JP2002170566A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JP2002170566A JP2002170566A JP2000368174A JP2000368174A JP2002170566A JP 2002170566 A JP2002170566 A JP 2002170566A JP 2000368174 A JP2000368174 A JP 2000368174A JP 2000368174 A JP2000368174 A JP 2000368174A JP 2002170566 A JP2002170566 A JP 2002170566A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- lithium
- battery
- active material
- electrode active
- 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.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000007774 positive electrode material Substances 0.000 claims abstract description 43
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052796 boron Inorganic materials 0.000 claims abstract description 22
- 239000011572 manganese Substances 0.000 claims abstract description 19
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 6
- 239000011029 spinel Substances 0.000 claims abstract description 6
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 43
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 40
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- -1 G a Inorganic materials 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052727 yttrium 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
- 229910013716 LiNi Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 23
- 239000002131 composite material Substances 0.000 abstract description 7
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011149 active material Substances 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract 1
- 239000002033 PVDF binder Substances 0.000 description 24
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000006258 conductive agent Substances 0.000 description 17
- 239000011230 binding agent Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 15
- 239000006230 acetylene black Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical class [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000011888 foil Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000011255 nonaqueous electrolyte Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 230000035515 penetration Effects 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000002003 electrode paste Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 229910003786 Li1.08Mn1.92O4 Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000011076 safety test Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018087 Al-Cd Inorganic materials 0.000 description 1
- 229910018188 Al—Cd Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- SWTCCCJQNPGXLQ-UHFFFAOYSA-N acetaldehyde di-n-butyl acetal Natural products CCCCOC(C)OCCCC SWTCCCJQNPGXLQ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 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
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- KQFUCKFHODLIAZ-UHFFFAOYSA-N manganese Chemical compound [Mn].[Mn] KQFUCKFHODLIAZ-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000009782 nail-penetration test Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Carbon And Carbon Compounds (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
(57)【要約】
【課題】 スピネルマンガン系活物質を用い、長期保存
性に優れたリチウム二次電池を提供することを目的とす
る。
【解決手段】 結晶構造組成がＬｉ1+x｛Ｍｎ(2-x-y)Ｍ
y｝Ｏ4で表されるリチウムマンガン複合酸化物を主成分
とする正極活物質であって、前記正極活物質中にホウ素
がＭｎ(2-x-y)Ｍy：Ｂ＝２：０．０１〜０．１の比で含
まれる正極活物質を用いることで、上記課題を解決でき
る。
(57) [Problem] To provide a lithium secondary battery having excellent long-term storage properties using a spinel manganese-based active material. SOLUTION: The crystal structure composition is Li 1 + x ｛Mn (2-xy) M
A positive electrode active material containing a lithium manganese composite oxide represented by y ｝ O 4 as a main component, wherein boron is contained in the positive electrode active material by Mn (2-xy) M y : B = 2: 0.01 to The above problem can be solved by using the positive electrode active material contained at a ratio of 0.1.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウムマンガン
酸化物を正極に用いたリチウム二次電池に関する。The present invention relates to a lithium secondary battery using lithium manganese oxide for a positive electrode.
【０００２】[0002]
【従来の技術】近年、リチウム二次電池は、携帯電話，
簡易携帯電話（ＰＨＳ），小型コンピュータ等の携帯機
器類用電源、電力貯蔵用電源、電気自動車用電源として
注目されている。このようなリチウム二次電池は、一般
に、固有の電位においてリチウムイオンを放出・吸蔵可
能な正極及び負極、正極と負極とを隔壁するセパレー
タ、非水系電解液から構成される。特に４Ｖ級の正極に
用いる正極活物質としては、層状構造のＬｉＣｏＯ2や
ＬｉＮｉＯ2、またはスピネル構造のＬｉＭｎ2Ｏ4等が知
られており、負極材料としては、炭素材料が広く一般的
に知られている。2. Description of the Related Art In recent years, lithium secondary batteries have been used in mobile phones,
Attention has been paid to a power supply for portable equipment such as a simple portable telephone (PHS) and a small computer, a power storage power supply, and a power supply for an electric vehicle. Such a lithium secondary battery generally includes a positive electrode and a negative electrode capable of releasing and occluding lithium ions at a specific potential, a separator partitioning the positive electrode and the negative electrode, and a nonaqueous electrolyte. In particular, as a positive electrode active material used for a 4V-class positive electrode, LiCoO 2 or LiNiO 2 having a layered structure or LiMn 2 O 4 having a spinel structure is known, and a carbon material is widely and generally known as a negative electrode material. Have been.
【０００３】ＬｉＣｏＯ2は重量あたりの電気化学的容
量が大きく、しかもリチウムの挿入・脱離に伴う構造安
定性が高いため、定格容量２Ａｈ級未満の市販用途の電
池として広く一般に採用されている。しかし、電力貯蔵
用電源、高出力の駆動力源等への用途のため、電池の定
格容量が２Ａｈ級以上の大型大容量電池に適用した場
合、安全性の確保は困難となる。電池の運用面からは電
池外部に保護回路を設置することで過充電や外部短絡等
による過電流等については回避することはできるが、元
来ＬｉＣｏＯ2の反応性が高いため、電池内部で発生す
る内部短絡や外部からの衝撃などによる破損に対して安
全性を確保することが難しいといった問題点があった。Since LiCoO 2 has a large electrochemical capacity per weight and a high structural stability accompanying the insertion and desorption of lithium, it is widely and generally employed as a battery for commercial use having a rated capacity of less than 2 Ah class. However, when the battery is applied to a large-capacity battery with a rated capacity of 2 Ah class or more, it is difficult to ensure safety because it is used for a power storage power source, a high-output driving power source, and the like. In terms of battery operation, by installing a protection circuit outside the battery, it is possible to avoid overcurrent due to overcharging or external short-circuit, etc., but since the reactivity of LiCoO 2 is originally high, it is generated inside the battery. There is a problem that it is difficult to ensure safety against damage due to an internal short circuit or an external impact.
【０００４】一方、スピネル構造を有するＬｉＭｎ2Ｏ4
等のリチウムマンガン酸化物は、重量あたりの電気化学
的容量はＬｉＣｏＯ2に劣るが、原料が安価であり、且
つ、高い安全性を示すといった利点がある。しかしなが
ら、特に高温環境下における充放電サイクル特性や保存
性能は、ＬｉＣｏＯ2に比較して著しく劣るといった問
題点があった。On the other hand, LiMn 2 O 4 having a spinel structure
Although lithium manganese oxides are inferior in electrochemical capacity per weight to LiCoO 2, they have advantages such as low cost of raw materials and high safety. However, there is a problem that the charge / discharge cycle characteristics and storage performance particularly under a high temperature environment are significantly inferior to LiCoO 2 .
【０００５】リチウムマンガン酸化物にホウ素を添加す
ることで保存性能を向上させる技術が特開平９−１１５
５１５号公報等に開示されている。しかしながら、この
技術を用いてもなお、ＬｉＣｏＯ2に匹敵する保存性能
を得るには不充分であった。A technique for improving the storage performance by adding boron to a lithium manganese oxide is disclosed in Japanese Patent Laid-Open No. 9-115.
No. 515, for example. However, using this technique was still insufficient to achieve storage performance comparable to LiCoO 2 .
【０００６】リチウムマンガン酸化物の電気化学的容量
が低いという欠点を補い、充放電サイクル特性を向上さ
せる目的で、リチウムマンガン酸化物にリチウムニッケ
ル酸化物を混合する技術が特開平７−２３５２９１号公
報、特開平１０−１１２３１８号公報、特開平１１−５
４１２２号公報等に開示されている。しかしながら、こ
の技術を用いても、リチウムマンガン酸化物の保存性能
が低いといった問題を解決するものではなかった。さら
に、リチウムニッケル酸化物を混合することによって、
安全性が低下するといった欠点が新たに生じるといった
問題点があった。Japanese Patent Laid-Open No. 7-235291 discloses a technique of mixing lithium nickel oxide with lithium manganese oxide for the purpose of compensating for the drawback of the low electrochemical capacity of lithium manganese oxide and improving the charge / discharge cycle characteristics. JP-A-10-112318, JP-A-11-5
No. 4122 and the like. However, the use of this technique has not solved the problem that the storage performance of lithium manganese oxide is low. Furthermore, by mixing lithium nickel oxide,
There has been a problem that a defect such as a decrease in safety is newly generated.
【０００７】また、特開２０００−７７０７１号公報、
特開２０００−７７０７２号公報には、リチウムマンガ
ン酸化物に混合するリチウムニッケル酸化物の物性や混
合比率を規定することで、充放電サイクル特性の向上、
保存特性の向上、容量の増大、安全性の向上を図る技術
が開示されている。しかしながら、この技術を用いても
なお、上記問題点の解決には必ずしも充分ではなかっ
た。Further, Japanese Patent Application Laid-Open No. 2000-77071,
Japanese Patent Application Laid-Open No. 2000-77072 discloses an improvement in charge / discharge cycle characteristics by defining physical properties and a mixing ratio of lithium nickel oxide mixed with lithium manganese oxide.
Techniques for improving storage characteristics, increasing capacity, and improving safety have been disclosed. However, even if this technique is used, it is not always enough to solve the above problems.
【０００８】さらに、上記公報に記載されている安全性
試験は18650型の市販円筒型電池により確認されたもの
であり、前記した大型大容量電池に適用した場合の安全
性については検討がされていない。一般に、電池の安全
性は、その構成部材の耐久性に大きく依存する。特に大
型大容量電池の場合、この検証は必須である。具体的に
内部短絡の発生を想定すると、１５Ａｈ級の電池でさ
え、内部短絡部分には局所的に数百アンペアもの大電流
が流れる可能性がある。このような大電流が電池内部で
発生すると、過熱による電解液の分解や、電極と電解液
との反応が爆発的に同時進行し、熱暴走を引き起こし、
忽ち危険な状態を生み出す虞がある。Further, the safety test described in the above publication has been confirmed with a commercially available 18650 type cylindrical battery, and the safety when applied to the above-mentioned large-sized large-capacity battery has been studied. Absent. In general, the safety of a battery largely depends on the durability of its components. This verification is essential especially for large-capacity large-capacity batteries. Assuming a specific occurrence of an internal short circuit, a large current of several hundred amperes may locally flow in the internal short circuit even in a 15 Ah class battery. When such a large current is generated inside the battery, the decomposition of the electrolyte due to overheating and the reaction between the electrode and the electrolyte proceed explosively at the same time, causing thermal runaway,
There is a risk of creating a dangerous situation immediately.
【０００９】一方、上記したように、リチウムマンガン
酸化物は安価で安全であるという利点を有する一方、高
温環境下での充放電サイクル性能や保存性能をはじめと
する電池性能が不十分である。この改善を目的として、
リチウムマンガン酸化物のマンガン１６ｄサイトをリチ
ウムやマンガン以外の遷移金属元素で置換する等、活物
質組成を変える試みが数多くなされているものの、Ｌｉ
ＣｏＯ2に匹敵する特性を有するには至っていない。On the other hand, as described above, lithium manganese oxide has the advantage of being inexpensive and safe, but has insufficient battery performance including charge / discharge cycle performance and storage performance under a high temperature environment. For this improvement,
Although many attempts have been made to change the active material composition, such as replacing the manganese 16d site of lithium manganese oxide with a transition metal element other than lithium and manganese,
It does not have properties comparable to CoO 2 .
【００１０】しかしながら、定格容量２Ａｈ級以上の大
型リチウム電池においては、電池性能のみならず電池単
体での安全性確保が必須であり、そのためにはリチウム
マンガン酸化物を正極活物質の主要構成成分として使用
することが適当と判断される。従って、リチウムマンガ
ン酸化物の高い安全性を確保したまま、電池性能を向上
させることが、極めて重要な開発課題となっていた。However, in a large lithium battery having a rated capacity of 2 Ah class or more, it is essential to ensure not only the performance of the battery but also the safety of the battery alone. To this end, lithium manganese oxide is used as a main component of the positive electrode active material. It is deemed appropriate to use. Therefore, improving battery performance while securing high safety of lithium manganese oxide has been a very important development task.
【００１１】[0011]
【発明が解決しようとする課題】本発明は、上記課題を
解決するためになされたものであって、正極活物質にリ
チウムマンガン酸化物を用いたリチウム二次電池におい
て、リチウムマンガン酸化物が有する高い安全性を損な
うことなく、保存性能及び充放電サイクル性能を向上さ
せることを目的とする。SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a lithium secondary battery using a lithium manganese oxide as a positive electrode active material. It is an object to improve storage performance and charge / discharge cycle performance without impairing high safety.
【００１２】[0012]
【課題を解決するための手段】本発明のリチウム二次電
池は、請求項１に記載したように、負極と、正極活物質
を主体とする正極とを具備し、前記正極活物質はリチウ
ムマンガン酸化物とリチウムニッケル酸化物とを含むリ
チウム二次電池において、前記リチウムマンガン酸化物
はホウ素を含むことを特徴としている。According to a first aspect of the present invention, there is provided a lithium secondary battery comprising a negative electrode and a positive electrode mainly composed of a positive electrode active material, wherein the positive electrode active material is lithium manganese. In a lithium secondary battery containing an oxide and a lithium nickel oxide, the lithium manganese oxide contains boron.
【００１３】ここで、ホウ素の含有量は、式Ｌｉ
1+x｛Ｍｎ(2-x-y)Ｍy｝Ｏ4で表されるリチウムマンガン
酸化物に対して、Ｍｎ(2-x-y)Ｍy：Ｂ＝２：０．０１〜
０．１の割合とすると、保存性を向上する効果を発現さ
せる必要充分な量である点で好ましい。ホウ素は正極活
物質の合成時、焼成原料と一緒に添加することができ
る。前記ホウ素は、前記リチウムマンガン酸化物の結晶
構造中に取り込まれている必要はない。実際、エックス
線回折分析によれば、前記ホウ素はそのほとんどがリチ
ウムマンガン酸化物の粒子表面に存在し、水洗洗浄する
と容易に取り除かれる。このように、ホウ素が粒子表面
に存在するのみの状態であっても、高温環境下における
保存性能を改善する効果を示す。この理由については必
ずしも明らかではないが、電池を構成した際、ホウ素が
電解液中に溶解し、負極及び／又はリチウムニッケル複
合酸化物に何らかの好ましい影響を与える作用があるも
のと考えられる。Here, the boron content is expressed by the formula Li
1 + relative x {Mn (2-xy) M y} lithium manganese oxide represented by O 4, Mn (2-xy ) M y: B = 2: 0.01~
A ratio of 0.1 is preferred because it is a necessary and sufficient amount for exhibiting the effect of improving storage stability. Boron can be added together with the firing raw material during the synthesis of the positive electrode active material. The boron does not need to be incorporated in the crystal structure of the lithium manganese oxide. In fact, according to the X-ray diffraction analysis, most of the boron is present on the surface of the lithium manganese oxide particles, and is easily removed by washing with water. As described above, even when boron is only present on the particle surface, the effect of improving storage performance under a high-temperature environment is exhibited. Although the reason for this is not necessarily clear, when the battery is constructed, it is considered that boron dissolves in the electrolytic solution and has an effect of giving some favorable effect to the negative electrode and / or the lithium nickel composite oxide.
【００１４】また、本発明のリチウム二次電池は、請求
項２に記載したように、前記正極活物質中に占める前記
リチウムニッケル酸化物の含有率は重量比で５〜２０％
であることを特徴としている。Further, in the lithium secondary battery of the present invention, the content of the lithium nickel oxide in the positive electrode active material is 5 to 20% by weight.
It is characterized by being.
【００１５】また、本発明のリチウム二次電池は、請求
項３に記載したように、前記リチウムマンガン酸化物は
次式で表されるスピネル構造を有するマンガン酸リチウ
ムを主成分とすることを特徴としている。 Ｌｉ1+x｛Ｍｎ(2-x-y)Ｍy｝Ｏ4 但し、 ０≦ｘ≦０．３ ０≦ｙ≦０．２ （Ｍは、Ｂｅ，Ｃ，Ｓｉ，Ｐ，Ｓｃ，Ｃｕ，Ｚｎ，Ｇ
ａ，Ｇｅ，Ａｓ，Ｓｅ，Ｓｒ，Ｍｏ，Ｐｄ，Ａｇ，Ｃ
ｄ，Ｉｎ，Ｓｎ，Ｓｂ，Ｔｅ，Ｂａ，Ｔａ，Ｗ．Ｐｂ，
Ｂｉ，Ｃｏ，Ｆｅ，Ｃｒ，Ｎｉ，Ｔｉ，Ｚｒ，Ｎｂ，
Ｙ，Ａｌ，Ｎａ，Ｋ，Ｍｇ，Ｃａ，Ｃｓ，Ｌａ，Ｃｅ，
Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂから構成される群から選択され
た少なくとも１つ以上の元素）Further, in the lithium secondary battery of the present invention, the lithium manganese oxide is mainly composed of lithium manganate having a spinel structure represented by the following formula. And Li 1 + x {Mn (2 -xy) M y} O 4 where, 0 ≦ x ≦ 0.3 0 ≦ y ≦ 0.2 (M is, Be, C, Si, P , Sc, Cu, Zn, G
a, Ge, As, Se, Sr, Mo, Pd, Ag, C
d, In, Sn, Sb, Te, Ba, Ta, W.S. Pb,
Bi, Co, Fe, Cr, Ni, Ti, Zr, Nb,
Y, Al, Na, K, Mg, Ca, Cs, La, Ce,
At least one element selected from the group consisting of Nd, Sm, Eu, and Tb)
【００１６】ここで、リチウムマンガン酸化物は、Ｍｎ
の一部がＬｉ及び／又は異種元素Ｍで置換された構造を
有している。上記式において、Ｌｉによる置換量がｘ
に、Ｍによる置換量がｙに関連づけられる。元素Ｍとし
ては、上記の中でも、特にＭｇ、Ａｌ、Ｔｉ、Ｖ、Ｃ
ｒ、Ｆｅ、Ｃｏ、Ｎｉを用いると、Ｍｎの溶出を抑制す
る効果が高い点で好ましい。Here, the lithium manganese oxide is Mn
Has a structure in which Li is partially replaced with Li and / or a different element M. In the above formula, the substitution amount by Li is x
Is associated with y. As the element M, among the above, Mg, Al, Ti, V, C
It is preferable to use r, Fe, Co, and Ni because the effect of suppressing elution of Mn is high.
【００１７】上記式において、ｘ＝ｙ＝０であってもよ
いが、特に、ｘ+ｙ＞０とすると、良好な充放電サイク
ル性能を得ることができる点で好ましい。In the above formula, x = y = 0 may be satisfied. However, it is particularly preferable that x + y> 0 since good charge / discharge cycle performance can be obtained.
【００１８】また、本発明のリチウム二次電池は、請求
項３に記載したように、前記リチウムニッケル酸化物は
次式で表されるニッケル酸リチウムを主成分とすること
を特徴としている。 ＬｉＮｉ1-zＡzＯ2 但し、０≦z≦０．３ （Ａは、Ｂｅ，Ｃ，Ｓｉ，Ｐ，Ｓｃ，Ｃｕ，Ｚｎ，Ｇ
ａ，Ｇｅ，Ａｓ，Ｓｅ，Ｓｒ，Ｍｏ，Ｐｄ，Ａｇ，Ｃ
ｄ，Ｉｎ，Ｓｎ，Ｓｂ，Ｔｅ，Ｂａ，Ｔａ，Ｗ．Ｐｂ，
Ｂｉ，Ｃｏ，Ｆｅ，Ｃｒ，Ｎｉ，Ｔｉ，Ｚｒ，Ｎｂ，
Ｙ，Ａｌ，Ｎａ，Ｋ，Ｍｇ，Ｃａ，Ｃｓ，Ｌａ，Ｃｅ，
Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂから構成される群から選択され
た少なくとも１つ以上の元素）Further, the lithium secondary battery of the present invention is characterized in that the lithium nickel oxide contains lithium nickel oxide represented by the following formula as a main component. LiNi 1-z A z O 2 where 0 ≦ z ≦ 0.3 (A is Be, C, Si, P, Sc, Cu, Zn, G
a, Ge, As, Se, Sr, Mo, Pd, Ag, C
d, In, Sn, Sb, Te, Ba, Ta, W.S. Pb,
Bi, Co, Fe, Cr, Ni, Ti, Zr, Nb,
Y, Al, Na, K, Mg, Ca, Cs, La, Ce,
At least one element selected from the group consisting of Nd, Sm, Eu, and Tb)
【００１９】このようなリチウムニッケル酸化物は、一
般に層状構造を有する。Such a lithium nickel oxide generally has a layered structure.
【００２０】元素Ａとしては、上記の中でも、Ｍｇ、Ａ
ｌ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｏ、Ｎｉを用いると、結
晶構造が安定し、高いサイクル性能が得られる点で好ま
しい。As the element A, among the above, Mg, A
The use of l, Ti, V, Cr, Fe, Co, and Ni is preferable in that the crystal structure is stable and high cycle performance can be obtained.
【００２１】即ち、本発明者らは前記課題を解決するた
め鋭意検討を行った結果、リチウムマンガン酸化物を主
体とする正極にリチウムニッケル酸化物が添加混合さ
れ、さらに前記リチウムマンガン複合酸化物表面にホウ
素が存在することで高い充放電容量、保存性能、そして
安全性を兼ね備えたリチウム二次電池を提供することが
可能となった。That is, the present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, lithium nickel oxide was added and mixed to a positive electrode mainly composed of lithium manganese oxide, and the surface of the lithium manganese composite oxide was further mixed. The presence of boron makes it possible to provide a lithium secondary battery having high charge / discharge capacity, storage performance, and safety.
【００２２】正極活物質としてのリチウムマンガン酸化
物にホウ素元素を添加する効果は、前述のように従来か
ら認められている。一方、正極活物質としてのリチウム
ニッケル酸化物にホウ素元素を添加しても、その効果は
さほど顕著ではない。しかしながら、本発明者らの検討
の結果、驚くべきことに、リチウムマンガン酸化物の表
面にホウ素が多く分布する活物質に、リチウムニッケル
酸化物を混合した場合、保存性能の改善効果は両者の効
果の単純加算によって予想される効果をさらに上回る効
果を示すことを見出した。このように、リチウムマンガ
ン酸化物とリチウムニッケル酸化物の混合正極は、本発
明のようにリチウムマンガン正極組成を好適に選択する
ことで、協奏的に電池性能を改善する効果をもたらすこ
とが可能となる。The effect of adding boron element to lithium manganese oxide as a positive electrode active material has been conventionally recognized as described above. On the other hand, even if a boron element is added to lithium nickel oxide as a positive electrode active material, the effect is not so remarkable. However, as a result of the study of the present inventors, surprisingly, when lithium nickel oxide is mixed with an active material in which a large amount of boron is distributed on the surface of lithium manganese oxide, the effect of improving the storage performance is the effect of both. It is found that the effect of the simple addition of exceeds the expected effect. Thus, the mixed positive electrode of lithium manganese oxide and lithium nickel oxide can bring about the effect of improving the battery performance in a concerted manner by suitably selecting the lithium manganese positive electrode composition as in the present invention. Become.
【００２３】[0023]
【発明の実施の形態】以下に、本発明の実施の形態を例
示するが、本発明は、以下の実施の形態に限定されるも
のではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.
【００２４】本発明の正極活物質の合成に用いる原料と
しては、リチウム源として、炭酸リチウム，水酸化リチ
ウム，酸化リチウム等のリチウム化合物、マンガン源と
して、硝酸マンガン，酢酸マンガン，二酸化マンガン等
のマンガン化合物、ニッケル源として、硝酸ニッケル，
酢酸ニッケル，酸化ニッケル等のニッケル化合物、置換
元素として、前記置換元素の酸化物または塩等の化合
物、ホウ素源として、Ｂ 2Ｏ3、Ｈ3ＢＯ3、ＨＢＯ2、Ｈ2
Ｂ2Ｏ7等のホウ素化合物等が挙げられる。中でも、リチ
ウム源として水酸化リチウム、マンガン源として二酸化
マンガン、ニッケル源として酸化ニッケル、ホウ素源と
してホウ酸を用いた固相反応法によると、組成及び粉体
特性の制御が容易である点で好ましい。Raw materials used for synthesizing the positive electrode active material of the present invention
Lithium carbonate, lithium hydroxide
Compounds such as lithium and lithium oxide, and manganese sources
Manganese nitrate, manganese acetate, manganese dioxide, etc.
Manganese compound, nickel nitrate as nickel source,
Nickel compounds such as nickel acetate and nickel oxide, substitution
As the element, a compound such as an oxide or a salt of the substitution element
Material, boron source, B TwoOThree, HThreeBOThree, HBOTwo, HTwo
BTwoO7And the like. Among them, Richi
Lithium hydroxide as a source of chromium and dioxide as a source of manganese
Manganese and nickel sources as nickel oxide and boron sources
According to the solid-phase reaction method using boric acid, the composition and powder
This is preferable in that characteristics can be easily controlled.
【００２５】本発明のリチウム二次電池は、正極、負極
及びセパレータを有し、正極は本発明の正極活物質を主
要構成成分とする。The lithium secondary battery of the present invention has a positive electrode, a negative electrode and a separator, and the positive electrode has the positive electrode active material of the present invention as a main component.
【００２６】負極に用いる負極材料としては、リチウム
を吸蔵、放出可能な炭素材料を挙げることができ、特に
エックス線回折法より見積もられる面間隔（ｄ002）が
０．３３５４〜０．３３６９ｎｍで、ｃ軸方向の結晶の
大きさ（Ｌｃ）が２０ｎｍ以上である炭素粒子が好まし
い。As the negative electrode material used for the negative electrode, a carbon material capable of inserting and extracting lithium can be cited. In particular, the plane spacing (d 002 ) estimated by X-ray diffraction method is 0.3354 to 0.3369 nm, and Carbon particles having an axial crystal size (Lc) of 20 nm or more are preferred.
【００２７】正極及び負極は、導電剤及び結着剤を構成
成分として加えてもよい。The positive electrode and the negative electrode may contain a conductive agent and a binder as constituents.
【００２８】導電剤としては、電池性能に悪影響を及ぼ
さない電子伝導性材料であれば限定されないが、例え
ば、天然黒鉛（鱗状黒鉛，鱗片状黒鉛，土状黒鉛等）、
人造黒鉛、カーボンブラック、アセチレンブラック、ケ
ッチェンブラック、カーボンウイスカー、炭素繊維、金
属（銅，ニッケル，アルミニウム，銀，金等）粉、金属
繊維、導電性セラミックス材料等の導電性材料を１種ま
たはそれらの混合物として含ませることができる。中で
も、導電性及び塗工性の観点よりアセチレンブラックを
用いることが望ましい。導電剤の添加量は、正極または
負極の総重量に対して１〜５０重量％が好ましく、特に
２重量％〜３０重量％が好ましい。活物質と導電剤との
混合方法は、物理的な混合であり、その理想とするとこ
ろは均一混合である。例えば、Ｖ型混合機、Ｓ型混合
機、擂かい機、ボールミル、遊星ボールミルといったよ
うな粉体混合機を乾式、あるいは湿式で混合することが
好ましい。The conductive agent is not limited as long as it is an electron conductive material which does not adversely affect battery performance. Examples of the conductive agent include natural graphite (scale graphite, flake graphite, earth graphite, etc.),
One or more conductive materials such as artificial graphite, carbon black, acetylene black, Ketjen black, carbon whiskers, carbon fiber, metal (copper, nickel, aluminum, silver, gold, etc.) powder, metal fiber, and conductive ceramic material They can be included as a mixture thereof. Above all, it is desirable to use acetylene black from the viewpoint of conductivity and coatability. The amount of the conductive agent to be added is preferably 1 to 50% by weight, and particularly preferably 2 to 30% by weight, based on the total weight of the positive electrode or the negative electrode. The method of mixing the active material and the conductive agent is physical mixing, and ideally, uniform mixing. For example, it is preferable to dry or wet mix a powder mixer such as a V-type mixer, an S-type mixer, a grinder, a ball mill, and a planetary ball mill.
【００２９】結着剤としては、通常、ポリテトラフルオ
ロエチレン，ポリフッ化ビニリデン，ポリエチレン，ポ
リプロピレン等の熱可塑性樹脂、エチレン−プロピレン
系ゴム（ＥＰＲ)，スルホン化エチレン−プロピレン系
ゴム，スチレンブタジエンゴム（ＳＢＲ）、フッ素ゴム
等のゴム弾性を有するポリマー、カルボキシメチルセル
ロース等の多糖類等を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は、例えばメチル化等
によりその官能基を失活させておくことが望ましい。結
着剤の添加量は、正極又は負極の総重量に対して１〜５
０重量％が好ましく、特に２〜３０重量％が好ましい。As the binder, thermoplastic resins such as polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, and polypropylene, ethylene-propylene rubber (EPR), sulfonated ethylene-propylene rubber, and styrene butadiene rubber are usually used. SBR), polymers having rubber elasticity such as fluororubber, and polysaccharides such as carboxymethylcellulose can be used alone or as a mixture of two or more. Further, it is desirable that a binder having a functional group that reacts with lithium, such as a polysaccharide, be deactivated by, for example, methylation. The amount of the binder added is 1 to 5 with respect to the total weight of the positive electrode or the negative electrode.
0% by weight is preferable, and 2 to 30% by weight is particularly preferable.
【００３０】正極及び負極は、例えば、前記正極活物質
または負極材料、導電剤及び結着剤等をトルエン等の有
機溶媒下で混練し、電極形状に成形して乾燥することに
よって作製することができる。前記乾燥は、例えば、混
練物を温度・時間等の乾燥条件が設定された公知の減圧
乾燥機を使用して減圧乾燥する方法等を用いることがで
きる。The positive electrode and the negative electrode can be produced, for example, by kneading the positive electrode active material or the negative electrode material, a conductive agent and a binder in an organic solvent such as toluene, forming the mixture into an electrode shape, and drying. it can. For the drying, for example, a method of drying the kneaded material under reduced pressure using a known reduced-pressure dryer in which drying conditions such as temperature and time are set can be used.
【００３１】本発明に係るリチウム二次電池用発電要素
のセパレータとしては、イオンの等価性に優れ、加えて
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からポリプロピレンやポリエチレン
といったオレフィン系のポリマー、ガラス繊維、ポリフ
ッ化ビニリデン、ポリテトラフルオロエチレン等からつ
くられたシート、微孔膜、不織布、布が用いられる。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０．０１〜１０μｍである。また、その
厚みについても同様で、一般に電池に用いられる範囲の
ものであり、例えば５〜３００μｍである。As the separator of the power generating element for a lithium secondary battery according to the present invention, an insulating thin film having excellent ion equivalentity and mechanical strength can be used. Sheets, microporous membranes, nonwoven fabrics, and cloths made of olefin polymers such as polypropylene and polyethylene, glass fibers, polyvinylidene fluoride, polytetrafluoroethylene, and the like are used because of their resistance to organic solvents and hydrophobicity. The pore size of the separator is in a range generally used for a battery, and is, for example, 0.01 to 10 μm. The same applies to the thickness, which is in the range generally used for batteries, for example, 5 to 300 μm.
【００３２】正極、負極及びセパレータを有する発電要
素の形態としては、正極と負極とがセパレータを介して
密着した構成を例示できる。また、例えばコイン型電池
を作製する場合のように、正極，負極及びセパレータ
が、正極収納部，負極収納部，セパレータ収納部を有す
る電池用パッケージの各収納部にそれぞれ独立して収納
された場合においても、正極，負極，セパレータよりな
る集合体は、本発明に係るリチウム二次電池用発電要素
の実施の一形態である。As a form of the power generating element having a positive electrode, a negative electrode, and a separator, a configuration in which the positive electrode and the negative electrode are in close contact with each other via a separator can be exemplified. Further, when the positive electrode, the negative electrode, and the separator are individually stored in the respective storage portions of the battery package having the positive electrode storage portion, the negative electrode storage portion, and the separator storage portion, for example, when a coin-type battery is manufactured. In this case, the assembly including the positive electrode, the negative electrode, and the separator is one embodiment of the power generating element for a lithium secondary battery according to the present invention.
【００３３】本発明に係るリチウム二次電池は、以上に
詳述した本発明に係るリチウム二次電池用発電要素に、
含フッ素系電解質を含有する非水系電解液が注液される
ことにより作製される。The lithium secondary battery according to the present invention includes the power generating element for a lithium secondary battery according to the present invention described in detail above,
It is produced by injecting a non-aqueous electrolyte containing a fluorinated electrolyte.
【００３４】含フッ素系電解質塩としては、高いリチウ
ムイオン伝導性を示すＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓ
Ｆ6、ＬｉＯＳＯ2ＣＦ3等が好適に使用される。これら
含フッ素電解質は、非水電解液中に０．１Ｍ〜３．０
Ｍ、好ましくは０．５Ｍ〜２．０Ｍの濃度となるように
溶解される。Examples of the fluorinated electrolyte salt include LiPF 6 , LiBF 4 and LiAs exhibiting high lithium ion conductivity.
F 6 , LiOSO 2 CF 3 and the like are preferably used. These fluorinated electrolytes are contained in a non-aqueous electrolyte at 0.1 M to 3.0 M.
M, preferably from 0.5M to 2.0M.
【００３５】前記含フッ素系電解質塩は、高誘電率溶媒
及び／又は低粘度溶媒と組み合わせて非水系電解液とさ
れるのが好ましい。高誘電率溶媒としては、例えば、エ
チレンカーボネート（ＥＣ）、プロピレンカーボネート
（ＰＣ）等の環状カーボネート類等が好適に挙げられ
る。これら高誘電率溶媒は単独で使用してもよく、また
２種類以上の組み合わせで使用してもよい。The fluorinated electrolyte salt is preferably used as a non-aqueous electrolyte in combination with a high dielectric constant solvent and / or a low viscosity solvent. Preferred examples of the high dielectric constant solvent include cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC). These high dielectric constant solvents may be used alone or in combination of two or more.
【００３６】低粘度溶媒としては、例えば、ジメチルカ
ーボネート（ＤＭＣ）、メチルエチルカーボネート（Ｍ
ＥＣ）、ジエチルカーボネート（ＤＥＣ）等の鎖状カー
ボネート類、テトラヒドロフラン（ＴＨＦ）、２−メチ
ルテトラヒドロフラン、１，４−ジオキサン、１，２−
ジメトキエタン、１，２−ジエトキシエタン、１，２−
ジブトキシエタン等のエーテル類、γーブチロラクトン
等のラクトン類、アセトニトリル等のニトリル類、ジメ
チルホルムアミド等のアミド類、ギ酸メチル、酢酸メチ
ル等のエステル類等が挙げられる。これら低粘度溶媒は
単独で使用してもよく、また２種類以上で組み合わせて
使用してもよい。Examples of the low viscosity solvent include dimethyl carbonate (DMC) and methyl ethyl carbonate (M
EC), chain carbonates such as diethyl carbonate (DEC), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-
Dimethokiethane, 1,2-diethoxyethane, 1,2-
Ethers such as dibutoxyethane; lactones such as γ-butyrolactone; nitriles such as acetonitrile; amides such as dimethylformamide; esters such as methyl formate and methyl acetate. These low viscosity solvents may be used alone or in combination of two or more.
【００３７】本発明に係るリチウム二次電池は、例え
ば、正極と負極とがセパレータを介して密着したリチウ
ム二次電池用発電要素を電池用パッケージ内に入れ、次
いで電池用パッケージ内に非水系電解液を注液し、最終
的に封止することによって得られる。また、前記したよ
うに、正極，負極，セパレータを、正極収納部，負極収
納部，セパレータ収納部を有する電池用パッケージの各
収納部にそれぞれ独立して収納し、次いで電池用パッケ
ージ内に非水系電解液を注液し、最終的に封止すること
によって得られてもよい。In the lithium secondary battery according to the present invention, for example, a power generating element for a lithium secondary battery in which a positive electrode and a negative electrode are in close contact with each other via a separator is placed in a battery package, and then the non-aqueous electrolyte is placed in the battery package. It is obtained by injecting a liquid and finally sealing. Further, as described above, the positive electrode, the negative electrode, and the separator are individually stored in the respective storage portions of the battery package having the positive electrode storage portion, the negative electrode storage portion, and the separator storage portion. It may be obtained by injecting an electrolytic solution and finally sealing.
【００３８】なお、前記発電要素は、リチウム二次電池
用発電要素が電池用パッケージ内に装填された場合に、
正極と密着できる正極用集電体と負極と密着できる負極
用集電体とを有しているものが好ましく、例えば、正極
用集電体としては、アルミニウム、チタン、ステンレス
鋼、ニッケル、焼成炭素、導電性高分子、導電性ガラス
等の他に、接着性、導電性及び耐酸化性向上の目的で、
アルミニウムや銅等の表面をカーボン、ニッケル、チタ
ンや銀等で処理した物を用いることができる。負極用集
電体としては、銅、ニッケル、鉄、ステンレス鋼、チタ
ン、アルミニウム、焼成炭素、導電性高分子、導電性ガ
ラス、Ａｌ−Ｃｄ合金等の他に、接着性、導電性、耐酸
化性向上の目的で、銅等の表面をカーボン、ニッケル、
チタンや銀等で処理した物を用いることができる。これ
らの材料については表面を酸化処理することも可能であ
る。The power generating element is provided when the power generating element for a lithium secondary battery is loaded in a battery package.
It is preferable to have a current collector for the positive electrode that can adhere to the positive electrode and a current collector for the negative electrode that can adhere to the negative electrode. Examples of the current collector for the positive electrode include aluminum, titanium, stainless steel, nickel, and calcined carbon. , In addition to conductive polymers, conductive glass, etc., for the purpose of improving adhesion, conductivity and oxidation resistance,
A material obtained by treating the surface of aluminum, copper, or the like with carbon, nickel, titanium, silver, or the like can be used. Examples of the current collector for the negative electrode include copper, nickel, iron, stainless steel, titanium, aluminum, calcined carbon, conductive polymer, conductive glass, and Al-Cd alloy, as well as adhesiveness, conductivity, and oxidation resistance. For the purpose of improving the performance, the surface of copper etc.
A material treated with titanium, silver, or the like can be used. These materials can be oxidized on the surface.
【００３９】集電体の形状については、フォイル状の
他、フィルム状、シート状、ネット状、パンチ又はエキ
スパンドされた物、ラス体、多孔質体、発砲体、繊維群
の形成体等が用いられる。厚みの限定は特にないが、１
〜５００μｍのものが用いられる。これらの集電体の中
で、正極用集電体としては、耐酸化性に優れているアル
ミニウム箔が、負極用集電体としては、還元場において
安定であり、且つ導電性に優れ、安価な銅箔、ニッケル
箔、鉄箔、及びそれらの一部を含む合金箔を使用するこ
とが好ましい。さらに、粗面表面粗さが０．２μｍＲａ
以上の箔であることが好ましく、これにより正極及び負
極と集電体との密着性は優れたものとなる。よって、こ
のような粗面を有することから、電解箔を使用するのが
好ましい。特に、ハナ付き処理を施した電解箔は最も好
ましい。The current collector may be in the form of a foil, a film, a sheet, a net, a punched or expanded material, a lath, a porous material, a foamed material, a formed fiber group, or the like. Can be There is no particular limitation on the thickness.
〜500 μm is used. Among these current collectors, as the current collector for the positive electrode, an aluminum foil having excellent oxidation resistance is used, and as the current collector for the negative electrode, the aluminum foil is stable in a reduction field, and has excellent conductivity, and is inexpensive. It is preferable to use a copper foil, a nickel foil, an iron foil, and an alloy foil including a part thereof. Furthermore, the rough surface roughness is 0.2 μm Ra.
The above-mentioned foil is preferable, whereby the adhesion between the positive electrode and the negative electrode and the current collector becomes excellent. Therefore, it is preferable to use an electrolytic foil because of having such a rough surface. In particular, an electrolytic foil subjected to a napping treatment is most preferable.
【００４０】[0040]
【実施例】以下に、実施例に基づき本発明をさらに詳細
に説明するが、本発明は以下の記載により限定されるも
のではなく、試験方法や構成する電池の正極活物質、負
極活物質、正極、負極、電解質、セパレータ並びに電池
形状等は任意である。本発明電池の実施形態の一例を図
１に示す。EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following description, and the test method and the positive electrode active material, the negative electrode active material, The shape of the positive electrode, the negative electrode, the electrolyte, the separator, the battery, and the like are arbitrary. FIG. 1 shows an example of an embodiment of the battery of the present invention.
【００４１】（実施例１） （リチウムマンガン複合酸化物の調製）ＬｉＯＨ、Ｍｎ
Ｏ2及びＨ3ＢＯ3を、元素比Ｌｉ：Ｍｎ：Ｂ＝１．０
８：１．９２：０．０５の割合で混合した懸濁水溶液と
し、ロータリーエバポレータを用いて前記懸濁水溶液を
減圧乾燥し、固形状の混合塩を得た。前記混合塩を乾燥
空気（酸素分率２０％）の気流下、温度４５０℃で１２
時間仮焼成を行い、続いて温度８００℃で２４時間加熱
処理を行い、Ｌｉ1.08Ｍｎ1.92Ｏ4＋０．０５Ｂの組成
の焼成物を得た。エックス線回折測定を行った結果、立
方晶系のスピネル構造を有するマンガン酸リチウム相の
生成を確認した。(Example 1) (Preparation of lithium manganese composite oxide) LiOH, Mn
O 2 and H 3 BO 3 are converted to an elemental ratio of Li: Mn: B = 1.0.
The suspension was mixed at a ratio of 8: 1.92: 0.05, and the suspension was dried under reduced pressure using a rotary evaporator to obtain a solid mixed salt. The mixed salt was dried under a stream of dry air (oxygen content: 20%) at a temperature of 450 ° C. for 12 hours.
Temporary calcination was performed for 24 hours, followed by heat treatment at 800 ° C. for 24 hours to obtain a baked product having a composition of Li 1.08 Mn 1.92 O 4 + 0.05B. As a result of X-ray diffraction measurement, formation of a lithium manganate phase having a cubic spinel structure was confirmed.
【００４２】（リチウムニッケル複合酸化物の作製）Ｌ
ｉ2Ｏ2、ＮｉＯ、Ａｌ2Ｏ3及びＣｏ2Ｏ3を、元素比Ｌ
ｉ：Ｎｉ：Ａｌ：Ｃｏ＝１．０：０．８５：０．０２
５：０．１２５の割合で混合し、イソプロピルアルコー
ルを加え、遊星ボールミルを用いて混練した。得られた
混合物を乾燥空気（酸素分率２０％）の気流下、温度４
５０℃で１２時間仮焼成を行い、続いて温度７００℃で
４８時間加熱処理を行い、Ｌｉ1.0Ｎｉ0.85Ａｌ0.025Ｃ
ｏ0.125の組成の焼成物を得た。エックス線回折測定を
行った結果、層状構造を有するニッケル酸リチウム相の
生成を確認した。(Preparation of lithium nickel composite oxide) L
i 2 O 2 , NiO, Al 2 O 3 and Co 2 O 3 are converted to an element ratio L
i: Ni: Al: Co = 1.0: 0.85: 0.02
The mixture was mixed at a ratio of 5: 0.125, isopropyl alcohol was added, and the mixture was kneaded using a planetary ball mill. The resulting mixture was dried under a stream of dry air (oxygen content: 20%) at a temperature of 4 ° C.
It performed 12 hours calcined at 50 ° C., subjected to 48 hours of heat treatment followed by a temperature 700 ℃, Li 1.0 Ni 0.85 Al 0.025 C
o A fired product having a composition of 0.125 was obtained. As a result of X-ray diffraction measurement, generation of a lithium nickelate phase having a layered structure was confirmed.
【００４３】（正極の作製）上記のようにして調製した
正極活物質であるリチウムマンガン酸化物、同じく正極
活物質であるリチウムニッケル酸化物、導電剤であるア
セチレンブラック及び結着剤であるポリフッ化ビニリデ
ン（ＰＶｄＦ）を重量比８０．７５：４．２５：１０：
５の割合で混合し、Ｎ−メチル−２−ピロリドン（ＮＭ
Ｐ）を加えて十分混練し、正極ペーストを得た。前記正
極ペーストを厚さ２０μｍのアルミニウム箔集電体上に
両面塗布し、プレス加工した。減圧乾燥後、幅６１ｍ
ｍ、長さ１０７ｍｍの寸法に裁断し、シート末端に厚さ
２０μｍ、幅１０ｍｍのアルミニウム製正極リード板を
取り付け、正極７とした。さらに、２６．７Ｐａの減圧
下、温度１５０℃で１０時間乾燥した。前記正極板の設
計容量は６．３ｍＡｈ／ｃｍ2である。(Preparation of Positive Electrode) Lithium manganese oxide as a positive electrode active material prepared as described above, lithium nickel oxide as a positive electrode active material, acetylene black as a conductive agent, and polyfluoride as a binder Vinylidene (PVdF) in a weight ratio of 80.75: 4.25: 10:
5 and mixed with N-methyl-2-pyrrolidone (NM
P) was added and kneaded sufficiently to obtain a positive electrode paste. The positive electrode paste was applied on both sides of a 20-μm-thick aluminum foil current collector, and pressed. After drying under reduced pressure, width 61m
m, and cut into dimensions of 107 mm in length. An aluminum positive electrode lead plate having a thickness of 20 μm and a width of 10 mm was attached to the end of the sheet to obtain a positive electrode 7. Further, it was dried at a temperature of 150 ° C. for 10 hours under a reduced pressure of 26.7 Pa. The design capacity of the positive electrode plate is 6.3 mAh / cm 2 .
【００４４】（負極の作製）負極材料である人造黒鉛
（平均粒径６μｍ、エックス線回折法による面間隔（ｄ
002）０．３３７ｎｍ、ｃ軸方向の結晶の大きさ（Ｌ
ｃ）５５ｎｍ）及びポリフッ化ビニリデン（ＰＶｄＦ）
を重量比９５：５の割合で混合し、Ｎ―メチル−２−ピ
ロリドン（ＮＭＰ）を加えて十分混練し、負極ペースト
を得た。次に、前記負極ペーストを厚さ１５μｍの銅箔
集電体上に両面塗布後、プレス加工した。その後、幅６
５ｍｍ、長さ１１１ｍｍの寸法に裁断し、シート末端に
厚み１０μｍ、幅１０ｍｍのニッケル製負極リード板を
取り付け、負極９とした。さらに、２６．７Ｐａの減圧
下、１５０℃で１５時間乾燥した。前記負極板の設計容
量は７．０ｍＡｈ／ｃｍ2である。(Preparation of Negative Electrode) Artificial graphite (average particle size: 6 μm, surface spacing (d
002 ) 0.337 nm, crystal size in the c-axis direction (L
c) 55 nm) and polyvinylidene fluoride (PVdF)
Were mixed at a weight ratio of 95: 5, N-methyl-2-pyrrolidone (NMP) was added, and the mixture was sufficiently kneaded to obtain a negative electrode paste. Next, the negative electrode paste was applied on both sides of a copper foil current collector having a thickness of 15 μm, and then pressed. Then width 6
The sheet was cut into a size of 5 mm and a length of 111 mm, and a nickel negative electrode lead plate having a thickness of 10 μm and a width of 10 mm was attached to the end of the sheet to obtain a negative electrode 9. Further, it was dried at 150 ° C. under a reduced pressure of 26.7 Pa for 15 hours. The design capacity of the negative electrode plate is 7.0 mAh / cm 2 .
【００４５】（含フッ素系電解質塩を含有する非水系電
解液の調製）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の割合で混合した混合溶媒に、含
フッ素系電解質塩であるＬｉＰＦ6を１ｍｏｌ／ｌの濃
度で溶解させ、電解液を作成した。前記電解液中の水分
量は２０ｐｐｍ未満である。(Preparation of Nonaqueous Electrolyte Containing Fluorinated Electrolyte Salt) A mixed solvent of ethylene carbonate and diethyl carbonate mixed at a volume ratio of 1: 1 was mixed with 1 mol of LiPF 6 as a fluorinated electrolyte salt. / L to give an electrolyte solution. The amount of water in the electrolyte is less than 20 ppm.
【００４６】（１５Ａｈ級リチウム二次電池の作製）セ
パレータ８として、あらかじめ幅６５ｍｍ、高さ１１１
mmの袋形状に裁断してあるポリエチレン製微多孔膜の袋
に、前記正極７を挿入し、セパレータ８付き正極板を得
た。図１に示すように、前記セパレータ付き正極板及び
負極９を交互に積層して、セパレータ付き正極板４０枚
及び負極板４１枚からなる極群を得た。(Preparation of 15 Ah Class Lithium Secondary Battery) As the separator 8, a width of 65 mm and a height of 111
The positive electrode 7 was inserted into a polyethylene microporous membrane bag cut into a bag shape of mm to obtain a positive electrode plate with a separator 8. As shown in FIG. 1, the positive electrode plate with separator and the negative electrode 9 were alternately laminated to obtain an electrode group including 40 positive electrode plates with separator and 41 negative electrode plates.
【００４７】前記極群をポリエチレン樹脂製の絶縁フィ
ルムに包み込み、アルミニウム製の角形電槽缶１０に収
納し、前記正極リード板及び負極リード板を、安全弁１
を有するアルミニウム製の蓋２に取り付けられた正極端
子５及び負極端子４にそれぞれボルトによって接続し
た。なお、前記正極端子５及び負極端子４は、ポリプロ
ピレン樹脂製のガスケット６を用いて絶縁してある。The electrode group is wrapped in an insulating film made of polyethylene resin and housed in a rectangular battery case 10 made of aluminum. The positive electrode lead plate and the negative electrode lead plate are
The positive electrode terminal 5 and the negative electrode terminal 4 attached to the aluminum lid 2 having the following were connected by bolts, respectively. The positive electrode terminal 5 and the negative electrode terminal 4 are insulated using a gasket 6 made of polypropylene resin.
【００４８】前記蓋２と前記電槽缶１０とをレーザーで
溶接した。３はレーザー溶接部である。前記電解液を電
槽内に６５ｇ注入し、注液口を封口した後、２０℃にお
いて１．５Ａ、４．２Ｖの定電流定電圧充電を施した。
このようにして、横７０ｍｍ、高さ１３０ｍｍ（端子込
み１３６ｍｍ）、幅２２ｍｍの１５Ａｈ級角型電池を作
製した。これを本発明電池１とする。The lid 2 and the battery case 10 were welded by laser. 3 is a laser weld. After 65 g of the electrolytic solution was injected into the battery container and the inlet was closed, the battery was charged at 20 ° C. with a constant current and a constant voltage of 1.5 A and 4.2 V.
In this way, a 15 Ah class square battery having a width of 70 mm, a height of 130 mm (136 mm including terminals), and a width of 22 mm was produced. This is designated as Battery 1 of the invention.
【００４９】（実施例２）正極の作製において、実施例
１記載の方法で調製した正極活物質であるリチウムマン
ガン酸化物、同じく正極活物質であるリチウムニッケル
酸化物、導電剤であるアセチレンブラック及び結着剤で
あるポリフッ化ビニリデン（ＰＶｄＦ）を重量比７６．
５：８．５：１０：５の割合で混合したこと以外は実施
例１と同様にして１５Ａｈ級角型電池を作製した。これ
を本発明電池２とする。Example 2 In the preparation of the positive electrode, lithium manganese oxide as the positive electrode active material, lithium nickel oxide also as the positive electrode active material, acetylene black as the conductive agent, and the like were prepared by the method described in Example 1. Polyvinylidene fluoride (PVdF) as a binder was added in a weight ratio of 76.
A 15 Ah class prismatic battery was produced in the same manner as in Example 1 except that the mixture was mixed at a ratio of 5: 8.5: 10: 5. This is designated as Battery 2 of the invention.
【００５０】（実施例３）正極の作製において、実施例
１記載の方法で調製した正極活物質であるリチウムマン
ガン酸化物、同じく正極活物質であるリチウムニッケル
酸化物、導電剤であるアセチレンブラック及び結着剤で
あるポリフッ化ビニリデン（ＰＶｄＦ）を重量比７２．
２５：１２．７５：１０：５の割合で混合したこと以外
は実施例１と同様にして１５Ａｈ級角型電池を作製し
た。これを本発明電池３とする。Example 3 In the preparation of a positive electrode, lithium manganese oxide as a positive electrode active material, lithium nickel oxide also as a positive electrode active material, acetylene black as a conductive agent, and the like were prepared by the method described in Example 1. 72. Weight ratio of polyvinylidene fluoride (PVdF) as a binder
A 15 Ah class prismatic battery was produced in the same manner as in Example 1 except that the mixture was mixed at a ratio of 25: 12.75: 10: 5. This is designated as Battery 3 of the invention.
【００５１】（実施例４）正極の作製において、実施例
１記載の方法で調製した正極活物質であるリチウムマン
ガン酸化物、同じく正極活物質であるリチウムニッケル
酸化物、導電剤であるアセチレンブラック及び結着剤で
あるポリフッ化ビニリデン（ＰＶｄＦ）を重量比６８：
１７：１０：５の割合で混合したこと以外は実施例１と
同様にして１５Ａｈ級角型電池を作製した。これを本発
明電池４とする。Example 4 In the preparation of the positive electrode, lithium manganese oxide as the positive electrode active material, lithium nickel oxide also as the positive electrode active material, acetylene black as the conductive agent, and the like were prepared by the method described in Example 1. Polyvinylidene fluoride (PVdF) as a binder was added in a weight ratio of 68:
A 15 Ah class prismatic battery was produced in the same manner as in Example 1 except that the mixture was mixed at a ratio of 17: 10: 5. This is designated as Battery 4 of the invention.
【００５２】（実施例５）正極の作製において、実施例
１記載の方法で調製した正極活物質であるリチウムマン
ガン酸化物、同じく正極活物質であるリチウムニッケル
酸化物、導電剤であるアセチレンブラック及び結着剤で
あるポリフッ化ビニリデン（ＰＶｄＦ）を重量比５９．
５：２５．５：１０：５の割合で混合したこと以外は実
施例１と同様にして１５Ａｈ級角型電池を作製した。こ
れを本発明電池５とする。Example 5 In the preparation of the positive electrode, lithium manganese oxide as the positive electrode active material, lithium nickel oxide also as the positive electrode active material, acetylene black as the conductive agent, and the like were prepared by the method described in Example 1. Polyvinylidene fluoride (PVdF) as a binder was used in a weight ratio of 59.
A 15 Ah class prismatic battery was produced in the same manner as in Example 1 except that the mixture was mixed at a ratio of 5: 25.5: 10: 5. This is designated as Battery 5 of the invention.
【００５３】（実施例６）正極の作製において、実施例
１記載の方法で調製した正極活物質であるリチウムマン
ガン酸化物、同じく正極活物質であるリチウムニッケル
酸化物、導電剤であるアセチレンブラック及び結着剤で
あるポリフッ化ビニリデン（ＰＶｄＦ）を重量比５１：
３４：１０：５の割合で混合したこと以外は実施例１と
同様にして１５Ａｈ級角型電池を作製した。これを本発
明電池６とする。(Example 6) In the preparation of the positive electrode, lithium manganese oxide as the positive electrode active material, lithium nickel oxide as the positive electrode active material, acetylene black as the conductive agent, and the like were prepared by the method described in Example 1. Polyvinylidene fluoride (PVdF) as a binder was added in a weight ratio of 51:
A 15Ah-class square battery was produced in the same manner as in Example 1 except that the mixture was mixed at a ratio of 34: 10: 5. This is designated as Battery 6 of the invention.
【００５４】（実施例７）正極の作製において、実施例
１記載の方法で調製した正極活物質であるリチウムマン
ガン酸化物、同じく正極活物質であるリチウムニッケル
酸化物、導電剤であるアセチレンブラック及び結着剤で
あるポリフッ化ビニリデン（ＰＶｄＦ）を重量比４２．
５：４２．５：１０：５の割合で混合したこと以外は実
施例１と同様にして１５Ａｈ級角型電池を作製した。こ
れを本発明電池７とする。(Example 7) In the preparation of the positive electrode, lithium manganese oxide as the positive electrode active material, lithium nickel oxide as the positive electrode active material, acetylene black as the conductive agent, and the like were prepared by the method described in Example 1. A polyvinylidene fluoride (PVdF) as a binder is added at a weight ratio of 42.
A 15 Ah class prismatic battery was produced in the same manner as in Example 1 except that the mixture was mixed at a ratio of 5: 42.5: 10: 5. This is designated as Battery 7 of the invention.
【００５５】（比較例１）正極の作成において、実施例
１記載の方法で調製した正極活物質であるリチウムマン
ガン酸化物、導電剤であるアセチレンブラック、及び結
着剤であるポリフッ化ビニリデン（ＰＶｄＦ）を重量比
８５：１０：５の割合で混合した以外は実施例１と同様
の１５Ａｈ級角型電池を作製した。これを比較電池１と
する。Comparative Example 1 In the preparation of the positive electrode, lithium manganese oxide as the positive electrode active material, acetylene black as the conductive agent, and polyvinylidene fluoride (PVdF) as the binder were prepared by the method described in Example 1. ) Was mixed at a weight ratio of 85: 10: 5 to produce a 15Ah-class square battery similar to that of Example 1. This is designated as Comparative Battery 1.
【００５６】（比較例２）ＬｉＯＨ及びＭｎＯ2を元素
比Ｌｉ：Ｍｎ＝１．０８：１．９２の割合で混合した懸
濁水溶液とし、ロータリーエバポレータを用いて前記懸
濁水溶液を減圧乾燥し、固形状の混合塩を得た。前記混
合塩を乾燥空気（酸素分率２０％）の気流下、温度４５
０℃で１２時間仮焼成を行い、続いて温度８００℃で２
４時間加熱処理を行い、Ｌｉ1.08Ｍｎ1.92Ｏ4組成のリ
チウムマンガン酸化物を得た。正極の作成において、正
極活物質として該リチウムマンガン酸化物、導電剤であ
るアセチレンブラック及び結着剤であるポリフッ化ビニ
リデン（ＰＶｄＦ）を重量比８５：１０：５の割合で混
合した以外は実施例１と同様にして１５Ａｈ級角型電池
を作製した。これを比較電池２とする。Comparative Example 2 A suspension was prepared by mixing LiOH and MnO 2 at an elemental ratio of Li: Mn = 1.08: 1.92, and the suspension was dried under reduced pressure using a rotary evaporator. A solid mixed salt was obtained. The mixed salt was dried under a stream of dry air (oxygen content: 20%) at a temperature of 45 ° C.
Pre-baking is performed at 0 ° C. for 12 hours, followed by 800 ° C. for 2 hours.
Heat treatment was performed for 4 hours to obtain a lithium manganese oxide having a composition of Li 1.08 Mn 1.92 O 4 . Example 1 was repeated except that the lithium manganese oxide as a positive electrode active material, acetylene black as a conductive agent, and polyvinylidene fluoride (PVdF) as a binder were mixed at a weight ratio of 85: 10: 5 in the preparation of the positive electrode. In the same manner as in Example 1, a 15 Ah-class square battery was produced. This is designated as Comparative Battery 2.
【００５７】（比較例３）正極の作成において、比較例
１記載の方法で調製した正極活物質であるリチウムマン
ガン酸化物、実施例１記載の方法で調製した正極活物質
であるリチウムニッケル酸化物、導電剤であるアセチレ
ンブラック及び結着剤であるポリフッ化ビニリデン（Ｐ
ＶｄＦ）を重量比６８：１７：１０：５の割合で混合し
たこと以外は実施例１と同様にして１５Ａｈ級角型電池
を作製した。これを比較電池３とする。Comparative Example 3 In the preparation of the positive electrode, a lithium manganese oxide as the positive electrode active material prepared by the method described in Comparative Example 1 and a lithium nickel oxide as the positive electrode active material prepared according to the method described in Example 1 , Acetylene black as a conductive agent and polyvinylidene fluoride as a binder (P
VdF) was mixed in a weight ratio of 68: 17: 10: 5 to produce a 15 Ah-class square battery in the same manner as in Example 1. This is designated as Comparative Battery 3.
【００５８】（比較例４）ＬｉＯＨ及びＭｎＯ2を元素
比Ｌｉ：Ｍｎ＝１．００：２．００の割合で混合した懸
濁水溶液とし、ロータリーエバポレータを用いて前記懸
濁水溶液を減圧乾燥し、固形状の混合塩を得た。前記混
合塩を乾燥空気（酸素分率２０％）の気流下、温度４５
０℃で１２時間仮焼成を行い、続いて温度８００℃で２
４時間加熱処理を行い、ＬｉＭｎ2Ｏ4組成のリチウムマ
ンガン複合酸化物を得た。正極の作成において、正極活
物質として該リチウムマンガン酸化物、実施例１記載の
方法で調製した正極活物質であるリチウムニッケル酸化
物、導電剤であるアセチレンブラック及び結着剤である
ポリフッ化ビニリデン（ＰＶｄＦ）を重量比６８：１
７：１０：５の割合で混合したこと以外は実施例１と同
様にして１５Ａｈ級角型電池を作製した。これを比較電
池４とする。Comparative Example 4 A suspension was prepared by mixing LiOH and MnO 2 at an elemental ratio of Li: Mn = 1.00: 2.00, and the suspension was dried under reduced pressure using a rotary evaporator. A solid mixed salt was obtained. The mixed salt was dried under a stream of dry air (oxygen content: 20%) at a temperature of 45 ° C.
Pre-baking is performed at 0 ° C. for 12 hours, followed by 800 ° C. for 2 hours.
Heat treatment was performed for 4 hours to obtain a lithium manganese composite oxide having a composition of LiMn 2 O 4 . In producing the positive electrode, the lithium manganese oxide as the positive electrode active material, lithium nickel oxide as the positive electrode active material prepared by the method described in Example 1, acetylene black as the conductive agent, and polyvinylidene fluoride as the binder ( PVdF) in a weight ratio of 68: 1
A 15 Ah class square battery was produced in the same manner as in Example 1 except that the mixture was mixed at a ratio of 7: 10: 5. This is designated as Comparative Battery 4.
【００５９】（放電容量）本発明電池１〜７及び比較電
池１〜４をそれぞれ１０個用意し、上限４．２Ｖ、下限
３．０Ｖの電圧範囲で数サイクルの充放電を行うことに
より化成を行った。その後、０．５ＩｔＡ（２時間率）
で充放電サイクル試験を行った。基準として、比較電池
１の１０サイクル目ならびに１００サイクル目の放電容
量をそれぞれ１００とし、各電池の同一サイクル目の放
電容量との比を放電容量比として表１にまとめた。(Discharge Capacity) Ten batteries each of the present invention batteries 1 to 7 and comparative batteries 1 to 4 were prepared, and formed by performing several cycles of charge and discharge in a voltage range of an upper limit of 4.2 V and a lower limit of 3.0 V. went. Then 0.5 ItA (2 hour rate)
A charge / discharge cycle test was performed. As a reference, the discharge capacity at the 10th cycle and the 100th cycle of the comparative battery 1 was set to 100, respectively, and the ratio to the discharge capacity at the same cycle of each battery was summarized in Table 1 as the discharge capacity ratio.
【００６０】[0060]
【表１】 [Table 1]
【００６１】（保存性能試験）前記本発明電池１〜７及
び比較電池１〜４を、０．１ＩｔＡ（１０時間率）の電
流で４．２Ｖの定電流定電圧充電を行った。該充電後、
５０℃及び８０℃に設定した防爆構造の恒温槽内にそれ
ぞれ５個ずつ分けて保存した。７日後、電池を取り出
し、０．１ＩｔＡ（１０時間率）の電流で終止電圧を
３．０Ｖとして定電流放電を行い、「保存後放電容量」
を測定した。各電池について、次の算出式に従い「自己
放電率（％）」を算出した。結果を表２にまとめた。 自己放電率＝（保存前放電容量−保存後放電容量）／保
存前放電容量×１００（％）(Storage Performance Test) The batteries 1 to 7 of the present invention and the comparative batteries 1 to 4 were charged at a constant current of 4.2 V at a constant current and a constant voltage of 0.1 ItA (10 hour rate). After the charge,
Five samples were separately stored in an explosion-proof thermostat set at 50 ° C. and 80 ° C. After 7 days, the battery was taken out, a constant current discharge was performed at a current of 0.1 ItA (10 hour rate) with a final voltage of 3.0 V, and the “discharge capacity after storage”
Was measured. The “self-discharge rate (%)” was calculated for each battery according to the following calculation formula. The results are summarized in Table 2. Self-discharge rate = (discharge capacity before storage−discharge capacity after storage) / discharge capacity before storage × 100 (%)
【００６２】次に、同一条件で定電流定電圧充電及び定
電流充電を行った。これにより、得られた放電容量を
「回復放電容量」とし、各電池について、前記「保存前
放電容量」に対する比を求め、「回復容量率（％）」と
して表２に併せて示した。Next, constant current constant voltage charging and constant current charging were performed under the same conditions. The obtained discharge capacity was defined as “recovery discharge capacity”, and the ratio of each battery to the “discharge capacity before storage” was determined. The ratio was also shown in Table 2 as “recovery capacity ratio (%)”.
【００６３】[0063]
【表２】 [Table 2]
【００６４】（安全性試験）本発明電池１〜７及び比較
電池１〜４をそれぞれ５個用意し、上限４．２Ｖ、下限
３．０Ｖの電圧範囲で数サイクルの充放電を行うことに
より化成を行った。その後、電池を１１０％に充電した
状態で釘刺し試験を行った。釘には腐食がなく金属光沢
を有する3mm系のステンレス製釘を使用し、前記釘を電
極面に対して垂直に５mm/secの速度で電槽缶厚さ（２２
ｍｍ）の３／２深度に相当する１４ｍｍの深さまで貫通
させた。このときの釘刺し部分近傍の電池表面温度を記
録した。釘刺し後の電池の変化及び電池表面の釘刺し部
分における最高到達温度を表３にまとめて示した。(Safety test) Five batteries each of the present invention batteries 1 to 7 and comparative batteries 1 to 4 were prepared, and subjected to several cycles of charging and discharging in a voltage range of an upper limit of 4.2 V and a lower limit of 3.0 V to form a battery. Was done. Thereafter, a nail penetration test was performed with the battery charged to 110%. A 3 mm stainless steel nail having no metallic corrosion and having a metallic luster was used for the nail, and the nail was perpendicular to the electrode surface at a speed of 5 mm / sec.
mm) to a depth of 14 mm, which corresponds to a 3/2 depth. At this time, the battery surface temperature near the nail penetration portion was recorded. Table 3 summarizes the change in the battery after nail penetration and the maximum temperature at the nail penetration portion of the battery surface.
【００６５】[0065]
【表３】 [Table 3]
【００６６】（考察１：放電容量）単純比例計算によれ
ば、正極活物質中に占めるリチウムニッケル酸化物の含
有率が多いほど正極理論容量は直線的に増加する。しか
し、表１から明らかなように、比較電池１及び本発明電
池１〜７の５サイクル目放電容量を比較し、グラフ化す
ると（図示せず）、リチウムニッケル酸化物の含有率が
１０〜２０ｗｔ％の付近をひとつの変曲点とするＳ字曲
線を描いた。この結果を与えた原因については必ずしも
明らかではないが、電極の電子伝導性及びイオン伝導
性、各々の酸化物の粉体特性等に依存していると考えら
れる。(Discussion 1: Discharge Capacity) According to simple proportional calculation, the theoretical capacity of the positive electrode increases linearly as the content of lithium nickel oxide in the positive electrode active material increases. However, as is evident from Table 1, when the discharge capacity at the fifth cycle of the comparative battery 1 and the batteries 1 to 7 of the present invention were compared and graphed (not shown), the content of the lithium nickel oxide was 10 to 20 wt. An S-shaped curve having one inflection point near% was drawn. Although the cause of this result is not necessarily clear, it is considered that it depends on the electron conductivity and ionic conductivity of the electrode, the powder characteristics of each oxide, and the like.
【００６７】また、１００サイクル目の放電容量を比較
すると、リチウムニッケル酸化物の含有率が１５ｗｔ％
以上で顕著に増加している。この原因はＬｉＭｎ2Ｏ4の
サイクル性能が良好でなく、他方のＬｉＮｉＯ2のサイ
クル性能が良好であるためと考えられる。When the discharge capacity at the 100th cycle was compared, the content of lithium nickel oxide was 15 wt%.
Above, it has increased remarkably. This is probably because LiMn 2 O 4 has poor cycle performance and LiNiO 2 has good cycle performance.
【００６８】また、ホウ素を含まないマンガン酸リチウ
ムを用いた比較電池２及び比較電池３では、それぞれ対
応する比較電池１及び本発明電池４と比べて充放電サイ
クルに伴う放電容量の推移に差異は認められない。しか
し、式Ｌｉ1+x｛Ｍｎ(2-x-y)Ｍy｝Ｏ4においてｘ＝０と
したリチウムマンガン酸化物を用いた比較電池４では、
初期の放電容量は大きいが充放電サイクルに伴う容量低
下が激しい。Further, in Comparative Battery 2 and Comparative Battery 3 using lithium manganate containing no boron, the difference in the transition of the discharge capacity during the charge / discharge cycle is smaller than that of the corresponding Comparative Battery 1 and Battery 4 of the present invention, respectively. unacceptable. However, in Formula Li 1 + x {Mn (2 -xy) M y} comparative battery 4 in O 4 using lithium-manganese oxides with x = 0,
Although the initial discharge capacity is large, the capacity is significantly reduced with charge / discharge cycles.
【００６９】（考察２：保存性能）表２から明らかなよ
うに、いずれの保存温度においても、リチウムニッケル
酸化物の含有率が多いほど自己放電容量が減少し、回復
容量も増大している。また、リチウムマンガン酸化物が
ホウ素を含有している比較電池１及び本発明電池４で
は、ホウ素を含有していない比較電池２及び比較電池３
に比べて保存性能は改善されている。また、正極活物質
がリチウムニッケル複合酸化物を含むことによっても保
存性能は良好になる傾向が現れている。ところが、ホウ
素が添加されたリチウムマンガン酸化物と、リチウムニ
ッケル酸化物とを組み合わせることで、保存性能の改善
効果は両者の効果の単純加算によって予想される効果を
さらに上回る結果を与えている。この原因については、
必ずしも明らかではないが、リチウムニッケル酸化物が
リチウムマンガン酸化物からのＭｎ種の溶出を抑制する
効果を有し、また、リチウムマンガン酸化物表面に存在
するホウ素種がリチウムニッケル酸化物に何らかの好ま
しい影響を与えている可能性が示唆される。(Discussion 2: Storage Performance) As is clear from Table 2, the self-discharge capacity decreases and the recovery capacity increases as the content of lithium nickel oxide increases at any storage temperature. The comparative battery 1 and the battery 4 of the present invention in which the lithium manganese oxide contained boron contained the comparative battery 2 and the comparative battery 3 which did not contain boron.
The storage performance is improved as compared with. In addition, there is a tendency that the storage performance is improved even when the positive electrode active material contains the lithium nickel composite oxide. However, by combining the lithium manganese oxide to which boron is added and the lithium nickel oxide, the effect of improving the storage performance is more than the effect expected by simple addition of the two effects. For this reason,
Although not always clear, lithium nickel oxide has an effect of suppressing elution of Mn species from lithium manganese oxide, and boron species present on the surface of lithium manganese oxide has some favorable effects on lithium nickel oxide. It is suggested that it may be given.
【００７０】（考察３：安全性）表３から明らかなよう
に、正極活物質中に占めるリチウムニッケル酸化物の含
有率が２０ｗｔ％以下である本発明電池１〜４及び比較
電池では、釘刺し部分近傍の電池表面温度は１20℃未満
にとどまっている。この温度では、電解液と電極との間
の反応はほとんど起こっていないと考えられる。このと
き、釘刺し部分から若干の電解液の流出は認められたも
の、白煙の発生は観察されなかった。しかし、正極活物
質中に占めるリチウムニッケル酸化物の含有率が３０ｗ
ｔ％以上になると、釘刺し直後から電槽缶温度の加速的
な上昇が観察された。含有率３０ｗｔ％とした本発明電
池５では、セパレータが１５０〜２００℃付近で熱遮断
するため、安全弁からの白煙発生が見られたのみでかろ
うじて安全性を保つことができたが、含有率４０ｗｔ％
以上とした本発明電池６及び本発明電池７では、セパレ
ータでは反応を抑制できず、電池外表面は４００℃近く
にまで達し、同時に安全弁からの白煙及び発火が観察さ
れた。したがって、安全性の観点からはリチウムニッケ
ル酸化物の含有率を２０ｗｔ％以下とすることが好まし
い。(Discussion 3: Safety) As is apparent from Table 3, in the batteries 1 to 4 of the present invention in which the content of lithium nickel oxide in the positive electrode active material is 20 wt% or less and the comparative battery, nail penetration was performed. The battery surface temperature in the vicinity of the portion remains below 120 ° C. At this temperature, it is considered that the reaction between the electrolyte and the electrode hardly occurs. At this time, although a slight outflow of the electrolytic solution was observed from the nail penetration portion, generation of white smoke was not observed. However, the content of lithium nickel oxide in the positive electrode active material is 30 watts.
At t% or more, an accelerated rise in the battery case temperature was observed immediately after the nail was inserted. In the battery 5 of the present invention in which the content was 30 wt%, the separator shut off heat at around 150 to 200 ° C., so that the safety was barely maintained only by the generation of white smoke from the safety valve. 40wt%
In the battery 6 of the present invention and the battery 7 of the present invention described above, the reaction could not be suppressed by the separator, the outer surface of the battery reached nearly 400 ° C., and at the same time, white smoke and ignition from the safety valve were observed. Therefore, from the viewpoint of safety, the content of lithium nickel oxide is preferably set to 20 wt% or less.
【００７１】本実施例では、Ｍｎサイトへの置換元素と
してＬｉのみを用いた、即ち、式Ｌｉ1+x｛Ｍｎ(2-x-y)
Ｍy｝Ｏ4いにおいてｙ＝０とした、いわゆるＬｉリッチ
系について例示したが、置換元素として他の元素を選択
した場合でも同じ傾向が認められる。特に、置換元素Ｍ
としてＡｌ、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｇを選択した場合に
は、本実施例と全く同様な結果が得られることが確認さ
れた。In this embodiment, only Li was used as a substituting element for the Mn site, that is, the formula Li 1 + x ｛Mn (2-xy)
Although an example of a so-called Li-rich system in which y = 0 when M y 4O 4 is given, the same tendency is observed when another element is selected as a substitution element. In particular, the replacement element M
When Al, Fe, Co, Ni, and Mg were selected, it was confirmed that the same results as in the present example could be obtained.
【００７２】また、本実施例では、長型の積層式電極群
を発電要素とした角型電池を例示したが、本発明の効果
は電池形状に限定されるものではなく、例えば、捲回式
電極を発電要素とした場合や、電池形状を円筒型とした
場合でも、全く同様の結果が得られることが確認されて
いる。Further, in this embodiment, the prismatic battery in which the long stacked electrode group is used as the power generating element has been exemplified. However, the effect of the present invention is not limited to the battery shape. It has been confirmed that exactly the same results can be obtained when the electrode is a power generating element or when the battery is cylindrical.
【００７３】[0073]
【発明の効果】本発明によれば、リチウムマンガン酸化
物にリチウムニッケル酸化物を５〜２０ｗｔ％添加する
ことで放電容量が大きく、即ちエネルギー密度が高く、
充放電サイクルの繰り返しに伴う容量低下が小さく、高
温保存特性に優れ、さらに高い安全性を確保したマンガ
ン系リチウム二次電池を提供することができる。リチウ
ムマンガン酸化物がホウ素を含むことで、リチウムニッ
ケル酸化物による性能向上効果は相乗的に促進される。According to the present invention, the discharge capacity is increased by adding 5 to 20% by weight of lithium nickel oxide to lithium manganese oxide, that is, the energy density is increased.
It is possible to provide a manganese-based lithium secondary battery in which a decrease in capacity due to repetition of a charge / discharge cycle is small, excellent in high-temperature storage characteristics, and further secured. When the lithium manganese oxide contains boron, the performance improving effect of the lithium nickel oxide is synergistically promoted.
【図１】 本発明電池の断面図であるFIG. 1 is a cross-sectional view of a battery of the present invention.
１ 安全弁 ２ 蓋 ３ レーザー溶接部 ４ 負極端子 ５ 正極端子 ６ ガスケット ７ 正極 ８ セパレータ ９ 負極 １０ 電槽缶 DESCRIPTION OF SYMBOLS 1 Safety valve 2 Lid 3 Laser welding part 4 Negative terminal 5 Positive terminal 6 Gasket 7 Positive electrode 8 Separator 9 Negative electrode 10 Battery case
───────────────────────────────────────────────────── フロントページの続き (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 Ｆターム(参考） 4G048 AA04 AB02 AB05 AC06 AD03 5H029 AJ04 AJ05 AJ12 AK03 AK19 AL07 AM02 AM03 AM04 AM05 AM07 CJ08 DJ17 EJ03 HJ01 HJ02 5H050 AA07 AA09 AA15 BA17 CA08 CA09 CA29 DA09 EA01 FA19 GA10 HA01 HA02 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroshi Yufu, 2-3-1, Furube-cho, Takatsuki-shi, Osaka F-term in Yuasa Corporation (reference) 4G048 AA04 AB02 AB05 AC06 AD03 5H029 AJ04 AJ05 AJ12 AK03 AK19 AL07 AM02 AM03 AM04 AM05 AM07 CJ08 DJ17 EJ03 HJ01 HJ02 5H050 AA07 AA09 AA15 BA17 CA08 CA09 CA29 DA09 EA01 FA19 GA10 HA01 HA02
Claims (4)
を具備し、前記正極活物質はリチウムマンガン酸化物と
リチウムニッケル酸化物とを含むリチウム二次電池にお
いて、前記リチウムマンガン酸化物はホウ素を含むこと
を特徴とするリチウム二次電池。1. A lithium secondary battery comprising a negative electrode and a positive electrode mainly composed of a positive electrode active material, wherein the positive electrode active material includes lithium manganese oxide and lithium nickel oxide. A lithium secondary battery containing boron.
ニッケル酸化物の含有率は重量比で５〜２０％であるこ
とを特徴とする請求項１記載のリチウム二次電池。2. The lithium secondary battery according to claim 1, wherein the content of the lithium nickel oxide in the positive electrode active material is 5 to 20% by weight.
されるスピネル構造を有するマンガン酸リチウムを主成
分とすることを特徴とする請求項１又は２記載のリチウ
ム二次電池。 Ｌｉ1+x｛Ｍｎ(2-x-y)Ｍy｝Ｏ4 但し、 ０≦ｘ≦０．３ ０≦ｙ≦０．２ （Ｍは、Ｂｅ，Ｃ，Ｓｉ，Ｐ，Ｓｃ，Ｃｕ，Ｚｎ，Ｇ
ａ，Ｇｅ，Ａｓ，Ｓｅ，Ｓｒ，Ｍｏ，Ｐｄ，Ａｇ，Ｃ
ｄ，Ｉｎ，Ｓｎ，Ｓｂ，Ｔｅ，Ｂａ，Ｔａ，Ｗ．Ｐｂ，
Ｂｉ，Ｃｏ，Ｆｅ，Ｃｒ，Ｎｉ，Ｔｉ，Ｚｒ，Ｎｂ，
Ｙ，Ａｌ，Ｎａ，Ｋ，Ｍｇ，Ｃａ，Ｃｓ，Ｌａ，Ｃｅ，
Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂから構成される群から選択され
た少なくとも１つ以上の元素）3. The lithium secondary battery according to claim 1, wherein the lithium manganese oxide contains lithium manganate having a spinel structure represented by the following formula as a main component. Li 1 + x {Mn (2 -xy) M y} O 4 where, 0 ≦ x ≦ 0.3 0 ≦ y ≦ 0.2 (M is, Be, C, Si, P , Sc, Cu, Zn, G
a, Ge, As, Se, Sr, Mo, Pd, Ag, C
d, In, Sn, Sb, Te, Ba, Ta, W.S. Pb,
Bi, Co, Fe, Cr, Ni, Ti, Zr, Nb,
Y, Al, Na, K, Mg, Ca, Cs, La, Ce,
At least one element selected from the group consisting of Nd, Sm, Eu, and Tb)
されるニッケル酸リチウムを主成分とすることを特徴と
する請求項１〜３のいずれかに記載のリチウム二次電
池。 ＬｉＮｉ1-zＡzＯ2 但し、０≦z≦０．３ （Ａは、Ｂｅ，Ｃ，Ｓｉ，Ｐ，Ｓｃ，Ｃｕ，Ｚｎ，Ｇ
ａ，Ｇｅ，Ａｓ，Ｓｅ，Ｓｒ，Ｍｏ，Ｐｄ，Ａｇ，Ｃ
ｄ，Ｉｎ，Ｓｎ，Ｓｂ，Ｔｅ，Ｂａ，Ｔａ，Ｗ．Ｐｂ，
Ｂｉ，Ｃｏ，Ｆｅ，Ｃｒ，Ｎｉ，Ｔｉ，Ｚｒ，Ｎｂ，
Ｙ，Ａｌ，Ｎａ，Ｋ，Ｍｇ，Ｃａ，Ｃｓ，Ｌａ，Ｃｅ，
Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂから構成される群から選択され
た少なくとも１つ以上の元素）4. The lithium secondary battery according to claim 1, wherein the lithium nickel oxide contains lithium nickel oxide represented by the following formula as a main component. LiNi 1-z A z O 2 where 0 ≦ z ≦ 0.3 (A is Be, C, Si, P, Sc, Cu, Zn, G
a, Ge, As, Se, Sr, Mo, Pd, Ag, C
d, In, Sn, Sb, Te, Ba, Ta, W.S. Pb,
Bi, Co, Fe, Cr, Ni, Ti, Zr, Nb,
Y, Al, Na, K, Mg, Ca, Cs, La, Ce,
At least one element selected from the group consisting of Nd, Sm, Eu, and Tb)
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