JP5781411B2 - 非水系二次電池用正極活物質及びそれを用いた非水系二次電池 - Google Patents
非水系二次電池用正極活物質及びそれを用いた非水系二次電池 Download PDFInfo
- Publication number
- JP5781411B2 JP5781411B2 JP2011212803A JP2011212803A JP5781411B2 JP 5781411 B2 JP5781411 B2 JP 5781411B2 JP 2011212803 A JP2011212803 A JP 2011212803A JP 2011212803 A JP2011212803 A JP 2011212803A JP 5781411 B2 JP5781411 B2 JP 5781411B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- electrode active
- active material
- less
- secondary battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007774 positive electrode material Substances 0.000 title claims description 88
- 239000002131 composite material Substances 0.000 claims description 22
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 239000006104 solid solution Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 description 38
- 239000002245 particle Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 32
- 230000004907 flux Effects 0.000 description 29
- 239000000203 mixture Substances 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 23
- -1 transition metal salt Chemical class 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 21
- 229910052723 transition metal Inorganic materials 0.000 description 19
- 229910052744 lithium Inorganic materials 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 239000013078 crystal Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 235000002639 sodium chloride Nutrition 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 229910006290 γ-MnOOH Inorganic materials 0.000 description 13
- 239000011149 active material Substances 0.000 description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 12
- 150000002697 manganese compounds Chemical class 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 229940099596 manganese sulfate Drugs 0.000 description 11
- 235000007079 manganese sulphate Nutrition 0.000 description 11
- 239000011702 manganese sulphate Substances 0.000 description 11
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 229910003002 lithium salt Inorganic materials 0.000 description 10
- 159000000002 lithium salts Chemical class 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910015118 LiMO Inorganic materials 0.000 description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910003286 Ni-Mn Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- MWHSMSAKVHVSAS-UHFFFAOYSA-L cobalt(2+);oxalate;dihydrate Chemical compound O.O.[Co+2].[O-]C(=O)C([O-])=O MWHSMSAKVHVSAS-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- HDJUVFZHZGPHCQ-UHFFFAOYSA-L manganese(2+);oxalate;dihydrate Chemical compound O.O.[Mn+2].[O-]C(=O)C([O-])=O HDJUVFZHZGPHCQ-UHFFFAOYSA-L 0.000 description 1
- SCVOEYLBXCPATR-UHFFFAOYSA-L manganese(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Mn+2].[O-]S([O-])(=O)=O SCVOEYLBXCPATR-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- VNYOIRCILMCTHO-UHFFFAOYSA-L nickel(2+);oxalate;dihydrate Chemical compound O.O.[Ni+2].[O-]C(=O)C([O-])=O VNYOIRCILMCTHO-UHFFFAOYSA-L 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
結晶子の平均のサイズε(Å)とプロファイルの積分幅βi(ラジアン)との間ではK=1となり、式(1)が示される。
ε=λ/βicosθ −式(1)
また、不均一歪みηと積分幅βi ´(ラジアン)の間に式(2)の関係があることが示されている。
βi ´=2ηtanθ −式(2)
X線回折ピークに、結晶子の大きさと不均一歪みの両方による積分幅の拡がりがある場合、式(1)と(2)より
β=βi+βi ´=βcosθ/λ+2ηtanθ −式(3−1)
βcosθ/λ=2ηsinθ/λ+1/ε −式(3−2)
となる。上記式(3−2)に、2本以上の回折データを代入し、βcosθ/λをY軸、sinθ/λをX軸にプロットして得られた直線の勾配とY軸との交点より、不均一歪ηと結晶子サイズεを分離して算出することができる。本発明における結晶子サイズとは、Rigaku社製統合粉末X線解析ソフトウェアPDXL2を用いて上記Hallの方法より算出した値である。
(実施例)
本発明の正極活物質を以下の方法により作製した。
(針状マンガン化合物の作製)
針状オキシ水酸化マンガン(γ−MnOOH)は、以下のように作製した。硫酸マンガン五水和物(ナカライテスク社製、一級試薬、純度98%)12.301gを1000mlの蒸留水に溶解し、濃度0.05mol/lの硫酸マンガン水溶液を作製した。次に、アンモニア水(ナカライテスク社製、特級試薬、28%溶液)6.071gを2000mlの蒸留水で希釈した溶液(濃度0.05mol/l)と過酸化水素水(ナカライテスク社製、一級試薬、30%溶液)28.333g(水溶液中のマンガンに対してモル比で5倍量)とを混合した溶液を作製した。上記作製した硫酸マンガン水溶液を攪拌しながら、アンモニア水と過酸化水素水の混合溶液を4時間かけて少量ずつ滴下し、黒褐色の沈殿物を得た。黒褐色の粒子が沈降した後、デカンテーションを3回行ない、吸引濾過し、60℃で乾燥することで目的の試料を得た。得られた試料をSEM観察した結果、直径が10nm以上30nm未満であり、平均直径が19nm、長さが200nm以上600nm未満であり、平均の長さが424nmの針状粒子であった。
出発原料として、硝酸リチウム(ナカライテスク社製、特級試薬、純度98.0%)5.628g、上記作製した針状オキシ水酸化マンガン0.492g、硝酸コバルト六水和物(ナカライテスク社製、一級試薬、純度97.0%)0.210g、硝酸ニッケル六水和物(ナカライテスク社製、一級試薬、純度97.0%)0.596gを秤量し、瑪瑙乳鉢を用いて乾式混合した後、50mlのアルミナ坩堝に入れ、直径80mmの環状炉内で熱処理を行った。熱処理条件は、昇温速度2℃/minで260℃まで昇温、10時間熱処理し、その後昇温速度2℃/minで580℃まで昇温、60時間熱処理した後、室温まで降温した。上記熱処理工程は、いずれも大気中で実施した。得られた固形物に蒸留水を加え、充分に撹拌し、蒸留水で洗浄を5回繰り返した後、吸引濾過し、70℃で乾燥することで目的の試料を得た。得られた試料をSEM観察した結果、直径が20nm以上50nm未満、長さ100nm以上400nm未満の針状粒子であった。
実施例2として、実施例1と同様の原料、混合比で熱処理条件のみを変え、比較正極活物質を作製した。熱処理は昇温速度2℃/minで260℃まで昇温し、10時間熱処理し、その後昇温速度2℃/minで500℃(融剤である硝酸リチウムの分解温度以上)まで昇温し、60時間熱処理した後、室温まで降温した。得られた試料をSEM観察した結果、直径が10nm以上40nm未満、長さが200nm以上の針状粒子であった。
比較例1として、実施例1と同様の原料、混合比で熱処理条件のみを変え、比較正極活物質を作製した。熱処理は昇温速度2℃/minで260℃まで昇温し、10時間熱処理し、その後昇温速度2℃/minで650℃(融剤である硝酸リチウムの分解温度以上)まで昇温し、60時間熱処理した後、室温まで降温した。得られた試料をSEM観察した結果、直径が40nm以上200nm未満、長さが100nm以上400nm未満の針状粒子であった。
比較例2として、実施例1と同様の組成を有する正極活物質を、一般的な固相法により作製した。出発原料に、蓚酸マンガン二水和物(関東化学社製、一級試薬、純度95.0%)1.047g、蓚酸コバルト二水和物(アルドリッチ社製、純度98.0%)0.130g、蓚酸ニッケル二水和物(アルドリッチ社製、純度99.9%)0.309g、水酸化リチウム一水和物(ナカライテスク社製、特級試薬、純度99%)0.514gを秤量し、瑪瑙乳鉢を用いて乾式混合した後、50mlのアルミナ坩堝に入れ、直径80mmの環状炉内で熱処理を行った。熱処理条件は、昇温速度2℃/minで500℃まで昇温し、10時間熱処理し、その後2℃/minで800℃まで昇温し、20時間熱処理した後、室温まで降温した。得られた試料をSEM観察した結果、直径が100nm以上400nm未満の粒子(板状)であった。
上記実施例及び比較例のリチウム二次電池用正極活物質を用いて以下の手順で評価セルを作製し、初期充放電特性及び高い電流密度条件での放電特性を評価した。
Claims (2)
- 層状構造を有する一般式Li[LiaMnbMec]O2−d(MeはMn、Ni、Co、Zr、Zn、Cr、Fe、TiおよびVの中から選ばれる少なくとも1種類以上の元素)(0<a<1/3、0<b<2/3、0<c<1、0≦d≦0.2)で表わされるLi 2 MnO 3 ・LiMeO 2 系固溶体である複合酸化物正極活物質であって、粉末X線回折パターンにおける結晶子サイズが2nm以上19nm以下であることを特徴とする非水系二次電池用正極活物質。
- 請求項1に記載の非水系二次電池用正極活物質を正極に用いた非水系二次電池。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011212803A JP5781411B2 (ja) | 2011-09-28 | 2011-09-28 | 非水系二次電池用正極活物質及びそれを用いた非水系二次電池 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011212803A JP5781411B2 (ja) | 2011-09-28 | 2011-09-28 | 非水系二次電池用正極活物質及びそれを用いた非水系二次電池 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013073826A JP2013073826A (ja) | 2013-04-22 |
JP5781411B2 true JP5781411B2 (ja) | 2015-09-24 |
Family
ID=48478164
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2011212803A Active JP5781411B2 (ja) | 2011-09-28 | 2011-09-28 | 非水系二次電池用正極活物質及びそれを用いた非水系二次電池 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5781411B2 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5741371B2 (ja) * | 2011-10-25 | 2015-07-01 | トヨタ自動車株式会社 | リチウム複合酸化物とその製造方法、及びリチウムイオン二次電池 |
CN108370036A (zh) * | 2015-12-15 | 2018-08-03 | 株式会社杰士汤浅国际 | 锂二次电池用正极活性物质、正极活性物质的前体的制造方法、正极活性物质的制造方法、锂二次电池用正极和锂二次电池 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3559720B2 (ja) * | 1998-01-30 | 2004-09-02 | キヤノン株式会社 | リチウム二次電池及びその製造方法 |
JP2001076724A (ja) * | 1999-09-02 | 2001-03-23 | Sumitomo Metal Ind Ltd | リチウム電池用正極材料とその製造方法 |
US6960335B1 (en) * | 2001-09-20 | 2005-11-01 | Nanopowder Enterprises Inc | Nanostructured and layered lithium manganese oxide and method of manufacturing the same |
JP4190912B2 (ja) * | 2003-02-24 | 2008-12-03 | 住友大阪セメント株式会社 | リチウムイオン電池用正極活物質及びそれを有するリチウムイオン電池 |
JP3979994B2 (ja) * | 2003-12-26 | 2007-09-19 | 独立行政法人科学技術振興機構 | リチウム複酸化物超微粒子の製造方法 |
JP2006114408A (ja) * | 2004-10-15 | 2006-04-27 | Izumi Taniguchi | リチウムマンガン複合酸化物粒子及びそれを用いた二次電池用正極、並びにリチウム二次電池 |
JP4213768B2 (ja) * | 2007-01-26 | 2009-01-21 | 三井金属鉱業株式会社 | 層構造を有するリチウム遷移金属酸化物 |
KR101757490B1 (ko) * | 2009-10-22 | 2017-07-12 | 도다 고교 가부시끼가이샤 | 니켈·코발트·망간계 화합물 입자 분말 및 그의 제조 방법, 리튬 복합 산화물 입자 분말 및 그의 제조 방법, 및 비수전해질 이차 전지 |
-
2011
- 2011-09-28 JP JP2011212803A patent/JP5781411B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
JP2013073826A (ja) | 2013-04-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6462250B2 (ja) | リチウム二次電池用正極活物質、その製造方法、そしてこれを含むリチウム二次電池用正極およびリチウム二次電池 | |
KR101762980B1 (ko) | 정극 활성 물질 입자 분말 및 그의 제조 방법, 및 비수전해질 이차 전지 | |
KR101587293B1 (ko) | 비수전해액 이차 전지용 Li-Ni계 복합 산화물 입자 분말 및 그의 제조 방법, 및 비수전해질 이차 전지 | |
KR101989632B1 (ko) | 정극 활물질 입자 분말 및 그의 제조 방법, 및 비수전해질 이차 전지 | |
JP5440614B2 (ja) | 複合酸化物の製造方法、リチウムイオン二次電池用正極活物質およびリチウムイオン二次電池 | |
JP5803539B2 (ja) | リチウム含有複合酸化物粉末の製造方法 | |
WO2010113512A1 (ja) | リチウムイオン二次電池用正極活物質及びその製造方法並びにリチウムイオン二次電池 | |
JP5987401B2 (ja) | 非水系電解質二次電池用正極活物質とその製造方法および二次電池 | |
KR101463881B1 (ko) | 망간계 스피넬형 리튬 천이 금속 산화물 | |
JP5552685B2 (ja) | 複合酸化物の製造方法、リチウムイオン二次電池用正極活物質およびリチウムイオン二次電池 | |
JPWO2011111364A1 (ja) | 複合酸化物の製造方法、リチウムイオン二次電池用正極活物質およびリチウムイオン二次電池 | |
JP6408097B2 (ja) | 正極活物質及び非水電解質二次電池 | |
JPWO2012176471A1 (ja) | リチウム含有複合酸化物粉末およびその製造方法 | |
CN109716564B (zh) | 正极活性物质及其制造方法、以及非水电解质二次电池 | |
WO2015001957A1 (ja) | リチウムイオン二次電池用正極活物質、リチウムイオン二次電池用正極、リチウムイオン二次電池及びこれらの製造方法 | |
JP5674055B2 (ja) | 複合酸化物の製造方法、二次電池用正極活物質および二次電池 | |
JP5733571B2 (ja) | リチウム含有複合酸化物の製造方法、正極活物質および二次電池 | |
JP2013073833A (ja) | リチウムイオン二次電池用正極活物質の製造方法 | |
JP5370501B2 (ja) | 複合酸化物の製造方法、リチウムイオン二次電池用正極活物質およびリチウムイオン二次電池 | |
KR102468733B1 (ko) | 양극 활물질 및 그 제조 방법, 및 비수전해질 이차 전지 | |
JP2013012336A (ja) | 二次電池およびその充電方法 | |
JP5641132B2 (ja) | リチウム含有複合酸化物の製造方法、正極活物質および二次電池 | |
JP5447452B2 (ja) | リチウムイオン二次電池用正極活物質、その正極活物質を用いたリチウムイオン二次電池及びリチウムマンガン銀複合酸化物の製造方法 | |
JP5781411B2 (ja) | 非水系二次電池用正極活物質及びそれを用いた非水系二次電池 | |
JP2013004401A (ja) | 非水系二次電池用正極活物質及びその製造方法並びに非水系二次電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140326 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140827 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20141216 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150216 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150630 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150715 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5781411 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |