JP3503688B2 - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JP3503688B2 JP3503688B2 JP36870899A JP36870899A JP3503688B2 JP 3503688 B2 JP3503688 B2 JP 3503688B2 JP 36870899 A JP36870899 A JP 36870899A JP 36870899 A JP36870899 A JP 36870899A JP 3503688 B2 JP3503688 B2 JP 3503688B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- lithium
- active material
- powder
- positive electrode
- 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.)
- Expired - Fee Related
Links
- 229910052744 lithium Inorganic materials 0.000 title claims description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 47
- 239000011572 manganese Substances 0.000 claims description 42
- 239000007774 positive electrode material Substances 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 24
- 229910052796 boron Inorganic materials 0.000 claims description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052596 spinel Inorganic materials 0.000 claims description 14
- 239000011029 spinel Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000002344 surface layer Substances 0.000 claims description 8
- 229910052771 Terbium Inorganic materials 0.000 claims description 6
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 51
- 150000003839 salts Chemical class 0.000 description 29
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 25
- 239000004327 boric acid Substances 0.000 description 25
- 238000010304 firing Methods 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 21
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 17
- 239000003575 carbonaceous material Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 229910017604 nitric acid Inorganic materials 0.000 description 14
- 239000000523 sample Substances 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 239000011149 active material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 11
- 238000006467 substitution reaction Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 10
- 239000011651 chromium Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical group [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 241000556720 Manga Species 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004452 microanalysis Methods 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- JQBILSNVGUAPMM-UHFFFAOYSA-K terbium(3+);triacetate Chemical compound [Tb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JQBILSNVGUAPMM-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910018680 LixCo Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- IDKDPHXGGRAHER-UHFFFAOYSA-N [Li].O.O.O.O Chemical compound [Li].O.O.O.O IDKDPHXGGRAHER-UHFFFAOYSA-N 0.000 description 1
- CSIBUAXGMIKQMF-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Li+].[Mn+2] Chemical compound [Mn](=O)(=O)([O-])[O-].[Li+].[Mn+2] CSIBUAXGMIKQMF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910000833 kovar Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 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
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- Carbon And Carbon Compounds (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
【０００１】
【発明の属する技術分野】本発明は非水電解質電池に関
するもので、さらに詳しくは非水電解質電池に用いる正
極活物質に関する。
【０００２】
【従来の技術】現在、４Ｖ級の作動電圧を示すリチウム
二次電池の正極活物質として、ＬｉＣｏＯ2、ＬｉＮｉ
Ｏ2等のα−ＮａＦｅＯ2構造を有する含リチウム酸化物
や、ＬｉＭｎ2Ｏ4等のスピネル構造を有する含リチウム
酸化物などが用いられている。中でも、スピネル構造を
有するＬｉＭｎ2Ｏ4は、製造コストが低く、安全性に優
れた正極活物質である。一方、負極活物質には、リチウ
ム金属、リチウム合金、炭素材料などが用いられてい
る。
【０００３】炭素材料の中でも、特に黒鉛化の進んだグ
ラファイトを負極に用い、例えばマンガン酸リチウムを
正極に用いると、平坦な作動電池電圧が得られるので、
各種携帯機器の作動時間を長くすることができる利点が
ある。しかしながら、この系の電池は、充放電サイクル
を繰り返すと、充電時の負極の単極電位が０Ｖ付近とな
り、リチウムが析出する反応との競争反応となる。その
ことが、サイクル劣化を起こす要因の一つとなってい
た。
【０００４】一方、マンガン酸リチウム材料のサイクル
劣化を改良するため、特開平４−２３３１６１号公報、
特開平５−２１０６７号公報、特開平６−１８７９９３
号公報には、スピネル構造を有するマンガン酸リチウム
のMnの一部を他の元素で置換する技術が示されている。
しかしながら、特に電池を高温で放置しておくと、Mnが
電解液に溶出することから、充放電サイクルの繰り返し
に伴って電池容量が低下するといった問題があった。
【０００５】
【発明が解決しようとする課題】本発明は、上記問題点
に鑑みなされたものであり、炭素材料を負極に用い、マ
ンガン酸リチウムを正極に用いた電池において、負極及
び正極のサイクル容量劣化を改良し、高温においても高
容量、高エネルギー密度で、不可逆容量の少ない充放電
サイクル特性の優れたリチウム二次電池を提供すること
を目的とする。
【０００６】
【課題を解決するための手段】上記課題を解決するた
め、本発明は、リチウムマンガン複合酸化物を構成する
Ｍｎ元素の一部がＬｉ、Ｂ、Ｖ、Ａｌ、Ｎｉ、Ｃｏ、Ｍ
ｇ、Ｃｒ、Ｔｂから選ばれる少なくとも一種の異種元素
で置換された電極活物質を用いたリチウム二次電池にお
いて、前記電極活物質の粒子表層部における前記異種元
素の濃度が、粒子内部における前記濃度に比べて高いこ
とを特徴とするリチウム二次電池である。また、前記電
極活物質の一般式が下記の式で示される組成であること
を特徴とするリチウム二次電池である。
Ｌｉ(1-z)［Ｍｎ(2-x-y-w)ＭxＢwＬｉyＯ4］
（ＭはＶ、Ａｌ、Ｎｉ、Ｃｏ、Ｍｇ、Ｃｒ、Ｔｂの中か
ら選ばれた少なくとも１種の元素、ｘ＝０．０１〜０．
１、ｙ＝０〜０．２、ｘ＋ｙ＋ｗ≦０．２、ｗ＝０．０
００５〜０．０１）
【０００７】ここで、ｚは可逆的に使用可能なリチウム
量を示し、０≦ｚ≦１である。活物質の粒子表層部の少
なくとも一部においては、上記の値は特にｘ＝０．０５
〜０．１、ｗ＝０．０５〜０．０１となる。
【０００８】負極活物質に炭素材料を用いた場合、炭素
材料へのリチウムの吸蔵反応や放出反応は、電解液と炭
素表面との間に生じる被膜状態によって大きく支配され
る。リチウム金属負極をモデルに説明すると、リチウム
金属表面に、緻密でイオン導伝性の高い被膜があると、
優れた電池特性を示すが、逆に厚くイオン伝導性の低い
被膜があると、電池のレート特性や、サイクル特性が悪
くなる。ここで、前者の被膜成分は炭酸リチウムや酸化
リチウム等であり、後者の被膜成分はフッ化リチウム等
であることが知られている。同様のことが炭素材料の表
面に生じる被膜についても言える。即ち、炭素材料の界
面抵抗を増大させる要因の一つに、炭素材料表面に、フ
ッ化リチウム等のイオン伝導度の低い被膜が形成される
ことが挙げられる。前記フッ化リチウムの被膜が形成さ
れる過程においては、正極材料等から持ち込まれた水分
により電解質が分解して生成するフッ酸が関与している
と考えられる。
【０００９】本発明者らは、上記の点について研究を進
めた結果、スピネル構造を有するマンガン酸リチウムに
おいて、マンガンの一部をリチウム、ホウ素及びその他
の金属（バナジウム、アルミニウム、ニッケル、コバル
ト、マグネシウム、クロム、テルビウム等）の元素で置
換することにより、電池内部で生成するフッ酸の量を抑
制することができることを見い出した。さらに、本発明
の正極活物質材料を用いると、高温保存中の電解液への
Ｍｎの溶出も抑制する効果がある。
【００１０】ここで、マンガンと置換された他元素の量
が多いほど、上記効果が高い一方、可逆的に利用できる
Ｌｉの量が少なくなるといった問題が生じる。そこで、
前記置換の程度が、活物質粒子の表層部に高く、内部に
低くなるようにすることにより、置換によって得られる
効果を下げることなく、活物質の容量を高く保つことが
できる。なかでも、置換元素にホウ素を用いると、活物
質粒子の表層部の置換量のみを多くすることが容易にで
きる点で好ましい。
【００１１】正極活物質の主構成物質であるＬｉ(1-z)
［Ｍｎ(2-x-y-w)ＭxＢwＬｉyＯ4］において、ＭはＭ
ｎ、Ｌｉ以外の元素で、Ｍｎと置換しうる元素が好まし
い。例えば、Ｂｅ、Ｂ、Ｖ、Ｃ、Ｓｉ、Ｐ、Ｓｃ、Ｃ
ｕ、Ｚｎ、Ｇａ、Ｇｅ、Ａｓ、Ｓｅ、Ｓｒ、Ｍｏ、Ｐ
ｄ、Ａｇ、Ｃｄ、Ｉｎ、Ｓｎ、Ｓｂ、Ｔｅ、Ｂａ、Ｔ
ａ、Ｗ．Ｐｂ、Ｂｉ、Ｃｏ、Ｆｅ、Ｃｒ、Ｎｉ、Ｔｉ、
Ｚｒ、Ｎｂ、Ｙ、Ａｌ、Ｎａ、Ｋ、Ｍｇ、Ｃａ、Ｃｓ、
Ｌａ、Ｃｅ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ等が挙げられる。
高温保存による電解液へのＭｎの溶出抑制に対しては、
Ｂ、Ｖ、Ｎｉ、Ｃｏ、Ｍｇ、Ｃｒ、Ｔｂ等を用いると、
その効果が顕著であり、特に好ましい。ここで、Ｍｎの
置換量を示すｘ、ｙ、wの値は、０＜ｘ＋ｙ＋w≦０．２
である。ｘ＋ｙ＋wの値が０.２を超えると、可逆的に使
用可能なリチウム量が減少し、電池性能に与える影響が
大きい。可逆的に使用可能なリチウム量を示すｚは、Ｍ
ｎの置換量が多いほど少なくなり、Ｍｎの置換量が少な
いほど多くなる。高温保存時の劣化は、０＜ｘ＋ｙ＋w
≦０．２の範囲内であれば、Ｍｎの置換量が多いほど抑
制される。
【００１２】
【発明の実施の形態】正極活物質の主構成物質であるＬ
ｉ(1-z)［Ｍｎ(2-x-y-w)ＭxＢwＬｉyＯ4］において、Ｍ
ｎの一部をリチウムや異種元素で置換する方法として
は、焼成原料にあらかじめ置換する元素を添加する方法
や、ＬｉＭｎ2Ｏ4を焼成した後にイオン交換等により異
種元素を置換する方法等が挙げられるが、これらに限定
されるものではない。
【００１３】負極活物質に用いる炭素材料は、リチウム
を吸蔵、放出可能な炭素材料であればよく、特に、Ｘ線
回折法による面間隔（ｄ００２）が３. ３５４〜３. ３
６９Åで、Ｃ軸方向の結晶の大きさ（Ｌｃ）が２００Å
以上である炭素粒子は、高容量が得られるため好まし
い。
【００１４】正極活物質の主構成物質にＬｉ(1-z)［Ｍ
ｎ(2-x-y-w)ＭxＢwＬｉyＯ4］を用いる場合、ＬｉxＣｏ
Ｏ2、ＬｉxＮｉＯ2 等の金属酸化物をさらに添加しても
よい。本発明に用いる正極活物質や負極活物質は、平均
粒子サイズ１００μｍ以下であることが望ましい。所定
の形状を得るため、粉砕機や分級機を用いてもよい。例
えば、ボールミル、遊星ボールミル、ジェットミル、旋
回気流型ジェットミルや篩等が用いられる。粉砕時には
水、あるいはヘキサン等の有機溶剤を共存させた湿式粉
砕を用いてもよい。分級方法としては、篩や風力分級機
などを乾式、湿式ともに必要に応じて用いてもよい。
【００１５】正極及び負極には、活物質に導電剤、結着
剤、フィラー等を添加してもよい。導電剤には、アセチ
レンブラック、ケッチェンブラック等の炭素材料を用い
ることができる。これらの中で、アセチレンブラックと
ケッチェンブラックを併用することが好ましい。導電剤
の添加量が多すぎると、電極密度を低下させ、少なすぎ
ると、電極の十分な電子伝導性が得られない。このた
め、導電剤の添加量は１〜１０重量％が好ましく、さら
に好ましくは３〜６重量％である。
【００１６】結着剤には、ポリテトラフルオロエチレ
ン、ポリフッ化ビニリデン、フッ素ゴム、カルボキシメ
チルセルロース等の熱可塑性樹脂、ゴム弾性を有するポ
リマー、多糖類等を１種または２種以上の混合物として
用いることができる。また、多糖類のように、リチウム
と反応する官能基を有する結着剤を用いる場合には、前
記反応基をメチル化するなどの方法で失活させておくこ
とが好ましい。結着剤の添加量が多すぎると、電極密度
を低下させ、少なすぎると、電極の十分な結着効果が得
られない。このため、結着剤の添加量は、１〜１０重量
％が好ましく、さらに好ましくは３〜６重量％である。
【００１７】正極集電体には、アルミニウム、チタン、
ステンレス鋼、等を用いることができる。負極集電体に
は、銅、ステンレス鋼、ニッケル等を用いることができ
る。集電体は、フォイル状、多孔板又はエキスパンド等
の形状のものを用いることができる。厚みは特に限定は
ないが、５〜３０μｍのものが用いることができる。
【００１８】電解質には、例えば有機電解液、高分子固
体電解質、無機固体電解質、溶融塩等を用いることがで
きる。有機電解液の有機溶媒としては、プロピレンカー
ボネート、エチレンカーボネート、ジエチルカーボネー
ト、ジメチルカーボネート、メチルエチルカーボネー
ト、γ−ブチロラクトン等のエステル類が挙げられ、こ
れらを単独又は混合溶媒として用いることができる。ま
た、支持電解質塩としては、ＬｉＰＦ6、ＬｉＢＦ4、Ｌ
ｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、Ｌｉ
Ｎ（ＣＦ3ＳＯ2）（Ｃ4Ｆ9ＳＯ2）2 等が挙げられ、こ
れらを単独又は混合塩として用いることができる。高分
子固体電解質としては、上記のような支持電解質塩をポ
リエチレンオキシドやその架橋体、ポリフォスファゼン
やその架橋体等といったポリマーの中に溶かし込んだも
のを用いることができる。
【００１９】セパレータには、イオンの透過度が優れ、
機械的強度のある絶縁性薄膜を用いることができる。耐
有機溶剤性と疎水性の点から、ポリプロピレン、ポリエ
チレン等オレフィン系ポリマー、ポリフッ化ビニリデ
ン、ポリテトラフルオロエチレン等を原料とするシー
ト、微孔膜、不織布等が用いられる。セパレータの孔径
は、一般に電池に用いられる範囲のものであり、例えば
０．０１〜１μｍである。また、その厚さについても同
様に、一般に電池に用いられる範囲のものであり、例え
ば２０〜４０μｍである。
【００２０】本発明の電池が、従来電池に比べ、充放電
特性、特にサイクル特性が向上する理由については、必
ずしも明確ではないが、以下のように考察される。一般
に、電池内部には、種々の不純物が含まれていると考え
られる。例えば、ＬｉＰＦ6を電解質塩に用いる場合、
塩そのものに含まれる不純物が考えられる。また、前記
塩が電池内部や溶媒中に含まれる微量の水分と反応する
と、フッ酸（ＨＦ）を生じる。炭素材料と電解液との界
面においては、炭素材料がリチウムを吸蔵する際、炭酸
リチウム等のイオン伝導性の高い被膜を形成する。しか
しながら、このときフッ酸等の酸が存在すると、イオン
伝導性の低いハロゲン化リチウムを生じる。生じたハロ
ゲン化リチウムは、リチウムの吸蔵放出を妨げるので、
負極の界面抵抗を増大させ、放電容量を低減させる原因
の一つとなる。従って、電池内部に存在するフッ酸の量
を低減させることで、この問題が解決できると考えられ
る。
【００２１】発明者らは、前記電解質塩が分解してフッ
酸を生成する反応に対し、正極活物質であるマンガン酸
リチウムが触媒的に作用していると考えた。そこで、ス
ピネル構造を有するマンガン酸リチウムのマンガン元素
の一部をリチウム、マンガン以外の元素で置換し、触媒
的活性を低下させることで、前記反応によって生じるフ
ッ酸を低減させる方策を試みた。また、前記触媒的活性
は、スピネル構造を有するＬｉＭｎ2Ｏ4の充電末物質で
あるγ−ＭｎＯ2が最も高いと考え、これについても、
スピネル構造を有するマンガン酸リチウムのマンガン元
素の一部をリチウム、マンガン以外の元素で置換するこ
とで、前記γ−ＭｎＯ2の生成を抑制できないかを検討
した。
【００２２】その結果、上記方策を施した本発明電池
は、炭素材料を用いた負極の界面抵抗増大が抑制され、
サイクル特性が向上することを見いだした。また、この
マンガンの一部をリチウムとマンガン以外の元素で置換
したスピネル構造を有するマンガン酸リチウムは、触媒
活性が低減しただけでなく、高温における活物質自身の
安定性も向上し、高温におけるサイクル特性も向上する
ことが分かった。
【００２３】
【実施例】以下、実施例に基づき、本発明をさらに詳細
に説明する。
（本発明電池１）酢酸リチウム二水和物、酢酸マンガン
（ＩＩ）四水和物及び硼酸を、Ｌｉ：Ｍｎ：Ｂの元素比
が１．１０：１．８５：０．０５となるように混合し、
これを酢酸に加え、熱を加えながら撹拌し、完全に溶解
させた。次に、酢酸を蒸発させ、混合塩を得た。この混
合塩を空気中５００℃で仮焼成した後、８５０℃で本焼
成した。焼成後、粉砕し、粉末を得た。この粉末をエッ
クス線回折法により分析したところ、スピネル構造を有
するマンガン酸リチウムが得られていることが確認され
た。また、この粉末粒子に対し、エックス線光電子分光
法（ＸＰＳ）により、深さ方向のホウ素の分布を測定し
た。ここで、エッチング時間０秒における定量値は、多
くのコンタミネーションを含むと考えられるため、以降
の考察から省く。図１に示すように、粒子表層部ホウ素
の濃度は、粒子の内部に比べ、約２〜５倍高いことが確
認された。
【００２４】この粉末を正極活物質として用い、次のよ
うにして図２に示す容量１６〜１７ｍＡｈのコイン型リ
チウム電池を試作した。
【００２５】正極１は、前記粉末、アセチレンブラック
及びポリテトラフルオロエチレン粉末を、重量比８５：
１０：５で混合し、トルエンを加えて十分混練した。こ
れをローラープレスにより、厚さ０．８ｍｍのシート状
に成形した。次に、前記シートを直径１６ｍｍの円形に
打ち抜き、減圧下２００℃で１５時間乾燥し正極１を得
た。正極１は、正極集電体６の付いた正極缶４に圧着し
て用いた。
【００２６】負極２は、人造黒鉛及びポリテトラフルオ
ロエチレン粉末を、重量比９５：５で混合し、トルエン
を加えて十分混練した。これをローラープレスにより厚
み０．１ｍｍのシート状に成形した。次に、前記シート
を直径１６ｍｍの円形に打ち抜き、減圧下２００℃で１
５時間乾燥して負極２を得た。前記人造黒鉛は、平均粒
径６μｍ、エックス線回折法による面間隔（ｄ002）
３．３７Å、Ｃ軸方向の結晶の大きさ（Ｌｃ）５５０Å
のものを用いた。負極２は、負極集電体７の付いた負極
缶５に圧着して用いた。
【００２７】電解液は、エチレンカーボネート及びジエ
チルカーボネートを、体積比１：１で混合した溶剤に、
ＬｉＰＦ6を１ｍｏｌ／ｌの濃度で溶解したものを用い
た。セパレータ３は、ポリプロピレン製微多孔膜を用い
た。上記正極１、負極２、セパレータ３及び電解液を用
い、直径２０ｍｍ、厚さ１．６ｍｍのコイン型リチウム
電池を作製した。この電池を本発明電池１とする。
【００２８】（本発明電池２）酢酸リチウム二水和物、
酢酸マンガン（ＩＩ）四水和物及び硼酸を、Ｌｉ：Ｍ
ｎ：Ｂの元素比が１．１０：１．８０：０．１０となる
ように混合し、これを酢酸に加え、熱を加えながら撹拌
し、完全に溶解させた。次に、酢酸を蒸発させ、混合塩
を得た。この混合塩を空気中５００℃で仮焼成した後、
８５０℃で本焼成した。焼成後、粉砕し、粉末を得た。
この粉末をエックス線回折法により分析したところ、ス
ピネル構造を有するマンガン酸リチウムが得られている
ことが確認された。また、この粉末粒子に対し、エック
ス線光電子分光法（ＸＰＳ）により、深さ方向のホウ素
の分布を測定したところ、図１の、本発明電池１と同様
の結果を示した。この粉末を正極活物質として用いたこ
と以外は、本発明電池１と同様にして、コイン型リチウ
ム電池を試作した。この電池を本発明電池２とする。
【００２９】（本発明電池３）酢酸リチウム二水和物、
酢酸マンガン（ＩＩ）四水和物及び硼酸を、Ｌｉ：Ｍ
ｎ：Ｂの元素比が１．１０：１．８５：０．０５となる
ように混合し、これを酢酸に加え、熱を加えながら撹拌
し、完全に溶解させた。次に、酢酸を蒸発させ、混合塩
を得た。この混合塩を空気中を３００℃で仮焼成した。
次に、先に用いた硼酸の、２％量に相当する硼酸が溶解
している水溶液を、前記仮焼成後の試料に加えた後、５
００℃で第二焼成し、空気中８５０℃で本焼成した。焼
成後、粉砕し、粉末を得た。この粉末をエックス線回折
法により分析したところ、スピネル構造を有するマンガ
ン酸リチウムが得られていることが確認された。また、
この粉末粒子に対し、エックス線光電子分光法（ＸＰ
Ｓ）により、深さ方向のホウ素の分布を測定したとこ
ろ、図１に示すように、粒子の表層部におけるホウ素の
濃度は、粒子の内部に比べ、約３倍〜１０倍高くなって
いることが確認された。この粉末を正極活物質として用
いたこと以外は、本発明電池１と同様にして、コイン型
リチウム電池を試作した。この電池を本発明電池３とす
る。
【００３０】（本発明電池４）酢酸リチウム二水和物、
酢酸マンガン（ＩＩ）四水和物、バナジウム及び硼酸
を、Ｌｉ：Ｍｎ：Ｖ：Ｂの元素比が１．１０：１．８４
９：０．０５：０．００１となるように混合し、これを
硝酸に加え、熱を加えながら撹拌し、完全に溶解させ
た。次に、硝酸を蒸発させ、混合塩を得た。この混合塩
を３００℃で仮焼成した。次に、先に用いた硼酸と同量
硼酸が溶解している水溶液を、前記仮焼成後の試料に加
えた後、５００℃で第二焼成し、空気中８５０℃で本焼
成した。焼成後、粉砕し、粉末を得た。この粉末をエッ
クス線回折法により分析したところ、スピネル構造を有
するマンガン酸リチウムが得られていることが確認され
た。次に、エネルギー分散型電子プローブマイクロアナ
リシス（ＥＰＭＡ）により、バナジウムの分散状態を観
察したところ、バナジウムはマンガン酸リチウムの全面
に分布していた。また、この粉末粒子に対し、エックス
線光電子分光法（ＸＰＳ）により、深さ方向のホウ素の
分布を測定したところ、図１の、本発明電池３と同様の
結果を示した。この粉末を正極活物質として用いたこと
以外は、本発明電池１と同様にして、コイン型リチウム
電池を試作した。この電池を本発明電池４とする。
【００３１】（本発明電池５）酢酸リチウム二水和物、
酢酸マンガン（ＩＩ）四水和物、硝酸アルミニウム九水
和物及び硼酸を、Ｌｉ：Ｍｎ：Ａｌ：Ｂの元素比が１．
１０：１．８４９：０．０５：０．００１となるように
混合し、これを硝酸に加え、熱を加えながら撹拌し、完
全に溶解させた。次に、硝酸を蒸発させ、混合塩を得
た。この混合塩を３００℃で仮焼成した。次に、先に用
いた硼酸と同量硼酸が溶解している水溶液を、前記仮焼
成後の試料に加えた後、５００℃で第二焼成し、空気中
８５０℃で本焼成した。焼成後、粉砕し、粉末を得た。
この粉末をエックス線回折法により分析したところ、ス
ピネル構造を有するマンガン酸リチウムが得られている
ことが確認された。次に、エネルギー分散型電子プロー
ブマイクロアナリシス（ＥＰＭＡ）により、アルミニウ
ムの分散状態を観察したところ、アルミニムはマンガン
酸リチウムの全面に分布していた。また、この粉末粒子
に対し、エックス線光電子分光法（ＸＰＳ）により、深
さ方向のホウ素の分布を測定したところ、図１の、本発
明電池３と同様の結果を示した。この粉末を正極活物質
として用いたこと以外は、本発明電池１と同様にして、
コイン型リチウム電池を試作した。この電池を本発明電
池５とする。
【００３２】（本発明電池６）酢酸リチウム二水和物、
酢酸マンガン（II）四水和物、硝酸ニッケル（II）六水
和物及び硼酸を、Ｌｉ：Ｍｎ：Ｎｉ：Ｂの元素比が１．
１０：１．８４９：０．０５：０．００１となるように
混合し、これを硝酸に加え、熱を加えながら撹拌し、完
全に溶解させた。次に、硝酸を蒸発させ、混合塩を得
た。この混合塩を３００℃で仮焼成した。次に、先に用
いた硼酸と同量硼酸が溶解している水溶液を、前記仮焼
成後の試料に加えた後、５００℃で第二焼成し、空気中
８５０℃で本焼成した。焼成後、粉砕し、粉末を得た。
この粉末をエックス線回折法により分析したところ、ス
ピネル構造を有するマンガン酸リチウムが得られている
ことが確認された。次に、エネルギー分散型電子プロー
ブマイクロアナリシス（ＥＰＭＡ）により、ニッケルの
分散状態を観察したところ、ニッケルはマンガン酸リチ
ウムの全面に分布していた。また、この粉末粒子に対
し、エックス線光電子分光法（ＸＰＳ）により、深さ方
向のホウ素の分布を測定したところ、図１の、本発明電
池３と同様の結果を示した。この粉末を正極活物質とし
て用いたこと以外は、本発明電池１と同様にして、コイ
ン型リチウム電池を試作した。この電池を本発明電池６
とする。
【００３３】（本発明電池７）酢酸リチウム二水和物、
酢酸マンガン（II）四水和物、酢酸コバルト（II）四水
和物及び硼酸を、Ｌｉ：Ｍｎ：Co：Ｂの元素比が１．１
０：１．８４９：０．０５：０．００１となるように混
合し、これを硝酸に加え、熱を加えながら撹拌し、完全
に溶解させた。次に、硝酸を蒸発させ、混合塩を得た。
この混合塩を３００℃で仮焼成した。次に、先に用いた
硼酸と同量硼酸が溶解している水溶液を、前記仮焼成後
の試料に加えた後、５００℃で第二焼成し、空気中８５
０℃で本焼成した。焼成後、粉砕し、粉末を得た。この
粉末をエックス線回折法により分析したところ、スピネ
ル構造を有するマンガン酸リチウムが得られていること
が確認された。次に、エネルギー分散型電子プローブマ
イクロアナリシス（ＥＰＭＡ）により、コバルトの分散
状態を観察したところ、コバルトはマンガン酸リチウム
の全面に分布していた。また、この粉末粒子に対し、エ
ックス線光電子分光法（ＸＰＳ）により、深さ方向のホ
ウ素の分布を測定したところ、図１の、本発明電池３と
同様の結果を示した。この粉末を正極活物質として用い
たこと以外は、本発明電池１と同様にして、コイン型リ
チウム電池を試作した。この電池を本発明電池７とす
る。
【００３４】（本発明電池８）酢酸リチウム二水和物、
酢酸マンガン（ＩＩ）四水和物、酢酸マグネシウム四水
和物及び硼酸を、Ｌｉ：Ｍｎ：Ｍｇ：Ｂの元素比が１．
１０：１．８４９：０．０５：０．００１となるように
混合し、これを硝酸に加え、熱を加えながら撹拌し、完
全に溶解させた。次に、硝酸を蒸発させ、混合塩を得
た。この混合塩を３００℃で仮焼成した。次に、先に用
いた硼酸と同量硼酸が溶解している水溶液を、前記仮焼
成後の試料に加えた後、５００℃で第二焼成し、空気中
８５０℃で本焼成した。焼成後、粉砕し、粉末を得た。
この粉末をエックス線回折法により分析したところ、ス
ピネル構造を有するマンガン酸リチウムが得られている
ことが確認された。次に、エネルギー分散型電子プロー
ブマイクロアナリシス（ＥＰＭＡ）により、マグネシウ
ムの分散状態を観察したところ、マグネシウムはマンガ
ン酸リチウムの全面に分布していた。また、この粉末粒
子に対し、エックス線光電子分光法（ＸＰＳ）により、
深さ方向のホウ素の分布を測定したところ、図１の、本
発明電池３と同様の結果を示した。この粉末を正極活物
質として用いたこと以外は、本発明電池１と同様にし
て、コイン型リチウム電池を試作した。この電池を本発
明電池８とする。
【００３５】（本発明電池９）酢酸リチウム二水和物、
酢酸マンガン（II）四水和物、酢酸クロム（III）及び
硼酸を、Ｌｉ：Ｍｎ：Ｃｒ：Ｂの元素比が１．１０：
１．８４９：０．０５：０．００１となるように混合
し、これを硝酸に加え、熱を加えながら撹拌し、完全に
溶解させた。次に、硝酸を蒸発させ、混合塩を得た。こ
の混合塩を３００℃で仮焼成した。次に、先に用いた硼
酸と同量硼酸が溶解している水溶液を、前記仮焼成後の
試料に加えた後、５００℃で第二焼成し、空気中８５０
℃で本焼成した。焼成後、粉砕し、粉末を得た。この粉
末をエックス線回折法により分析したところ、スピネル
構造を有するマンガン酸リチウムが得られていることが
確認された。次に、エネルギー分散型電子プローブマイ
クロアナリシス（ＥＰＭＡ）により、クロムの分散状態
を観察したところ、クロムはマンガン酸リチウムの全面
に分布していた。また、この粉末粒子に対し、エックス
線光電子分光法（ＸＰＳ）により、深さ方向のホウ素の
分布を測定したところ、図１の、本発明電池３と同様の
結果を示した。この粉末を正極活物質として用いたこと
以外は、本発明電池１と同様にして、コイン型リチウム
電池を試作した。この電池を本発明電池９とする。
【００３６】（本発明電池１０）酢酸リチウム二水和
物、酢酸マンガン（ＩＩ）四水和物、酢酸テルビウム
（III）４水和物及び硼酸を、Ｌｉ：Ｍｎ：Ｔｂ：Ｂの
元素比が１．１０：１．８４９：０．０５：０．００１
となるように混合し、これを硝酸に加え、熱を加えなが
ら撹拌し、完全に溶解させた。次に、硝酸を蒸発させ、
混合塩を得た。この混合塩を３００℃で仮焼成した。次
に、先に用いた硼酸と同量硼酸が溶解している水溶液
を、前記仮焼成後の試料に加えた後、５００℃で第二焼
成し、空気中８５０℃で本焼成した。焼成後、粉砕し、
粉末を得た。この粉末をエックス線回折法により分析し
たところ、スピネル構造を有するマンガン酸リチウムが
得られていることが確認された。次に、エネルギー分散
型電子プローブマイクロアナリシス（ＥＰＭＡ）によ
り、テルビクムの分散状態を観察したところ、テルビウ
ムはマンガン酸リチウムの全面に分布していた。また、
この粉末粒子に対し、エックス線光電子分光法（ＸＰ
Ｓ）により、深さ方向のホウ素の分布を測定したとこ
ろ、図１の、本発明電池３と同様の結果を示した。この
粉末を正極活物質として用いたこと以外は、本発明電池
１と同様にして、コイン型リチウム電池を試作した。こ
の電池を本発明電池１０とする。
【００３７】（本発明電池１１〜２０）負極は、人造黒
鉛に代えて、厚み０．１ｍｍのＬｉ金属を用いたこと以
外は、本発明電池１〜１０と同様して電池を作製した。
この電池をそれぞれ本発明電池１１〜２０とする。
【００３８】（比較電池１）酢酸リチウム二水和物及び
酢酸マンガン（ＩＩ）四水和物を、Ｌｉ：Ｍｎの元素比
が１．１０：１．９０となるように混合し、これを酢酸
に加え、熱を加えながら撹拌し、完全に溶解させた。次
に、酢酸を蒸発させ、混合塩を得た。この混合塩を空気
中５００℃で仮焼成した後、８５０℃で本焼成した。焼
成後、粉砕し、粉末を得た。この粉末をエックス線回折
法により分析したところ、スピネル構造を有するマンガ
ン酸リチウムが得られていることが確認された。この粉
末を正極活物質として用いたこと以外は、本発明電池１
と同様にして、コイン型リチウム電池を試作した。この
電池を比較電池１とする。
【００３９】（比較電池２）負極は、人造黒鉛に代え
て、厚み０．１ｍｍのＬｉ金属を用いたこと以外は、比
較電池１と同様して電池を作製した。この電池を比較電
池２とする。
【００４０】以上、各電池に用いた正極活物質につい
て、焼成原料の元素構成比をＬｉ［Ｍｎ(2-x-y-w)ＭxＢ
wＬｉyＯ4］式に当てはめて表１に示す。
【００４１】
【表１】
【００４２】負極に用いた炭素材料の影響を除き、正極
の単極に近い挙動を観察するため、本発明電池１１〜２
０及び比較電池２を用いて、充放電試験を行なった。充
電は、電流０．０５ｍＡ、終止電圧４．２Ｖの定電流充
電とし、放電は、電流０．０５ｍＡ、終止電圧３．０Ｖ
の定電流放電とした。試験温度は２５℃とした。１サイ
クル目の充電容量に対する放電容量の比を初期充放電効
率として、表２に示した。
【００４３】
【表２】
【００４４】また、本発明電池１〜１０及び比較電池１
を用いて、充放電試験を行なった。充電は、電流１ｍ
Ａ、終止電圧４．２Ｖの定電流充電とし、放電は、電流
１ｍＡ、終止電圧３．０Ｖの定電流放電とした。試験温
度は２５℃及び５０℃とした。５サイクル目の放電容量
の結果を表３に示した。また、放電容量が初期の８０％
に低下した時点のサイクル数を測定し、サイクル寿命と
して示した。
【００４５】
【表３】
【００４６】表２において、本発明電池１１〜２０及び
比較電池２の結果を比較すると、初期の充放電効率は、
Ｍｎを他元素で置換している本発明電池１１〜２０で
は、置換していない比較電池２に比べ、向上している。
ただ、本発明電池１１及び本発明電池１２と、これらの
電池よりも粒子表層部の他元素濃度が高い活物質を用い
た本発明電池１３〜２０を比較すると、粒子表層部の他
元素濃度を高くすることによる充放電効率への効果には
前記実施例の範囲において変化がない。
【００４７】また、本発明電池１１〜２０の１サイクル
目の放電容量はいずれも、比較電池２に比べてやや低下
しているが、表３の結果より、それぞれ同じ活物質を用
いた本発明電池１〜１０及び比較電池１の結果を比較す
ると、２０℃においても５０℃においてもサイクル寿命
が飛躍的に向上していることがわかる。
【００４８】次に、置換する他元素の量との関係につい
て考察する。表２において、比較電池２、本発明電池１
１及び本発明電池１２は、この順でホウ素の置換量が増
えているが、これに伴い、１サイクル目の放電容量は減
少している。これは、置換量の増加、即ちＭｎ量の減少
に伴って、可逆的な充放電反応にかかるＬｉの量が減少
するためである。一方、表３において、それぞれ同じ活
物質を用いた比較電池１、本発明電池１及び本発明電池
２を比べると、ホウ素置換量の増加に伴って、サイクル
寿命が向上し、特に５０℃におけるサイクル寿命は飛躍
的な向上がみられる。
【００４９】以上のように、本発明の正極活物質を用い
ることにより、サイクル特性が向上した。これは、本発
明の正極活物質が電解質の分解を抑え、フッ酸の生成が
抑制されたため、炭素表面に生成する表面被膜の組成に
影響を与えたものと考えることができる。即ち、前記表
面被膜が、フッ酸の存在下で生成する抵抗の高いフッ化
リチウムの被膜ではなく、フッ素の関与しない状態で生
成する比較的抵抗の低い炭酸リチウムや酸化リチウムと
いった成分の被膜が形成されるため、充放電サイクルに
伴う界面抵抗増大が抑制されたものと考えられる。
【００５０】また、本発明の正極活物質を用いることに
より、５０℃での高温サイクル特性も向上した。これ
は、本発明の正極活物質が、Ｍｎの電解液中への溶出を
抑える効果があり、このため、活物質の容量低下も抑制
されたと考えることができる。
【００５１】Ｍｎが他の元素と置換されることによる放
電容量の低下については、活物質表層部に限定した前記
置換が行われるため、前記低下を最小限に抑えることが
できる。
【００５２】上記実施例においては、正極活物質におけ
る主構成物質にＬｉ［Ｍｎ1.85Ｂ0. 05Ｌｉ0.10Ｏ4］、
Ｌｉ［Ｍｎ1.849Ｖ0.05Ｂ0.001Ｌｉ0.10Ｏ4］、Ｌｉ
［Ｍｎ1. 849Ａｌ0.05Ｂ0.001Ｌｉ0.10Ｏ4］、Ｌｉ［Ｍ
ｎ1.849Ｎｉ0.05Ｂ0.001Ｌｉ0.10Ｏ4］、Ｌｉ［Ｍｎ
1.849Ｃｏ0.05Ｂ0.001Ｌｉ0.10Ｏ4］、Ｌｉ［Ｍｎ1.849
Ｍｇ0 .05Ｂ0.001Ｌｉ0.10Ｏ4］、Ｌｉ［Ｍｎ1.849Ｃｒ
0.05Ｂ0.001Ｌｉ0.10Ｏ4］、Ｌｉ［Ｍｎ1.849Ｔｂ0.05
Ｂ0.001Ｌｉ0.10Ｏ4］を用い、その後、ホウ素を添加し
焼成することによって、表層部に限定してホウ素の濃度
を増加させることについて記載したが、ホウ素の代わり
に他の元素を用いても、同様の効果が得られることが確
認されている。
【００５３】図１にみられるように、エックス線光電子
分光法によるエッチング時間が約３０００秒に達する
と、ホウ素濃度が粒子内部と同程度にまで低減してい
る。ここで、深さ方向のエッチング速度は０．７Å／秒
である。このことから、本発明の効果を発現させるため
に必要な正極活物質粒子の表層部の厚みは、高々２１０
ｎｍ（＝０．２１μｍ）あれば十分であることがわか
る。正極活物質粒子の平均粒径は２０μｍであるので、
前記厚みは粒子の直径の１％に相当する。ただし、ホウ
素の代わりに他の元素を用いた場合には、元素の種類に
よっては、本発明の効果を得るため、前記厚みを直径の
１０％程度とする必要がある場合もある。また、表層部
の置換元素濃度は、内部の同元素濃度の２倍以上有する
部分があれば、効果が得られることがわかった。
【００５４】ここでは、負極材料として人造黒鉛を用い
たリチウム二次電池について実施例を挙げたが、同様の
効果は、その他の負極材料についても確認されている。
【００５５】なお、本発明は上記実施例に記載された活
物質の出発原料、製造方法、正極、負極、電解質、セパ
レータ及び電池形状などに限定されるものではない。
【００５６】
【発明の効果】以上述べたように、本発明は、正極活物
質の主構成物質であるスピネル構造を有するマンガン酸
リチウムのマンガンの一部をマンガン以外の元素及びリ
チウムで置換し、置換元素の粒子表層部濃度を粒子内部
より大きくすることにより、容量を低下させることな
く、負極活物質である炭素材料界面での抵抗増大を抑制
し、さらに正極活物質自身のサイクル特性を向上させる
ことができる。また、これらの材料は安全性に優れ、安
価であるので、正極材料の優れた改質の方法であり、そ
の結果得られる電池は、高容量、高エネルギー密度で、
高温においても優れた充放電サイクル特性を示す。DETAILED DESCRIPTION OF THE INVENTION
[0001]
[0001] The present invention relates to a non-aqueous electrolyte battery.
More specifically, the positive electrode used for non-aqueous electrolyte batteries
Regarding polar active materials.
[0002]
2. Description of the Related Art At present, lithium having an operating voltage of 4V class is used.
LiCoO as a positive electrode active material of a secondary batteryTwo, LiNi
OTwoΑ-NaFeOTwoLithium-containing oxide having a structure
And LiMnTwoOFourContaining lithium having spinel structure
An oxide or the like is used. Among them, the spinel structure
LiMn havingTwoOFourHas low manufacturing cost and excellent safety
Positive electrode active material. On the other hand, negative electrode active materials include lithium
Metal, lithium alloy, carbon material, etc.
You.
[0003] Among carbon materials, particularly graphitized carbon
Using graphite for the negative electrode, for example, lithium manganate
When used for the positive electrode, a flat operating battery voltage can be obtained.
The advantage that the operating time of various portable devices can be extended
is there. However, this type of battery has a charge / discharge cycle
Is repeated, the unipolar potential of the negative electrode during charging becomes close to 0 V.
Therefore, it becomes a competitive reaction with the reaction of depositing lithium. That
Is one of the factors that cause cycle deterioration.
Was.
On the other hand, the cycle of lithium manganate material
In order to improve the deterioration, JP-A-4-233161,
JP-A-5-21067, JP-A-6-187793
Patent Literature discloses lithium manganate having a spinel structure
A technique for substituting a part of Mn with another element is disclosed.
However, especially when batteries are left at high temperatures, Mn
Because of elution into the electrolyte, repeated charge / discharge cycles
, There is a problem that the battery capacity is reduced.
[0005]
SUMMARY OF THE INVENTION The present invention has the above problems.
The carbon material was used for the negative electrode,
In batteries using lithium manganate for the positive electrode,
And cycle cycle deterioration of the positive electrode
Charge and discharge with low irreversible capacity with high capacity and high energy density
To provide a lithium secondary battery with excellent cycle characteristics
With the goal.
[0006]
Means for Solving the Problems To solve the above problems,
Therefore, the present invention constitutes a lithium manganese composite oxide
Part of the Mn element is Li, B, V, Al, Ni, Co, M
at least one kind of different element selected from g, Cr and Tb
Lithium secondary battery using the electrode active material substituted with
The heterogeneous element in the surface layer of the particles of the electrode active material.
Element concentration is higher than the concentration inside the particle.
And a lithium secondary battery. In addition, the electric
The general formula of the polar active material is a composition represented by the following formula
And a lithium secondary battery.
Li(1-z)[Mn(2-xyw)MxBwLiyOFour]
(M is V, Al, Ni, Co, Mg, Cr, Tb
At least one element selected from the group consisting of x = 0.01 to 0.1.
1, y = 0 to 0.2, x + y + w ≦ 0.2, w = 0.0
005-0.01)
Here, z is lithium which can be used reversibly.
Indicates the quantity, and 0 ≦ z ≦ 1. Small amount of active material particles
In at least some cases, the above values are especially at x = 0.05
０．１0.1, w = 0.05０．０１0.01.
When a carbon material is used as the negative electrode active material, carbon
The absorption and desorption reactions of lithium into the material depend on the electrolyte and the charcoal.
Is largely governed by the state of the film that forms between
You. If the lithium metal anode is used as a model, lithium
If there is a dense and highly conductive film on the metal surface,
Shows excellent battery characteristics, but is thick and has low ion conductivity
If the film is present, the battery's rate characteristics and cycle characteristics will be poor.
It becomes. Here, the former film component is composed of lithium carbonate or oxide.
Lithium etc., and the latter film component is lithium fluoride etc.
It is known that The same is true for carbon materials
The same can be said of a film formed on a surface. In other words, the carbon material world
One of the factors that increase the sheet resistance is that the surface of the carbon material
Film with low ionic conductivity such as lithium nitride is formed
It is mentioned. The lithium fluoride coating is formed
In the process, moisture introduced from the cathode material etc.
Is related to hydrofluoric acid generated by decomposition of electrolyte due to
it is conceivable that.
The present inventors have advanced research on the above points.
As a result, lithium manganate with spinel structure
Of manganese, lithium, boron and other
Metals (Vanadium, Aluminum, Nickel, Kovar
, Magnesium, chromium, terbium, etc.)
This reduces the amount of hydrofluoric acid generated inside the battery.
Found that it can be controlled. Furthermore, the present invention
The use of the positive electrode active material of
There is also an effect of suppressing the dissolution of Mn.
[0010] Here, the amount of other elements replaced by manganese
The higher the number, the higher the above effects, but reversibly available
There is a problem that the amount of Li decreases. Therefore,
The degree of the substitution is high in the surface layer of the active material particles,
Obtained by substitution by lowering
It is possible to keep the capacity of the active material high without reducing the effect
it can. Above all, if boron is used as a substitution element,
It is easy to increase only the replacement amount of the surface layer of the porous particles.
It is preferable in that it can be cut.
Li, which is a main component of the positive electrode active material,(1-z)
[Mn(2-xyw)MxBwLiyOFour], M is M
Elements other than n and Li that can be substituted for Mn are preferred.
No. For example, Be, B, V, C, Si, P, Sc, C
u, Zn, Ga, Ge, As, Se, Sr, Mo, P
d, Ag, Cd, In, Sn, Sb, Te, Ba, T
a, W.S. Pb, Bi, Co, Fe, Cr, Ni, Ti,
Zr, Nb, Y, Al, Na, K, Mg, Ca, Cs,
La, Ce, Nd, Sm, Eu, Tb and the like can be mentioned.
To suppress the elution of Mn into the electrolyte by high temperature storage,
When B, V, Ni, Co, Mg, Cr, Tb, etc. are used,
The effect is remarkable and particularly preferable. Where Mn
The values of x, y and w indicating the replacement amount are 0 <x + y + w ≦ 0.2
It is. When the value of x + y + w exceeds 0.2, it is used reversibly.
The amount of available lithium decreases and the effect on battery performance
large. Z indicating the amount of lithium that can be used reversibly is M
The larger the substitution amount of n, the smaller the substitution amount and the smaller the substitution amount of Mn.
More. Degradation during high temperature storage is 0 <x + y + w
Within the range of ≦ 0.2, the more the substitution amount of Mn, the more suppressed.
Is controlled.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION L which is a main constituent material of a positive electrode active material
i(1-z)[Mn(2-xyw)MxBwLiyOFour], M
As a method for replacing part of n with lithium or a different element
Is a method in which the element to be replaced is added to the raw material in advance
And LiMnTwoOFourAfter baking
Methods for replacing seed elements, but are not limited to these
It is not done.
The carbon material used for the negative electrode active material is lithium.
Any carbon material capable of occluding and releasing X-rays can be used.
The plane distance (d002) by the diffraction method is 3.354 to 3.3.
69 °, the crystal size (Lc) in the C-axis direction is 200 °
Carbon particles that are above are preferred because of their high capacity.
No.
The main constituent material of the positive electrode active material is Li(1-z)[M
n(2-xyw)MxBwLiyOFourIs used, LixCo
OTwo, LixNiOTwo Even if a metal oxide such as
Good. The positive electrode active material and the negative electrode active material used in the present invention are average.
The particle size is desirably 100 μm or less. Predetermined
A pulverizer or a classifier may be used in order to obtain the above shape. An example
For example, ball mills, planetary ball mills, jet mills,
A centrifugal jet mill or a sieve is used. When grinding
Wet powder mixed with water or organic solvent such as hexane
Crushing may be used. Classification methods include sieves and air classifiers
And the like may be used as needed in both dry and wet methods.
The positive electrode and the negative electrode have a conductive agent and a binder for the active material.
Agents, fillers and the like may be added. The conductive agent includes acetyl
Using carbon materials such as Lenblack and Ketjenblack
Can be Among these, acetylene black and
It is preferable to use Ketjen Black. Conductive agent
If the addition amount is too large, the electrode density decreases, and the addition amount is too small.
Then, sufficient electron conductivity of the electrode cannot be obtained. others
Therefore, the amount of the conductive agent to be added is preferably 1 to 10% by weight.
It is preferably 3 to 6% by weight.
As the binder, polytetrafluoroethylene is used.
, Polyvinylidene fluoride, fluoro rubber, carboxyme
Thermoplastic resin such as chill cellulose, rubber elastic
Rimers, polysaccharides, etc. as one kind or a mixture of two or more kinds
Can be used. Also, like polysaccharides, lithium
When using a binder having a functional group that reacts with
It is necessary to deactivate the reactive group by methylating it.
Is preferred. If too much binder is added, the electrode density
If the amount is too small, sufficient binding effect of the electrode is obtained.
I can't. For this reason, the addition amount of the binder is 1 to 10 weight
%, More preferably 3 to 6% by weight.
The positive electrode current collector includes aluminum, titanium,
Stainless steel or the like can be used. For negative electrode current collector
Can use copper, stainless steel, nickel, etc.
You. Current collector, foil, perforated plate or expanded, etc.
Can be used. The thickness is not particularly limited
Although not available, those having a thickness of 5 to 30 μm can be used.
The electrolyte includes, for example, an organic electrolyte, a polymer
Body electrolyte, inorganic solid electrolyte, molten salt, etc.
Wear. As the organic solvent of the organic electrolyte, propylene car
Carbonate, ethylene carbonate, diethyl carbonate
G, dimethyl carbonate, methyl ethyl carbonate
And esters such as γ-butyrolactone.
These can be used alone or as a mixed solvent. Ma
Further, as the supporting electrolyte salt, LiPF6, LiBFFour, L
iN (CFThreeSOTwo)Two, LiN (CTwoFFiveSOTwo)Two, Li
N (CFThreeSOTwo) (CFourF9SOTwo)Two And the like.
These can be used alone or as a mixed salt. Takaita
As the solid electrolyte, the supporting electrolyte salt as described above is used.
Polyethylene oxide and its crosslinked product, polyphosphazene
Dissolved in a polymer such as
Can be used.
The separator has excellent ion permeability,
An insulating thin film having mechanical strength can be used. Endurance
From the viewpoint of organic solvent properties and hydrophobicity,
Olefin polymers such as Tylene, polyvinylidene fluoride
Sheet made from ethylene, polytetrafluoroethylene, etc.
, A microporous membrane, a nonwoven fabric, etc. are used. Separator pore size
Is a range generally used for batteries, for example,
It is 0.01 to 1 μm. The same applies to the thickness.
The range is generally used for batteries.
For example, it is 20 to 40 μm.
The battery of the present invention has a higher charge / discharge rate than the conventional battery.
The reasons why the characteristics, especially the cycle characteristics,
Although it is not clear, it is considered as follows. General
In addition, it is thought that various impurities are contained inside the battery.
Can be For example, LiPF6Is used for the electrolyte salt,
Impurities contained in the salt itself can be considered. In addition,
Salt reacts with a small amount of water inside the battery or in the solvent
Produces hydrofluoric acid (HF). Boundary between carbon material and electrolyte
On the surface, when the carbon material absorbs lithium,
A film having high ion conductivity such as lithium is formed. Only
However, if an acid such as hydrofluoric acid is present,
This produces a poorly conductive lithium halide. The resulting halo
Lithium Genide interferes with the insertion and extraction of lithium,
Causes of increasing negative electrode interface resistance and reducing discharge capacity
It becomes one of. Therefore, the amount of hydrofluoric acid present inside the battery
It is thought that reducing this will solve this problem.
You.
The inventors have found that the electrolyte salt is decomposed and
Manganese acid, a positive electrode active material, reacts with the acid
We thought that lithium was acting catalytically. So,
Manganese element of lithium manganate having pinel structure
Is replaced by an element other than lithium and manganese, and the catalyst
By reducing the catalytic activity, the
Attempts were made to reduce hydrofluoric acid. Also, said catalytic activity
Is LiMn having a spinel structureTwoOFourOf the end-of-charge material
Some γ-MnOTwoIs considered the highest, and
Manganese source of lithium manganate having spinel structure
Replace some of the elements with elements other than lithium and manganese.
And the γ-MnOTwoThe possibility of suppressing the generation of
did.
As a result, the battery of the present invention having the above measures taken
Reduces the increase in the interface resistance of the negative electrode using a carbon material,
It was found that the cycle characteristics were improved. Also this
Part of manganese is replaced with elements other than lithium and manganese
Lithium manganate having a modified spinel structure
Not only is the activity reduced, but the active material
Improved stability and improved cycle characteristics at high temperatures
I found out.
[0023]
EXAMPLES Hereinafter, the present invention will be described in more detail based on Examples.
Will be described.
(Invention Battery 1) Lithium acetate dihydrate, manganese acetate
(II) Tetrahydrate and boric acid are converted to Li: Mn: B element ratio
Are mixed so as to be 1.10: 1.85: 0.05,
Add this to acetic acid, stir while applying heat, and dissolve completely
I let it. Next, the acetic acid was evaporated to obtain a mixed salt. This mix
After pre-firing the mixed salt at 500 ° C in air, then firing at 850 ° C
Done. After firing, the powder was pulverized to obtain a powder. Remove this powder
X-ray diffraction analysis showed a spinel structure
Lithium manganate was obtained.
Was. X-ray photoelectron spectroscopy was applied to the powder particles.
Method (XPS) to measure the distribution of boron in the depth direction
Was. Here, the quantitative value at the etching time of 0 second is many
Is considered to contain many contaminations.
Omitted from consideration. As shown in FIG.
Concentration is about 2-5 times higher than inside the particles.
It has been certified.
Using this powder as a positive electrode active material,
As a result, a coin type recharger having a capacity of 16 to 17 mAh shown in FIG.
We prototyped a lithium battery.
The positive electrode 1 is made of the above powder, acetylene black
And polytetrafluoroethylene powder in a weight ratio of 85:
The mixture was mixed at 10: 5, and toluene was added and kneaded well. This
This is a 0.8mm thick sheet by roller pressing
Molded. Next, the sheet was formed into a circle having a diameter of 16 mm.
Punched and dried at 200 ° C. under reduced pressure for 15 hours to obtain positive electrode 1
Was. The positive electrode 1 is press-bonded to a positive electrode can 4 having a positive electrode current collector 6.
Used.
The negative electrode 2 is made of artificial graphite and polytetrafluoro
Ethylene oxide powder in a weight ratio of 95: 5,
And kneaded well. Thick this with a roller press
It was formed into a sheet having a thickness of 0.1 mm. Next, the sheet
Was punched out into a circle having a diameter of 16 mm.
After drying for 5 hours, negative electrode 2 was obtained. The artificial graphite has an average grain size.
Diameter 6 μm, X-ray diffraction plane spacing (d002)
3.37 °, crystal size (Lc) 550 ° in the C-axis direction
Was used. The negative electrode 2 is a negative electrode with a negative electrode current collector 7
It was used by being pressed against a can 5.
The electrolytic solution is ethylene carbonate and die
To a solvent obtained by mixing tilcarbonate at a volume ratio of 1: 1
LiPF6Is dissolved at a concentration of 1 mol / l
Was. The separator 3 uses a microporous polypropylene membrane.
Was. Using the above positive electrode 1, negative electrode 2, separator 3, and electrolyte
A coin-shaped lithium with a diameter of 20 mm and a thickness of 1.6 mm
A battery was manufactured. This battery is referred to as Battery 1 of the invention.
(Invention Battery 2) Lithium acetate dihydrate,
Manganese (II) acetate tetrahydrate and boric acid were converted to Li: M
The element ratio of n: B becomes 1.10: 1.80: 0.10.
And add it to acetic acid and stir while applying heat
And completely dissolved. Then the acetic acid is evaporated and the mixed salt
Got. After calcining the mixed salt at 500 ° C. in the air,
The main firing was performed at 850 ° C. After firing, the powder was pulverized to obtain a powder.
When this powder was analyzed by X-ray diffraction,
Lithium manganate with pinel structure has been obtained
It was confirmed that. In addition, this powder particles
Boron in the depth direction by x-ray photoelectron spectroscopy (XPS)
Was measured, the result was the same as that of the battery 1 of the present invention in FIG.
The result was shown. This powder was used as a positive electrode active material.
Other than the above, a coin-shaped lithium
Prototype battery. This battery is referred to as Battery 2 of the invention.
(Battery 3 of the Invention) Lithium acetate dihydrate,
Manganese (II) acetate tetrahydrate and boric acid were converted to Li: M
The element ratio of n: B is 1.10: 1.85: 0.05.
And add it to acetic acid and stir while applying heat
And completely dissolved. Then the acetic acid is evaporated and the mixed salt
Got. This mixed salt was calcined in air at 300 ° C.
Next, the boric acid equivalent to 2% of the boric acid used previously was dissolved.
After adding the aqueous solution to the pre-baked sample,
The second baking was performed at 00 ° C., and the main baking was performed at 850 ° C. in the air. Burning
After the formation, the mixture was pulverized to obtain a powder. X-ray diffraction of this powder
Analysis of the manga with spinel structure
It was confirmed that lithium acidate was obtained. Also,
X-ray photoelectron spectroscopy (XP
According to S), the distribution of boron in the depth direction was measured.
In addition, as shown in FIG.
The concentration is about 3 to 10 times higher than inside the particles
Was confirmed. Use this powder as a positive electrode active material
Other than that, the coin-shaped
A lithium battery was prototyped. This battery is referred to as Battery 3 of the invention.
You.
(Invention Battery 4) Lithium acetate dihydrate,
Manganese (II) acetate tetrahydrate, vanadium and boric acid
Has an element ratio of Li: Mn: V: B of 1.10: 1.84.
9: 0.05: 0.001 and mixed.
Add to the nitric acid, stir while applying heat to completely dissolve
Was. Next, the nitric acid was evaporated to obtain a mixed salt. This mixed salt
Was calcined at 300 ° C. Next, the same amount as boric acid used earlier
An aqueous solution in which boric acid is dissolved is added to the pre-baked sample.
After firing, second firing at 500 ° C and main firing at 850 ° C in air
Done. After firing, the powder was pulverized to obtain a powder. Remove this powder
X-ray diffraction analysis showed a spinel structure
Lithium manganate was obtained.
Was. Next, an energy dispersive electron probe microanalyzer
Observation of vanadium dispersion state by lysis (EPMA)
I found that vanadium is the entire surface of lithium manganate.
Was distributed. In addition, X
X-ray photoelectron spectroscopy (XPS)
When the distribution was measured, the distribution was the same as that of the battery 3 of the present invention in FIG.
The results are shown. Using this powder as a positive electrode active material
Other than the above, a coin-shaped lithium
A battery was prototyped. This battery is referred to as Battery 4 of the invention.
(Battery 5 of the Invention) Lithium acetate dihydrate,
Manganese (II) acetate tetrahydrate, aluminum nitrate nonaqueous
The hydrate and boric acid have an element ratio of Li: Mn: Al: B of 1.
10: 1.849: 0.05: 0.001
Mix, add to nitric acid, stir while applying heat,
It was completely dissolved. Next, the nitric acid is evaporated to obtain a mixed salt.
Was. This mixed salt was calcined at 300 ° C. Next, first
The aqueous solution in which the same amount of boric acid as the boric acid was dissolved was calcined.
After adding to the sample after the synthesis, the second baking at 500 ℃, in air
The main firing was performed at 850 ° C. After firing, the powder was pulverized to obtain a powder.
When this powder was analyzed by X-ray diffraction,
Lithium manganate with pinel structure has been obtained
It was confirmed that. Next, the energy dispersive electron probe
Aluminum microscopy by EPMA
When observing the dispersion state of aluminum, aluminum
It was distributed over the entire surface of the lithium oxide. Also, this powder particles
X-ray photoelectron spectroscopy (XPS)
The distribution of boron in the vertical direction was measured.
The same result as that of the light battery 3 was shown. This powder is used as a positive electrode active material.
Except that it was used as
A prototype lithium coin battery was manufactured. This battery is
Pond 5
(Battery 6 of the Invention) Lithium acetate dihydrate,
Manganese (II) acetate tetrahydrate, nickel (II) nitrate hexahydrate
The hydrate and boric acid have an element ratio of Li: Mn: Ni: B of 1.
10: 1.849: 0.05: 0.001
Mix, add to nitric acid, stir while applying heat,
It was completely dissolved. Next, the nitric acid is evaporated to obtain a mixed salt.
Was. This mixed salt was calcined at 300 ° C. Next, first
The aqueous solution in which the same amount of boric acid as the boric acid was dissolved was calcined.
After adding to the sample after the synthesis, the second baking at 500 ℃, in air
The main firing was performed at 850 ° C. After firing, the powder was pulverized to obtain a powder.
When this powder was analyzed by X-ray diffraction,
Lithium manganate with pinel structure has been obtained
It was confirmed that. Next, the energy dispersive electron probe
Nickel micro-analysis (EPMA)
When the dispersion state was observed, nickel was found to be lithium manganate.
Was distributed over the entire surface of the um. In addition, this powder particle
X-ray photoelectron spectroscopy (XPS)
The distribution of boron in the direction was measured.
Pond 3 showed similar results. This powder is used as the positive electrode active material.
Except that the coil was used in the same manner as the battery 1 of the present invention.
Prototype lithium-ion battery. This battery is referred to as Battery 6 of the invention.
And
(Invention Battery 7) Lithium acetate dihydrate,
Manganese (II) acetate tetrahydrate, cobalt (II) acetate tetrahydrate
The hydrate and boric acid have an element ratio of Li: Mn: Co: B of 1.1.
0: 1.849: 0.05: 0.001
Add this to nitric acid, stir while applying heat,
Was dissolved. Next, the nitric acid was evaporated to obtain a mixed salt.
This mixed salt was calcined at 300 ° C. Next, we used
An aqueous solution in which the same amount of boric acid as boric acid is dissolved,
After the second baking at 500 ° C.
The main firing was performed at 0 ° C. After firing, the powder was pulverized to obtain a powder. this
When the powder was analyzed by X-ray diffraction,
That lithium manganate having
Was confirmed. Next, the energy dispersive electron probe
Dispersion of cobalt by ichroanalysis (EPMA)
When observing the state, cobalt is lithium manganate
Was distributed over the entire surface. In addition, the powder particles
X-ray photoelectron spectroscopy (XPS)
When the distribution of iodine was measured, the battery 3 of the present invention and the battery 3 of FIG.
Similar results were shown. Use this powder as the positive electrode active material
Other than that, in the same manner as the battery 1 of the present invention,
We prototyped a lithium battery. This battery is referred to as Battery 7 of the invention.
You.
(Battery 8 of the Invention) Lithium acetate dihydrate,
Manganese (II) acetate tetrahydrate, magnesium acetate tetrahydrate
The hydrate and boric acid have an element ratio of Li: Mn: Mg: B of 1.
10: 1.849: 0.05: 0.001
Mix, add to nitric acid, stir while applying heat,
It was completely dissolved. Next, the nitric acid is evaporated to obtain a mixed salt.
Was. This mixed salt was calcined at 300 ° C. Next, first
The aqueous solution in which the same amount of boric acid as the boric acid was dissolved was calcined.
After adding to the sample after the synthesis, the second baking at 500 ℃, in air
The main firing was performed at 850 ° C. After firing, the powder was pulverized to obtain a powder.
When this powder was analyzed by X-ray diffraction,
Lithium manganate with pinel structure has been obtained
It was confirmed that. Next, the energy dispersive electron probe
Magnesium by microanalysis (EPMA)
When observing the dispersion state of magnesium, magnesium
It was distributed over the entire surface of the lithium acid. Also this powder grain
X-ray photoelectron spectroscopy (XPS)
The distribution of boron in the depth direction was measured.
The result was the same as that of the inventive battery 3. This powder is used as the positive electrode active material.
Except that it was used as a battery.
A prototype coin-type lithium battery was manufactured. This battery
The battery 8 is assumed to be a clear battery.
(Invention Battery 9) Lithium acetate dihydrate,
Manganese (II) acetate tetrahydrate, chromium (III) acetate and
When boric acid is used, the element ratio of Li: Mn: Cr: B is 1.10:
1.849: 0.05: 0.001
Add this to nitric acid, stir while applying heat,
Dissolved. Next, the nitric acid was evaporated to obtain a mixed salt. This
Was temporarily calcined at 300 ° C. Next, the previously used boron
An aqueous solution in which boric acid is dissolved in the same amount as the acid,
After adding to the sample, a second baking at 500 ° C.
The main calcination was performed at ℃. After firing, the powder was pulverized to obtain a powder. This powder
When the powder was analyzed by X-ray diffraction,
That lithium manganate having a structure is obtained
confirmed. Next, the energy dispersive electron probe
Dispersion state of chromium by chroma analysis (EPMA)
Observation shows that chromium is on the entire surface of lithium manganate.
Was distributed. In addition, X
X-ray photoelectron spectroscopy (XPS)
When the distribution was measured, the distribution was the same as that of the battery 3 of the present invention in FIG.
The results are shown. Using this powder as a positive electrode active material
Other than the above, a coin-shaped lithium
A battery was prototyped. This battery is referred to as Battery 9 of the invention.
(Battery 10 of the Invention) Lithium acetate dihydrate
, Manganese (II) acetate tetrahydrate, terbium acetate
(III) Lithium tetrahydrate and boric acid are converted to Li: Mn: Tb: Bof
Element ratio is 1.10: 1.849: 0.05: 0.001
And add it to the nitric acid and heat
And the mixture was completely dissolved. Next, the nitric acid is evaporated,
A mixed salt was obtained. This mixed salt was calcined at 300 ° C. Next
First, an aqueous solution in which the same amount of boric acid as the previously used boric acid is dissolved
Was added to the sample after the preliminary baking, and then the second baking was performed at 500 ° C.
And baked at 850 ° C. in the air. After firing, pulverize,
A powder was obtained. This powder was analyzed by X-ray diffraction.
As a result, lithium manganate having a spinel structure
It was confirmed that it was obtained. Next, energy dispersion
Type electron probe microanalysis (EPMA)
Observation of the dispersion state of terbicum revealed
Was distributed over the entire surface of the lithium manganate. Also,
X-ray photoelectron spectroscopy (XP
According to S), the distribution of boron in the depth direction was measured.
1, the same result as that of the battery 3 of the present invention shown in FIG. this
Battery of the present invention except that powder was used as a positive electrode active material
In the same manner as in Example 1, a coin-type lithium battery was prototyped. This
This battery is referred to as Battery 10 of the present invention.
(Batteries 11 to 20 of the present invention)
Instead of using lead, 0.1mm thick Li metal was used.
Outside, batteries were produced in the same manner as the batteries 1 to 10 of the present invention.
The batteries are referred to as batteries 11 to 20 of the invention, respectively.
(Comparative Battery 1) Lithium acetate dihydrate and
Manganese (II) acetate tetrahydrate was converted to Li: Mn element ratio
Was mixed to give 1.10: 1.90.
And the mixture was stirred while applying heat to completely dissolve it. Next
The acetic acid was evaporated to give a mixed salt. This mixed salt is air
After pre-baking at 500 ° C., main firing at 850 ° C. Burning
After the formation, the mixture was pulverized to obtain a powder. X-ray diffraction of this powder
Analysis of the manga with spinel structure
It was confirmed that lithium acidate was obtained. This powder
Battery 1 of the present invention except that powder was used as the positive electrode active material.
A coin-type lithium battery was prototyped in the same manner as described above. this
The battery is referred to as Comparative Battery 1.
(Comparative Battery 2) The negative electrode was replaced with artificial graphite.
Except that a 0.1 mm thick Li metal was used.
A battery was produced in the same manner as Comparative Battery 1. Use this battery for comparison
It is called Pond 2.
As described above, the positive electrode active material used in each battery is described.
The elemental composition ratio of the firing raw material is Li [Mn(2-xyw)MxB
wLiyOFourTable 1 is applied to the equation.
[0041]
[Table 1]
Except for the influence of the carbon material used for the negative electrode,
Of the present invention batteries 11 to 2
0 and Comparative Battery 2 were used to perform a charge / discharge test. Filling
The power supply is a constant current charge with a current of 0.05 mA and a final voltage of 4.2 V.
And discharge was performed at a current of 0.05 mA and a final voltage of 3.0 V.
At a constant current. The test temperature was 25 ° C. 1 rhino
Initial charge / discharge effect
The ratio is shown in Table 2.
[0043]
[Table 2]
The batteries 1 to 10 of the present invention and the comparative battery 1
Was used to perform a charge / discharge test. Charging is 1m
A, constant-current charging with a final voltage of 4.2 V;
A constant current discharge of 1 mA and a final voltage of 3.0 V was performed. Test temperature
The degrees were 25 ° C and 50 ° C. 5th cycle discharge capacity
Table 3 shows the results. The discharge capacity is 80% of the initial value.
The cycle life at the time when the
Shown.
[0045]
[Table 3]
In Table 2, batteries 11 to 20 of the present invention and
Comparing the results of the comparative battery 2, the initial charge / discharge efficiency is as follows:
In the batteries of the present invention 11 to 20 in which Mn is substituted with another element,
Is improved as compared with the comparative battery 2 without replacement.
However, the battery 11 of the present invention and the battery 12 of the present invention,
Use an active material with a higher concentration of other elements on the surface of the particles than the battery
When the batteries 13 to 20 of the present invention were compared with each other,
The effect of increasing element concentration on charge and discharge efficiency
There is no change in the range of the embodiment.
One cycle of the batteries 11 to 20 of the present invention
The discharge capacity of each eye was slightly lower than that of Comparative Battery 2.
However, from the results in Table 3, the same active material was used for each.
The results of the present batteries 1 to 10 and the comparative battery 1 were compared.
Cycle life at both 20 ° C and 50 ° C
It can be seen that is dramatically improved.
Next, the relationship with the amount of other elements to be replaced will be described.
To consider. In Table 2, Comparative Battery 2 and Inventive Battery 1
1 and the battery 12 of the present invention, the replacement amount of boron increased in this order.
As a result, the discharge capacity in the first cycle has decreased.
A little bit. This is because the substitution amount increases, that is, the Mn amount decreases.
The amount of Li involved in the reversible charge / discharge reaction decreases with
To do that. On the other hand, in Table 3,
Battery 1, inventive battery 1 and inventive battery using substance
Compared to No. 2, the cycle increased as the amount of boron substitution increased.
Improved service life, especially at 50 ° C cycle life
Improvement is seen.
As described above, using the cathode active material of the present invention
As a result, the cycle characteristics were improved. This is the original
The bright positive electrode active material suppresses the decomposition of the electrolyte and reduces the production of hydrofluoric acid.
The composition of the surface coating formed on the carbon surface
It can be considered as having influenced. That is, the table
The surface coating is a highly resistant fluorinated compound formed in the presence of hydrofluoric acid
Produced without the involvement of fluorine, not a lithium coating
With relatively low resistance lithium carbonate or lithium oxide
Is formed on the charge / discharge cycle.
It is considered that the accompanying increase in interface resistance was suppressed.
Further, the use of the positive electrode active material of the present invention
Thus, the high-temperature cycle characteristics at 50 ° C. were also improved. this
Indicates that the positive electrode active material of the present invention causes the elution of Mn into the electrolytic solution.
It has the effect of suppressing, and therefore, also reduces the capacity of the active material
It can be considered that it was done.
The emission due to the substitution of Mn with another element
Regarding the decrease of the electric capacity, the above-mentioned limitation to the surface layer of the active material
Since the replacement is performed, it is possible to minimize the decrease.
it can.
In the above embodiment, the positive electrode active material
Li [Mn]1.85B0. 05Li0.10OFour],
Li [Mn1.849V0.05B0.001Li0.10OFour], Li
[Mn1. 849Al0.05B0.001Li0.10OFour], Li [M
n1.849Ni0.05B0.001Li0.10OFour], Li [Mn
1.849Co0.05B0.001Li0.10OFour], Li [Mn1.849
Mg0 .05B0.001Li0.10OFour], Li [Mn1.849Cr
0.05B0.001Li0.10OFour], Li [Mn1.849Tb0.05
B0.001Li0.10OFour] And then add boron
By firing, the concentration of boron is limited to the surface layer
Has been described, but instead of boron
It is confirmed that the same effect can be obtained by using other elements for
It has been certified.
As seen in FIG. 1, X-ray photoelectrons
Spectroscopic etching time reaches about 3000 seconds
And the boron concentration is reduced to the same
You. Here, the etching rate in the depth direction is 0.7 ° / sec.
It is. From this, in order to express the effect of the present invention
The thickness of the surface layer of the positive electrode active material particles required for
It can be seen that nm (= 0.21 μm) is sufficient.
You. Since the average particle size of the positive electrode active material particles is 20 μm,
Said thickness corresponds to 1% of the diameter of the particles. However, Ho
If other elements are used instead of element,
Therefore, in order to obtain the effect of the present invention, the thickness is set to the diameter.
In some cases, it is necessary to set it to about 10%. Also, the surface layer
Has more than twice the concentration of the same element inside
It turns out that the effect can be obtained if there is a part.
Here, artificial graphite was used as the negative electrode material.
Examples have been given for lithium secondary batteries
The effect has also been confirmed for other negative electrode materials.
The present invention is not limited to the above-described embodiment.
Starting materials for materials, manufacturing method, positive electrode, negative electrode, electrolyte, separator
It is not limited to the shape of the generator and the battery.
[0056]
As described above, the present invention provides a positive electrode active material
With spinel structure as a main constituent
Some of the manganese in lithium is replaced with elements other than manganese and lithium.
Substitution with titanium and the concentration of the substituting element on the surface of the particle inside the particle
Do not reduce capacity by making it larger
And suppresses the increase in resistance at the carbon material interface as the negative electrode active material
And further improve the cycle characteristics of the positive electrode active material itself
be able to. In addition, these materials have excellent safety and
It is an excellent method of reforming the cathode material because it is
The resulting battery has high capacity, high energy density,
It shows excellent charge / discharge cycle characteristics even at high temperatures.
【図面の簡単な説明】
【図１】本発明の正極活物質粒子のホウ素分布を示した
図である。
【図２】本発明電池の断面図である。
【符号の説明】
１ 正極
２ 負極BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a boron distribution of positive electrode active material particles of the present invention. FIG. 2 is a sectional view of the battery of the present invention. [Description of Signs] 1 Positive electrode 2 Negative electrode
フロントページの続き (72)発明者 黄 修竹 大阪府高槻市古曽部町二丁目３番21号 株式会社 ユアサ コーポレーション 内 (72)発明者 油布 宏 大阪府高槻市古曽部町二丁目３番21号 株式会社 ユアサ コーポレーション 内 (56)参考文献 特開 平８−315858（ＪＰ，Ａ) 特開 平11−171551（ＪＰ，Ａ) 特開2000−340226（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/58 H01M 4/02 H01M 10/40 Continuing from the front page (72) Inventor Huang Shutake 2-3-1, Furusobe-cho, Takatsuki-shi, Osaka Yuasa Corporation Co., Ltd. Inside (72) Inventor Hiroshi Yufu 2-3-1-21, Kosobe-cho, Takatsuki-shi, Osaka Co., Ltd. (56) References JP-A-8-315858 (JP, A) JP-A-11-171551 (JP, A) JP-A-2000-340226 (JP, A) (58) Fields investigated (Int.Cl) . 7, DB name) H01M 4/58 H01M 4/02 H01M 10/40
Claims (1)
複合酸化物を構成するＭｎ元素の一部がＬｉ、Ｂ、Ｖ、
Ａｌ、Ｎｉ、Ｃｏ、Ｍｇ、Ｃｒ、Ｔｂから選ばれる少な
くとも一種の異種元素で置換された正極活物質を用いた
リチウム二次電池において、前記正極活物質の一般式が
下記の式で示される組成であり、前記正極活物質の粒子
表層部におけるホウ素の濃度が、粒子内部における前記
濃度に比べて高いことを特徴とする正極活物質を用いた
リチウム二次電池。Ｌｉ (1-z) ［Ｍｎ (2-x-y-w) Ｍ x Ｂ w Ｌｉ y Ｏ4］ （ＭはＶ、Ａｌ、Ｎｉ、Ｃｏ、Ｍｇ、Ｃｒ、Ｔｂの中か
ら選ばれた少なくとも１種の元素、ｘ＝０．０１〜０．
１、ｙ＝０〜０．２、０≦ｚ≦１、ｘ＋ｙ＋ｗ≦０．
２、ｗ＝０．０００５〜０．０１） (57) [Claim 1] Part of the Mn element constituting the lithium manganese composite oxide having a spinel structure is Li, B, V,
Al, Ni, Co, Mg, Cr, in a lithium secondary battery using the positive electrode active material which is substituted with at least one different element selected from Tb, the general formula of the positive electrode active material
Lithium having a composition represented by the following formula, wherein the concentration of boron in the surface layer of the particles of the positive electrode active material is higher than the concentration inside the particles. Secondary battery. Li (1-z) [Mn (2-xyw) M x B w Li y O 4] (M is V, Al, Ni, Co, Mg, Cr, Tb
At least one element selected from the group consisting of x = 0.01 to 0.1.
1, y = 0 to 0.2, 0 ≦ z ≦ 1, x + y + w ≦ 0.
2, w = 0.0005 to 0.01)
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|---|---|---|---|
| JP36870899A JP3503688B2 (en) | 1999-12-27 | 1999-12-27 | Lithium secondary battery |
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| AU2003221108A1 (en) * | 2002-03-28 | 2003-10-13 | Mitsubishi Chemical Corporation | Positive electrode material for lithium secondary cell and secondary cell using the same, and method for producing positive electrode material for lithium secondary cell |
| JP4655453B2 (en) * | 2002-03-28 | 2011-03-23 | 三菱化学株式会社 | Positive electrode material for lithium secondary battery, secondary battery using the same, and method for producing positive electrode material for lithium secondary battery |
| US7241532B2 (en) | 2002-03-28 | 2007-07-10 | Mitsubishi Chemical Corporation | Positive-electrode material for lithium secondary battery, secondary battery employing the same, and process for producing positive-electrode material for lithium secondary battery |
| JP5044882B2 (en) * | 2003-08-21 | 2012-10-10 | 日亜化学工業株式会社 | Cathode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| US7294435B2 (en) | 2003-05-15 | 2007-11-13 | Nichia Corporation | Positive electrode active material for nonaqueous electrolyte secondary battery, positive electrode mixture for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| KR100564748B1 (en) * | 2003-09-26 | 2006-03-27 | 한국전자통신연구원 | Cathode Material for Lithium Secondary Battery and Manufacturing Method Thereof |
| WO2010032449A1 (en) * | 2008-09-18 | 2010-03-25 | 戸田工業株式会社 | Method for producing lithium manganate particle powder and nonaqueous electrolyte secondary battery |
| JP5644176B2 (en) * | 2009-11-18 | 2014-12-24 | ソニー株式会社 | Positive electrode active material and lithium ion secondary battery |
| CN102024950B (en) | 2009-09-09 | 2018-05-25 | 株式会社村田制作所 | Positive electrode active material and preparation method thereof, positive electrode and non-aqueous electrolyte battery |
| JP2014197451A (en) * | 2011-07-29 | 2014-10-16 | Ａｇｃセイミケミカル株式会社 | Method of producing lithium cobalt-containing composite oxide for lithium ion secondary battery |
| KR102264804B1 (en) * | 2019-10-31 | 2021-06-15 | 주식회사 에코프로비엠 | Lithium composite oxide and lithium secondary battery comprising the same |
| CN114314690A (en) * | 2021-12-24 | 2022-04-12 | 合肥国轩高科动力能源有限公司 | Modified ternary cathode material, and preparation method and application thereof |
| JP2024037355A (en) * | 2022-09-07 | 2024-03-19 | 住友化学株式会社 | Positive electrode active material for lithium secondary batteries, electrodes for lithium secondary batteries, and lithium secondary batteries |
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