JP6649369B2 - Method for producing 5V-class spinel-type lithium manganese-containing composite oxide - Google Patents
Method for producing 5V-class spinel-type lithium manganese-containing composite oxide Download PDFInfo
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- JP6649369B2 JP6649369B2 JP2017515621A JP2017515621A JP6649369B2 JP 6649369 B2 JP6649369 B2 JP 6649369B2 JP 2017515621 A JP2017515621 A JP 2017515621A JP 2017515621 A JP2017515621 A JP 2017515621A JP 6649369 B2 JP6649369 B2 JP 6649369B2
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- JP
- Japan
- Prior art keywords
- spinel
- composite oxide
- containing composite
- type lithium
- lithium manganese
- Prior art date
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Links
- 239000002131 composite material Substances 0.000 title claims description 138
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title claims description 133
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 239000002994 raw material Substances 0.000 claims description 124
- 229910052760 oxygen Inorganic materials 0.000 claims description 94
- 238000010438 heat treatment Methods 0.000 claims description 90
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 88
- 239000001301 oxygen Substances 0.000 claims description 88
- 239000012298 atmosphere Substances 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 76
- 239000011572 manganese Substances 0.000 claims description 58
- 238000010304 firing Methods 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 37
- 229910052596 spinel Inorganic materials 0.000 claims description 36
- 239000011029 spinel Substances 0.000 claims description 36
- 229910052748 manganese Inorganic materials 0.000 claims description 32
- 229910052744 lithium Inorganic materials 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- 238000012545 processing Methods 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 238000010298 pulverizing process Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 description 110
- 239000002002 slurry Substances 0.000 description 68
- 239000002245 particle Substances 0.000 description 67
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 49
- 239000002270 dispersing agent Substances 0.000 description 40
- 239000007921 spray Substances 0.000 description 38
- 238000001035 drying Methods 0.000 description 32
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 30
- 238000005469 granulation Methods 0.000 description 27
- 230000003179 granulation Effects 0.000 description 27
- 239000013078 crystal Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- 239000010936 titanium Substances 0.000 description 23
- 239000007774 positive electrode material Substances 0.000 description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 21
- 239000007789 gas Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000126 substance Substances 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 15
- 229910052796 boron Inorganic materials 0.000 description 14
- 229910004356 Ti Raw Inorganic materials 0.000 description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 description 12
- 229910052573 porcelain Inorganic materials 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 239000013049 sediment Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 9
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 9
- 229920005646 polycarboxylate Polymers 0.000 description 9
- 238000005507 spraying Methods 0.000 description 9
- 239000012856 weighed raw material Substances 0.000 description 9
- 239000002798 polar solvent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 206010021143 Hypoxia Diseases 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- -1 lithium halide Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 238000010908 decantation Methods 0.000 description 6
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 229910005161 Ni5MnO4(BO3)2 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011899 heat drying method Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000001238 wet grinding Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910013184 LiBO Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 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
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- ZWOYKDSPPQPUTC-UHFFFAOYSA-N dimethyl carbonate;1,3-dioxolan-2-one Chemical compound COC(=O)OC.O=C1OCCO1 ZWOYKDSPPQPUTC-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011361 granulated particle Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 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
- IGLGDSDAIYIUDL-UHFFFAOYSA-N pentadecalithium pentaborate Chemical compound [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] IGLGDSDAIYIUDL-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003196 poly(1,3-dioxolane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005550 wet granulation Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- 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
Description
本発明は、リチウム二次電池の正極活物質として用いることができるスピネル型リチウムマンガン含有複合酸化物、中でも、金属Ｌｉ基準電位で４．５Ｖ以上の作動電位を有する５Ｖ級スピネル型リチウムマンガン含有複合酸化物の製造方法に関する。 The present invention relates to a spinel-type lithium manganese-containing composite oxide that can be used as a positive electrode active material of a lithium secondary battery, and in particular, a 5V-class spinel-type lithium manganese-containing composite oxide having an operating potential of 4.5 V or more as a metal Li reference potential. The present invention relates to a method for producing an oxide.
リチウム二次電池は、エネルギー密度が大きく、寿命が長いなどの特徴を有している。そのため、リチウム二次電池は、ビデオカメラ等の家電製品や、ノート型パソコン、携帯電話機等の携帯型電子機器、パワーツールなどの電動工具などの電源として広く用いられており、最近では、電気自動車（ＥＶ）やハイブリッド電気自動車（ＨＥＶ）などに搭載される大型電池へも応用されている。 Lithium secondary batteries have features such as high energy density and long life. For this reason, lithium secondary batteries have been widely used as power sources for home appliances such as video cameras, portable electronic devices such as notebook computers and mobile phones, and power tools such as power tools. It is also applied to large batteries mounted on (EV) and hybrid electric vehicles (HEV).
リチウム二次電池は、充電時には正極からリチウムがイオンとして溶け出して負極へ移動して吸蔵され、放電時には逆に負極から正極へリチウムイオンが戻る構造の二次電池であり、その高いエネルギー密度は正極材料の電位に起因することが知られている。 A lithium secondary battery is a secondary battery having a structure in which lithium is dissolved as ions from the positive electrode during charging, moves to the negative electrode and is occluded, and when discharged, lithium ions return from the negative electrode to the positive electrode in reverse. It is known that the potential is caused by the potential of the positive electrode material.
この種のリチウム二次電池の正極活物質としては、層構造をもつＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎＯ2などのリチウム遷移金属酸化物のほか、ＬｉＭｎ2Ｏ4、ＬｉＮｉ0.5Ｍｎ1.5Ｏ4などのマンガン系のスピネル構造（Ｆｄ-３ｍ）を有するスピネル型リチウムマンガン含有複合酸化物が知られている。Examples of the positive electrode active material of this type of lithium secondary battery include lithium transition metal oxides such as LiCoO 2 , LiNiO 2 , and LiMnO 2 having a layer structure, and manganese such as LiMn 2 O 4 and LiNi 0.5 Mn 1.5 O 4. A spinel-type lithium manganese-containing composite oxide having a system spinel structure (Fd-3m) is known.
この種のスピネル型リチウムマンガン含有複合酸化物は、原料価格が安く、毒性がなく安全であり、しかも過充電に強い性質を有することから、電気自動車（ＥＶ）やハイブリッド電気自動車（ＨＥＶ）などの大型電池用の次世代正極活物質として着目されている。また、３次元的にＬｉイオンの挿入・脱離が可能なスピネル型リチウム遷移金属酸化物（ＬＭＯ）は、層構造をもつＬｉＣｏＯ2などのリチウム遷移金属酸化物に比べて出力特性に優れているため、ＥＶ用電池、ＨＥＶ用電池などのように優れた出力特性が要求される用途に利用が期待されている。This kind of spinel-type lithium manganese-containing composite oxide is inexpensive in raw materials, safe without toxicity, and has a property of being resistant to overcharging, so that it can be used in electric vehicles (EV) and hybrid electric vehicles (HEV). It is receiving attention as a next-generation positive electrode active material for large batteries. Further, a spinel-type lithium transition metal oxide (LMO) capable of three-dimensionally inserting and removing Li ions has excellent output characteristics as compared with a lithium transition metal oxide such as LiCoO 2 having a layer structure. Therefore, it is expected to be used for applications requiring excellent output characteristics, such as batteries for EVs and batteries for HEVs.
中でも、ＬｉＭｎ2Ｏ4におけるＭｎサイトの一部を他の遷移金属（Ｃｒ、Ｃｏ、Ｎｉ、Ｆｅ、Ｃｕ）で置換することで、５Ｖ付近に作動電位を持つことが知られるようになり、現在、金属Ｌｉ基準電位で４．５Ｖ以上の作動電位を有する５Ｖ級スピネル型リチウムマンガン含有複合酸化物の開発が行われている。Above all, it has been known that by substituting a part of the Mn site in LiMn 2 O 4 with another transition metal (Cr, Co, Ni, Fe, Cu), it has an operating potential around 5V. A 5V-class spinel-type lithium manganese-containing composite oxide having an operating potential of 4.5 V or more as a metal Li reference potential has been developed.
例えば特許文献１には、５Ｖ級の起電力を示すリチウム二次電池の正極活物質として、スピネル型リチウムマンガン複合酸化物にクロムを必須添加成分とし、さらにニッケルまたはコバルトを添加してなる高容量スピネル型リチウムマンガン複合酸化物正極活物質が開示されている。 For example, Patent Document 1 discloses a high-capacity spin-type lithium-manganese composite oxide containing chromium as an essential component and further adding nickel or cobalt as a positive electrode active material of a lithium secondary battery exhibiting a 5V-class electromotive force. A spinel-type lithium manganese composite oxide positive electrode active material is disclosed.
特許文献２には、Ｌｉ金属に対して４．５Ｖ以上の電位で充放電を行うスピネル構造の結晶ＬｉＭｎ２−ｙ−ｚＮｉｙＭｚＯ４（但し、Ｍ：Ｆｅ，Ｃｏ，Ｔｉ，Ｖ，Ｍｇ，Ｚｎ，Ｇａ，Ｎｂ，Ｍｏ，Ｃｕよりなる群から選ばれた少なくとも一種、０．２５≦ｙ≦０．６、０≦ｚ≦０．１）が開示されている。Patent Literature 2 discloses a spinel-structured crystal LiMn 2-yz Ni y M z O 4 (where M: Fe, Co, Ti, and V) that charges and discharges Li metal at a potential of 4.5 V or more. , Mg, Zn, Ga, Nb, Mo, and Cu, at least one selected from the group consisting of 0.25 ≦ y ≦ 0.6 and 0 ≦ z ≦ 0.1).
特許文献３には、４．５Ｖ以上もの起電力を発生し、且つ放電容量を維持することができる正極活物質として、一般式：Ｌｉａ（ＭｘＭｎ２−ｘ−ｙＡｙ）Ｏ４（式中、０．４＜ｘ、０＜ｙ、ｘ＋ｙ＜２、０＜ａ＜１．２である。Ｍは、Ｎｉ、Ｃｏ、Ｆｅ、ＣｒおよびＣｕよりなる群から選ばれ、少なくともＮｉを含む一種以上の金属元素を含む。Ａは、Ｓｉ、Ｔｉから選ばれる少なくとも一種の金属元素を含む。但し、ＡがＴｉだけを含む場合には、Ａの比率ｙの値は、０．１＜ｙである。）で表されるスピネル型リチウムマンガン複合酸化物を含むことを特徴とする二次電池用正極活物質が開示され、その製造方法として、原料を秤量して混合し、混合粉を６００〜９５０℃の温度で、空気中又は酸素中で焼成することによって正極活物質を得る方法が開示されている。Patent Document 3 generates a well electromotive force than 4.5V, as the positive electrode active material capable of and maintaining the discharge capacity, the general formula: Lia (M x Mn 2- x-y A y) O 4 ( In the formula, 0.4 <x, 0 <y, x + y <2, and 0 <a <1.2, and M is selected from the group consisting of Ni, Co, Fe, Cr, and Cu, and includes at least Ni. A contains at least one metal element A contains at least one metal element selected from Si and Ti, provided that when A contains only Ti, the value of the ratio y of A is 0.1 <y The positive electrode active material for a secondary battery, comprising a spinel-type lithium manganese composite oxide represented by the formula (1), is disclosed. By firing in air or oxygen at a temperature of ~ 950 ° C. To obtain an active material is disclosed.
特許文献４には、金属Ｌｉ基準電位で４．５Ｖ以上の作動電位を有するスピネル型リチウムマンガン含有複合酸化物において、ＬｉＭｎ2Ｏ4-δにおけるＭｎサイトの一部を、Ｌｉと、Ｎｉを含む金属元素Ｍ1（Ｍ1はＮｉ、Ｃｏ及びＦｅのうちの少なくとも一種を含む金属元素である）と、他の金属元素Ｍ2（Ｍ2はＴｉであるか、又は、ＴｉとＭｇ、Ａｌ、Ｂａ、Ｃｒ及びＮｂのうちの少なくとも一種とを含む金属元素である）とで置換してなる結晶相を含有するスピネル型リチウムマンガン含有複合酸化物であって、Ｎｉ、Ｍｎ及びＢを含む複合酸化物相を含有することを特徴とするスピネル型リチウムマンガン含有複合酸化物が開示されている。Patent Document 4 discloses that in a spinel-type lithium manganese-containing composite oxide having an operating potential of 4.5 V or more as a metal Li reference potential, a part of the Mn site in LiMn 2 O 4-δ contains Li and Ni. A metal element M1 (M1 is a metal element containing at least one of Ni, Co and Fe) and another metal element M2 (M2 is Ti, or Ti and Mg, Al, Ba, Cr and Nb) is a spinel-type lithium manganese-containing composite oxide containing a crystal phase substituted with at least one of Nb) and a composite oxide phase containing Ni, Mn and B. A spinel-type lithium manganese-containing composite oxide is disclosed.
特許文献５には、Ｌｉ[ＮｉyＭｎ2-(a+b)-y-zＬｉaＴｉｂＭz]Ｏ4（式中、０≦z≦0.3、0.3≦y＜0.6であって、Ｍ＝Ａｌ、Ｍｇ、Ｆｅ及びＣｏからなる群のうちから少なくとも１つ以上選ばれる金属元素）で示されるマンガン系スピネル型リチウム遷移金属酸化物であって、前記式において、ａ＞０であり、ｂ＞０であり、２-（ａ+ｂ）-ｙ-ｚ＜１．７であり、かつ３≦ｂ／ａ≦８であることを特徴とするマンガン系スピネル型リチウム遷移金属酸化物が開示されている。Patent Document 5, Li in [Ni y Mn 2- (a + b) -yz Li a Ti b M z] O4 ( wherein A 0 ≦ z ≦ 0.3,0.3 ≦ y < 0.6, M = Al , Mg, Fe, and Co), a manganese-based spinel-type lithium transition metal oxide represented by the formula: a> 0, b> 0 And a manganese-based spinel-type lithium transition metal oxide characterized by 2- (a + b) -yz <1.7 and 3 ≦ b / a ≦ 8 is disclosed. .
また、特許文献６には、リチウムマンガン含有複合酸化物の製造方法に関し、結晶子サイズを大きくすることができ、それでいて結晶構造の歪みを抑制することができるリチウム遷移金属酸化物の製造方法として、原料を混合する工程、焼成する工程、熱処理する工程を備えたリチウム遷移金属酸化物の製造方法において、酸素分圧０．０１５ＭＰａ〜０．１５ＭＰａの雰囲気下にて８５０℃以上で焼成した後、酸素分圧０．０３ＭＰａ以上の雰囲気下にて、第１次酸素放出温度±５０℃の温度で熱処理することを特徴とするリチウムマンガン含有複合酸化物の製造方法が開示されている。 Patent Literature 6 relates to a method for producing a lithium manganese-containing composite oxide. As a method for producing a lithium transition metal oxide, which can increase the crystallite size while suppressing distortion of the crystal structure, In a method for producing a lithium transition metal oxide including a step of mixing raw materials, a step of firing, and a step of heat treatment, after firing at 850 ° C. or more in an atmosphere having an oxygen partial pressure of 0.015 MPa to 0.15 MPa, A method for producing a lithium manganese-containing composite oxide, characterized by performing a heat treatment at a primary oxygen release temperature of ± 50 ° C. in an atmosphere having a partial pressure of 0.03 MPa or more, is disclosed.
４．５Ｖ以上の作動電位を有する５Ｖ級スピネル型リチウムマンガン含有複合酸化物は、４Ｖ級スピネル型リチウムマンガン含有複合酸化物では殆ど生じない課題、すなわち、電解液との反応により発生するガスの発生量が多いという特徴的な課題を抱えていた。 The 5V-class spinel-type lithium manganese-containing composite oxide having an operating potential of 4.5 V or more has almost no problem with the 4V-class spinel-type lithium manganese-containing composite oxide, that is, generation of gas generated by reaction with the electrolytic solution. There was a characteristic problem that the amount was large.
５Ｖ級スピネル型リチウムマンガン複合酸化物を使用すると、４．５Ｖ付近のプラトー領域を拡大し、高電位容量域を拡張することができ、エネルギー密度を高くすることができる一方、ガスの発生量が増加することが分かってきた。そのため、５Ｖ級スピネル型リチウムマンガン含有複合酸化物に関しては、高電位容量域を拡張してエネルギー密度を高くすることと、ガスの発生量を抑えることを両立させることが困難であった。 When a 5V-class spinel-type lithium-manganese composite oxide is used, the plateau region around 4.5 V can be expanded, the high potential capacity region can be expanded, and the energy density can be increased. It has been found to increase. Therefore, it has been difficult for the 5V-class spinel-type lithium manganese-containing composite oxide to achieve both an increase in the energy density by expanding the high potential capacity region and a reduction in the amount of generated gas.
そこで、本願発明は、５Ｖ級スピネル型リチウムマンガン含有複合酸化物の製造方法に関して、かかる観点から、高電位容量域の拡大とガス発生の抑制を両立させることができる、新たな製造方法を提供せんとするものである。 In view of this, the present invention does not provide a new method for producing a 5V-class spinel-type lithium manganese-containing composite oxide, which can achieve both expansion of the high potential capacity region and suppression of gas generation from this viewpoint. It is assumed that.
本発明は、金属Ｌｉ基準電位で４．５Ｖ以上の作動電位を有するスピネル型リチウムマンガン含有複合酸化物の製造方法において、カールフィッシャー水分測定装置で測定される室温〜３００℃範囲の水分量（「ＫＦ水分」と称する）が２％以下であり、かつ、ＩＣＰにより分析される硫黄含有量が０．３４ｗｔ％未満であるスピネル型リチウムマンガン含有複合酸化物を、処理雰囲気の全体圧力が大気圧よりも高い圧力であって、かつ、該雰囲気における酸素分圧が大気中の酸素分圧よりも高い処理雰囲気において、５００℃より高く８５０℃より低い温度で熱処理する加圧熱処理工程を備えたスピネル型リチウムマンガン含有複合酸化物の製造方法を提案する。 The present invention relates to a method for producing a spinel-type lithium manganese-containing composite oxide having an operating potential of 4.5 V or higher as a metal Li reference potential, wherein a moisture content in a range from room temperature to 300 ° C. measured with a Karl Fischer moisture meter (““ KF moisture) is less than 2% and the sulfur content of the lithium manganese-containing composite oxide analyzed by ICP is less than 0.34 wt%. Spinel type having a pressure heat treatment step of performing heat treatment at a temperature higher than 500 ° C. and lower than 850 ° C. in a processing atmosphere where the pressure is high and the oxygen partial pressure in the atmosphere is higher than the oxygen partial pressure in the atmosphere. A method for producing a lithium manganese-containing composite oxide is proposed.
本発明が提案する製法によれば、処理雰囲気の全体圧力が大気圧よりも高い圧力であって、かつ、該雰囲気における酸素分圧が大気中の酸素分圧よりも高い処理雰囲気下で熱処理することによって、ガス発生を抑えることができると共に、４．５Ｖ付近のプラトー領域を拡大させることができ、高電位容量域を拡大させることができるため、エネルギー密度の向上を図ることもできる。このように、本発明が提案する製法によれば、高電位容量域の拡大とガス発生の抑制を両立させることができる。 According to the manufacturing method proposed by the present invention, the heat treatment is performed in a processing atmosphere in which the entire pressure of the processing atmosphere is higher than the atmospheric pressure, and the oxygen partial pressure in the atmosphere is higher than the oxygen partial pressure in the atmosphere. Thereby, gas generation can be suppressed, and the plateau region around 4.5 V can be expanded, and the high potential capacity region can be expanded, so that the energy density can be improved. As described above, according to the manufacturing method proposed by the present invention, both expansion of the high potential capacity region and suppression of gas generation can be achieved.
次に、本発明を実施するための形態例に基づいて本発明を説明する。但し、本発明が次に説明する実施形態に限定されるものではない。 Next, the present invention will be described based on embodiments for carrying out the present invention. However, the present invention is not limited to the embodiment described below.
＜本５Ｖ級スピネル＞
本発明の実施形態の一例に係るスピネル型リチウムマンガン含有複合酸化物（「本５Ｖ級スピネル」と称する）は、空間群Ｆｄ−３ｍ（Ｏｒｉｇｉｎ Ｃｈｏｉｃｅ２）の立方晶の結晶構造モデルとフィッティングし、観測強度と計算強度の一致の程度を表わすＲｗｐ、ＳがＲｗｐ＜１０、またはＳ＜２．５である５Ｖ級スピネルであって、金属Ｌｉ基準電位で４．５Ｖ以上の作動電位を有する５Ｖ級スピネル型リチウムマンガン含有複合酸化物である。<This 5V class spinel>
The spinel-type lithium manganese-containing composite oxide according to an example of the embodiment of the present invention (referred to as “the present 5V-class spinel”) is fitted with a cubic crystal structure model of space group Fd-3m (Origin Choice 2) and observed. A 5V-class spinel in which Rwp, S representing the degree of agreement between the strength and the calculated strength, where Rwp <10 or S <2.5, and having a working potential of 4.5 V or more at a metal Li reference potential of 5V-class spinel. It is a lithium-manganese-containing composite oxide.
本５Ｖ級スピネルは、Ｌi、Ｍｎ及びＯと、これら以外の２種以上の元素と、を含むものであればよい。
この際、「これら以外の２種以上の元素」のうちの少なくとも１元素は、Ｎｉ、Ｃｏ及びＦｅからなる群から選択される元素であり、他の１元素は、Ｍｇ、Ｔｉ、Ａｌ、Ｂａ、Ｃｒ、Ｗ、Ｍｏ、Ｙ、Ｚｒ及びＮｂからなる群から選択される元素であるのが好ましい。The present 5V class spinel may be any as long as it contains Li, Mn, and O, and two or more elements other than these.
At this time, at least one of the “two or more other elements” is an element selected from the group consisting of Ni, Co, and Fe, and the other one is Mg, Ti, Al, Ba. , Cr, W, Mo, Y, Zr and Nb.
本５Ｖ級スピネルとしては、ＬｉＭｎ2Ｏ4-δにおけるＭｎサイトの一部を、Ｌｉと、金属元素Ｍ1と、他の金属元素Ｍ2とで置換してなる結晶構造を有するスピネル型リチウムマンガン含有複合酸化物を含むものを挙げることができる。As the present 5V-class spinel, a spinel-type lithium manganese-containing composite having a crystal structure in which a part of the Mn site in LiMn 2 O 4-δ is replaced with Li, a metal element M1, and another metal element M2. Those containing an oxide can be given.
上記金属元素Ｍ1は、主に金属Ｌｉ基準電位で４．５Ｖ以上の作動電位を発現させるのに寄与する置換元素であり、Ｎｉ、Ｃｏ及びＦｅなどを挙げることができ、これらのうち少なくとも一種を含んでいればよく、Ｍ1として他の金属元素を含んでいてもよい。
金属元素Ｍ2は、主に結晶構造を安定化させて特性を高めるのに寄与する置換元素であり、例えば容量維持率向上に寄与する置換元素として、例えばＭｇ、Ｔｉ、Ａｌ、Ｂａ、Ｃｒ、Ｗ、Ｍｏ、Ｙ、Ｚｒ及びＮｂなどを挙げることができる。これらＭｇ、Ｔｉ、Ａｌ、Ｂａ、Ｃｒ、Ｗ、Ｍｏ、Ｙ、Ｚｒ及びＮｂのうちの少なくとも一種を含んでいればよく、Ｍ2として他の金属元素を含んでいてもよい。The metal element M1 is a substitution element that mainly contributes to exhibiting an operating potential of 4.5 V or more at a metal Li reference potential, and examples thereof include Ni, Co, and Fe. M1 may contain other metal elements.
The metal element M2 is a substitution element mainly contributing to stabilizing the crystal structure and improving the characteristics. For example, as a substitution element contributing to the improvement of the capacity retention ratio, for example, Mg, Ti, Al, Ba, Cr, W , Mo, Y, Zr and Nb. At least one of Mg, Ti, Al, Ba, Cr, W, Mo, Y, Zr, and Nb may be contained, and other metal element may be contained as M2.
本５Ｖ級スピネルの一例として、式（１）：Ｌｉ[ＬｉaＭｎ2-a-b-cＭ1bＭ2c]Ｏ4-δで示されるスピネル型リチウムマンガン含有複合酸化物を含むものを挙げることができる。式（１）におけるＭ1及びＭ2は上述のとおりである。As an example of the present 5V-class spinel, equation (1): can be mentioned those containing Li [Li a Mn 2-abc M1 b M2 c] spinel-type lithium manganese-containing complex oxide represented by O 4-δ. M1 and M2 in the equation (1) are as described above.
上記式（１）において、「ａ」は、０．００〜０．２０であればよく、中でも０．０１以上或いは０．１０以下、その中でも０．０２以上或いは０．０８以下であるのがより一層好ましい。
Ｍ1の含有量を示す「b」は、０．２０〜１．２０であればよく、中でも０．３０以上或いは１．１０以下、その中でも０．３５以上或いは１．０５以下であるのがより一層好ましい。
Ｍ2の含有量を示す「ｃ」は、０．００１〜０．４００であればよく、中でも０．００２以上或いは０．４００以下、その中でも０．００５以上或いは０．３０以下、さらにその中でも０．１０以上であるのがより一層好ましい。特に０．１０以上とすることで、より効果的にガス発生量を抑えることができる。
なお、上記各式における「４−δ」は、酸素欠損を含んでいてもよいことを示しており、酸素の一部がフッ素で置換されていてもよい。In the above formula (1), “a” may be 0.00 to 0.20, particularly 0.01 or more and 0.10 or less, and especially 0.02 or 0.08 or less. Even more preferred.
"B" indicating the content of M1 may be 0.20 to 1.20, more preferably 0.30 or more or 1.10 or less, more preferably 0.35 or more or 1.05 or less. More preferred.
"C" indicating the content of M2 may be 0.001 to 0.400, more preferably 0.002 or more and 0.400 or less, more preferably 0.005 or more or 0.30 or less, and more preferably 0 or less. It is even more preferable that the number is 10 or more. In particular, when the content is 0.10 or more, the amount of generated gas can be more effectively suppressed.
Note that “4-δ” in each of the above formulas indicates that oxygen deficiency may be included, and a part of oxygen may be substituted with fluorine.
但し、本５Ｖ級スピネルは、Ｌｉ、Ｍｎ、Ｍ1、Ｍ2及びＯ以外の他の成分を含有してもよい。特にその他の元素をそれぞれ０．５重量％以下であれば含んでいてもよい。この程度の量であれば、本５Ｖ級スピネルの性能にほとんど影響しないと考えられるからである。 However, the present 5V class spinel may contain components other than Li, Mn, M1, M2 and O. In particular, other elements may be contained as long as each is 0.5% by weight or less. This is because it is considered that such an amount hardly affects the performance of the present 5V class spinel.
また、本５Ｖ級スピネルの一例として、式（２）：Ｌｉ[ＬｉaＭｎ2-a-b-cＮｉbＭ2c]Ｏ4-δで示されるスピネル型リチウムマンガン含有複合酸化物を含むものを挙げることができる。
式（２）において、「ａ」、「ｂ」、「ｃ」及び「４−δ」は、上記式（１）のそれぞれと同様である。
また、式（２）におけるＭ2としては、Ｍｇ、Ｔｉ、Ａｌ、Ｂａ、Ｃｒ、Ｗ、Ｍｏ、Ｙ、Ｚｒ、Ｃｏ、Ｆｅ、Ｎｂなどを好ましい例として挙げることができ、これらＭｇ、Ｔｉ、Ａｌ、Ｂａ、Ｃｒ、Ｗ、Ｍｏ、Ｙ、Ｚｒ、Ｃｏ、Ｆｅ、Ｎｂのうちの少なくとも一種を含んでいればよく、Ｍ2として他の金属元素を含んでいてもよい。 Further, as an example of the present 5V class spinel, a spinel-type lithium manganese-containing composite oxide represented by the formula (2): Li [Li a Mn 2-abc Ni b M2 c ] O 4-δ may be mentioned. it can.
In the formula (2), “a”, “b”, “c” and “4-δ” are the same as in the above formula (1).
Preferred examples of M2 in Formula (2) include Mg, Ti, Al, Ba, Cr, W, Mo, Y, Zr, Co, Fe, and Nb. , Ba, Cr, W, Mo, Y, Zr, Co, Fe, and Nb only need to be included, and other metal elements may be included as M2.
式（２）において、「ａ」は、０．００〜０．２０であればよく、中でも０．０１以上或いは０．１０以下、その中でも０．０２以上或いは０．０８以下であるのがより一層好ましい。
Ｍ1の含有量を示す「b」は、０．２０〜０．７０であればよく、中でも０．３０以上或いは０．６０以下、その中でも０．３５以上或いは０．５５以下、さらにその中でも０．４９以下であるのがより一層好ましい。特に、０．４９以下とすることで、より効果的に高電位範囲のサイクル特性を向上させることができる。
Ｍ2の含有量を示す「ｃ」は、０．００１〜０．４００であればよく、中でも０．００２以上或いは０．４００以下、その中でも０．００５以上或いは０．３００以下、さらにその中でも０．１０以上であるのがより一層好ましい。特に、０．１０以上とすることで、より効果的にガス発生量を抑えることができる。In the formula (2), “a” may be 0.00 to 0.20, particularly 0.01 or more and 0.10 or less, and more preferably 0.02 or more and 0.08 or less. More preferred.
"B" indicating the content of M1 may be 0.20 to 0.70, more preferably 0.30 or more, or 0.60 or less, among which 0.35 or more, or 0.55 or less, and more preferably 0. .49 or less is still more preferable. In particular, by setting the ratio to 0.49 or less, the cycle characteristics in the high potential range can be more effectively improved.
"C" indicating the content of M2 may be 0.001 to 0.400, more preferably 0.002 or more, or 0.400 or less, more preferably 0.005 or more, or 0.300 or less, and more preferably 0 or less. It is even more preferable that the number is 10 or more. In particular, by setting it to 0.10 or more, the gas generation amount can be more effectively suppressed.
また、本５Ｖ級スピネルは、Ｂを含有していてもよい。この際、Ｂの存在状態としては、スピネルの結晶相のほかに、Ｎｉ、Ｍｎ及びＢを含む複合酸化物相を含有していてもよい。
Ｎｉ、Ｍｎ及びＢを含む前記複合酸化物相としては、例えばＮｉ5ＭｎＯ4（ＢＯ3）2の結晶相を挙げることができる。
Ｎｉ5ＭｎＯ4（ＢＯ3）2の結晶相を含有することは、Ｘ線回折（ＸＲＤ）により得られた回折パターンを、ＰＤＦ（Ｐｏｗｄｅｒ Ｄｉｆｆｒａｃｔｉｏｎ Ｆｉｌｅ）番号「０１−０７９−１０２９」と照合することにより確認することができる。
Ｎｉ、Ｍｎ及びＢを含む前記複合酸化物は、本５Ｖ級スピネル粒子の表面や粒界に存在しているものと推察される。Further, the present 5V class spinel may contain B. At this time, B may contain a composite oxide phase containing Ni, Mn, and B in addition to the spinel crystal phase.
Examples of the composite oxide phase containing Ni, Mn, and B include a crystal phase of Ni 5 MnO 4 (BO 3 ) 2 .
The inclusion of the Ni 5 MnO 4 (BO 3 ) 2 crystal phase means that the diffraction pattern obtained by X-ray diffraction (XRD) is compared with a PDF (Powder Diffraction File) number “01-079-1029”. Can be confirmed by
It is presumed that the composite oxide containing Ni, Mn, and B exists on the surface and grain boundaries of the present 5V class spinel particles.
Ｎｉ、Ｍｎ及びＢを含む前記複合酸化物相の含有量に関しては、本５Ｖ級スピネル中のＢ元素の含有量が０．０２〜０．８０質量％となるように前記複合酸化物相を含有するのが好ましく、中でも０．０５質量％以上或いは０．６０質量％以下、その中でも０．３０質量％以下、特に０．２５質量％以下となるように前記複合酸化物相を含有するのがさらに好ましい。
Ｂ元素の含有量が０．０２質量％以上であれば、高温（例えば４５℃）での放電容量を維持することができ、Ｂ元素の含有量が０．８０質量％以下であればレート特性を維持することができるから、好ましい。Regarding the content of the complex oxide phase containing Ni, Mn and B, the complex oxide phase is contained so that the content of the element B in the present 5V-class spinel is 0.02 to 0.80% by mass. It is preferable to include the composite oxide phase so that the content is at least 0.05% by mass or at most 0.60% by mass, especially at most 0.30% by mass, particularly at most 0.25% by mass. More preferred.
When the content of the element B is 0.02% by mass or more, the discharge capacity at a high temperature (for example, 45 ° C.) can be maintained, and when the content of the element B is 0.80% by mass or less, the rate characteristic is obtained. Is preferable since it is possible to maintain
＜本５Ｖ級スピネルの製造方法＞
本５Ｖ級スピネルの製造方法の一例として、加圧熱処理工程を備えた製造方法を挙げることができる。<Production method of the present 5V class spinel>
As an example of a method for producing the present 5V-class spinel, a production method including a pressure heat treatment step can be mentioned.
本５Ｖ級スピネルの製造方法としては、スピネル型リチウムマンガン含有複合酸化物、好ましくは５Ｖスピネル型リチウムマンガン含有複合酸化物を被処理物とする加圧熱処理工程を備えていればよい。この際、被処理物としてのスピネル型リチウムマンガン含有複合酸化物は、後述するように原料から製造してもよいし、本５Ｖ級スピネルの製造方法とは別に製造された物を入手して該被処理物として使用してもよい。 The method for producing the present 5V-class spinel may include a pressure heat treatment step using a spinel-type lithium manganese-containing composite oxide, preferably a 5V spinel-type lithium manganese-containing composite oxide as an object to be treated. At this time, the spinel-type lithium manganese-containing composite oxide as the object to be treated may be produced from a raw material as described later, or a material produced separately from the method for producing the present 5V-class spinel may be obtained. It may be used as an object to be processed.
本５Ｖ級スピネルの製造方法の一例として、原料混合工程、焼成工程及び加圧熱処理工程をこの順に備えると共に、さらに洗浄工程を備えた製造方法を挙げることができる。この際、洗浄工程は適宜順序で挿入することが可能である。例えば、原料混合工程の前に、原料混合工程の後に、焼成工程の前に、焼成工程の後に、加圧熱処理工程の前に、又は、焼成工程の後に挿入することも可能であるし、複数回洗浄工程を実施することも可能である。
また、上記工程の他に、他の工程を追加することも可能である。例えば、湿式粉砕工程、造粒工程、熱処理工程、その他の工程などをさらに追加することが可能である。また、各工程後に解砕して分級する解砕・分級工程を挿入することなどは必要に応じて実施するのが好ましい。As an example of a method for producing the present 5V-class spinel, a production method including a raw material mixing step, a firing step, and a pressure heat treatment step in this order, and further including a washing step can be mentioned. At this time, the cleaning steps can be inserted in an appropriate order. For example, before the raw material mixing step, after the raw material mixing step, before the firing step, after the firing step, before the pressure heat treatment step, or can be inserted after the firing step, It is also possible to carry out a multiple washing step.
In addition, other steps can be added in addition to the above steps. For example, a wet pulverization step, a granulation step, a heat treatment step, and other steps can be further added. In addition, it is preferable to insert a crushing / classifying step of crushing and classifying after each step as necessary.
（原料）
ここでは、式（１）：Ｌｉ[ＬｉaＭｎ2-a-b-cＭ1bＭ2c]Ｏ4-δ又は式（２）：Ｌｉ[ＬｉaＭｎ2-a-b-cＮｉbＭ2c]Ｏ4-δで示されるスピネル型リチウムマンガン含有複合酸化物を含有するものを製造するための原料について説明する。
但し、本発明の製造対象である本５Ｖ級スピネルは、上記式（１）（２）で示されるものに限定されるものではないから、原料は適宜変更可能である。(material)
Here, the formula (1): Li [Li a Mn 2-abc M1 b M2 c] O 4-δ or Formula (2): represented by Li [Li a Mn 2-abc Ni b M2 c] O 4-δ The raw material for producing the spinel-type lithium-manganese-containing composite oxide will be described.
However, the present 5V-class spinel to be produced in the present invention is not limited to those represented by the above formulas (1) and (2), so that the raw materials can be appropriately changed.
式（１）：Ｌｉ[ＬｉaＭｎ2-a-b-cＭ1bＭ2c]Ｏ4-δ又は式（２）：Ｌｉ[ＬｉaＭｎ2-a-b-cＮｉbＭ2c]Ｏ4-δで示されるスピネル型リチウムマンガン含有複合酸化物を製造するための原料としては、リチウム原料、マンガン原料、Ｍ1金属原料、Ｍ2金属原料、その他例えばホウ素原料などを挙げることができる。Equation (1): Li [Li a Mn 2-abc M1 b M2 c] O 4-δ or Formula (2): Li spinel represented by [Li a Mn 2-abc Ni b M2 c] O 4-δ As a raw material for producing the lithium manganese-containing composite oxide, a lithium raw material, a manganese raw material, an M1 metal raw material, an M2 metal raw material, and other materials such as a boron raw material can be exemplified.
リチウム原料としては、例えば水酸化リチウム（ＬｉＯＨ）、炭酸リチウム（Ｌｉ２ＣＯ３）、硝酸リチウム（ＬｉＮＯ3）、ＬｉＯＨ・Ｈ2Ｏ、酸化リチウム（Ｌｉ2Ｏ）、その他脂肪酸リチウムやリチウムハロゲン化物等を挙げることができる。
マンガン原料としては、例えば炭酸マンガン、硝酸マンガン、塩化マンガン、二酸化マンガン、三酸化二マンガン、四酸化三マンガン等を挙げることができ、中でも炭酸マンガン、二酸化マンガンが好ましい。その中でも、電解法によって得られる電解二酸化マンガンが特に好ましい。
Ｍ1金属原料及びＭ2金属原料としては、Ｍ1又はＭ2金属の炭酸塩、硝酸塩、塩化物、オキシ水酸化塩、水酸化物などを挙げることができる。Examples of the lithium raw material include lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ), lithium nitrate (LiNO 3 ), LiOH · H 2 O, lithium oxide (Li 2 O), other fatty acid lithium and lithium halide. And the like.
As the manganese raw material, for example, manganese carbonate, manganese nitrate, manganese chloride, manganese dioxide, dimanganese trioxide, trimanganese tetroxide and the like can be mentioned, among which manganese carbonate and manganese dioxide are preferable. Among them, electrolytic manganese dioxide obtained by an electrolytic method is particularly preferable.
Examples of the M1 metal raw material and the M2 metal raw material include carbonates, nitrates, chlorides, oxyhydroxides, and hydroxides of M1 or M2 metals.
また、原料中にホウ素化合物を配合することもできる。
ホウ素化合物としては、ホウ素（Ｂ元素）を含有する化合物であればよく、例えばホウ酸或いはホウ酸リチウムを使用するのが好ましい。ホウ酸リチウムとしては、例えばメタ硼酸リチウム（ＬｉＢＯ2）、四硼酸リチウム（Ｌｉ2Ｂ4Ｏ7）、五硼酸リチウム（ＬｉＢ5Ｏ8）及び過硼酸リチウム（Ｌｉ2Ｂ2Ｏ5）等の各種形態のものを用いることが可能である。
このようなホウ素化合物を配合すると、本５Ｖ級スピネルの結晶相のほかに、Ｎｉ、Ｍｎ及びＢを含む前記複合酸化物相、例えばＮｉ5ＭｎＯ4（ＢＯ3）2の結晶相が生じることがある。Further, a boron compound can be blended in the raw material.
As the boron compound, any compound containing boron (B element) may be used. For example, boric acid or lithium borate is preferably used. Examples of lithium borate include lithium metaborate (LiBO 2 ), lithium tetraborate (Li 2 B 4 O 7 ), lithium pentaborate (LiB 5 O 8 ), and lithium perborate (Li 2 B 2 O 5 ). Various forms can be used.
When such a boron compound is blended, a crystal phase of the composite oxide phase containing Ni, Mn and B, for example, a crystal phase of Ni 5 MnO 4 (BO 3 ) 2 may be generated in addition to the crystal phase of the present 5V class spinel. is there.
（洗浄工程）
洗浄工程に供する被処理物は、例えば、原料混合前の各原料、原料混合後の原料混合粉、加圧熱処理後の処理粉末、焼成工程で得られた処理物、さらには、後述する解砕・分級工程で得られた処理粉末であってもよい。これらのうちの一種類又は二種類以上を洗浄してもよい。(Washing process)
The materials to be subjected to the cleaning step include, for example, each raw material before mixing the raw materials, a raw material mixed powder after the raw material mixing, a processed powder after the pressure heat treatment, a processed material obtained in the firing step, and a crushing method described later. -The treated powder obtained in the classification step may be used. One or more of these may be washed.
洗浄工程では、被処理物（粉末）を、極性溶媒と接触させて、粉末中に含まれる不純物を離脱させるように洗浄するのが好ましい。
例えば、極性溶媒と混合し攪拌してスラリーとし、得られたスラリーをろ過などによって固液分離して不純物を除去するようにすればよい。この際、固液分離は後工程で行ってもよい。
なお、スラリーとは、極性溶媒中に処理粉末が分散した状態を意味する。In the washing step, it is preferable that the object to be treated (powder) is contacted with a polar solvent to be washed so as to remove impurities contained in the powder.
For example, the slurry may be mixed with a polar solvent and stirred to form a slurry, and the obtained slurry may be subjected to solid-liquid separation by filtration or the like to remove impurities. At this time, the solid-liquid separation may be performed in a subsequent step.
In addition, the slurry means a state in which the processing powder is dispersed in a polar solvent.
洗浄に用いる極性溶媒としては、水を用いるのが好ましい。
水としては、市水でもよいが、フィルターまたは湿式磁選機を通過させたイオン交換水や純水を用いるのが好ましい。
水のｐＨは４〜１０であるのが好ましく、中でも５以上或いは９以下であるのがさらに好ましい。
洗浄時の液温に関しては、洗浄時の液温が低ければ電池特性がより良好になることが確認されているため、かかる観点から、５〜７０℃であるのが好ましく、中でも６０℃以下であるのがより一層好ましく、その中でも特に４５℃以下であるのがより一層好ましい。さらには特に３０℃以下であるのがより一層好ましい。
洗浄時の液温が低ければ電池特性がより良好になる理由は、液温が高過ぎると、リチウムマンガン含有複合酸化物中のリチウムがイオン交換水のプロトンとイオン交換してリチウムが抜けて高温特性に影響するためであると推定できる。As the polar solvent used for washing, it is preferable to use water.
The water may be city water, but it is preferable to use ion-exchanged water or pure water that has passed through a filter or a wet magnetic separator.
The pH of water is preferably 4 to 10, and more preferably 5 or more or 9 or less.
Regarding the liquid temperature at the time of washing, it has been confirmed that the battery characteristics become better if the liquid temperature at the time of washing is low. Therefore, from such a viewpoint, the temperature is preferably 5 to 70 ° C., and particularly preferably 60 ° C. or less. More preferably, the temperature is particularly preferably 45 ° C. or lower. Furthermore, the temperature is particularly preferably 30 ° C. or lower.
If the liquid temperature during washing is low, the battery characteristics will be better because if the liquid temperature is too high, lithium in the lithium-manganese-containing composite oxide will ion-exchange with the protons of ion-exchanged water and lithium will escape, resulting in a high temperature. It can be estimated that this is because it affects the characteristics.
被処理物（粉末）と接触させる極性溶媒の量については、極性溶媒に対するリチウムマンガン含有複合酸化物の質量比（「スラリー濃度」とも称する）が１０〜７０ｗｔ％となるように調整するのが好ましく、中でも２０ｗｔ％以上或いは６０ｗｔ％以下、その中でも３０ｗｔ％以上或いは５０ｗｔ％以下となるように調整するのがより一層好ましい。極性溶媒の量が１０ｗｔ％以上であれば、ＳＯ4などの不純物を溶出させることが容易であり、逆に６０ｗｔ％以下であれば、極性溶媒の量に見合った洗浄効果を得ることができる。The amount of the polar solvent to be brought into contact with the object to be treated (powder) is preferably adjusted so that the mass ratio of the lithium manganese-containing composite oxide to the polar solvent (also referred to as “slurry concentration”) becomes 10 to 70 wt%. In particular, it is more preferable that the content is adjusted so as to be 20 wt% or more or 60 wt% or less, and particularly to 30 wt% or more or 50 wt% or less. If the amount of the polar solvent is 10 wt% or more, impurities such as SO 4 can be easily eluted. Conversely, if the amount is 60 wt% or less, a cleaning effect corresponding to the amount of the polar solvent can be obtained.
なお、原料混合前の各原料、及び、原料混合後の原料混合粉を洗浄する場合には、各原料又は原料混合粉を洗浄液に投入して撹拌後、静置して上澄み液を除去するなどの方法を採用すればよい。 In addition, when each raw material before mixing the raw materials and the raw material mixed powder after the raw material mixing are washed, each raw material or the raw material mixed powder is put into the cleaning liquid, stirred, and then left standing to remove the supernatant liquid. Method may be adopted.
また、焼成工程で得られた処理物、すなわちスピネル型リチウムマンガン含有複合酸化物を洗浄する際は、洗浄液に投入して撹拌後、静置して上澄み液を除去すればよい。例えば、スピネル型リチウムマンガン含有複合酸化物を洗浄液に投入して２０分撹拌後、１０分静置して上澄み液中に含まれるスピネル型リチウムマンガン含有複合酸化物を除去するのが好ましい。このように洗浄することで、スピネル型リチウムマンガン含有複合酸化物の不純物量、例えば硫黄含有量を低下させることができる。 Further, when washing the treated product obtained in the firing step, that is, the spinel-type lithium manganese-containing composite oxide, the supernatant may be removed by throwing into a washing solution, stirring, and then allowing to stand. For example, it is preferable that the spinel-type lithium-manganese-containing composite oxide contained in the supernatant is removed by throwing the spinel-type lithium-manganese-containing composite oxide into the cleaning solution, stirring for 20 minutes, and then allowing the mixture to stand for 10 minutes. By performing such washing, the amount of impurities, for example, the sulfur content of the spinel-type lithium manganese-containing composite oxide can be reduced.
また、加圧熱処理後の処理物を洗浄する際は、加圧熱処理して得られたスピネル型リチウムマンガン含有複合酸化物を洗浄液に投入して撹拌後、静置して上澄み液を除去すればよい。例えば、スピネル型リチウムマンガン含有複合酸化物を洗浄液に投入して２０分撹拌後、１０分静置して上澄み液中に含まれるスピネル型リチウムマンガン含有複合酸化物を除去するのが好ましい。 Also, when washing the treated product after the pressure heat treatment, the spinel-type lithium manganese-containing composite oxide obtained by the pressure heat treatment is put into the cleaning solution, stirred, and then left standing to remove the supernatant liquid. Good. For example, it is preferable that the spinel-type lithium-manganese-containing composite oxide contained in the supernatant is removed by throwing the spinel-type lithium-manganese-containing composite oxide into the cleaning solution, stirring for 20 minutes, and then allowing the mixture to stand for 10 minutes.
（原料の混合工程）
原料の混合は、原料を均一に混合できれば、その方法を特に限定するものではない。例えばミキサー等の公知の混合機を用いて各原料を同時又は適当な順序で加えて湿式又は乾式で攪拌混合して原料混合粉とすればよい。置換しにくい元素、例えばアルミニウムなどを添加する場合には湿式混合を採用するのが好ましい。(Material mixing process)
The method of mixing the raw materials is not particularly limited as long as the raw materials can be uniformly mixed. For example, using a known mixer such as a mixer, the respective raw materials may be added simultaneously or in an appropriate order, and may be mixed by stirring wet or dry to obtain a raw material mixed powder. When an element that is difficult to substitute, for example, aluminum, is added, it is preferable to employ wet mixing.
乾式混合としては、例えば高速で該原料混合粉を回転させる精密混合機を使用した混合方法を例示することができる。
他方、湿式混合としては、水や分散剤などの液媒体に上記原料混合粉を加えて湿式混合してスラリー化させる方法を挙げることができる。As the dry mixing, for example, a mixing method using a precision mixer that rotates the raw material mixed powder at high speed can be exemplified.
On the other hand, as the wet mixing, there can be mentioned a method in which the raw material mixture powder is added to a liquid medium such as water or a dispersant, and the mixture is wet-mixed to form a slurry.
（湿式粉砕工程）
湿式粉砕工程では、原料を水などの液媒体に投入して粉砕すればよい。原料を混合する前に湿式粉砕することもできるし、原料混合後に湿式粉砕することもできる。
原料混合後に湿式粉砕する場合は、上記のように、水や分散剤などの液媒体に上記原料混合粉を加えて湿式混合してスラリー化させた後、得られたスラリーを湿式粉砕機で粉砕すればよい。この際、特にサブミクロンオーダーまで粉砕するのが好ましい。サブミクロンオーダーまで粉砕した後、造粒及び焼成することにより、焼成反応前の各粒子の均一性を高めることができ、反応性を高めることができる。
他方、原料を混合する前に湿式粉砕する場合には、上記各原料をそれぞれ湿式粉砕し、混合した後、必要に応じてさらに湿式粉砕すればよい。
各原料をそれぞれ粉砕する場合には、原料混合時の均質性を高めるため、原料を混合する前に予め、Ｄｍａｘが大きい原料を先に粉砕しておくことが好ましい。例えばニッケル化合物を、必要に応じてニッケル化合物とマンガン化合物を、粉砕及び分級して、ニッケル化合物やマンガン化合物の最大粒径（Ｄｍａｘ）が１０μｍ以下、中でも５μｍ以下、その中でも４μｍ以下になるように調整するのが好ましい。(Wet grinding process)
In the wet pulverization step, the raw material may be introduced into a liquid medium such as water and pulverized. The wet pulverization can be performed before mixing the raw materials, or the wet pulverization can be performed after mixing the raw materials.
When wet grinding is performed after mixing the raw materials, as described above, the raw material mixed powder is added to a liquid medium such as water or a dispersant and wet-mixed to form a slurry, and the obtained slurry is ground with a wet grinding machine. do it. At this time, it is particularly preferable to pulverize to a submicron order. After pulverization to the submicron order, granulation and firing, the uniformity of each particle before the firing reaction can be increased, and the reactivity can be increased.
On the other hand, when the wet pulverization is performed before mixing the raw materials, the respective raw materials described above may be wet pulverized, mixed, and then further wet pulverized as necessary.
When each raw material is pulverized, it is preferable to pulverize a raw material having a large Dmax in advance before mixing the raw materials in order to increase the homogeneity at the time of mixing the raw materials. For example, a nickel compound and, if necessary, a nickel compound and a manganese compound are pulverized and classified so that the maximum particle diameter (Dmax) of the nickel compound or the manganese compound is 10 μm or less, particularly 5 μm or less, and among them, 4 μm or less. Adjustment is preferred.
（造粒工程）
上記の如く混合した原料は、必要に応じて所定の大きさに造粒した後、焼成するのが好ましい。但し、必ずしも造粒しなくてもよい。
造粒方法は、前工程で粉砕された各種原料が造粒粒子内で分散していれば、湿式でも乾式でもよく、押し出し造粒法、転動造粒法、流動造粒法、混合造粒法、噴霧乾燥造粒法、加圧成型造粒法、或いはロール等を用いたフレーク造粒法でもよい。但し、湿式造粒した場合には、焼成前に充分に乾燥させることが必要である。(Granulation process)
The raw materials mixed as described above are preferably granulated to a predetermined size, if necessary, and then fired. However, granulation does not necessarily have to be performed.
The granulation method may be wet or dry as long as the various raw materials pulverized in the previous step are dispersed in the granulated particles, and may be an extrusion granulation method, a tumbling granulation method, a fluidized granulation method, a mixed granulation method. Method, spray drying granulation method, pressure molding granulation method, or flake granulation method using a roll or the like. However, in the case of wet granulation, it is necessary to sufficiently dry before firing.
乾燥方法としては、噴霧熱乾燥法、熱風乾燥法、真空乾燥法、フリーズドライ法などの公知の乾燥方法によって乾燥させればよく、中でも噴霧熱乾燥法が好ましい。噴霧熱乾燥法は、熱噴霧乾燥機（スプレードライヤー）を用いて行なうのが好ましい。熱噴霧乾燥機（スプレードライヤー）を用いて造粒することにより、粒度分布をよりシャープにすることができるばかりか、丸く凝集してなる凝集粒子（２次粒子）を含むように２次粒子の形態を調製することができる。 The drying may be performed by a known drying method such as a spray heat drying method, a hot air drying method, a vacuum drying method, and a freeze drying method. Among them, the spray heat drying method is preferable. The spray heat drying method is preferably performed using a hot spray dryer (spray dryer). By granulating using a thermal spray drier (spray dryer), not only can the particle size distribution be sharpened, but also the secondary particles can be made to contain agglomerated particles (secondary particles) formed by round aggregation. The form can be prepared.
（焼成工程）
前記焼成工程では、酸素分圧が０．０１５ＭＰａ〜０．１５ＭＰａの雰囲気下、例えば大気雰囲気下で焼成を行うのが好ましい。
酸素分圧が０．１５ＭＰａより高いと、結晶成長を促進させることができず、結晶子サイズを大きくすることができない。また、後述するように、焼成によって結晶成長を促すためには、雰囲気の酸素分圧が低い方が好ましいが、焼成する際の酸素分圧が低過ぎると、酸素欠損が増大して熱処理によっても歪みを回復させることができなくなるため、酸素分圧０．０１５ＭＰａ以上で焼成するのが好ましい。
かかる観点から、焼成時の酸素分圧は０．０１５ＭＰａ〜０．１３ＭＰａであるのがさらに好ましく、特に０．０１５ＭＰａ〜０．１２ＭＰａ、中でも０．０１５ＭＰａ以上、或いは０．０８ＭＰａ未満、その中でも特に０．０１５ＭＰａ以上、或いは０．０６１ＭＰａ未満であるのがさらに好ましい。(Firing process)
In the firing step, firing is preferably performed in an atmosphere having an oxygen partial pressure of 0.015 MPa to 0.15 MPa, for example, in an air atmosphere.
If the oxygen partial pressure is higher than 0.15 MPa, crystal growth cannot be promoted, and the crystallite size cannot be increased. In addition, as described later, in order to promote crystal growth by firing, it is preferable that the oxygen partial pressure of the atmosphere is low. However, if the oxygen partial pressure during firing is too low, oxygen deficiency increases and heat treatment may be performed. Since the strain cannot be recovered, it is preferable to perform firing at an oxygen partial pressure of 0.015 MPa or more.
From this viewpoint, the oxygen partial pressure during firing is more preferably 0.015 MPa to 0.13 MPa, particularly 0.015 MPa to 0.12 MPa, especially 0.015 MPa or more, or less than 0.08 MPa, and particularly 0 More preferably, it is not less than 0.015 MPa or less than 0.061 MPa.
焼成温度は、高温焼成することにより、比表面積を低下させることができるため、７７０℃より高温、中でも８００℃以上、特に８５０℃以上で焼成することが好ましい。但し、焼成温度が高すぎると、酸素欠損が増大して熱処理によっても歪みを回復させることができなくなる可能性があるため、１０００℃以下、中でも９８０℃以下で焼成するのが好ましい。
なお、この焼成温度とは、焼成炉内の焼成物に熱電対を接触させて測定される焼成物の品温を意味する。
焼成時間、すなわち上記焼成温度を保持する時間は、焼成温度にもよるが、０．５時間〜１００時間とすればよい。
焼成炉の種類は特に限定するものではない。例えばロータリーキルン、静置炉、その他の焼成炉を用いて焼成することができる。Since the specific surface area can be reduced by firing at a high temperature, the firing is preferably performed at a temperature higher than 770 ° C., particularly 800 ° C. or higher, particularly 850 ° C. or higher. However, if the firing temperature is too high, the oxygen deficiency may increase and the strain may not be able to be recovered even by heat treatment. Therefore, it is preferable to perform firing at 1000 ° C. or lower, especially 980 ° C. or lower.
The firing temperature means the temperature of the fired product measured by bringing a thermocouple into contact with the fired product in the firing furnace.
The firing time, that is, the time for maintaining the firing temperature depends on the firing temperature, but may be 0.5 hours to 100 hours.
The type of the firing furnace is not particularly limited. For example, firing can be performed using a rotary kiln, a standing furnace, or another firing furnace.
なお、ホウ素化合物やフッ素化合物のように、焼成時の反応性を高める物質が共存する場合、低温でも比表面積を低下させることができる。そのような場合、焼成温度は７７０℃より高い温度で焼成することが好ましく、中でも８００℃以上、その中でも特に８５０℃以上で焼成することがより好ましい。但し、焼成温度が高すぎると、酸素欠損が増大して熱処理によっても歪みを回復させることができなくなる可能性があるため、９８０℃以下で焼成するのが好ましく、中でも９６０℃以下で焼成するのがより好ましい。
他方、上記のような焼成時に反応性を高める物質が共存しない場合は、８００℃より高温で焼成することが好ましく、中でも８４０℃以上、その中でも特に８８０℃以上で焼成することがより好ましい。但し、焼成温度が高すぎると、酸素欠損が増大して熱処理によっても歪みを回復させることができなくなる可能性があるため、１０００℃以下で焼成するのが好ましく、中でも９８０℃以下で焼成するのがより好ましい。When a substance that enhances the reactivity during firing, such as a boron compound or a fluorine compound, is present, the specific surface area can be reduced even at a low temperature. In such a case, the firing temperature is preferably higher than 770 ° C, more preferably 800 ° C or higher, and particularly preferably 850 ° C or higher. However, if the firing temperature is too high, oxygen deficiency may increase and distortion may not be able to be recovered even by heat treatment. Therefore, firing at 980 ° C or lower is preferable, and firing at 960 ° C or lower is particularly preferable. Is more preferred.
On the other hand, when there is no coexisting substance that increases the reactivity at the time of calcination as described above, it is preferable to perform calcination at a temperature higher than 800 ° C, more preferably 840 ° C or higher, and particularly preferably 880 ° C or higher. However, if the firing temperature is too high, oxygen deficiency may increase and distortion may not be able to be recovered even by heat treatment. Therefore, firing at 1000 ° C or lower is preferable, and firing at 980 ° C or lower is particularly preferable. Is more preferred.
（加圧熱処理工程）
加圧熱処理工程に供する被処理物は、カールフィッシャー水分測定装置（「ＫＦ水分測定装置」とも称する）で測定される「室温〜３００℃範囲のＫＦ水分」が２％以下であり、かつ、ＩＣＰにより分析される硫黄含有量が０．３４ｗｔ％未満であるスピネル型リチウムマンガン含有複合酸化物であるのが好ましい。
前記ＫＦ水分が２％より大きいと、加圧炉内雰囲気が多量の水蒸気を含むこととなり、所望とする熱処理雰囲気を作れない可能性がある。また、水分を多量に含んだ状態で、熱処理することにより、表面水分と５ＶスピネルのＬｉがプロトン交換を起こすなどの副反応が起こる可能性がある。
かかる観点から、前記ＫＦ水分は１％以下であるのが好ましく、特に５０００ｐｐｍ未満、中でも２０００ｐｐｍ、その中でもさらに１０００ｐｐｍ以下が好ましい。
他方、硫黄含有量が０．３４ｗｔ％以上ということは、表面に多量のＮａ２ＳＯ４やＬｉ２ＳＯ４などの硫酸塩が存在することになり、熱処理効果が妨げられる可能性がある。かかる観点から、硫黄含有量は０．３４ｗｔ％未満であるのが好ましく、特に０．２８ｗｔ％未満が好ましい。(Pressure heat treatment step)
The object to be subjected to the pressure heat treatment step has a "KF moisture in a range from room temperature to 300 ° C." measured by a Karl Fischer moisture analyzer (also referred to as a "KF moisture analyzer") of 2% or less and an ICP Is preferably a spinel-type lithium manganese-containing composite oxide having a sulfur content of less than 0.34% by weight.
If the KF water content is more than 2%, the atmosphere in the pressure furnace contains a large amount of water vapor, and a desired heat treatment atmosphere may not be created. Further, by performing heat treatment in a state where a large amount of water is contained, there is a possibility that a side reaction such as proton exchange between surface water and Li of 5V spinel may occur.
From this viewpoint, the KF water content is preferably 1% or less, particularly less than 5000 ppm, especially 2000 ppm, and more preferably 1000 ppm or less.
On the other hand, when the sulfur content is 0.34 wt% or more, a large amount of sulfate such as Na 2 SO 4 or Li 2 SO 4 is present on the surface, and the heat treatment effect may be hindered. From this viewpoint, the sulfur content is preferably less than 0.34 wt%, and particularly preferably less than 0.28 wt%.
このようなＫＦ水分及び硫黄含有量を有するスピネル型リチウムマンガン含有複合酸化物は、例えば焼成工程や洗浄工程の条件を調整することで得ることができる。例えば、混合前原料を６００℃以上の高温で焼成したり、混合前原料を洗浄したり、焼成工程で得られた処理物、すなわちスピネル型リチウムマンガン含有複合酸化物を洗浄したりることで、硫黄含有量を０．３４ｗｔ％未満にすることができる。他方、例えば、焼成工程で８００℃以上の高温で焼成したりすることで、ＫＦ水分量を２％以下にすることができる。 Such a spinel-type lithium manganese-containing composite oxide having a KF moisture and sulfur content can be obtained, for example, by adjusting the conditions of a firing step and a washing step. For example, the raw material before mixing is fired at a high temperature of 600 ° C. or higher, the raw material before mixing is washed, or the processed product obtained in the firing step, that is, the spinel-type lithium manganese-containing composite oxide is washed, The sulfur content can be less than 0.34 wt%. On the other hand, for example, by firing at a high temperature of 800 ° C. or more in the firing step, the KF water content can be reduced to 2% or less.
なお、ＫＦ水分測定装置で測定される「室温〜３００℃範囲のＫＦ水分」とは、ＫＦ水分測定装置の測定室内を窒素雰囲気として１７０℃に加熱した後、該測定室内にサンプルを入れて、該サンプルを１７０℃で４５分間静置した際に放出される水分量を測定して「室温〜１７０℃のＫＦ水分（ｐｐｍ）」を得た後、続いて３００℃まで昇温し、該サンプルを３００℃で４５分間静置した際に放出される水分量を測定して「１７０℃〜３００℃のＫＦ水分（ｐｐｍ）」を得、前記「室温〜１７０℃のＫＦ水分量（ｐｐｍ）」と前記「１７０℃〜３００℃のＫＦ水分量（ｐｐｍ）」とを合計して求めることができる。 The “KF moisture in a range from room temperature to 300 ° C.” measured by a KF moisture measuring device means that the measuring room of the KF moisture measuring device is heated to 170 ° C. in a nitrogen atmosphere, and then a sample is put in the measuring room. The amount of water released when the sample was allowed to stand at 170 ° C. for 45 minutes was measured to obtain “KF water (ppm) from room temperature to 170 ° C.”, and then the temperature was raised to 300 ° C. The amount of water released when the sample was allowed to stand at 300 ° C. for 45 minutes was measured to obtain “KF moisture from 170 ° C. to 300 ° C. (ppm)”, and the above “KF moisture from room temperature to 170 ° C. (ppm)” And the above-mentioned “KF moisture content (ppm) at 170 ° C. to 300 ° C.”.
加圧熱処理工程では、処理雰囲気の全体圧力が大気圧よりも高い圧力であって、かつ、該雰囲気における酸素分圧が大気中の酸素分圧よりも高い処理雰囲気おいて、５００℃より高く８５０℃より低い温度で熱処理するのが好ましい。
このように加圧熱処理することにより、５Ｖ本スピネルの構造中に酸素が取り込まれることで、酸素欠損が低減し構造が安定化するため、たとえ上述のように高温焼成した場合であっても、４．５Ｖ付近のプラトー領域が拡大して高電位容量域を拡大させることができるため、エネルギー密度の向上を図ることができるものと考えることができる。
なお、大気圧よりも高い圧力雰囲気とは、密閉容器内を加熱して、一定容積内の気体を温度上昇させることで、圧力が上昇し、大気圧よりも高い圧力になる場合を含む。In the pressurized heat treatment step, the total pressure of the processing atmosphere is higher than the atmospheric pressure, and in a processing atmosphere in which the oxygen partial pressure in the atmosphere is higher than the oxygen partial pressure in the atmosphere, the temperature is higher than 500 ° C. and 850 ° C. Preferably, the heat treatment is performed at a temperature lower than ℃.
By performing pressure heat treatment in this manner, oxygen is taken into the structure of the 5V spinel, thereby reducing oxygen vacancies and stabilizing the structure. Since the plateau region around 4.5 V is expanded to expand the high potential capacity region, it can be considered that the energy density can be improved.
In addition, the pressure atmosphere higher than the atmospheric pressure includes a case where the pressure in the closed container is increased by heating the inside of the closed vessel to raise the temperature of the gas in a certain volume to be higher than the atmospheric pressure.
加圧熱処理工程における処理雰囲気は、処理雰囲気の全体圧力が、大気圧（０．１ＭＰａ）よりも大きい圧力、例えば０．１９ＭＰａよりも大きく、中でも０．２０ＭＰａ以上の雰囲気の圧力であるのが特に好ましい。但し、処理雰囲気の圧力が高すぎると、加圧炉の強度上の問題から製造が不安定となる可能性があるため、かかる観点からすると１．５ＭＰａ以下、中でも１．０ＭＰａ以下の雰囲気圧力で熱処理するのが好ましい。このように、加圧状態で熱処理することで、より一層酸素を取り込み易くなり、酸素欠損をより一層抑えることができる。 The processing atmosphere in the pressurized heat treatment step is preferably a pressure in which the entire pressure of the processing atmosphere is higher than the atmospheric pressure (0.1 MPa), for example, higher than 0.19 MPa, and especially higher than 0.20 MPa. preferable. However, if the pressure of the processing atmosphere is too high, the production may become unstable due to the problem of the strength of the pressure furnace. Therefore, from such a viewpoint, the atmosphere pressure of 1.5 MPa or less, especially 1.0 MPa or less, is used. Heat treatment is preferred. As described above, by performing the heat treatment in a pressurized state, oxygen can be more easily taken in, and oxygen vacancies can be further suppressed.
さらに、加圧熱処理工程における処理雰囲気は、大気中の酸素分圧よりも高い酸素分圧、例えば０．０６ＰＭａ以上の酸素分圧であるのが好ましく、中でも０．１０ＭＰａより高い酸素分圧であるのが好ましく、その中でも０．１５ＭＰａ以上、特にその中でも０．１９ＭＰａより高い酸素分圧であるのがさらに好ましく、その中でもさらに０．２０ＭＰａ以上の酸素分圧であるのが特に好ましい。但し、該酸素分圧が高すぎると、加圧炉の強度上の問題から製造が不安定となる可能性があるため、かかる観点からすると１．５ＭＰａ以下、中でも１．０ＭＰａ以下の酸素分圧下で熱処理するのが好ましい。 Further, the processing atmosphere in the pressurized heat treatment step is preferably an oxygen partial pressure higher than the atmospheric oxygen partial pressure, for example, an oxygen partial pressure of 0.06 PMa or more, and more preferably an oxygen partial pressure higher than 0.10 MPa. Among them, the oxygen partial pressure is more preferably 0.15 MPa or more, particularly preferably higher than 0.19 MPa, and particularly preferably the oxygen partial pressure is 0.20 MPa or more. However, if the oxygen partial pressure is too high, the production may become unstable due to the problem of the strength of the pressurizing furnace. From such a viewpoint, the oxygen partial pressure is 1.5 MPa or less, particularly 1.0 MPa or less. The heat treatment is preferably performed.
加圧熱処理工程での熱処理温度、すなわち保持温度は５００℃より高く８５０℃より低い温度に制御するのが好ましい。
本工程での熱処理温度が５００℃より高ければ、酸素を強制的に供給しながら熱処理することにより、結晶構造中に酸素を取り込んで歪みを効果的に低減することができる。かかる観点から、熱処理温度は５００℃より高温であることが好ましく、中でも６００℃以上、その中でも７００℃以上、その中でも７００℃より高温であるのが特に好ましい。
他方、熱処理温度が高すぎると、酸素欠損が増大して熱処理によっても歪みを回復させることができなくなる可能性があるため、熱処理温度は８５０℃より低温であることが好ましく、中でも８２０℃以下、その中でも８００℃以下であるのが特に好ましい。
なお、この熱処理温度とは、炉内の処理物に熱電対を接触させて測定される処理物の品温を意味する。The heat treatment temperature in the pressure heat treatment step, that is, the holding temperature, is preferably controlled to a temperature higher than 500 ° C. and lower than 850 ° C.
If the heat treatment temperature in this step is higher than 500 ° C., by performing the heat treatment while forcibly supplying oxygen, oxygen can be taken into the crystal structure and strain can be effectively reduced. From such a viewpoint, the heat treatment temperature is preferably higher than 500 ° C., particularly preferably 600 ° C. or higher, more preferably 700 ° C. or higher, and particularly preferably 700 ° C. or higher.
On the other hand, if the heat treatment temperature is too high, the oxygen deficiency may increase and the strain may not be able to be recovered by the heat treatment. Therefore, the heat treatment temperature is preferably lower than 850 ° C., especially 820 ° C. or lower. Among them, the temperature is particularly preferably 800 ° C. or lower.
In addition, this heat treatment temperature means the temperature of the processed product measured by bringing a thermocouple into contact with the processed product in the furnace.
好ましい加圧熱処理条件の一例として、処理雰囲気の全体圧力が大気圧よりも高い圧力であって、且つ、０．１９ＭＰａより高い酸素分圧であり、５００℃より高く８５０℃より低い温度、中でも６００℃以上或いは８５０℃より低く、その中でも７００℃より高く或いは８００℃以下の温度で加圧熱処理する条件を挙げることができる。 As an example of a preferable pressure heat treatment condition, the entire pressure of the processing atmosphere is a pressure higher than the atmospheric pressure and an oxygen partial pressure higher than 0.19 MPa, and a temperature higher than 500 ° C. and lower than 850 ° C., particularly 600 The conditions for pressure heat treatment at a temperature of at least 700C or below 850C, especially above 700C or below 800C can be mentioned.
上記熱処理温度すなわち保持温度まで加熱する際の昇温速度は、０．１℃／ｍｉｎ〜２０℃／ｍｉｎとするのが好ましく、中でも０．２５℃／ｍｉｎ以上或いは１０℃／ｍｉｎ以下、その中でも特に０．５℃／ｍｉｎ以上或いは５℃／ｍｉｎ以下とするのがさらに好ましい。 The heating rate at the time of heating to the heat treatment temperature, that is, the holding temperature, is preferably 0.1 ° C./min to 20 ° C./min, and more preferably 0.25 ° C./min or more or 10 ° C./min or less, among which In particular, the temperature is more preferably 0.5 ° C / min or more or 5 ° C / min or less.
加圧熱処理工程で、上記熱処理温度を保持する時間は、少なくとも１分間以上である必要がある。結晶構造内に酸素を十分に取り込ませるためには、少なくとも１分間は必要であると考えられる。かかる観点から、上記熱処理温度を保持する時間は、好ましくは５分以上、特に好ましくは１０分以上である。また、熱処理により、結晶構造内に酸素を取りこませる効果は保持時間が２００時間以下であれば十分効果があると考えられる。 In the pressure heat treatment step, the time for maintaining the heat treatment temperature needs to be at least 1 minute or more. It is considered that at least one minute is required to sufficiently incorporate oxygen into the crystal structure. From such a viewpoint, the time for maintaining the heat treatment temperature is preferably 5 minutes or more, particularly preferably 10 minutes or more. In addition, the effect of incorporating oxygen into the crystal structure by the heat treatment is considered to be sufficiently effective if the holding time is 200 hours or less.
熱処理後の降温速度は、少なくとも５００℃までは１０℃／ｍｉｎ以下の冷却速度でゆっくり冷却するのが好ましく、特に０．１℃／ｍｉｎ〜８℃／ｍｉｎ、中でも特に０．２℃／ｍｉｎ〜５℃／ｍｉｎに制御するのがさらに好ましい。
５００℃近辺で取り込んだ酸素が安定化すると考えられるため、少なくとも５００℃まではゆっくり１０℃／ｍｉｎ以下の降温速度で冷却するのが好ましいと考えることができる。The rate of temperature decrease after the heat treatment is preferably slow cooling at a cooling rate of 10 ° C./min or less up to at least 500 ° C., particularly 0.1 ° C./min to 8 ° C./min, and especially 0.2 ° C./min to It is more preferable to control the temperature to 5 ° C./min.
Since the oxygen taken in at around 500 ° C. is considered to be stabilized, it can be considered that it is preferable to cool at least to 500 ° C. slowly at a temperature lowering rate of 10 ° C./min or less.
このような加圧熱処理は、加圧炉(加圧可能圧力１．０ＭＰａ)のような装置を用いて加熱することにより、処理雰囲気の全体圧力が大気圧よりも高い圧力であって、かつ、該雰囲気における酸素分圧が大気中の酸素分圧よりも高い処理雰囲気において、加熱することができる。 Such pressurized heat treatment is performed by using a device such as a pressurized furnace (pressurizable pressure of 1.0 MPa), so that the entire pressure of the processing atmosphere is higher than the atmospheric pressure, and Heating can be performed in a processing atmosphere in which the oxygen partial pressure in the atmosphere is higher than the atmospheric oxygen partial pressure.
（その他）
上記加圧熱処理工程の前又は後又は両方に、後述する洗浄工程を挿入することも可能である。(Other)
Before or after or both of the above-mentioned pressurized heat treatment step, it is also possible to insert a washing step described later.
＜他の実施形態＞
本５Ｖ級スピネルの製造方法の他例として、原料混合工程、造粒工程、焼成工程、熱処理工程及び加圧熱処理工程をこの順に備えると共に、洗浄工程をさらに備えた製造方法を挙げることができる。
この際、洗浄工程は適宜順序で挿入することが可能である。例えば、上記工程のうちの１つの工程或いは２つ以上の工程の前に、或いは、後に挿入することも可能である。
造粒工程、熱処理工程及び洗浄工程のいずれか或いは２工程以上を省略することも可能であるし、また、他の工程を追加することも可能である。例えば、湿式粉砕工程、その他の工程などをさらに追加することが可能である。また、各工程後に解砕して分級する解砕・分級工程を挿入することなどは必要に応じて実施するのが好ましい。<Other embodiments>
As another example of the method for producing the present 5V-class spinel, there can be mentioned a production method including a raw material mixing step, a granulation step, a firing step, a heat treatment step, and a pressure heat treatment step in this order, and further including a washing step.
At this time, the cleaning steps can be inserted in an appropriate order. For example, it can be inserted before or after one of the above steps or two or more steps.
Any one or more of the granulation step, heat treatment step, and washing step can be omitted, and other steps can be added. For example, it is possible to further add a wet pulverizing step and other steps. In addition, it is preferable to insert a crushing / classifying step of crushing and classifying after each step as necessary.
原料混合工程、湿式粉砕工程、造粒工程、焼成工程、加圧熱処理工程及び洗浄工程については、それぞれ上記と同様に実施すればよい。 The raw material mixing step, the wet pulverizing step, the granulating step, the firing step, the pressure heat treatment step, and the washing step may be performed in the same manner as described above.
（熱処理工程）
熱処理工程は、大気雰囲気下において、５００℃〜８５０℃、好ましくは６００℃以上或いは８００℃以下の環境下に０．５〜３００時間置き、酸素を取り込みし易くするようにするのが好ましい。(Heat treatment process)
The heat treatment step is preferably performed in an atmosphere of 500 ° C. to 850 ° C., preferably 600 ° C. or more or 800 ° C. or less for 0.5 to 300 hours in an air atmosphere so as to easily take in oxygen.
（解砕・分級工程）
上記熱処理工程後、必要に応じて、解砕若しくは粉砕するのが好ましい。
この際、解砕の程度は一次粒子を崩壊させないようにするのが好ましい。
そして、解砕後は、分級するのが好ましい。(Crushing and classification process)
After the heat treatment step, it is preferable to crush or pulverize as necessary.
At this time, it is preferable that the degree of pulverization is such that the primary particles are not disintegrated.
And after crushing, it is preferable to classify.
＜本５Ｖ級スピネルの特徴＞
本製造方法によれば、本５Ｖ級スピネルの比表面積を小さくすることができ、リチウム２次電池の正極活物質として利用すると、ガス発生を抑えることができる。また、４．５Ｖ付近のプラトー領域を拡大させることができる。<Features of this 5V class spinel>
According to the present manufacturing method, the specific surface area of the present 5V-class spinel can be reduced, and when used as a positive electrode active material of a lithium secondary battery, gas generation can be suppressed. Further, the plateau region around 4.5 V can be enlarged.
（比表面積）
本５Ｖ級スピネルは、その比表面積を１．５ｍ2／ｇ以下とすることができ、中でも、０．１ｍ2／ｇ以上或いは１．０ｍ2／ｇ以下、その中でも０．８ｍ2／ｇ以下とするのが特に好ましい。
このように比表面積が比較的小さければ、電解液との反応性が高くなり、５Ｖ級スピネルが特徴的に抱えている課題であるガス発生量を抑えることができる。(Specific surface area)
This 5V-class spinel, the specific surface area can be 1.5 m 2 / g or less, preferably, 0.1 m 2 / g or more or 1.0 m 2 / g or less, 0.8 m 2 / g or less among them It is particularly preferred that
If the specific surface area is relatively small as described above, the reactivity with the electrolytic solution is increased, and the amount of gas generation, which is a characteristic problem of the 5V-class spinel, can be suppressed.
＜本５Ｖ級スピネルの用途＞
本５Ｖ級スピネルは、必要に応じて解砕・分級した後、各種リチウム電池の正極活物質として有効に利用することができる。
本５Ｖ級スピネルを各種リチウム電池の正極活物質として利用する場合、例えば、本５Ｖ級スピネルと、カーボンブラック等からなる導電材と、テフロン（登録商標）バインダー等からなる結着剤とを混合して正極合剤を製造することができる。そしてそのような正極合剤を正極に用い、負極にはリチウムまたはカーボン等のリチウムを吸蔵、脱蔵できる材料を用い、非水系電解質には六フッ化リン酸リチウム（ＬｉＰＦ６）等のリチウム塩をエチレンカーボネート−ジメチルカーボネート等の混合溶媒に溶解したものを用いてリチウム電池を構成することができる。<Use of this 5V class spinel>
This 5V class spinel can be effectively used as a positive electrode active material of various lithium batteries after being crushed and classified as necessary.
When the present 5V class spinel is used as a positive electrode active material of various lithium batteries, for example, a mixture of the present 5V class spinel, a conductive material such as carbon black, and a binder such as Teflon (registered trademark) binder is used. To produce a positive electrode mixture. Then, such a positive electrode mixture is used for the positive electrode, a material such as lithium or carbon capable of absorbing and desorbing lithium is used for the negative electrode, and a lithium salt such as lithium hexafluorophosphate (LiPF6) is used for the non-aqueous electrolyte. A lithium battery can be constituted by using one dissolved in a mixed solvent such as ethylene carbonate-dimethyl carbonate.
このように構成したリチウム電池は、例えばノート型パソコン、携帯電話、コードレスフォン子機、ビデオムービー、液晶テレビ、電気シェーバー、携帯ラジオ、ヘッドホンステレオ、バックアップ電源、メモリーカード等の電子機器、ペースメーカー、補聴器等の医療機器、電気自動車搭載用の駆動電源に使用することができる。中でも、優れたサイクル特性が要求される携帯電話機、ＰＤＡ（携帯情報端末）やノート型パソコンなどの各種携帯型コンピュータ、電気自動車（ハイブリッド自動車を含む）、電力貯蔵用電源などの駆動用電源として特に有効である。 Lithium batteries configured in this way include notebook computers, mobile phones, cordless phone handsets, video movies, LCD televisions, electric shavers, portable radios, headphone stereos, backup power supplies, electronic devices such as memory cards, pacemakers, hearing aids, etc. It can be used for a drive power supply for mounting on medical equipment such as an electric vehicle. In particular, as a driving power source such as a mobile phone, a portable computer such as a PDA (Personal Digital Assistant) and a notebook personal computer, an electric vehicle (including a hybrid vehicle), and a power storage power source that require excellent cycle characteristics. It is valid.
＜語句の説明＞
本明細書において「Ｘ〜Ｙ」（Ｘ，Ｙは任意の数字）と表現する場合、特にことわらない限り「Ｘ以上Ｙ以下」の意と共に、「好ましくはＸより大きい」或いは「好ましくはＹより小さい」の意も包含する。
また、「Ｘ以上」（Ｘは任意の数字）或いは「Ｙ以下」（Ｙは任意の数字）と表現した場合、「Ｘより大きいことが好ましい」或いは「Ｙ未満であることが好ましい」旨の意図も包含する。<Explanation of terms>
In the present specification, when expressed as “X to Y” (X and Y are arbitrary numbers), “preferably larger than X” or “preferably Y” together with “X or more and Y or less” unless otherwise specified. "Smaller" is also included.
In addition, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is expressed as “preferably larger than X” or “preferably smaller than Y”. Includes intent.
次に、実施例及び比較例に基づいて、本発明について更に説明する。但し、本発明が以下に示す実施例に限定されるものではない。 Next, the present invention will be further described based on examples and comparative examples. However, the present invention is not limited to the embodiments described below.
＜実施例１＞
平均粒径（Ｄ５０）７μｍの炭酸リチウムと、平均粒径（Ｄ５０）２３μｍで比表面積が４０ｍ2／ｇの電解二酸化マンガンと、平均粒径（Ｄ５０）２２μｍの水酸化ニッケルと、平均粒径（Ｄ５０）２μｍの酸化チタンと、平均粒径（Ｄ５０）６０μｍの四ホウ酸リチウムをそれぞれ秤量した。
イオン交換水中へ、分散剤としてポリカルボン酸アンモニウム塩水溶液（サンノプコ（株）製 ＳＮディスパーサント５４６８）を添加した。この際、分散剤の添加量は、前述のＬｉ原料、Ｎｉ原料、Ｍｎ原料、Ｔｉ原料及びＢ原料の合計に対して、６ｗｔ％になるようにし、イオン交換水中へ十分に溶解混合させた。そして、秤量しておいた原料を、あらかじめ分散剤を溶解させた前記イオン交換水中へ加えて、混合撹拌して、固形分濃度４０ｗｔ％のスラリーを調整した。続いて、湿式粉砕機で１３００ｒｐｍ、６０分間粉砕して平均粒径（Ｄ５０）０．６０μｍ以下の粉砕スラリーを得た。
得られた粉砕スラリーを熱噴霧乾燥機（スプレードライヤー、大川原化工機（株）製「ＲＬ−１０」）を用いて造粒乾燥させた。この際、噴霧にはツインジェットノズルを用い、噴霧圧を０．３３ＭＰａ、スラリー供給量３５０ｍｌ／ｍｉｎ、乾燥塔の出口温度が１００〜１１０℃となるように温度を調節して造粒乾燥を行った。
得られた造粒粉を、静置式電気炉を用いて、酸素分圧０．０２１ＭＰａの雰囲気において、８８０℃を３８時間保持するように焼成した後、酸素分圧０．０２１ＭＰａの雰囲気において７５０℃を３７時間保持するように熱処理した。
熱処理して得られた焼成塊を乳鉢に入れて乳棒で解砕し、目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末を得た。<Example 1>
Lithium carbonate having an average particle size (D50) of 7 μm; electrolytic manganese dioxide having an average particle size (D50) of 23 μm and a specific surface area of 40 m 2 / g; nickel hydroxide having an average particle size (D50) of 22 μm; D50) 2 μm of titanium oxide and lithium tetraborate having an average particle size (D50) of 60 μm were weighed.
An aqueous solution of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water. At this time, the dispersant was added in an amount of 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material and B raw material, and was sufficiently dissolved and mixed in ion-exchanged water. Then, the weighed raw materials were added to the ion-exchanged water in which a dispersant was previously dissolved, and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%. Subsequently, the mixture was pulverized with a wet pulverizer at 1300 rpm for 60 minutes to obtain a pulverized slurry having an average particle diameter (D50) of 0.60 μm or less.
The obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Kakoki Co., Ltd.). At this time, a twin jet nozzle was used for spraying, and the granulation drying was performed by adjusting the spray pressure to 0.33 MPa, the slurry supply amount to 350 ml / min, and the temperature at the outlet of the drying tower to 100 to 110 ° C. Was.
The obtained granulated powder was calcined in a static electric furnace in an atmosphere with an oxygen partial pressure of 0.021 MPa so as to maintain 880 ° C. for 38 hours, and then 750 ° C. in an atmosphere with an oxygen partial pressure of 0.021 MPa. Was heat-treated so as to be maintained for 37 hours.
The calcined mass obtained by the heat treatment was put into a mortar, crushed with a pestle, classified with a sieve having a mesh size of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder.
次に、このように篩下粉を回収して得られたスピネル型リチウムマンガン含有複合酸化物粉末１ｋｇを、ｐＨ６〜７、温度２５℃のイオン交換水２０００ｍＬを入れたプラスチックビーカー（容量５０００ｍＬ）の中に投入し、攪拌機（プロペラ面積３３ｃｍ２）を用いて４００〜５５０ｒｐｍの回転で２０分間撹拌した。撹拌後、撹拌を停止して攪拌機を水中から取り出し、１０分間静置した。そして、デカンテーションにより上澄み液を除去し、残りのスラリーを吸引ろ過器（ろ紙Ｎｏ．１３１）により、ろ過し、沈降物を回収した。回収した沈降物を１２０℃環境下で１０時間乾燥させた。その後、品温が５００℃となるように加熱した状態で７時間乾燥させた。乾燥後、目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。Next, 1 kg of the spinel-type lithium manganese-containing composite oxide powder obtained by collecting the undersize powder in a plastic beaker (capacity 5000 mL) containing 2000 mL of ion-exchanged water having a pH of 6 to 7 and a temperature of 25 ° C. Then, the mixture was stirred with a stirrer (propeller area: 33 cm 2 ) at a rotation of 400 to 550 rpm for 20 minutes. After the stirring, the stirring was stopped, and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant was removed by decantation, and the remaining slurry was filtered with a suction filter (filter paper No. 131) to collect a sediment. The collected sediment was dried at 120 ° C. for 10 hours. Thereafter, the product was dried for 7 hours while being heated so that the product temperature became 500 ° C. After drying, the powder was classified with a sieve having a mesh size of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder (sample).
さらに、このスピネル型リチウムマンガン含有複合酸化物粉末（ＫＦ水分量：１４４ｐｐｍ、硫黄含有量：０．０２％）を、加圧炉（株式会社広築製）を使用して加圧熱処理した。すなわち、サンプル２００ｇを磁製るつぼに充填し、この磁製るつぼを加圧炉内に設置した。その後、酸素ガス（酸素濃度９９％）を加圧炉内に流入させて、酸素分圧を０．２０ＭＰａ、処理雰囲気の全体圧力を０．２１ＭＰａに調整して、１．５℃／ｍｉｎの昇温速度で７４０℃まで加熱して１４時間保持し、その後、酸素流入を継続しながら、室温まで０．３℃／ｍｉｎの降温速度で冷却してスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
スピネル型リチウムマンガン含有複合酸化物粉末（サンプル）の化学分析を実施したところ、Ｌｉ：３．９ｗｔ％、Ｎｉ：１４．１ｗｔ％、Ｍｎ：４４．１ｗｔ％、Ｔｉ：３．６％、Ｂ：０．１％であった。Further, this spinel-type lithium manganese-containing composite oxide powder (KF moisture content: 144 ppm, sulfur content: 0.02%) was subjected to pressure heat treatment using a pressure furnace (produced by Hiroki Corporation). That is, 200 g of the sample was filled in a porcelain crucible, and the porcelain crucible was placed in a pressure furnace. Thereafter, an oxygen gas (oxygen concentration: 99%) is caused to flow into the pressurized furnace, the oxygen partial pressure is adjusted to 0.20 MPa, the total pressure of the processing atmosphere is adjusted to 0.21 MPa, and the temperature is increased by 1.5 ° C./min. Heated to 740 ° C. at a temperature rate and maintained for 14 hours, and then cooled to room temperature at a rate of 0.3 ° C./min while continuing oxygen inflow, and spinel-type lithium manganese-containing composite oxide powder (sample) I got
When the spinel-type lithium manganese-containing composite oxide powder (sample) was subjected to chemical analysis, Li: 3.9 wt%, Ni: 14.1 wt%, Mn: 44.1 wt%, Ti: 3.6%, B: 0.1%.
なお、酸素濃度は、酸素濃度計(ＸＰＯ−３１８（新コスモス電機株式会社）)を用い測定した。後述する実施例・比較例についても同じである。
また、上記焼成時及び熱処理時の温度は、炉内の処理物に熱電対を接触させて測定した処理物の品温である。後述する実施例・比較例についても同じである。The oxygen concentration was measured using an oxygen concentration meter (XPO-318 (Shin Cosmos Electric)). The same applies to examples and comparative examples described later.
Further, the temperatures during the firing and the heat treatment are the product temperatures of the processed products measured by bringing a thermocouple into contact with the processed products in the furnace. The same applies to examples and comparative examples described later.
＜実施例２＞
平均粒径（Ｄ５０）７μｍの炭酸リチウムと、平均粒径（Ｄ５０）２３μｍで比表面積が４０ｍ2／ｇの電解二酸化マンガンと、平均粒径（Ｄ５０）２２μｍの水酸化ニッケルと、平均粒径（Ｄ５０）２μｍの酸化チタンをそれぞれ秤量した。
イオン交換水中へ、分散剤としてポリカルボン酸アンモニウム塩水溶液（サンノプコ（株）製 ＳＮディスパーサント５４６８）を添加した。この際、分散剤の添加量は、前述のＬｉ原料、Ｎｉ原料、Ｍｎ原料及びＴｉ原料の合計に対して、６ｗｔ％になるようにし、イオン交換水中へ十分に溶解混合させた。秤量しておいた原料のうち、Ｎｉ原料とＭｎ原料だけを、あらかじめ分散剤を溶解させた前記イオン交換水中へ加えて、混合撹拌し、スラリーを得た。得られたスラリーを湿式粉砕機で１３００ｒｐｍ、１２０分間粉砕した。続いて、Ｌｉ原料とＴｉ原料を添加し、混合撹拌し、固形分濃度４０ｗｔ％のスラリーを調整した。続いてさらに、湿式粉砕機で１３００ｒｐｍ、６０分間粉砕して平均粒径（Ｄ５０）０．６０μｍ以下の粉砕スラリーを得た。
得られた粉砕スラリーを熱噴霧乾燥機（スプレードライヤー、大川原化工機（株）製「ＲＬ−１０」）を用いて造粒乾燥させた。この際、噴霧にはツインジェットノズルを用い、噴霧圧を０．１５ＭＰａ、スラリー供給量４００ｍｌ／ｍｉｎ、乾燥塔の出口温度が１００〜１１０℃となるように温度を調節して造粒乾燥を行った。
得られた造粒粉を、静置式電気炉を用いて、酸素分圧０．０２１ＭＰａの雰囲気において、９５０℃を３６時間保持するように焼成した後、酸素分圧０．０２１ＭＰａの雰囲気において７５０℃を３７時間保持するように熱処理した。
熱処理して得られた焼成塊を乳鉢に入れて乳棒で解砕し、目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末を得た。<Example 2>
Lithium carbonate having an average particle size (D50) of 7 μm; electrolytic manganese dioxide having an average particle size (D50) of 23 μm and a specific surface area of 40 m 2 / g; nickel hydroxide having an average particle size (D50) of 22 μm; D50) 2 μm of titanium oxide was weighed.
An aqueous solution of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water. At this time, the amount of the dispersant added was 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material and Ti raw material, and the dispersing agent was sufficiently dissolved and mixed in ion-exchanged water. Of the weighed raw materials, only the Ni raw material and the Mn raw material were added to the ion-exchanged water in which a dispersant was previously dissolved, and mixed and stirred to obtain a slurry. The obtained slurry was pulverized with a wet pulverizer at 1300 rpm for 120 minutes. Subsequently, a Li raw material and a Ti raw material were added, mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%. Subsequently, the mixture was further pulverized with a wet pulverizer at 1300 rpm for 60 minutes to obtain a pulverized slurry having an average particle diameter (D50) of 0.60 μm or less.
The obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Kakoki Co., Ltd.). At this time, a twin jet nozzle is used for spraying, and granulation drying is performed by adjusting the spray pressure to 0.15 MPa, the slurry supply amount to 400 ml / min, and the temperature of the drying tower so that the outlet temperature becomes 100 to 110 ° C. Was.
The obtained granulated powder is calcined by using a stationary electric furnace in an atmosphere of an oxygen partial pressure of 0.021 MPa so as to be maintained at 950 ° C. for 36 hours, and then is heated to 750 ° C. in an atmosphere of an oxygen partial pressure of 0.021 MPa. Was heat-treated so as to be maintained for 37 hours.
The calcined mass obtained by the heat treatment was put into a mortar, crushed with a pestle, classified with a sieve having a mesh size of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder.
次に、このように篩下粉を回収して得られたスピネル型リチウムマンガン含有複合酸化物粉末１ｋｇを、ｐＨ６〜７、温度２５℃のイオン交換水２０００ｍＬを入れたプラスチックビーカー（容量５０００ｍＬ）の中に投入し、攪拌機（プロペラ面積３３ｃｍ２）を用いて４００〜５５０ｒｐｍの回転で２０分間撹拌した。撹拌後、撹拌を停止して攪拌機を水中から取り出し、１０分間静置した。そして、デカンテーションにより上澄み液を除去し、残りのスラリーを吸引ろ過器（ろ紙Ｎｏ．１３１）により、ろ過し、沈降物を回収した。回収した沈降物を１２０℃環境下で１０時間乾燥させた。その後、品温が５００℃となるように加熱した状態で７時間乾燥させた。乾燥後、目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。Next, 1 kg of the spinel-type lithium manganese-containing composite oxide powder obtained by collecting the undersize powder in a plastic beaker (capacity 5000 mL) containing 2000 mL of ion-exchanged water having a pH of 6 to 7 and a temperature of 25 ° C. Then, the mixture was stirred with a stirrer (propeller area: 33 cm 2 ) at a rotation of 400 to 550 rpm for 20 minutes. After the stirring, the stirring was stopped, and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant was removed by decantation, and the remaining slurry was filtered with a suction filter (filter paper No. 131) to collect a sediment. The collected sediment was dried at 120 ° C. for 10 hours. Thereafter, the product was dried for 7 hours while being heated so that the product temperature became 500 ° C. After drying, the powder was classified with a sieve having a mesh size of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder (sample).
さらに、このスピネル型リチウムマンガン含有複合酸化物粉末（ＫＦ水分量：１３０ｐｐｍ、硫黄含有量：０．０３％）を、加圧炉（株式会社広築製）を使用して加圧熱処理した。すなわち、サンプル２００ｇを磁製るつぼに充填し、この磁製るつぼを加圧炉内に設置した。その後、酸素ガス（酸素濃度９９％）を加圧炉内に流入させて、酸素分圧を０．２０ＭＰａ、処理雰囲気の全体圧力を０．２１ＭＰａに調整して、１．５℃／ｍｉｎの昇温速度で７２０℃まで加熱して１６時間保持し、その後、酸素流入を継続しながら、室温まで０．３℃／ｍｉｎの降温速度で冷却してスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
スピネル型リチウムマンガン含有複合酸化物粉末（サンプル）の化学分析を実施したところ、Ｌｉ：４．１ｗｔ％、Ｎｉ：１３．２ｗｔ％、Ｍｎ：４１．８ｗｔ％、Ｔｉ：５．２０％であった。Further, this spinel-type lithium manganese-containing composite oxide powder (KF moisture content: 130 ppm, sulfur content: 0.03%) was subjected to pressure heat treatment using a pressure furnace (manufactured by Hiroki Corporation). That is, 200 g of the sample was filled in a porcelain crucible, and the porcelain crucible was placed in a pressure furnace. Thereafter, an oxygen gas (oxygen concentration: 99%) is caused to flow into the pressurized furnace, the oxygen partial pressure is adjusted to 0.20 MPa, the total pressure of the processing atmosphere is adjusted to 0.21 MPa, and the temperature is increased by 1.5 ° C./min. Heated to a temperature of 720 ° C. at a temperature rate and maintained for 16 hours, and then cooled to a room temperature at a rate of 0.3 ° C./min while continuing the inflow of oxygen to obtain a spinel-type lithium manganese-containing composite oxide powder (sample) I got
Chemical analysis of the spinel-type lithium manganese-containing composite oxide powder (sample) was carried out to find that Li: 4.1 wt%, Ni: 13.2 wt%, Mn: 41.8 wt%, and Ti: 5.20%. .
＜実施例３＞
平均粒径（Ｄ５０）７μｍの炭酸リチウムと、平均粒径（Ｄ５０）２３μｍで比表面積が４０ｍ2／ｇの電解二酸化マンガンと、平均粒径（Ｄ５０）２２μｍの水酸化ニッケルと、平均粒径（Ｄ５０）２μｍの酸化チタンと、平均粒径（Ｄ５０）６０μｍの四ホウ酸リチウムをそれぞれ秤量した。
イオン交換水中へ、分散剤としてポリカルボン酸アンモニウム塩水溶液（サンノプコ（株）製 ＳＮディスパーサント５４６８）を添加した。この際、分散剤の添加量は、前述のＬｉ原料、Ｎｉ原料、Ｍｎ原料、Ｔｉ原料及びＢ原料の合計に対して、６ｗｔ％になるようにし、イオン交換水中へ十分に溶解混合させた。秤量しておいた原料のうち、Ｎｉ原料とＭｎ原料だけを、あらかじめ分散剤を溶解させた前記イオン交換水中へ加えて、混合撹拌し、スラリーを得た。得られたスラリーを湿式粉砕機で１３００ｒｐｍ、１２０分間粉砕した。続いて、Ｌｉ原料、Ｔｉ原料及びＢ原料を添加し、混合撹拌し、固形分濃度４０ｗｔ％のスラリーを調整した。続いてさらに、湿式粉砕機で１３００ｒｐｍ、１２０分間粉砕して平均粒径（Ｄ５０）０．６０μｍ以下の粉砕スラリーを得た。
得られた粉砕スラリーを熱噴霧乾燥機（スプレードライヤー、大川原化工機（株）製「ＲＬ−１０」）を用いて造粒乾燥させた。この際、噴霧にはツインジェットノズルを用い、噴霧圧を０．１５ＭＰａ、スラリー供給量４００ｍｌ／ｍｉｎ、乾燥塔の出口温度が１００〜１１０℃となるように温度を調節して造粒乾燥を行った。
得られた造粒粉を、静置式電気炉を用いて、酸素分圧０．０２１ＭＰａの雰囲気において、９５０℃を３７時間保持するように焼成した後、酸素分圧０．０２１ＭＰａの雰囲気において７５０℃を３７時間保持するように熱処理した。
熱処理して得られた焼成塊を乳鉢に入れて乳棒で解砕し、目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末を得た。<Example 3>
Lithium carbonate having an average particle size (D50) of 7 μm; electrolytic manganese dioxide having an average particle size (D50) of 23 μm and a specific surface area of 40 m 2 / g; nickel hydroxide having an average particle size (D50) of 22 μm; D50) 2 μm of titanium oxide and lithium tetraborate having an average particle size (D50) of 60 μm were weighed.
An aqueous solution of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water. At this time, the dispersant was added in an amount of 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material and B raw material, and was sufficiently dissolved and mixed in ion-exchanged water. Of the weighed raw materials, only the Ni raw material and the Mn raw material were added to the ion-exchanged water in which a dispersant was previously dissolved, and mixed and stirred to obtain a slurry. The obtained slurry was pulverized with a wet pulverizer at 1300 rpm for 120 minutes. Subsequently, a Li raw material, a Ti raw material, and a B raw material were added and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%. Subsequently, the mixture was further pulverized with a wet pulverizer at 1300 rpm for 120 minutes to obtain a pulverized slurry having an average particle diameter (D50) of 0.60 μm or less.
The obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Kakoki Co., Ltd.). At this time, a twin jet nozzle is used for spraying, and granulation drying is performed by adjusting the spray pressure to 0.15 MPa, the slurry supply amount to 400 ml / min, and the temperature of the drying tower so that the outlet temperature becomes 100 to 110 ° C. Was.
The obtained granulated powder was calcined in a static electric furnace in an atmosphere of an oxygen partial pressure of 0.021 MPa so as to be maintained at 950 ° C. for 37 hours, and then heated in an atmosphere of an oxygen partial pressure of 0.021 MPa to 750 ° C. Was heat-treated so as to be maintained for 37 hours.
The calcined mass obtained by the heat treatment was put into a mortar, crushed with a pestle, classified with a sieve having a mesh size of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder.
次に、このように篩下粉を回収して得られたスピネル型リチウムマンガン含有複合酸化物粉末１ｋｇを、ｐＨ６〜７、温度２５℃のイオン交換水２０００ｍＬを入れたプラスチックビーカー（容量５０００ｍＬ）の中に投入し、攪拌機（プロペラ面積３３ｃｍ２）を用いて４００〜５５０ｒｐｍの回転で２０分間撹拌した。撹拌後、撹拌を停止して攪拌機を水中から取り出し、１０分間静置した。そして、デカンテーションにより上澄み液を除去し、残りのスラリーを吸引ろ過器（ろ紙Ｎｏ．１３１）により、ろ過し、沈降物を回収した。回収した沈降物を１２０℃環境下で１０時間乾燥させた。その後、品温が５００℃となるように加熱した状態で７時間乾燥させた。乾燥後、目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。Next, 1 kg of the spinel-type lithium manganese-containing composite oxide powder obtained by collecting the undersize powder in a plastic beaker (capacity 5000 mL) containing 2000 mL of ion-exchanged water having a pH of 6 to 7 and a temperature of 25 ° C. Then, the mixture was stirred with a stirrer (propeller area: 33 cm 2 ) at a rotation of 400 to 550 rpm for 20 minutes. After the stirring, the stirring was stopped, and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant was removed by decantation, and the remaining slurry was filtered with a suction filter (filter paper No. 131) to collect a sediment. The collected sediment was dried at 120 ° C. for 10 hours. Thereafter, the product was dried for 7 hours while being heated so that the product temperature became 500 ° C. After drying, the powder was classified with a sieve having a mesh size of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder (sample).
さらに、このスピネル型リチウムマンガン含有複合酸化物粉末（ＫＦ水分量：１００ｐｐｍ、硫黄含有量：０．０４％）を、加圧炉（株式会社広築製）を使用して加圧熱処理した。すなわち、サンプル２００ｇを磁製るつぼに充填し、この磁製るつぼを加圧炉内に設置した。その後、酸素ガス（酸素濃度９９％）を加圧炉内に流入させて、酸素分圧を０．２０ＭＰａ、処理雰囲気の全体圧力を０．２１ＭＰａに調整して、１．５℃／ｍｉｎの昇温速度で７３０℃まで加熱して１５時間保持し、その後、酸素流入を継続しながら、室温まで０．３℃／ｍｉｎの降温速度で冷却してスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
スピネル型リチウムマンガン含有複合酸化物粉末（サンプル）の化学分析を実施したところ、Ｌｉ：４．０ｗｔ％、Ｎｉ：１５．６ｗｔ％、Ｍｎ：３９．４ｗｔ％、Ｔｉ：５．０％、Ｂ：０．１％であった。Further, this spinel-type lithium manganese-containing composite oxide powder (KF water content: 100 ppm, sulfur content: 0.04%) was subjected to pressure heat treatment using a pressure furnace (produced by Hiroki Corporation). That is, 200 g of the sample was filled in a porcelain crucible, and the porcelain crucible was placed in a pressure furnace. Thereafter, an oxygen gas (oxygen concentration: 99%) is caused to flow into the pressurized furnace, the oxygen partial pressure is adjusted to 0.20 MPa, the total pressure of the processing atmosphere is adjusted to 0.21 MPa, and the temperature is increased by 1.5 ° C./min. Heated to 730 ° C. at a temperature rate and maintained for 15 hours, and then cooled to a room temperature at a rate of 0.3 ° C./min while continuing oxygen inflow, and spinel-type lithium manganese-containing composite oxide powder (sample) I got
Chemical analysis of the spinel-type lithium manganese-containing composite oxide powder (sample) was carried out. As a result, Li: 4.0 wt%, Ni: 15.6 wt%, Mn: 39.4 wt%, Ti: 5.0%, B: 0.1%.
＜実施例４＞
平均粒径（Ｄ５０）７μｍの炭酸リチウムと、平均粒径（Ｄ５０）２３μｍで比表面積が４０ｍ2／ｇの電解二酸化マンガンと、平均粒径（Ｄ５０）２２μｍの水酸化ニッケルと、平均粒径（Ｄ５０）２μｍの酸化チタンと、平均粒径（Ｄ５０）６０μｍの四ホウ酸リチウムをそれぞれ秤量した。
イオン交換水中へ、分散剤としてポリカルボン酸アンモニウム塩水溶液（サンノプコ（株）製 ＳＮディスパーサント５４６８）を添加した。この際、分散剤の添加量は、前述のＬｉ原料、Ｎｉ原料、Ｍｎ原料、Ｔｉ原料及びＢ原料の合計に対して、６ｗｔ％になるようにし、イオン交換水中へ十分に溶解混合させた。秤量しておいた原料のうち、Ｎｉ原料とＭｎ原料だけを、あらかじめ分散剤を溶解させた前記イオン交換水中へ加えて、混合撹拌し、スラリーを得た。得られたスラリーを湿式粉砕機で１３００ｒｐｍ、１２０分間粉砕した。続いて、Ｌｉ原料、Ｔｉ原料及びＢ原料を添加し、混合撹拌し、固形分濃度４０ｗｔ％のスラリーを調整した。続いてさらに、湿式粉砕機で１３００ｒｐｍ、１２０分間粉砕して平均粒径（Ｄ５０）０．６０μｍ以下の粉砕スラリーを得た。
得られた粉砕スラリーを熱噴霧乾燥機（スプレードライヤー、大川原化工機（株）製「ＲＬ−１０」）を用いて造粒乾燥させた。この際、噴霧にはツインジェットノズルを用い、噴霧圧を０．１６ＭＰａ、スラリー供給量３９０ｍｌ／ｍｉｎ、乾燥塔の出口温度が１００〜１１０℃となるように温度を調節して造粒乾燥を行った。
得られた造粒粉を、静置式電気炉を用いて、酸素分圧０．０２１ＭＰａの雰囲気において、９５０℃を３７時間保持するように焼成した後、得られた焼成塊を乳鉢に入れて乳棒で解砕し、目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末を得た。<Example 4>
Lithium carbonate having an average particle size (D50) of 7 μm; electrolytic manganese dioxide having an average particle size (D50) of 23 μm and a specific surface area of 40 m 2 / g; nickel hydroxide having an average particle size (D50) of 22 μm; D50) 2 μm of titanium oxide and lithium tetraborate having an average particle size (D50) of 60 μm were weighed.
An aqueous solution of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water. At this time, the dispersant was added in an amount of 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material and B raw material, and was sufficiently dissolved and mixed in ion-exchanged water. Of the weighed raw materials, only the Ni raw material and the Mn raw material were added to the ion-exchanged water in which a dispersant was previously dissolved, and mixed and stirred to obtain a slurry. The obtained slurry was pulverized with a wet pulverizer at 1300 rpm for 120 minutes. Subsequently, a Li raw material, a Ti raw material, and a B raw material were added and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%. Subsequently, the mixture was further pulverized with a wet pulverizer at 1300 rpm for 120 minutes to obtain a pulverized slurry having an average particle diameter (D50) of 0.60 μm or less.
The obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Kakoki Co., Ltd.). At this time, a twin jet nozzle is used for spraying, and the granulation drying is performed by controlling the temperature so that the spray pressure is 0.16 MPa, the slurry supply amount is 390 ml / min, and the outlet temperature of the drying tower is 100 to 110 ° C. Was.
The obtained granulated powder is fired in a static electric furnace in an atmosphere of an oxygen partial pressure of 0.021 MPa at 950 ° C. for 37 hours, and the obtained fired mass is put into a mortar and pestle. , And classified by a sieve having an opening of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder.
さらに、このスピネル型リチウムマンガン含有複合酸化物粉末（ＫＦ水分量：２７７ｐｐｍ、硫黄含有量：０．２７％）を、加圧炉（株式会社広築製）を使用して加圧熱処理した。すなわち、サンプル２００ｇを磁製るつぼに充填し、この磁製るつぼを加圧炉内に設置した。その後、酸素ガス（酸素濃度９９％）を加圧炉内に流入させて、酸素分圧を０．２０ＭＰａ、処理雰囲気の全体圧力を０．２１ＭＰａに調整して、１．７℃／ｍｉｎの昇温速度で７３０℃まで加熱して１５時間保持し、その後、酸素流入を継続しながら、室温まで０．３℃／ｍｉｎの降温速度で冷却してスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。 Further, this spinel-type lithium manganese-containing composite oxide powder (KF water content: 277 ppm, sulfur content: 0.27%) was subjected to pressure heat treatment using a pressure furnace (produced by Hiroki Corporation). That is, 200 g of the sample was filled in a porcelain crucible, and the porcelain crucible was placed in a pressure furnace. After that, oxygen gas (99% oxygen concentration) is flowed into the pressurized furnace, the oxygen partial pressure is adjusted to 0.20 MPa, the total pressure of the processing atmosphere is adjusted to 0.21 MPa, and the temperature is increased by 1.7 ° C./min. Heated at a temperature rate of 730 ° C. and maintained for 15 hours, and then cooled to a room temperature at a rate of 0.3 ° C./min while continuing the inflow of oxygen to obtain a spinel-type lithium manganese-containing composite oxide powder (sample) I got
次に、得られたスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を目開き５３μｍの篩で分級した。その後、サンプル１ｋｇを、ｐＨ６〜７、温度２５℃のイオン交換水２０００ｍＬを入れたプラスチックビーカー（容量５０００ｍＬ）の中に投入し、攪拌機（プロペラ面積３３ｃｍ２）を用いて４００〜５５０ｒｐｍの回転で２０分間撹拌した。撹拌後、撹拌を停止して攪拌機を水中から取り出し、１０分間静置した。そして、デカンテーションにより上澄み液を除去し、残りのスラリーを吸引ろ過器（ろ紙Ｎｏ．１３１）により、ろ過し、沈降物を回収した。回収した沈降物を１２０℃環境下で１０時間乾燥させた。その後、品温が５００℃となるように加熱した状態で７時間乾燥させた。乾燥後、目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
スピネル型リチウムマンガン含有複合酸化物粉末（サンプル）の化学分析を実施したところ、Ｌｉ：３．９ｗｔ％、Ｎｉ：１５．６ｗｔ％、Ｍｎ：３９．４ｗｔ％、Ｔｉ：５．０％、Ｂ：０．２％であった。Next, the obtained spinel-type lithium manganese-containing composite oxide powder (sample) was classified using a sieve having a mesh size of 53 μm. Thereafter, 1 kg of the sample is put into a plastic beaker (capacity 5000 mL) containing 2000 mL of ion-exchanged water having a pH of 6 to 7 and a temperature of 25 ° C., and rotated at 400 to 550 rpm using a stirrer (propeller area: 33 cm 2 ). Stirred for minutes. After the stirring, the stirring was stopped, and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant was removed by decantation, and the remaining slurry was filtered with a suction filter (filter paper No. 131) to collect a sediment. The collected sediment was dried at 120 ° C. for 10 hours. Thereafter, the product was dried for 7 hours while being heated so that the product temperature became 500 ° C. After drying, the powder was classified with a sieve having a mesh size of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder (sample).
When the spinel-type lithium manganese-containing composite oxide powder (sample) was subjected to chemical analysis, Li: 3.9 wt%, Ni: 15.6 wt%, Mn: 39.4 wt%, Ti: 5.0%, B: 0.2%.
＜実施例５＞
実施例３において、原料の秤量値を変更し、造粒時の噴霧圧を０．１９ＭＰａ、スラリー供給量３５０ｍｌ／ｍｉｎに変更し、加圧処理条件を酸素分圧０．８９ＭＰａ、処理雰囲気の全体圧力０．９０ＭＰａに変更した以外、実施例３と同様にしてスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
サンプルの化学分析を実施したところ、Ｌｉ：４．０ｗｔ％、Ｎｉ：１５．５ｗｔ％、Ｍｎ：３９．３ｗｔ％、Ｔｉ：５．１％、Ｂ：０．１％であった。<Example 5>
In Example 3, the weighing value of the raw materials was changed, the spray pressure at the time of granulation was changed to 0.19 MPa, the slurry supply amount was changed to 350 ml / min, the pressure treatment condition was set to an oxygen partial pressure of 0.89 MPa, and the entire treatment atmosphere was changed. A spinel-type lithium manganese-containing composite oxide powder (sample) was obtained in the same manner as in Example 3, except that the pressure was changed to 0.90 MPa.
Chemical analysis of the sample revealed that Li: 4.0 wt%, Ni: 15.5 wt%, Mn: 39.3 wt%, Ti: 5.1%, and B: 0.1%.
＜実施例６＞
平均粒径（Ｄ５０）７μｍの炭酸リチウムと、平均粒径（Ｄ５０）２３μｍで比表面積が４０ｍ2／ｇの電解二酸化マンガンと、平均粒径（Ｄ５０）２２μｍの水酸化ニッケルと、平均粒径（Ｄ５０）１μｍの酸化チタン、平均粒径（Ｄ５０）３１μｍの酸化ジルコニウムをそれぞれ秤量した。
イオン交換水中へ、分散剤としてポリカルボン酸アンモニウム塩水溶液（サンノプコ（株）製 ＳＮディスパーサント５４６８）を添加した。この際、分散剤の添加量は、前述のＬｉ原料、Ｎｉ原料、Ｍｎ原料、Ｔｉ原料、Ｚｒ原料の合計に対して、６ｗｔ％になるようにし、イオン交換水中へ十分に溶解混合させた。次に秤量しておいた前述の原料を添加し、混合撹拌し、固形分濃度４０ｗｔ％のスラリーを調整した。続いてさらに、湿式粉砕機で１３００ｒｐｍ、６０分間粉砕して平均粒径（Ｄ５０）０．６０μｍ以下の粉砕スラリーを得た。
得られた粉砕スラリーを熱噴霧乾燥機（スプレードライヤー、大川原化工機（株）製「ＲＬ−１０」）を用いて造粒乾燥させた。この際、噴霧にはツインジェットノズルを用い、噴霧圧を０．５１ＭＰａ、スラリー供給量３１３ｍｌ／ｍｉｎ、乾燥塔の出口温度１００〜１１０℃となるように温度を調節して造粒乾燥を行なった。<Example 6>
Lithium carbonate having an average particle size (D50) of 7 μm; electrolytic manganese dioxide having an average particle size (D50) of 23 μm and a specific surface area of 40 m 2 / g; nickel hydroxide having an average particle size (D50) of 22 μm; D50) 1 μm of titanium oxide and zirconium oxide having an average particle diameter (D50) of 31 μm were weighed.
An aqueous solution of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water. At this time, the added amount of the dispersant was 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material, and Zr raw material, and was sufficiently dissolved and mixed in ion-exchanged water. Next, the above-mentioned weighed raw materials were added, mixed and stirred to prepare a slurry having a solid content of 40 wt%. Subsequently, the mixture was further pulverized with a wet pulverizer at 1300 rpm for 60 minutes to obtain a pulverized slurry having an average particle diameter (D50) of 0.60 μm or less.
The obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Kakoki Co., Ltd.). At this time, a twin jet nozzle was used for spraying, and granulation drying was performed by adjusting the temperature so that the spray pressure was 0.51 MPa, the slurry supply amount was 313 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C. .
得られた造粒粉を、静置式電気炉を用いて、酸素分圧０．０２１ＭＰａの雰囲気において、８８０℃を２２時間保持するように焼成した後、酸素分圧０．０２１ＭＰａの雰囲気において７４０℃を３７時間保持するように熱処理した。
熱処理して得られた焼成粉を乳鉢に入れて乳棒で解砕し、目開き５３μｍの篩で分級し、篩下を回収してスピネル型リチウムマンガン含有複合酸化物粉末を得た。The obtained granulated powder was calcined by using a stationary electric furnace in an atmosphere with an oxygen partial pressure of 0.021 MPa at 880 ° C. for 22 hours, and then 740 ° C. in an atmosphere with an oxygen partial pressure of 0.021 MPa. Was heat-treated so as to be maintained for 37 hours.
The calcined powder obtained by the heat treatment was put into a mortar, crushed with a pestle, classified with a sieve having an opening of 53 μm, and recovered under the sieve to obtain a spinel-type lithium manganese-containing composite oxide powder.
次に、篩下を回収して得られたスピネル型リチウムマンガン含有複合酸化物粉末１ｋｇを、ｐＨ６〜７、温度２５℃のイオン交換水２０００ｍＬを入れたプラスチックビーカー（容量５０００ｍＬ）の中に投入し、攪拌機（プロペラ面積３３ｃｍ２）を用いて４００〜５５０ｒｐｍの回転で２０分間撹拌した。撹拌後、撹拌を停止して攪拌機を水中から取り出し、１０分間静置した。そして、デカンテーションにより上澄み液を除去し、残りについて吸引ろ過器（ろ紙Ｎｏ．１３１）を使用して沈降物を回収し、回収した沈降物を１２０℃環境下で１２時間乾燥させた。その後、品温が５００℃となるように加熱した状態で７時間乾燥させた。乾燥後、目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末を得た。Next, 1 kg of the spinel-type lithium manganese-containing composite oxide powder obtained by collecting the under sieve is put into a plastic beaker (capacity 5000 mL) containing 2000 mL of ion-exchanged water having a pH of 6 to 7 and a temperature of 25 ° C. The mixture was stirred at 400 to 550 rpm for 20 minutes using a stirrer (propeller area: 33 cm 2 ). After the stirring, the stirring was stopped, and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant was removed by decantation, and the remaining precipitate was collected using a suction filter (filter paper No. 131), and the collected precipitate was dried at 120 ° C. for 12 hours. Thereafter, the product was dried for 7 hours while being heated so that the product temperature became 500 ° C. After drying, the particles were classified with a sieve having a mesh size of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder.
さらに、このスピネル型リチウムマンガン含有複合酸化物粉末を、加圧炉（株式会社広築製）を使用して酸素含有雰囲気加圧熱処理した。すなわち、スピネル型リチウムマンガン含有複合酸化物粉末２００ｇを磁製るつぼに充填し、この磁製るつぼを加圧炉内に設置した。その後、酸素ガス（酸素濃度９９％）を加圧炉内に流入させて、酸素分圧を０．２０ＭＰａ、処理雰囲気の全体圧力を０．２１ＭＰａに調整して、１．７℃／ｍｉｎの昇温速度で７３０℃まで加熱して１５時間保持し、その後、酸素流入を継続しながら、室温まで０．３℃／ｍｉｎの降温速度で冷却してスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
スピネル型リチウムマンガン含有複合酸化物粉末（サンプル）の化学分析を実施したところ、Ｌｉ：４．１ｗｔ％、Ｎｉ：１４．２ｗｔ％、Ｍｎ：４０．１ｗｔ％、Ｔｉ：５．３ｗｔ％、Ｚｒ：０．５ｗｔ％であった。Further, the spinel-type lithium manganese-containing composite oxide powder was subjected to a pressure heat treatment in an oxygen-containing atmosphere using a pressure furnace (manufactured by Hiroki Corporation). That is, 200 g of the spinel-type lithium manganese-containing composite oxide powder was filled in a porcelain crucible, and the porcelain crucible was placed in a pressure furnace. Thereafter, an oxygen gas (oxygen concentration: 99%) is caused to flow into the pressurized furnace, the oxygen partial pressure is adjusted to 0.20 MPa, the overall pressure of the processing atmosphere is adjusted to 0.21 MPa, and the temperature is increased by 1.7 ° C./min. Heated to 730 ° C. at a temperature rate and maintained for 15 hours, and then cooled to a room temperature at a rate of 0.3 ° C./min while continuing oxygen inflow, and spinel-type lithium manganese-containing composite oxide powder (sample) I got
Chemical analysis of the spinel-type lithium manganese-containing composite oxide powder (sample) was carried out. As a result, Li: 4.1 wt%, Ni: 14.2 wt%, Mn: 40.1 wt%, Ti: 5.3 wt%, Zr: It was 0.5 wt%.
＜実施例７＞
実施例６において、原料として、平均粒径（Ｄ５０）７μｍの炭酸リチウムと、平均粒径（Ｄ５０）２３μｍで比表面積が４０ｍ2／ｇの電解二酸化マンガンと、平均粒径（Ｄ５０）２２μｍの水酸化ニッケルと、平均粒径（Ｄ５０）１μｍの酸化チタンを使用し、原料の秤量値を変更し、造粒乾燥時の噴霧圧を０．４７ＭＰａに変更し、スラリー供給量３３６ｍｌ／ｍｉｎとし、８５０℃を３７時間保持するように焼成した点以外は、実施例６と同様にしてスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
実施例７で得られたスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）の化学分析を実施したところ、Ｌｉ：４．１ｗｔ％、Ｎｉ：１５．１ｗｔ％、Ｍｎ：４２．５ｗｔ％、Ｔｉ：２．７ｗｔ％であった。<Example 7>
In Example 6, as raw materials, lithium carbonate having an average particle size (D50) of 7 μm, electrolytic manganese dioxide having an average particle size (D50) of 23 μm and a specific surface area of 40 m 2 / g, and water having an average particle size (D50) of 22 μm Nickel oxide and titanium oxide having an average particle diameter (D50) of 1 μm were used, the weighing value of the raw materials was changed, the spray pressure during granulation drying was changed to 0.47 MPa, the slurry supply rate was 336 ml / min, and 850 A spinel-type lithium manganese-containing composite oxide powder (sample) was obtained in the same manner as in Example 6, except that the firing was performed at 37 ° C. for 37 hours.
Chemical analysis of the spinel-type lithium manganese-containing composite oxide powder (sample) obtained in Example 7 showed that Li: 4.1 wt%, Ni: 15.1 wt%, Mn: 42.5 wt%, and Ti: 2.7 wt%.
＜実施例８＞
実施例６において、原料として、平均粒径（Ｄ５０）７μｍの炭酸リチウムと、平均粒径（Ｄ５０）２３μｍで比表面積が４０ｍ2／ｇの電解二酸化マンガンと、平均粒径（Ｄ５０）２２μｍの水酸化ニッケルと、平均粒径（Ｄ５０）１μｍの酸化チタンを使用し、原料の秤量値を変更し、造粒乾燥時の噴霧圧を０．４８ＭＰａに変更し、スラリー供給量３１６ｍｌ／ｍｉｎとし、８５０℃を３７時間保持するように焼成し、酸素含有雰囲気加圧熱処理の温度を７２０℃とした点以外は、実施例６と同様にしてスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
実施例８で得られたスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）の化学分析を実施したところ、Ｌｉ：４．１ｗｔ％、Ｎｉ：１４．７ｗｔ％、Ｍｎ：４１．４ｗｔ％、Ｔｉ：４．０ｗｔ％であった。<Example 8>
In Example 6, as raw materials, lithium carbonate having an average particle size (D50) of 7 μm, electrolytic manganese dioxide having an average particle size (D50) of 23 μm and a specific surface area of 40 m 2 / g, and water having an average particle size (D50) of 22 μm Nickel oxide and titanium oxide having an average particle size (D50) of 1 μm were used, the weighing value of the raw materials was changed, the spray pressure during granulation drying was changed to 0.48 MPa, and the slurry supply amount was set to 316 ml / min. The mixture was fired at 37 ° C. for 37 hours, and a spinel-type lithium manganese-containing composite oxide powder (sample) was obtained in the same manner as in Example 6 except that the temperature of the oxygen-containing atmosphere pressure heat treatment was set to 720 ° C. .
Chemical analysis of the spinel-type lithium manganese-containing composite oxide powder (sample) obtained in Example 8 showed that Li: 4.1 wt%, Ni: 14.7 wt%, Mn: 41.4 wt%, and Ti: It was 4.0 wt%.
＜実施例９＞
平均粒径（Ｄ５０）７μｍの炭酸リチウムと、平均粒径（Ｄ５０）２３μｍで比表面積が４０ｍ2／ｇの電解二酸化マンガンと、平均粒径（Ｄ５０）２２μｍの水酸化ニッケルと、平均粒径（Ｄ５０）１μｍの酸化チタンと、平均粒径（Ｄ５０）２μｍの水酸化アルミニウムをそれぞれ秤量した。
イオン交換水中へ、分散剤としてポリカルボン酸アンモニウム塩水溶液（サンノプコ（株）製 ＳＮディスパーサント５４６８）を添加した。この際、分散剤の添加量は、前述のＬｉ原料、Ｎｉ原料、Ｍｎ原料、Ｔｉ原料、Ａｌ原料の合計に対して、６ｗｔ％になるようにし、イオン交換水中へ十分に溶解混合させた。秤量しておいた原料のうち、Ｎｉ原料とＭｎ原料とＡｌ原料だけを、あらかじめ分散剤を溶解させた前記イオン交換水中へ加えて、混合撹拌し、スラリーを得た。得られたスラリーを湿式粉砕機で１３００ｒｐｍ、１２０分間粉砕した。続いて、前記スラリーにＬｉ原料、Ｔｉ原料を添加し、混合撹拌し、固形分濃度４０ｗｔ％のスラリーを調整した。続いてさらに、湿式粉砕機で１３００ｒｐｍ、１２０分間粉砕して平均粒径（Ｄ５０）０．６０μｍ以下の粉砕スラリーを得た。
得られた粉砕スラリーを熱噴霧乾燥機（スプレードライヤー、大川原化工機（株）製「ＲＬ−１０」）を用いて造粒乾燥させた。この際、噴霧にはツインジェットノズルを用い、噴霧圧を０．１４ＭＰａ、スラリー供給量４００ｍｌ／ｍｉｎ、乾燥塔の出口温度が１００〜１１０℃となるように温度を調節して造粒乾燥を行った。
得られた造粒粉を、静置式電気炉を用いて、酸素分圧０．０２１ＭＰａの雰囲気において、９４０℃を３７時間保持するように焼成した後、酸素分圧０．０２１ＭＰａの雰囲気において７４０℃を３７時間保持するように熱処理した。
熱処理して得られた焼成塊を乳鉢に入れて乳棒で解砕し、目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末を得た。<Example 9>
Lithium carbonate having an average particle size (D50) of 7 μm; electrolytic manganese dioxide having an average particle size (D50) of 23 μm and a specific surface area of 40 m 2 / g; nickel hydroxide having an average particle size (D50) of 22 μm; D50) 1 μm of titanium oxide and aluminum hydroxide having an average particle size (D50) of 2 μm were weighed.
An aqueous solution of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water. At this time, the amount of the dispersant added was 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material, and Al raw material, and was sufficiently dissolved and mixed in ion-exchanged water. Of the weighed raw materials, only the Ni raw material, the Mn raw material, and the Al raw material were added to the ion-exchanged water in which a dispersant was previously dissolved, and mixed and stirred to obtain a slurry. The obtained slurry was pulverized with a wet pulverizer at 1300 rpm for 120 minutes. Subsequently, a Li raw material and a Ti raw material were added to the slurry, mixed and stirred to prepare a slurry having a solid content concentration of 40% by weight. Subsequently, the mixture was further pulverized with a wet pulverizer at 1300 rpm for 120 minutes to obtain a pulverized slurry having an average particle diameter (D50) of 0.60 μm or less.
The obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Kakoki Co., Ltd.). At this time, a twin jet nozzle is used for spraying, and granulation drying is performed by adjusting the temperature so that the spray pressure is 0.14 MPa, the slurry supply amount is 400 ml / min, and the outlet temperature of the drying tower is 100 to 110 ° C. Was.
The obtained granulated powder was calcined in a static electric furnace in an atmosphere of an oxygen partial pressure of 0.021 MPa so as to be maintained at 940 ° C. for 37 hours, and then 740 ° C. in an atmosphere of an oxygen partial pressure of 0.021 MPa. Was heat-treated so as to be maintained for 37 hours.
The calcined mass obtained by the heat treatment was put into a mortar, crushed with a pestle, classified with a sieve having a mesh size of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder.
次に、このように篩下粉を回収して得られたスピネル型リチウムマンガン含有複合酸化物粉末１ｋｇを、ｐＨ６〜７、温度２５℃のイオン交換水２０００ｍＬを入れたプラスチックビーカー（容量５０００ｍＬ）の中に投入し、攪拌機（プロペラ面積３３ｃｍ２）を用いて４００〜５５０ｒｐｍの回転で２０分間撹拌した。撹拌後、撹拌を停止して攪拌機を水中から取り出し、１０分間静置した。そして、デカンテーションにより上澄み液を除去し、残りのスラリーを吸引ろ過器（ろ紙Ｎｏ．１３１）により、ろ過し、沈降物を回収した。回収した沈降物を１２０℃環境下で１０時間乾燥させた。その後、品温が５００℃となるように加熱した状態で７時間乾燥させた。乾燥後、目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。Next, 1 kg of the spinel-type lithium manganese-containing composite oxide powder obtained by collecting the undersize powder in a plastic beaker (capacity 5000 mL) containing 2000 mL of ion-exchanged water having a pH of 6 to 7 and a temperature of 25 ° C. Then, the mixture was stirred with a stirrer (propeller area: 33 cm 2 ) at a rotation of 400 to 550 rpm for 20 minutes. After the stirring, the stirring was stopped, and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant was removed by decantation, and the remaining slurry was filtered with a suction filter (filter paper No. 131) to collect a sediment. The collected sediment was dried at 120 ° C. for 10 hours. Thereafter, the product was dried for 7 hours while being heated so that the product temperature became 500 ° C. After drying, the powder was classified with a sieve having a mesh size of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder (sample).
さらに、このスピネル型リチウムマンガン含有複合酸化物粉末（ＫＦ水分量：１００ｐｐｍ、硫黄含有量：０．０４％）を、加圧炉（株式会社広築製）を使用して加圧熱処理した。すなわち、サンプル２００ｇを磁製るつぼに充填し、この磁製るつぼを加圧炉内に設置した。その後、酸素ガス（酸素濃度９９％）を加圧炉内に流入させて、酸素分圧を０．２０ＭＰａ、処理雰囲気の全体圧力を０．２２ＭＰａに調整して、１．５℃／ｍｉｎの昇温速度で７３０℃まで加熱して１５時間保持し、その後、酸素流入を継続しながら、室温まで０．３℃／ｍｉｎの降温速度で冷却してスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
スピネル型リチウムマンガン含有複合酸化物粉末（サンプル）の化学分析を実施したところ、Ｌｉ：４．１ｗｔ％、Ｎｉ：１６．４ｗｔ％、Ｍｎ：４１．８ｗｔ％、Ｔｉ：４．５％、Ａｌ：０．４％であった。Further, this spinel-type lithium manganese-containing composite oxide powder (KF water content: 100 ppm, sulfur content: 0.04%) was subjected to pressure heat treatment using a pressure furnace (produced by Hiroki Corporation). That is, 200 g of the sample was filled in a porcelain crucible, and the porcelain crucible was placed in a pressure furnace. Thereafter, an oxygen gas (oxygen concentration: 99%) is caused to flow into the pressurized furnace, the oxygen partial pressure is adjusted to 0.20 MPa, the overall pressure of the processing atmosphere is adjusted to 0.22 MPa, and the temperature is increased by 1.5 ° C./min. Heated to 730 ° C. at a temperature rate and maintained for 15 hours, and then cooled to a room temperature at a rate of 0.3 ° C./min while continuing oxygen inflow, and spinel-type lithium manganese-containing composite oxide powder (sample) I got
When the spinel-type lithium manganese-containing composite oxide powder (sample) was subjected to chemical analysis, Li: 4.1 wt%, Ni: 16.4 wt%, Mn: 41.8 wt%, Ti: 4.5%, Al: 0.4%.
＜実施例１０＞
実施例９において、原料として、平均粒径（Ｄ５０）７μｍの炭酸リチウムと、平均粒径（Ｄ５０）２３μｍで比表面積が４０ｍ2／ｇの電解二酸化マンガンと、平均粒径（Ｄ５０）２２μｍの水酸化ニッケルと、平均粒径（Ｄ５０）１μｍの酸化チタンと、平均粒径（Ｄ５０）２μｍの水酸化アルミニウムと、平均粒径（Ｄ５０）６０μｍの四ホウ酸リチウムを使用し、原料の秤量値を変更し、Ｂ原料はＬｉ原料、Ｔｉ原料と同じタイミングでスラリーに添加して混合撹拌し、造粒乾燥時の噴霧圧を０．１４ＭＰａに変更し、スラリー供給量４２１ｍｌ／ｍｉｎとし、酸素含有雰囲気加圧熱処理の温度を７２０℃とし、酸素含有雰囲気加圧熱処理雰囲気の全体圧力を０．２３ＭＰａにした点以外は、実施例９と同様にしてスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
実施例１０で得られたスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）の化学分析を実施したところ、Ｌｉ：４．１ｗｔ％、Ｎｉ：１６．１ｗｔ％、Ｍｎ：４１．４ｗｔ％、Ｔｉ：４．４ｗｔ％、Ａｌ：０．４％、Ｂ：０．１３ｗｔ％であった。<Example 10>
In Example 9, as raw materials, lithium carbonate having an average particle size (D50) of 7 μm, electrolytic manganese dioxide having an average particle size (D50) of 23 μm and a specific surface area of 40 m 2 / g, and water having an average particle size (D50) of 22 μm Using nickel oxide, titanium oxide having an average particle diameter (D50) of 1 μm, aluminum hydroxide having an average particle diameter (D50) of 2 μm, and lithium tetraborate having an average particle diameter (D50) of 60 μm, the weighed value of the raw material was measured. The raw material B was added to the slurry at the same timing as the Li raw material and the Ti raw material and mixed and stirred. The spray pressure during granulation and drying was changed to 0.14 MPa, the slurry supply amount was 421 ml / min, and the oxygen-containing atmosphere was changed. Except that the temperature of the pressure heat treatment was set to 720 ° C. and the total pressure of the oxygen-containing atmosphere pressure heat treatment atmosphere was set to 0.23 MPa, a spinel-type lithium polymer To obtain a cancer-containing composite oxide powder (sample).
Chemical analysis of the spinel-type lithium manganese-containing composite oxide powder (sample) obtained in Example 10 showed that Li: 4.1 wt%, Ni: 16.1 wt%, Mn: 41.4 wt%, and Ti: 4.4 wt%, Al: 0.4%, B: 0.13 wt%.
＜比較例１＞
平均粒径（Ｄ５０）７μｍの炭酸リチウムと、平均粒径（Ｄ５０）２３μｍで比表面積が４０ｍ2／ｇの電解二酸化マンガンと、平均粒径（Ｄ５０）２２μｍの水酸化ニッケルをそれぞれ秤量した。イオン交換水中へ、分散剤としてポリカルボン酸アンモニウム塩水溶液（サンノプコ（株）製 ＳＮディスパーサント５４６８）を添加した。この際、分散剤の添加量は、前述のＬｉ原料、Ｎｉ原料及びＭｎ原料の合計に対して、６ｗｔ％になるようにし、イオン交換水中へ十分に溶解混合させた。秤量しておいた原料を、あらかじめ分散剤を溶解させた前記イオン交換水中へ加えて、混合撹拌して、固形分濃度４０ｗｔ％のスラリーを調整した。
湿式粉砕機で１３００ｒｐｍ、１２０分間粉砕して平均粒径（Ｄ５０）を０．６０μｍ以下とした。
得られた粉砕スラリーを熱噴霧乾燥機（スプレードライヤー、大川原化工機（株）製「ＲＬ−１０」）を用いて造粒乾燥させた。この際、噴霧にはツインジェットノズルを用い、噴霧圧を０．１９ＭＰａ、スラリー供給量３５０ｍｌ／ｍｉｎ、乾燥塔の出口温度が１００〜１１０℃となるように温度を調節して造粒乾燥を行なった。
得られた造粒粉を、静置式電気炉を用いて、酸素分圧０．０２１ＭＰａの雰囲気において、９５０℃を３７時間保持するように焼成した後、酸素分圧０．０２１ＭＰａの雰囲気において７５０℃を３７時間保持するように熱処理した。
熱処理して得られた焼成粉を目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末を得た。
サンプルの化学分析を実施したところ、Ｌｉ：３．９ｗｔ％、Ｎｉ：１６．０ｗｔ％、Ｍｎ：４３．０ｗｔ％であった。<Comparative Example 1>
Lithium carbonate having an average particle size (D50) of 7 μm, electrolytic manganese dioxide having an average particle size (D50) of 23 μm and a specific surface area of 40 m 2 / g, and nickel hydroxide having an average particle size (D50) of 22 μm were weighed. An aqueous solution of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water. At this time, the addition amount of the dispersant was 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material and Mn raw material, and the dispersing agent was sufficiently dissolved and mixed in ion-exchanged water. The weighed raw materials were added to the ion-exchanged water in which a dispersant was previously dissolved, and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%.
The powder was pulverized with a wet pulverizer at 1300 rpm for 120 minutes to reduce the average particle size (D50) to 0.60 μm or less.
The obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Kakoki Co., Ltd.). At this time, a twin jet nozzle is used for spraying, and granulation drying is performed by adjusting the temperature so that the spray pressure is 0.19 MPa, the slurry supply amount is 350 ml / min, and the outlet temperature of the drying tower is 100 to 110 ° C. Was.
The obtained granulated powder was calcined in a static electric furnace in an atmosphere of an oxygen partial pressure of 0.021 MPa so as to be maintained at 950 ° C. for 37 hours, and then heated in an atmosphere of an oxygen partial pressure of 0.021 MPa to 750 ° C. Was heat-treated so as to be maintained for 37 hours.
The calcined powder obtained by the heat treatment was classified with a sieve having an opening of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder.
Chemical analysis of the sample revealed that Li was 3.9 wt%, Ni was 16.0 wt%, and Mn was 43.0 wt%.
＜比較例２＞
平均粒径（Ｄ５０）７μｍの炭酸リチウムと、平均粒径（Ｄ５０）２３μｍで比表面積が４０ｍ2／ｇの電解二酸化マンガンと、平均粒径（Ｄ５０）２２μｍの水酸化ニッケルと、平均粒径（Ｄ５０）２μｍの酸化チタンと、平均粒径（Ｄ５０）６０μｍの四ホウ酸リチウムをそれぞれ秤量した。
イオン交換水中へ、分散剤としてポリカルボン酸アンモニウム塩水溶液（サンノプコ（株）製 ＳＮディスパーサント５４６８）を添加した。この際、分散剤の添加量は、前述のＬｉ原料、Ｎｉ原料、Ｍｎ原料、Ｔｉ原料及びＢ原料の合計に対して、６ｗｔ％になるようにし、イオン交換水中へ十分に溶解混合させた。秤量しておいた原料を、あらかじめ分散剤を溶解させた前記イオン交換水中へ加えて、混合撹拌して、固形分濃度４０ｗｔ％のスラリーを調整した。続いてさらに、湿式粉砕機で１３００ｒｐｍ、６０分間粉砕して平均粒径（Ｄ５０）０．６０μｍ以下の粉砕スラリーを得た。
得られた粉砕スラリーを熱噴霧乾燥機（スプレードライヤー、大川原化工機（株）製「ＲＬ−１０」）を用いて造粒乾燥させた。この際、噴霧にはツインジェットノズルを用い、噴霧圧を０．３３ＭＰａ、スラリー供給量３５０ｍｌ／ｍｉｎ、乾燥塔の出口温度が１００〜１１０℃となるように温度を調節して造粒乾燥を行なった。
得られた造粒粉を、静置式電気炉を用いて、酸素分圧０．０２１ＭＰａの雰囲気において、８８０℃を３７時間保持するように焼成した後、酸素分圧０．０２１ＭＰａの雰囲気において７５０℃を３７時間保持するように熱処理した。
熱処理して得られた焼成粉を乳棒で解砕し、目開き５３μｍの篩で分級し、スピネル型リチウムマンガン含有複合酸化物粉末を得た。<Comparative Example 2>
Lithium carbonate having an average particle size (D50) of 7 μm; electrolytic manganese dioxide having an average particle size (D50) of 23 μm and a specific surface area of 40 m 2 / g; nickel hydroxide having an average particle size (D50) of 22 μm; D50) 2 μm of titanium oxide and lithium tetraborate having an average particle size (D50) of 60 μm were weighed.
An aqueous solution of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water. At this time, the dispersant was added in an amount of 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material and B raw material, and was sufficiently dissolved and mixed in ion-exchanged water. The weighed raw materials were added to the ion-exchanged water in which a dispersant was previously dissolved, and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%. Subsequently, the mixture was further pulverized with a wet pulverizer at 1300 rpm for 60 minutes to obtain a pulverized slurry having an average particle diameter (D50) of 0.60 μm or less.
The obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Kakoki Co., Ltd.). At this time, a twin jet nozzle is used for spraying, and granulation drying is performed by adjusting the temperature so that the spray pressure is 0.33 MPa, the slurry supply amount is 350 ml / min, and the outlet temperature of the drying tower is 100 to 110 ° C. Was.
The obtained granulated powder was calcined in a static electric furnace in an atmosphere of an oxygen partial pressure of 0.021 MPa at 880 ° C. for 37 hours, and then 750 ° C. in an atmosphere of an oxygen partial pressure of 0.021 MPa. Was heat-treated so as to be maintained for 37 hours.
The fired powder obtained by the heat treatment was crushed with a pestle and classified with a sieve having a mesh size of 53 μm to obtain a spinel-type lithium manganese-containing composite oxide powder.
次に、このように篩下粉を回収して得られたスピネル型リチウムマンガン含有複合酸化物粉末１ｋｇを、ｐＨ６〜７、温度２５℃のイオン交換水２０００ｍＬを入れたプラスチックビーカー（容量５０００ｍＬ）の中に投入し、攪拌機（プロペラ面積３３ｃｍ２）を用いて４００〜５００ｒｐｍの回転で２０分間撹拌した。撹拌後、吸引ろ過器（ろ紙Ｎｏ．１３１）を使用して沈降物を回収し、回収した沈降物を１２０℃環境下で１２時間乾燥させた。その後、品温が５００℃となるように加熱した状態で７時間乾燥させた。乾燥後、目開き５３μｍの篩で分級し、篩下粉を回収してスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
スピネル型リチウムマンガン含有複合酸化物粉末（サンプル）の化学分析を実施したところ、Ｌｉ：３．９ｗｔ％、Ｎｉ：１４．１ｗｔ％、Ｍｎ：４４．１ｗｔ％、Ｔｉ：３．６％、Ｂ：０．１％であった。Next, 1 kg of the spinel-type lithium manganese-containing composite oxide powder obtained by collecting the undersize powder in a plastic beaker (capacity 5000 mL) containing 2000 mL of ion-exchanged water having a pH of 6 to 7 and a temperature of 25 ° C. Then, the mixture was stirred for 20 minutes at 400 to 500 rpm using a stirrer (propeller area: 33 cm 2 ). After stirring, the precipitate was collected using a suction filter (filter paper No. 131), and the collected precipitate was dried under a 120 ° C. environment for 12 hours. Thereafter, the product was dried for 7 hours while being heated so that the product temperature became 500 ° C. After drying, the powder was classified with a sieve having a mesh size of 53 μm, and the powder under the sieve was recovered to obtain a spinel-type lithium manganese-containing composite oxide powder (sample).
When the spinel-type lithium manganese-containing composite oxide powder (sample) was subjected to chemical analysis, Li: 3.9 wt%, Ni: 14.1 wt%, Mn: 44.1 wt%, Ti: 3.6%, B: 0.1%.
＜比較例３＞
平均粒径（Ｄ５０）７μｍの炭酸リチウムと、平均粒径（Ｄ５０）２３μｍで比表面積が４０ｍ2／ｇの電解二酸化マンガンと、平均粒径（Ｄ５０）２２μｍの水酸化ニッケルと、平均粒径（Ｄ５０）２μｍの酸化チタンをそれぞれ秤量した。
イオン交換水中へ、分散剤としてポリカルボン酸アンモニウム塩水溶液（サンノプコ（株）製 ＳＮディスパーサント５４６８）を添加した。この際、分散剤の添加量は、前述のＬｉ原料、Ｎｉ原料、Ｍｎ原料及びＴｉ原料の合計に対して、６ｗｔ％になるようにし、イオン交換水中へ十分に溶解混合させた。秤量しておいた原料を、あらかじめ分散剤を溶解させた前記イオン交換水中へ加えて、混合撹拌して、固形分濃度４０ｗｔ％のスラリーを調整した。湿式粉砕機で１３００ｒｐｍ、６０分間粉砕して平均粒径（Ｄ５０）を０．６０μｍ以下の粉砕スラリーを得た。
得られた粉砕スラリーを熱噴霧乾燥機（スプレードライヤー、大川原化工機（株）製「ＲＬ−１０」）を用いて造粒乾燥させた。この際、噴霧にはツインジェットノズルを用い、噴霧圧を０．４６ＭＰａ、スラリー供給量２５０ｍｌ／ｍｉｎ、乾燥塔の出口温度が１００〜１１０℃となるように温度を調節して造粒乾燥を行なった。
得られた造粒粉を、静置式電気炉を用いて、酸素分圧０．０２１ＭＰａの雰囲気において、７５０℃を３７時間保持するように焼成した。
得られた焼成粉を乳棒で解砕し、目開き５３μｍの篩で分級し、スピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
サンプルの化学分析を実施したところ、Ｌｉ：４．０ｗｔ％、Ｎｉ：１５．２ｗｔ％、Ｍｎ：３９．７ｗｔ％、Ｔｉ：５．０％であった。<Comparative Example 3>
Lithium carbonate having an average particle size (D50) of 7 μm; electrolytic manganese dioxide having an average particle size (D50) of 23 μm and a specific surface area of 40 m 2 / g; nickel hydroxide having an average particle size (D50) of 22 μm; D50) 2 μm of titanium oxide was weighed.
An aqueous solution of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water. At this time, the amount of the dispersant added was 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material and Ti raw material, and the dispersing agent was sufficiently dissolved and mixed in ion-exchanged water. The weighed raw materials were added to the ion-exchanged water in which a dispersant was previously dissolved, and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%. The mixture was pulverized with a wet pulverizer at 1300 rpm for 60 minutes to obtain a pulverized slurry having an average particle diameter (D50) of 0.60 μm or less.
The obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Kakoki Co., Ltd.). At this time, a twin jet nozzle was used for spraying, and the granulation drying was performed by adjusting the temperature so that the spray pressure was 0.46 MPa, the slurry supply amount was 250 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C. Was.
The obtained granulated powder was calcined in a static electric furnace in an atmosphere having an oxygen partial pressure of 0.021 MPa at 750 ° C. for 37 hours.
The obtained calcined powder was crushed with a pestle and classified with a sieve having a mesh size of 53 μm to obtain a spinel-type lithium manganese-containing composite oxide powder (sample).
Chemical analysis of the sample revealed that Li was 4.0 wt%, Ni was 15.2 wt%, Mn was 39.7 wt%, and Ti was 5.0%.
＜比較例４＞
比較例３において、焼成温度を８００℃に変更した以外、比較例３と同様にしてスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を得た。
サンプルの化学分析を実施したところ、Ｌｉ：４．０ｗｔ％、Ｎｉ：１５．２ｗｔ％、Ｍｎ：３９．７ｗｔ％、Ｔｉ：５．０％であった。<Comparative Example 4>
In Comparative Example 3, a spinel-type lithium manganese-containing composite oxide powder (sample) was obtained in the same manner as in Comparative Example 3, except that the firing temperature was changed to 800 ° C.
Chemical analysis of the sample revealed that Li was 4.0 wt%, Ni was 15.2 wt%, Mn was 39.7 wt%, and Ti was 5.0%.
＜各種物性値の測定方法＞
実施例及び比較例で得られたスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）の各種物性値を次のように測定した。<Methods for measuring various physical properties>
Various physical properties of the spinel-type lithium manganese-containing composite oxide powders (samples) obtained in Examples and Comparative Examples were measured as follows.
（化学分析）
実施例及び比較例で得られたスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）について、誘導結合プラズマ（ＩＣＰ）発光分光分析により、各元素の含有量を測定した。硫黄量についても同様に測定した。(Chemical analysis)
For the spinel-type lithium manganese-containing composite oxide powders (samples) obtained in the examples and comparative examples, the content of each element was measured by inductively coupled plasma (ICP) emission spectroscopy. The sulfur content was measured in the same manner.
（Ｄ５０）
実施例及び比較例で得られたスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）について、レーザー回折粒子径分布測定装置用自動試料供給機（日機装株式会社製「Ｍｉｃｒｏｔｏｒａｃ ＳＤＣ」）を用い、サンプル（粉体）を水溶性溶媒に投入し、４０％の流速中、４０Ｗの超音波を３６０秒間照射した後、日機装株式会社製レーザー回折粒度分布測定機「ＭＴ３０００ＩＩ」を用いて粒度分布を測定し、得られた体積基準粒度分布のチャートからＤ５０を測定した。
なお、測定の際の水溶性溶媒は６０μｍのフィルターを通し、溶媒屈折率を１．３３、粒子透過性条件を透過、粒子屈折率２．４６、形状を非球形とし、測定レンジを０．１３３〜７０４．０μｍ、測定時間を３０秒とし、２回測定した平均値をＤ５０とした。(D50)
About the spinel-type lithium manganese-containing composite oxide powder (sample) obtained in Examples and Comparative Examples, the sample (“Microtorac SDC” manufactured by Nikkiso Co., Ltd.) was used for the sample ( Powder) into a water-soluble solvent, and irradiated with 40 W ultrasonic waves for 360 seconds at a flow rate of 40%, and then measured the particle size distribution using a laser diffraction particle size distribution analyzer “MT3000II” manufactured by Nikkiso Co., Ltd. D50 was measured from the obtained chart of the volume-based particle size distribution.
The water-soluble solvent at the time of measurement was passed through a 60 μm filter, the solvent refractive index was 1.33, the particle permeability condition was transmitted, the particle refractive index was 2.46, the shape was non-spherical, and the measurement range was 0.133. ７０704.0 μm, the measurement time was 30 seconds, and the average value measured twice was D50.
（比表面積）
実施例及び比較例で得られたスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）の比表面積（ＳＳＡ）を次のようにして測定した。
先ず、サンプル（粉体）０．５ｇを流動方式ガス吸着法比表面積測定装置ＭＯＮＯＳＯＲＢ ＬＯＯＰ（ユアサアイオニクス株式会社製「製品名ＭＳ‐１８」）用ガラスセルに秤量し、前記ＭＯＮＯＳＯＲＢ ＬＯＯＰ用前処理装置にて、３０ｍＬ／ｍｉｎのガス量にて５分間窒素ガスでガラスセル内を置換した後、前記窒素ガス雰囲気中で２５０℃１０分間、熱処理を行った。その後、前記ＭＯＮＯＳＯＲＢ ＬＯＯＰを用い、サンプル（粉体）をＢＥＴ一点法にて測定した。
なお、測定時の吸着ガスは、窒素３０％：ヘリウム７０％の混合ガスを用いた。(Specific surface area)
The specific surface area (SSA) of the spinel-type lithium manganese-containing composite oxide powder (sample) obtained in each of Examples and Comparative Examples was measured as follows.
First, 0.5 g of a sample (powder) is weighed into a glass cell for a fluid-type gas adsorption method specific surface area measuring apparatus MONOSORB LOOP (product name MS-18, manufactured by Yuasa Ionics Co., Ltd.), and the MONOSORB LOOP pretreatment is performed. After replacing the inside of the glass cell with nitrogen gas at a gas flow rate of 30 mL / min for 5 minutes using an apparatus, heat treatment was performed at 250 ° C. for 10 minutes in the nitrogen gas atmosphere. Then, the sample (powder) was measured by the BET one-point method using the MONOSORB LOOP.
Note that a mixed gas of 30% nitrogen and 70% helium was used as an adsorption gas at the time of measurement.
(カールフィッシャー法による水分量の測定方法)
実施例・比較例で得たスピネル型リチウム遷移金属酸化物（粉末）を、カールフィッシャー水分計(三菱化学株式会社製ＣＡ−１００型)を用いて、窒素雰囲気中で１７０℃にした装置内で４５分間加熱した際に放出される水分量を測定し、続いて３００℃に昇温した後、３００℃で４５分間加熱した際に放出される水分量を測定した。
そして、窒素雰囲気中で１７０℃にした装置内で４５分間加熱した際に放出される水分量の測定値を「室温〜１７０℃のＫＦ水分（ｐｐｍ）」とし、３００℃で４５分間加熱した際に放出される水分量を「１７０℃〜３００℃のＫＦ水分（ｐｐｍ）」とし、前記「室温〜１７０℃のＫＦ水分量（ｐｐｍ）」と前記「１７０℃〜３００℃のＫＦ水分量（ｐｐｍ）」の合計量を「ＫＦ水分量（ｐｐｍ）」とした。(Method of measuring water content by Karl Fischer method)
The spinel-type lithium transition metal oxide (powder) obtained in Examples and Comparative Examples was placed in a nitrogen atmosphere at 170 ° C. using a Karl Fischer moisture meter (Model CA-100 manufactured by Mitsubishi Chemical Corporation). The amount of water released when heated for 45 minutes was measured, then, after the temperature was raised to 300 ° C., the amount of water released when heated at 300 ° C. for 45 minutes was measured.
The measured value of the amount of water released when heated in an apparatus heated to 170 ° C. in a nitrogen atmosphere for 45 minutes is defined as “KF water (ppm) from room temperature to 170 ° C.”, and when heated at 300 ° C. for 45 minutes. The amount of water released to the water is referred to as “KF water content at 170 ° C. to 300 ° C. (ppm)”, and the “KF water content at room temperature to 170 ° C. (ppm)” and the “KF water content at 170 ° C. to 300 ° C. )) Is referred to as "KF water content (ppm)".
（結晶構造の同定）
ＸＲＤ測定は、装置名「ＵｌｔｉｍａIV、（株）リガク製」を用い、下記測定条件１で測定を行って、ＸＲＤパターンを得た。統合粉末Ｘ線解析ソフトウェアＰＤＸＬ（（株）リガク製）を用いて、得られたＸＲＤパターンについて結晶相情報を決定し、ＷＰＰＦ（Ｗｈｏｌｅ ｐｏｗｄｅｒ ｐａｔｔｅｒｎ ｆｉｔｔｉｎｇ）法で精密化を行った。ここで結晶相情報としては、空間群Ｆｄ−３ｍ（Ｏｒｉｇｉｎ Ｃｈｏｉｃｅ２）の立方晶に帰属され、８ａサイトにＬｉ、１６ｄサイトにＭｎ、Ｍ１元素、Ｍ２元素、そして過剰なＬｉ分ａ、３２ｅサイトにＯが占有されていると仮定し、各サイトの席占有率及び原子変位パラメータＢを１とし、観測強度と計算強度の一致の程度を表わすＲｗｐ、Ｓが収束するまで繰り返し計算を行った。この際、Ｒｗｐ＜１０、またはＳ＜２．５であれば、観測強度と計算強度が十分に一致していると考えられる。このような観点から、Ｒｗｐは８未満がより好ましく、中でもさらに６未満が好ましく、Ｓは２．３未満がより好ましく、中でもさらに２．１未満がより好ましい。観測強度と計算強度が十分に一致しているということは、得られたサンプルが空間群に限定されず、スピネル型の結晶構造である信頼性が高いことを意味している。(Identification of crystal structure)
The XRD measurement was performed under the following measurement conditions 1 using an apparatus name "Ultima IV, manufactured by Rigaku Corporation" to obtain an XRD pattern. Using integrated powder X-ray analysis software PDXL (manufactured by Rigaku Corporation), crystal phase information was determined for the obtained XRD pattern, and refinement was performed by a whole powder pattern fitting (WPPF) method. Here, the crystal phase information is attributed to a cubic crystal of the space group Fd-3m (Origin Choice 2), and Li is assigned to the 8a site, Mn, M1 and M2 elements are assigned to the 16d site, and excess Li components a and 32e are assigned to the sites a and 32e. Assuming that O was occupied, the seat occupancy of each site and the atomic displacement parameter B were set to 1, and the calculation was repeatedly performed until Rwp and S indicating the degree of agreement between the observed intensity and the calculated intensity converged. At this time, if Rwp <10 or S <2.5, it is considered that the observed intensity and the calculated intensity sufficiently match. From such a viewpoint, Rwp is more preferably less than 8, more preferably less than 6, and S is more preferably less than 2.3, and particularly preferably less than 2.1. The fact that the observed intensity and the calculated intensity are sufficiently coincident means that the obtained sample is not limited to the space group and has high reliability as a spinel-type crystal structure.
＝ＸＲＤ測定条件１＝
線源：ＣｕＫα（線焦点）、波長：１．５４１８３６Å
操作軸：２θ／θ、測定方法：連続、計数単位：ｃｐｓ
開始角度：１５．０°、終了角度：１２０．０°、積算回数：１回
サンプリング幅：０．０１°、スキャンスピード：１．０°/ｍｉｎ
電圧：４０ｋＶ、電流：４０ｍＡ
発散スリット：０．２ｍｍ、発散縦制限スリット：２ｍｍ
散乱スリット：２°、受光スリット：０．１５ｍｍ
オフセット角度：０°
ゴニオメーター半径：２８５ｍｍ、光学系：集中法
アタッチメント：ＡＳＣ−４８
スリット：Ｄ／ｔｅＸ Ｕｌｔｒａ用スリット
検出器：Ｄ／ｔｅＸ Ｕｌｔｒａ
インシデントモノクロ：ＣＢＯ
Ｎｉ−Ｋβフィルター：無
回転速度：５０ｒｐｍ= XRD measurement condition 1 =
Source: CuKα (line focus), wavelength: 1.541836 °
Operating axis: 2θ / θ, measuring method: continuous, counting unit: cps
Start angle: 15.0 °, End angle: 120.0 °, Number of integration: 1 Sampling width: 0.01 °, Scan speed: 1.0 ° / min
Voltage: 40 kV, current: 40 mA
Divergence slit: 0.2 mm, divergence vertical restriction slit: 2 mm
Scattering slit: 2 °, receiving slit: 0.15 mm
Offset angle: 0 °
Goniometer radius: 285 mm, optical system: focusing method attachment: ASC-48
Slit: D / teX Ultra Slit Detector: D / teX Ultra
Incident monochrome: CBO
Ni-Kβ filter: No rotation speed: 50 rpm
（２θが１４．０−１６．５°のピーク有無確認）
ＸＲＤ測定は、装置名「ＵｌｔｉｍａIV、（株）リガク製」を用い、下記測定条件２で測定を行って、ＸＲＤパターンを得た。(Confirmation of peak at 2θ of 14.0-16.5 °)
The XRD measurement was performed under the following measurement conditions 2 using an apparatus name “Ultima IV, manufactured by Rigaku Corporation” to obtain an XRD pattern.
＝ＸＲＤ測定条件２＝
線源：ＣｕＫα（線焦点）、波長：１．５４１８３６Å
操作軸：２θ／θ、測定方法：連続、計数単位：ｃｐｓ
開始角度：１４．０°、終了角度：１６．５°、積算回数：１５回
サンプリング幅：０．０１°、スキャンスピード：０．１°/ｍｉｎ
電圧：４０ｋＶ、電流：４０ｍＡ
発散スリット：０．２ｍｍ、発散縦制限スリット：２ｍｍ
散乱スリット：２°、受光スリット：０．１５ｍｍ
オフセット角度：０°
ゴニオメーター半径：２８５ｍｍ、光学系：集中法
アタッチメント：ＡＳＣ−４８
スリット：Ｄ／ｔｅＸ Ｕｌｔｒａ用スリット
検出器：Ｄ／ｔｅＸ Ｕｌｔｒａ
インシデントモノクロ：ＣＢＯ
Ｎｉ−Ｋβフィルター：無
回転速度：５０ｒｐｍ= XRD measurement condition 2 =
Source: CuKα (line focus), wavelength: 1.541836 °
Operating axis: 2θ / θ, measuring method: continuous, counting unit: cps
Start angle: 14.0 °, End angle: 16.5 °, Number of accumulations: 15 Sampling width: 0.01 °, Scan speed: 0.1 ° / min
Voltage: 40 kV, current: 40 mA
Divergence slit: 0.2 mm, divergence vertical restriction slit: 2 mm
Scattering slit: 2 °, receiving slit: 0.15 mm
Offset angle: 0 °
Goniometer radius: 285 mm, optical system: focusing method attachment: ASC-48
Slit: D / teX Ultra Slit Detector: D / teX Ultra
Incident monochrome: CBO
Ni-Kβ filter: No rotation speed: 50 rpm
そして、ピークの有無は下記のとおり判定を行った。すなわち、２θが１４．０−１４．５°および１６．０°〜１６．５°のｃｐｓの平均値をバックグラウンド（ＢＧ）の強度Ａとし、１４．５〜１６．０のｃｐｓの最大値をピーク強度Ｂとしたときに、その差（Ｂ−Ａ）が２５ｃｐｓ以上であれば、ピークが存在していることとした。この差が大きいほど、本発明における効果を享受できると考えられるため、好ましくは３０ｃｐｓ以上、より好ましくは４０ｃｐｓ以上、さらに好ましくは５０ｃｐｓ以上が望ましい。 The presence or absence of a peak was determined as follows. That is, the average value of cps at 2θ of 14.0-14.5 ° and 16.0 ° -16.5 ° is defined as the intensity A of the background (BG), and the maximum value of cps at 14.5-16.0 is obtained. Is the peak intensity B, and if the difference (BA) is 25 cps or more, it is determined that a peak exists. It is considered that the larger the difference is, the more the effect of the present invention can be enjoyed.
＜電池評価＞
実施例及び比較例で作製したスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を正極活物質として用いて、２０３２型コイン電池およびラミネート型電池を作製し、これを用いて以下に示す電池性能評価試験、サイクル特性評価試験およびガス発生評価試験を行った。<Battery evaluation>
Using the spinel-type lithium manganese-containing composite oxide powder (sample) prepared in Examples and Comparative Examples as a positive electrode active material, a 2032 type coin battery and a laminate type battery were manufactured, and the battery performance evaluation shown below was performed using the same. A test, a cycle characteristic evaluation test, and a gas generation evaluation test were performed.
（コイン電池の作製）
正極活物質として実施例及び比較例で作製したスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を８９質量部と、アセチレンブラック５質量部と、ポリフッ化ビニリデン（ＰＶＤＦ）６質量部とを秤量して混合し、これに１−メチル−２−ピロリドン（ＮＭＰ）１００質量部を加えて正極合剤スラリー（固形分濃度５０質量％）を調製した。このとき、予めＰＶＤＦをＮＭＰに溶解させておき、正極活物質及びアセチレンブラックを加えて固練りして、正極合剤スラリー（固形分濃度５０質量％）を調製した。
この正極合剤スラリーを、集電体であるアルミ箔上に、塗工機を用いて搬送速度２０ｃｍ／ｍｉｎにて塗工した後、該塗工機を使用して７０℃を２分間保持するように加熱した後、１２０℃を２分間保持するように乾燥させて、正極合剤層を形成して正極合剤層付きアルミ箔を得た。次に、この正極合剤層付きアルミ箔を、５０ｍｍ×１００ｍｍのサイズに電極を打ち抜いてからロールプレス機を使用してプレス線圧３t／ｃｍでプレス厚密した後、１３ｍｍφに打ち抜いた。次に、真空状態において、室温から２００℃まで加熱し、２００℃で６時間保持するように加熱乾燥し、正極とした。
負極はφ１４ｍｍ×厚み０．６ｍｍの金属Ｌｉとし、カーボネート系の混合溶媒に、ＬｉＰＦ６を１ｍｏｌ／Ｌになるように溶解させた電解液を含浸させたセパレータ（多孔性ポリエチレンフィルム製）を置き、２０３２型コイン電池を作製した。(Production of coin battery)
89 parts by mass of the spinel-type lithium manganese-containing composite oxide powder (sample) prepared in Examples and Comparative Examples as the positive electrode active material, 5 parts by mass of acetylene black, and 6 parts by mass of polyvinylidene fluoride (PVDF) were weighed. Then, 100 parts by mass of 1-methyl-2-pyrrolidone (NMP) was added thereto to prepare a positive electrode mixture slurry (solid content concentration: 50% by mass). At this time, PVDF was dissolved in NMP in advance, and the positive electrode active material and acetylene black were added and kneaded to prepare a positive electrode mixture slurry (solid content concentration: 50% by mass).
This positive electrode material mixture slurry is coated on an aluminum foil as a current collector at a transport speed of 20 cm / min using a coating machine, and then maintained at 70 ° C. for 2 minutes using the coating machine. After heating in this manner, drying was carried out at 120 ° C. for 2 minutes to form a positive electrode mixture layer to obtain an aluminum foil with a positive electrode mixture layer. Next, the aluminum foil with the positive electrode mixture layer was punched out of an electrode having a size of 50 mm × 100 mm, and then pressed and densified at a press linear pressure of 3 t / cm using a roll press, and then punched out to 13 mmφ. Next, in a vacuum state, the cathode was heated from room temperature to 200 ° C., and dried by heating at 200 ° C. for 6 hours to obtain a positive electrode.
The negative electrode was made of metal Li having a diameter of 14 mm and a thickness of 0.6 mm, and a separator (made of a porous polyethylene film) impregnated with an electrolyte in which a carbonate-based mixed solvent was dissolved with LiPF 6 at a concentration of 1 mol / L was placed. A 2032 type coin battery was produced.
（電池性能評価試験）
上記のようにして準備した２０３２型コイン電池を用いて次に記述する方法で初期活性を行った。２５℃にて０．１Ｃで４．９９９Ｖまで定電流定電位充電した後、０．１Ｃで３．０Ｖまで定電流放電した。これを３サイクル繰り返した。なお、実際に設定した電流値は正極中の正極活物質の含有量から算出した。
上記評価にて、４．９９９−４．５Ｖまでの放電容量をＡ、４．９９９−３．０Ｖまでの放電容量をＢとし、Ａ／Ｂを求めた。Ａ／Ｂが大きくなるほど、高電位容量域が拡大していると考えることができる。(Battery performance evaluation test)
Using the 2032 type coin battery prepared as described above, initial activation was performed by the method described below. The battery was charged at 25 ° C. at a constant current and a constant potential of 4.99 V at 0.1 C, and then discharged at a constant current of 0.1 C to 3.0 V. This was repeated three cycles. The actually set current value was calculated from the content of the positive electrode active material in the positive electrode.
In the above evaluation, the discharge capacity up to 4.999-4.5V was A, and the discharge capacity up to 4.999-3.0V was B, and A / B was determined. It can be considered that the higher the A / B, the larger the high potential capacity region.
（４５℃サイクル特性評価）
上記と同様にコイン電池用の正極を準備した。負極は天然球状グラファイトを塗布した負極電極シート（パイオトレック株式会社 電極容量１．６ｍＡｈ/ｃｍ2）を使用し、φ１４ｍｍのサイズに打ち抜いた。カーボネート系の混合溶媒に、ＬｉＰＦ６を１ｍｏｌ／Ｌになるように溶解させた電解液を含浸させたセパレータ（多孔性ポリエチレンフィルム製）を置き、２０３２型コイン電池を作製した。
上記のようにして準備した２０３２型コイン電池を用いて次に記述する方法で初期活性を行った。２５℃にて０．１Ｃで４．９Ｖまで定電流定電位充電した後、０．１Ｃで２．９Ｖまで定電流放電した。これを３サイクル繰り返した。なお、実際に設定した電流値は正極中の正極活物質の含有量から算出した。(Evaluation of 45 ° C cycle characteristics)
A positive electrode for a coin battery was prepared in the same manner as described above. The negative electrode was punched into a φ14 mm size using a negative electrode sheet coated with natural spherical graphite (Piotrek Co., Ltd., electrode capacity 1.6 mAh / cm 2 ). A separator (made of a porous polyethylene film) impregnated with an electrolytic solution in which LiPF 6 was dissolved at a concentration of 1 mol / L in a carbonate-based mixed solvent was placed to manufacture a 2032 type coin battery.
Using the 2032 type coin battery prepared as described above, initial activation was performed by the method described below. The battery was charged at a constant current and a constant potential of 4.9 V at 0.1 C at 25 ° C. and then discharged at a constant current of 2.9 V at 0.1 C. This was repeated three cycles. The actually set current value was calculated from the content of the positive electrode active material in the positive electrode.
上記のようにして初期活性を行った後のコイン電池を用いて下記に記述する方法で充放電試験し、高温サイクル寿命特性を評価した。電池を充放電する環境温度を４５℃となるようにセットした環境試験機内にセルを入れ、充放電できるように準備し、セル温度が環境温度になるように４時間静置後、充放電範囲を４．９Ｖ〜２．９Ｖとし、充電は０．１Ｃ定電流定電位、放電は０．１Ｃ定電流で１サイクル充放電行った後に、１Ｃにて充放電サイクルを２００回行った。Ｃレートは初期活性時の２５℃、３サイクル目の放電容量を元に計算した。
２００サイクル目の放電容量を２サイクル目の放電容量で割り算して求めた数値の百分率（％）を高温サイクル寿命特性値として求めた。
表１には、各実施例及び比較例の高温サイクル寿命特性値を、比較例２の高温サイクル寿命特性値を１００とした場合の相対値として示した。Using the coin battery after the initial activation as described above, a charge / discharge test was performed by the method described below, and the high-temperature cycle life characteristics were evaluated. The cells were placed in an environmental tester in which the environmental temperature for charging and discharging the battery was set to 45 ° C., prepared for charging and discharging, and allowed to stand for 4 hours so that the cell temperature reached the environmental temperature. Was set to 4.9 V to 2.9 V, charging was performed at 0.1 C constant current and constant potential, discharging was performed at 0.1 C constant current for one cycle, and then charging and discharging were performed 200 times at 1 C. The C rate was calculated based on the discharge capacity of the third cycle at 25 ° C. during the initial activation.
The percentage (%) of the numerical value obtained by dividing the discharge capacity at the 200th cycle by the discharge capacity at the second cycle was obtained as a high-temperature cycle life characteristic value.
Table 1 shows the high-temperature cycle life characteristic values of the respective Examples and Comparative Examples as relative values when the high-temperature cycle life characteristic value of Comparative Example 2 was set to 100.
（ラミネート型電池の作製）
正極活物質として実施例及び比較例で作製したスピネル型リチウムマンガン含有複合酸化物粉末（サンプル）を８９質量部と、アセチレンブラック５質量部と、ポリフッ化ビニリデン（ＰＶＤＦ）６質量部とを秤量して混合し、これに１−メチル−２−ピロリドン（ＮＭＰ）１００質量部を加えて正極合剤スラリー（固形分濃度５０質量％）を調製した。このとき、予めＰＶＤＦをＮＭＰに溶解させておき、正極活物質及びアセチレンブラックを加えて固練りして、正極合剤スラリー（固形分濃度５０質量％）を調製した。
この正極合剤スラリーを、集電体であるアルミ箔上に、塗工機を用いて搬送速度２０ｃｍ／ｍｉｎにて塗工した後、該塗工機を使用して７０℃を２分間保持するように加熱した後、１２０℃を２分間保持するように乾燥させて、正極合剤層を形成して正極合剤層付きアルミ箔を得た。次に、この正極合剤層付きアルミ箔を、５０ｍｍ×１００ｍｍのサイズに電極を打ち抜いてからロールプレス機を使用してプレス線圧３t／ｃｍでプレス厚密した後、４０ｍｍ×２９ｍｍ角に打ち抜いた。次に、真空状態において、室温から２００℃まで加熱し、２００℃で６時間保持するように加熱乾燥し、正極とした。(Production of laminated battery)
89 parts by mass of the spinel-type lithium manganese-containing composite oxide powder (sample) prepared in Examples and Comparative Examples as the positive electrode active material, 5 parts by mass of acetylene black, and 6 parts by mass of polyvinylidene fluoride (PVDF) were weighed. Then, 100 parts by mass of 1-methyl-2-pyrrolidone (NMP) was added thereto to prepare a positive electrode mixture slurry (solid content concentration: 50% by mass). At this time, PVDF was dissolved in NMP in advance, and the positive electrode active material and acetylene black were added and kneaded to prepare a positive electrode mixture slurry (solid content concentration: 50% by mass).
This positive electrode material mixture slurry is coated on an aluminum foil as a current collector at a transport speed of 20 cm / min using a coating machine, and then maintained at 70 ° C. for 2 minutes using the coating machine. After heating in this manner, drying was carried out at 120 ° C. for 2 minutes to form a positive electrode mixture layer to obtain an aluminum foil with a positive electrode mixture layer. Next, the aluminum foil with the positive electrode mixture layer was punched out of an electrode having a size of 50 mm × 100 mm, pressed and densified with a press linear pressure of 3 t / cm using a roll press, and then punched into a square of 40 mm × 29 mm. Was. Next, in a vacuum state, the mixture was heated from room temperature to 200 ° C., and dried by heating at 200 ° C. for 6 hours to obtain a positive electrode.
上記で得られた正極シートと天然球状グラファイトを塗布した負極電極シート（パイオトレック株式会社 電極容量１．６ｍＡｈ/ｃｍ2）をを３．１ｃｍ×４．２ｃｍの大きさに切り出して負極とし、正極と負極の間に、カーボネート系の混合溶媒に、ＬｉＰＦ６を１ｍｏｌ／Ｌになるように溶解させた電解液を含浸させたセパレータ（多孔性ポリエチレンフィルム）を置き、ラミネート型電池を作製した。The positive electrode sheet obtained above and a negative electrode sheet coated with natural spherical graphite (Piotrek Co., Ltd., electrode capacity 1.6 mAh / cm 2 ) were cut out into a size of 3.1 cm × 4.2 cm to obtain a negative electrode. A separator (porous polyethylene film) impregnated with an electrolyte obtained by dissolving LiPF 6 at a concentration of 1 mol / L in a carbonate-based mixed solvent was placed between the negative electrode and the negative electrode to produce a laminated battery.
（ガス発生評価試験）
上記した方法で作製したラミネート型電池を１２時間放置した後、２５℃にて０．０５Ｃで４．９Ｖまで定電流定電位充電した後、２．９Ｖまで定電流放電した。その後、測定環境温度を４５℃にして４時間放置し、０．０５Ｃにて４．９Ｖになるまで充電を行い、その電圧を７日間維持した後、２．９Ｖまで放電を行った。ここまでに発生するガス発生量（ｍＬ）は、浸漬容積法（アルキメデスの原理に基づく溶媒置換法）により計測した。得られたガス発生量と正極シート中の正極活物質量から、正極活物質量当たりのガス発生量（ｍＬ／ｇ）を算出した。なお、表には比較例２の数値を１００として指数で記載を行なった。(Gas generation evaluation test)
After the laminated battery manufactured by the above method was allowed to stand for 12 hours, it was charged at 25 ° C. and 0.05 C at a constant current and a constant potential of 4.9 V, and then discharged at a constant current of 2.9 V. Thereafter, the temperature was set at 45 ° C. for 4 hours, charged at 0.05 C to 4.9 V, and maintained at the voltage for 7 days, and then discharged to 2.9 V. The gas generation amount (mL) generated so far was measured by the immersion volume method (solvent replacement method based on Archimedes' principle). From the obtained gas generation amount and the positive electrode active material amount in the positive electrode sheet, a gas generation amount (mL / g) per positive electrode active material amount was calculated. In the table, the numerical value of Comparative Example 2 was set to 100, and the values were described as indices.
なお、下記表１中のＭ元素とは、Ｌi、Ｍｎ及びＯ以外のスピネル型リチウムマンガン含有複合酸化物の構成元素の意味である。 The M element in Table 1 below means a constituent element of the spinel-type lithium manganese-containing composite oxide other than Li, Mn, and O.
（考察）
焼成後に得られたリチウムマンガン含有複合酸化物及び最終的に得られたリチウムマンガン含有複合酸化物は、実施例１〜１０のいずれにおいても、ＸＲＤ測定より、空間群Ｆｄ−３ｍ（Ｏｒｉｇｉｎ Ｃｈｏｉｃｅ２）の立方晶の結晶構造モデルとフィッティングし、観測強度と計算強度の一致の程度を表わすＲｗｐ、ＳがＲｗｐ＜１０、またはＳ＜２．５である５Ｖ級スピネルであることが確認された。また、ＸＲＤパターン（２θが１４．５〜１６．０°）にピークを持つ、スピネル型リチウムマンガン含有複合酸化物であることが確認された。また、電池性能評価試験の結果から、実施例１〜１０のいずれにおいても、最終的に得られたリチウムマンガン含有複合酸化物は、金属Ｌｉ基準電位で４．５Ｖ以上の作動電位を有するものであることが確認された。(Discussion)
In any of Examples 1 to 10, the lithium manganese-containing composite oxide obtained after the calcination and the finally obtained lithium manganese-containing composite oxide were in the space group Fd-3m (Origin Choice 2) by XRD measurement. By fitting with a cubic crystal structure model, it was confirmed that Rwp and S representing the degree of agreement between the observed intensity and the calculated intensity were 5V-class spinels with Rwp <10 or S <2.5. In addition, it was confirmed that the compound was a spinel-type lithium manganese-containing composite oxide having a peak in the XRD pattern (2θ is 14.5 to 16.0 °). In addition, from the results of the battery performance evaluation test, in any of Examples 1 to 10, the finally obtained lithium manganese-containing composite oxide had an operating potential of 4.5 V or more as a metal Li reference potential. It was confirmed that there was.
過去の技術文献から、Ｌｉ，Ｎｉ，Ｍｎ及びＯからなるスピネル型リチウムマンガン含有複合酸化物であれば、ＸＲＤパターンにおいて２θが１４．５〜１６．０°の範囲でピークの存在が確認されていた。
しかし、Ｌｉ，Ｎｉ，Ｍｎ及びＯからなるスピネル型リチウムマンガン含有複合酸化物以外では、例えばＬi、Ｍｎ及びＯとこれら以外の２種以上の元素とを含むスピネル型リチウムマンガン含有複合酸化物などでは、本願発明以外、当該範囲にピークが見られた例は確認されていなかった。From the technical literature in the past, it has been confirmed that a spinel-type lithium manganese-containing composite oxide composed of Li, Ni, Mn and O has a peak in the XRD pattern at 2θ of 14.5 to 16.0 °. Was.
However, other than the spinel-type lithium manganese-containing composite oxide composed of Li, Ni, Mn, and O, for example, the spinel-type lithium manganese-containing composite oxide containing Li, Mn, and O and two or more other elements is not included. Other than the invention of the present application, no example in which a peak was observed in the range was confirmed.
なお、特開２０１４−１１０１７６の段落［００４０］に記載されている手法に準じて、実施例１〜１０で得られたリチウムマンガン含有複合酸化物についてラマン分光分析（測定条件はレーザー波長：５３２ｎｍ、対物レンズ：５０倍、露光時間：１０秒、積算回数：２０回、測定範囲：１００−１０００ｎｍ）を行ったところ、実施例１〜１０で得られたリチウムマンガン含有複合酸化物のいずれについても、１５５〜６５０ｃｍ−１の範囲に現れるピークは１１本でないことがわかった。In addition, according to the method described in paragraph [0040] of JP-A-2014-110176, the lithium-manganese-containing composite oxide obtained in Examples 1 to 10 was subjected to Raman spectroscopic analysis (measurement conditions: laser wavelength: 532 nm, Objective lens: 50 times, exposure time: 10 seconds, integration frequency: 20 times, measurement range: 100-1000 nm), and all of the lithium-manganese-containing composite oxides obtained in Examples 1 to 10 were: It was found that not 11 peaks appeared in the range of 155 to 650 cm -1 .
以上の実施例の結果並びに、これまで本発明者が行ってきた試験結果から、５Ｖ級スピネル型リチウムマンガン含有複合酸化物の製造工程において、焼成後に、処理雰囲気の全体圧力が大気圧よりも高い圧力であって、かつ、該雰囲気における酸素分圧が大気中の酸素分圧よりも高い処理雰囲気において、５００℃より高く８５０℃より低い温度に加熱して、スピネル型リチウムマンガン含有複合酸化物、特に５Ｖ級スピネル型リチウムマンガン含有複合酸化物の加圧熱処理を行うことにより、構造中に酸素が取り込まれ、安定した結晶構造が得られるようになるものと推察される。またこの際、構造中に生じていた酸素欠損の抑制を行なうことができ、高電位容量域も増大するものと推察される。これらの結晶構造の安定化により、サイクル特性が向上しているものと推定される。
また、高温焼成を行っているため、比表面積を低下させることができ、この点からもガス発生を抑制することができるため、構造安定性と低比表面積の両方の点から、効果的にガス発生を抑制できるものと推察される。
From the results of the above examples and the test results conducted by the present inventors, in the manufacturing process of the 5V-class spinel-type lithium manganese-containing composite oxide, after firing, the overall pressure of the processing atmosphere is higher than the atmospheric pressure. Pressure, and in a processing atmosphere in which the oxygen partial pressure in the atmosphere is higher than the oxygen partial pressure in the atmosphere, the mixture is heated to a temperature higher than 500 ° C. and lower than 850 ° C. In particular, it is presumed that by performing pressure heat treatment of the 5V-class spinel-type lithium manganese-containing composite oxide, oxygen is taken into the structure and a stable crystal structure can be obtained. At this time, it is supposed that the oxygen deficiency generated in the structure can be suppressed, and the high potential capacity region also increases. It is presumed that the stabilization of these crystal structures has improved the cycle characteristics.
In addition, since high-temperature sintering is performed, the specific surface area can be reduced, and gas generation can be suppressed from this point as well. Therefore, gas can be effectively reduced in terms of both structural stability and low specific surface area. It is presumed that generation can be suppressed.
Claims (9)
カールフィッシャー水分測定装置で測定される室温〜３００℃範囲の水分量（「ＫＦ水分」と称する）が２％以下であり、かつ、ＩＣＰにより分析される硫黄含有量が０．３４ｗｔ％未満であるスピネル型リチウムマンガン含有複合酸化物を、処理雰囲気の全体圧力が大気圧よりも高い圧力であって、かつ、該雰囲気における酸素分圧が大気中の酸素分圧よりも高い処理雰囲気において、５００℃より高く８５０℃より低い温度で熱処理する加圧熱処理工程を備えたスピネル型リチウムマンガン含有複合酸化物の製造方法。In a method for producing a spinel-type lithium manganese-containing composite oxide having an operating potential of 4.5 V or more at a metal Li reference potential,
The water content in the range from room temperature to 300 ° C. (referred to as “KF water content”) measured by a Karl Fischer moisture meter is 2% or less, and the sulfur content analyzed by ICP is less than 0.34 wt%. The spinel-type lithium manganese-containing composite oxide is heated at 500 ° C. in a processing atmosphere where the total pressure of the processing atmosphere is higher than the atmospheric pressure and the oxygen partial pressure in the atmosphere is higher than the atmospheric oxygen partial pressure. A method for producing a spinel-type lithium manganese-containing composite oxide, comprising a pressure heat treatment step of performing a heat treatment at a temperature higher than 850 ° C.
原料混合工程、焼成工程、加圧熱処理工程及び洗浄工程を備えており、
前記焼成工程では、酸素分圧０．０１５ＭＰａ〜０．１５ＭＰａの雰囲気において、７７０℃より高く１０００℃以下の温度で焼成してスピネル型リチウムマンガン含有複合酸化物を得ることを特徴とし、
前記加圧熱処理工程では、カールフィッシャー水分測定装置で測定される室温〜３００℃範囲のＫＦ水分が２％以下であり、かつ、ＩＣＰにより分析される硫黄含有量が０．３４ｗｔ％未満であるスピネル型リチウムマンガン含有複合酸化物を、処理雰囲気の全体圧力が大気圧よりも高い圧力であって、かつ、該雰囲気における酸素分圧が大気中の酸素分圧よりも高い処理雰囲気において、５００℃より高く、且つ８５０℃より低い温度で熱処理することを特徴とするスピネル型リチウムマンガン含有複合酸化物の製造方法。In a method for producing a spinel-type lithium manganese-containing composite oxide having an operating potential of 4.5 V or more at a metal Li reference potential,
It has a raw material mixing step, a firing step, a pressure heat treatment step and a cleaning step,
In the firing step, in an atmosphere having an oxygen partial pressure of 0.015 MPa to 0.15 MPa, firing is performed at a temperature higher than 770 ° C. and equal to or lower than 1000 ° C. to obtain a spinel-type lithium manganese-containing composite oxide,
In the pressure heat treatment step, spinel having a KF moisture content of 2% or less in a range from room temperature to 300 ° C. measured by a Karl Fischer moisture meter and a sulfur content analyzed by ICP of less than 0.34 wt%. Type lithium manganese-containing composite oxide, the total pressure of the processing atmosphere is higher than the atmospheric pressure, and the oxygen partial pressure in the atmosphere is higher than the oxygen partial pressure in the atmosphere, the processing atmosphere from 500 ℃ A method for producing a spinel-type lithium manganese-containing composite oxide, wherein the heat treatment is performed at a high temperature and at a temperature lower than 850 ° C.
In the above-mentioned washing step, the spinel-type lithium manganese-containing composite oxide contained in the supernatant is removed by putting the spinel-type lithium manganese-containing composite oxide into the cleaning liquid, stirring for 20 minutes, and then allowing the mixture to stand for 10 minutes. The method for producing a spinel-type lithium manganese-containing composite oxide according to claim 2 .
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