metal composite oxide having a layered structure and containing cobalt and a strontium compound.
The lithium transition metal composite oxide is a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery in which the ratio of the number of moles of cobalt to the total number of moles of metals other than lithium is 0.9 or more.
ＬｉｐＣｏ（１−ｘ−ｙ）ＳｒｘＭｙＯ２ （１）
（式（１）中、Ｍは、Ｎｉ、Ｍｎ、Ａｌ、Ｍｇ、Ｃａ、Ｔｉ、Ｚｒ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｆｅ、Ｃｕ、Ｓｉ、Ｓｎ、Ｂｉ、Ｇａ、Ｙ、Ｓｍ、Ｅｒ、Ｃｅ、Ｎｄ、Ｌａ、Ｃｄ及びＬｕからなる群より選択される少なくとも１種であって、０．９≦ｐ≦１．２、０≦ｘ＜０．０００５、０≦ｙ≦０．１、ｘ＋ｙ≦０．１を満たす。） The production method according to any one of claims 1 to 3, wherein the lithium transition metal composite oxide has a composition represented by the following formula (1).
Li p Co (1-x- y) Sr x M y O 2 (1)
(In the formula (1), M is Ni, Mn, Al, Mg, Ca, Ti, Zr, Nb, Ta, Cr, Mo, Fe, Cu, Si, Sn, Bi, Ga, Y, Sm, Er, At least one selected from the group consisting of Ce, Nd, La, Cd and Lu, 0.9 ≦ p ≦ 1.2, 0 ≦ x <0.0005, 0 ≦ y ≦ 0.1, x + y. ≤0.1 is satisfied.)
前記リチウム遷移金属複合酸化物におけるリチウム以外の金属の総モル数に対するコバルトのモル数の比が０．９以上であり、
リチウム遷移金属複合酸化物に含まれるコバルトのモル数に対する、ストロンチウム化合物に含まれるストロンチウムのモル数の比が０．０００１より大きく、０．０００５未満である非水系電解質二次電池用正極活物質。 It contains a lithium transition metal composite oxide having a layered structure containing cobalt and a strontium compound.
The ratio of the number of moles of cobalt to the total number of moles of metals other than lithium in the lithium transition metal composite oxide is 0.9 or more.
A positive electrode active material for a non-aqueous electrolyte secondary battery in which the ratio of the number of moles of strontium contained in a strontium compound to the number of moles of cobalt contained in a lithium transition metal composite oxide is more than 0.0001 and less than 0.0005.
ＬｉｐＣｏ（１−ｘ−ｙ）ＳｒｘＭｙＯ２ （１）
（式（２）中、Ｍは、Ｎｉ、Ｍｎ、Ａｌ、Ｍｇ、Ｃａ、Ｔｉ、Ｚｒ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｆｅ、Ｃｕ、Ｓｉ、Ｓｎ、Ｂｉ、Ｇａ、Ｙ、Ｓｍ、Ｅｒ、Ｃｅ、Ｎｄ、Ｌａ、Ｃｄ及びＬｕからなる群より選択される少なくとも１種であって、０．９≦ｐ≦１．２、０≦ｘ＜０．０００５、０≦ｙ≦０．１、ｘ＋ｙ≦０．１を満たす。） The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 6 or 7, wherein the lithium transition metal composite oxide has a composition represented by the following formula (1).
Li p Co (1-x- y) Sr x M y O 2 (1)
(In the formula (2), M is Ni, Mn, Al, Mg, Ca, Ti, Zr, Nb, Ta, Cr, Mo, Fe, Cu, Si, Sn, Bi, Ga, Y, Sm, Er, At least one selected from the group consisting of Ce, Nd, La, Cd and Lu, 0.9 ≦ p ≦ 1.2, 0 ≦ x <0.0005, 0 ≦ y ≦ 0.1, x + y. ≤0.1 is satisfied.)
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| JP2002319398A (en) * | 2001-04-20 | 2002-10-31 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2013182757A (en) * | 2012-03-01 | 2013-09-12 | Nippon Chem Ind Co Ltd | Positive electrode active material for lithium secondary battery, manufacturing method thereof and lithium secondary battery |
| JP2013182758A (en) * | 2012-03-01 | 2013-09-12 | Nippon Chem Ind Co Ltd | Manufacturing method of positive electrode active material for lithium secondary battery, positive electrode active material for lithium secondary battery and lithium secondary battery |
| JP2014523383A (en) * | 2011-05-31 | 2014-09-11 | オーエムジー・コッコラ・ケミカルズ・オイ | Lithium cobalt oxide material |
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| JP7085135B2 (en) | 2018-10-12 | 2022-06-16 | トヨタ自動車株式会社 | A positive electrode active material and a secondary battery including the positive electrode active material. |
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| JP2002319398A (en) * | 2001-04-20 | 2002-10-31 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2014523383A (en) * | 2011-05-31 | 2014-09-11 | オーエムジー・コッコラ・ケミカルズ・オイ | Lithium cobalt oxide material |
| JP2013182757A (en) * | 2012-03-01 | 2013-09-12 | Nippon Chem Ind Co Ltd | Positive electrode active material for lithium secondary battery, manufacturing method thereof and lithium secondary battery |
| JP2013182758A (en) * | 2012-03-01 | 2013-09-12 | Nippon Chem Ind Co Ltd | Manufacturing method of positive electrode active material for lithium secondary battery, positive electrode active material for lithium secondary battery and lithium secondary battery |
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