WO1999033128A1 - Manganate de lithium, procede de production, et pile au lithium produite d'apres ce procede - Google Patents
Manganate de lithium, procede de production, et pile au lithium produite d'apres ce procede Download PDFInfo
- Publication number
- WO1999033128A1 WO1999033128A1 PCT/JP1998/005798 JP9805798W WO9933128A1 WO 1999033128 A1 WO1999033128 A1 WO 1999033128A1 JP 9805798 W JP9805798 W JP 9805798W WO 9933128 A1 WO9933128 A1 WO 9933128A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- manganese
- lithium manganate
- manganese oxide
- compound
- Prior art date
Links
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 62
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims description 28
- 239000002245 particle Substances 0.000 claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 187
- 239000002243 precursor Substances 0.000 claims description 50
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 42
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 42
- 239000012736 aqueous medium Substances 0.000 claims description 35
- 239000011572 manganese Substances 0.000 claims description 34
- 239000003513 alkali Substances 0.000 claims description 28
- 150000002642 lithium compounds Chemical class 0.000 claims description 27
- 150000002697 manganese compounds Chemical class 0.000 claims description 25
- 239000007774 positive electrode material Substances 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 125000005385 peroxodisulfate group Chemical group 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 239000002609 medium Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000007792 gaseous phase Substances 0.000 claims description 2
- 239000011149 active material Substances 0.000 abstract 3
- 239000011148 porous material Substances 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 60
- 230000015572 biosynthetic process Effects 0.000 description 40
- 238000003786 synthesis reaction Methods 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 21
- 238000010335 hydrothermal treatment Methods 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 239000012065 filter cake Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000010304 firing Methods 0.000 description 11
- -1 for example Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000007664 blowing Methods 0.000 description 8
- 239000011800 void material Substances 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 229910001882 dioxygen Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000011437 continuous method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002003 electron diffraction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011261 inert gas 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
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 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
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to lithium manganate, which is a compound useful as a positive electrode active material of a lithium battery, a method for producing the same, a positive electrode for a lithium battery using the same as a positive electrode active material, and a lithium battery.
- Lithium manganate is a compound represented by formula L i x M n y 0 4 , as a representative compound, a spinel L i M n 2 0 4, L i 4/3 M n 5/3 O There is ci.
- a method for obtaining such lithium manganate a method of firing a mixture of a manganese compound and a lithium compound at a temperature of about 800 ° C. has been used.
- Lithium manganate obtained by the above-mentioned prior art method is obtained by calcining a mixture of a manganese compound and a lithium compound at a temperature of about 80 ° C. or outside for the purpose of adjusting the valence of manganese and reducing by-products. Therefore, sintering between particles tends to be a non-homogeneous sintered body, and the size of the particles cannot be controlled. In addition, a mixture of a manganese compound and a lithium compound has poor reactivity even when fired at a high temperature, so that it is difficult for the mixture to have a uniform composition and has many lattice defects. To avoid these problems, firing and mechanical grinding must be repeated many times.
- a lithium secondary battery using lithium manganate obtained by the above method as a positive electrode active material has not only a low initial charge / discharge capacity but also a remarkable decrease in capacity as charging / discharging is repeated. This is because the crystals of lithium manganate collapse during charge and discharge, and are thought to be caused by the presence of lattice defects and low lithium ion conductivity.
- the present inventors have conducted various studies to obtain lithium manganate useful as a positive electrode active material of a lithium battery.
- lithium manganate having a cubic particle shape and having voids in the particles has a high initial charge-discharge capacity and high charge-discharge when used as a lithium secondary battery incorporating this as a positive electrode active material. It was found that the cycle characteristics were excellent due to the repetition, etc., and further studies were made to complete the present invention. That is, the present invention is a lithium manganate having a cubic particle shape and an initial discharge capacity of at least 95 mAh / g when used as a positive electrode active material of a lithium battery.
- the present invention is a method capable of advantageously producing the lithium manganate
- the first production method comprises the steps of reacting a manganese compound with an aluminum alloy to obtain a manganese hydroxide; Oxidizing the hydroxide in an aqueous medium or gas phase to obtain a manganese oxide; reacting the manganese oxide with a lithium compound in an aqueous medium to obtain a lithium manganate precursor; A step of heating and firing the precursor to obtain lithium manganate.
- the second production method comprises a step of reacting a manganese compound with an alkali to obtain a manganese hydroxide, and oxidizing the hydroxide in an aqueous medium or in a gas phase to convert the manganese oxide.
- the present invention provides a positive electrode for a lithium battery using the above-mentioned lithium manganate as a positive electrode active material, and a lithium battery using the same.
- Figure 1 is the X-ray diffraction chart of sample a.
- Figure 2 is the X-ray diffraction chart of Sample A.
- Figure 3 is a scanning electron micrograph (magnification: 50,000) showing the particle structure of Sample A.
- Figure 4 is a scanning electron micrograph (magnification: 50,000) showing the particle structure of Sample C.
- Figure 5 is a transmission electron micrograph (magnification: 150,000 times) showing the particle structure of Sample A. You.
- Figure 6 is an electron diffraction photograph of Sample A.
- Figure 7 is a scanning electron micrograph (magnification: 50,000) showing the particle structure of Sample L. BEST MODE FOR CARRYING OUT THE INVENTION
- the present invention has a cubic particle shape, has voids in the particles, and has an initial discharge capacity of at least 95 mAh / g, preferably at least 10 OmAh / g when used as a positive electrode active material of a lithium battery.
- This is lithium manganate.
- the lithium manganate may be a single phase, or a mixture containing lithium manganate and impurities from the production process, for example, manganese oxide as long as the discharge capacity is at least 95 mAh / g. . If the discharge capacity is lower than the above range, the amount of lithium manganate required to obtain a battery having a desired capacity increases, which is not industrially preferable.
- lithium manganate is represented by the general formula
- L i is the x Mn y 0 4 compounds represented by, X in the formula, the value of Y is 0.3 to 1 represents the value of X / Y. 5 is preferably in the range of.
- Preferred compositions for example, spinel L iMn 2 0 4, L i 4/3 Mn 5/3 0 4, etc.
- the cubic particle shape refers to a cube or a rectangular parallelepiped like a dice, and also includes a shape in which some of its corners, that is, some vertices and sides are missing.
- the shapes of the individual particles need not all be the same, and if the particles are mainly composed of cubic shapes, some irregularly shaped particles may be included.
- the presence of voids in the particles can be confirmed by measuring the amount of voids. If the amount of voids is 0.005 milliliter / g or more, it can be recognized that the particles have voids.
- the void volume is preferably in the range of 0.01 to 1.5 ml / g, and more preferably in the range of 0.01 to 0.7 ml / g.
- the fact that the initial discharge capacity is at least 95 mAh / g when used as a positive electrode active material of a lithium battery can be easily confirmed by measuring under the battery form and measurement conditions described later.
- the lithium secondary battery incorporating the lithium manganate of the present invention as the positive electrode active material has a high initial charge / discharge capacity and a high cycle characteristic. Will also be excellent.
- the specific surface area of the lithium manganate is preferably 1 ⁇ 1 0 O m 2 / g , more preferably 1 ⁇ 3 0 m 2 / g.
- the particle size is preferably in the range of 0.01 to 10 zm, and more preferably in the range of 0.05 to 5 m. The particle size can be measured by reading the maximum length of each particle from an electron micrograph.
- the present invention relates to a method for producing lithium manganate.
- the first production method comprises the following steps: 1) a step of reacting a manganese compound with an aluminum alloy to obtain a manganese hydroxide; A step of obtaining a manganese oxide by oxidation in a medium or a gaseous phase, 3 a step of reacting the manganese oxide and a lithium compound in water to obtain a lithium manganate precursor, 4 heating and firing the precursor And obtaining a lithium manganate by the method.
- the second production method is: (1) a step of reacting a manganese compound with an alkali to obtain a manganese hydroxide; (2) obtaining a manganese oxide by oxidizing the hydroxide in an aqueous medium or gas phase. Step, 2) reacting the manganese oxide with an acid in an aqueous medium to obtain a proton-substituted manganese oxide in which a part of manganese has been replaced with a proton, and 3 converting the proton-substituted manganese oxide and a lithium compound to an aqueous system.
- the step (2) is a step of obtaining a manganese hydroxide by reacting a manganese compound with an aluminum alloy.
- a water-soluble manganese compound is reacted with an alcohol in an aqueous medium, or a water-insoluble manganese compound is dissolved in an acid to obtain Mn 2+ , M
- the reaction can be carried out by reacting a manganese solution containing n 3 + and M n 4 + ions with an aqueous solution in an aqueous medium.
- a more preferred method is to react the water-soluble manganese compound with an aqueous solution in an aqueous medium.
- a water-soluble inorganic manganese compound such as manganese sulfate, manganese chloride and manganese nitrate, and a water-soluble organic manganese compound such as manganese acetate
- the poorly water-soluble manganese compound, M n 0 2 and its hydrated Things, M n 2 0 3 and hydrates thereof, M N_ ⁇ , and manganese oxides such as M n 3 ⁇ 4 may be an organic manganese compound, such as Ma emissions cancer alkoxide.
- the acid used include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and formic acid.
- alkali examples include alkali hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; ammonia compounds such as ammonia gas and ammonia water; and alkali carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, and ammonium carbonate. Force compounds can be used.
- the reaction can be carried out in the atmosphere or in an inert gas, but it is preferable to carry out the reaction in an inert gas atmosphere in order to control the oxidation level of manganese hydroxide.
- the reaction is preferably carried out at a temperature of 10 to 80 ° C. in order to control the particle shape.
- the manganese hydroxide thus obtained may be filtered or washed as necessary.
- the following step (2) is a step of oxidizing the manganese hydroxide obtained in the above step (2) in an aqueous medium or in a gas phase to obtain a manganese oxide.
- oxidize in an aqueous medium air, oxygen, ozone, etc. are blown into an aqueous medium containing manganese hydroxide, or hydrogen peroxide, peroxodisulfate, etc. are added.
- the peroxodisulfate for example, lithium peroxodisulfate can be used.
- the temperature of the oxidation treatment in the aqueous medium is preferably from 10 ° C. to the boiling point, more preferably from room temperature to 90 ° C.
- the oxidation in the gas phase can be carried out by filtering or washing the aqueous medium containing manganese hydroxide, if necessary, and then drying in air.
- the temperature of the oxidation treatment in the gas phase is preferably from room temperature to 300 ° C., more preferably from 50 to 130 ° C.
- the manganese hydroxide obtained in the step 1 is oxidized in an aqueous medium, or ii) first partially oxidized in an aqueous medium, and then oxidized in an aqueous medium. It is preferable to oxidize in the gas phase.
- the degree of oxidation of the manganese hydroxide can be set as appropriate, but if the degree of oxidation is small, the manganese oxide contains divalent, trivalent, tetravalent, etc. It is considered that oxides or hydroxides are present.
- State preferred manganese oxide in the present invention a 2 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ 0 2 as a main component, ⁇ 2 + / ⁇ ⁇ 4 + molar ratio is what is in the range of 1-3.
- Such a manganese oxide having a large specific surface area and a large amount of voids can be obtained by employing the preferable conditions for the oxidation treatment.
- step (1) while reacting the manganese compound with the alkali, for example, adding alkali to an aqueous solution of the manganese compound, adding air, oxygen, ozone, aqueous hydrogen peroxide, peroxodisulfate, or the like. It may be oxidized.
- Steps (2) and (3) are steps in which the manganese oxide obtained in step (2) is reacted with an acid in an aqueous medium to obtain a proton-substituted manganese oxide in which a part of manganese is replaced by protons.
- the proton-substituted manganese oxide is preferable because of its high reactivity with the lithium compound in the step (3) for obtaining the lithium manganate precursor.
- any inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid, and any water-soluble organic acid such as acetic acid and formic acid can be used.
- Inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid can be used. This is preferable because it can be carried out industrially advantageously.
- the temperature for the reaction with the acid is preferably in the range of room temperature to 90 ° C, more preferably in the range of 40 to 70 ° C.
- the manganese oxide thus obtained may be filtered, washed, or dried as necessary.
- step (3) the manganese oxide or the proton-substituted manganese oxide obtained in step (1) or (2) is reacted with a lithium compound in an aqueous medium to obtain a lithium manganate precursor.
- a lithium compound lithium hydroxide, lithium carbonate, and the like can be used, but lithium hydroxide is preferable because of its high reactivity.
- the reaction proceeds by mixing the lithium compound and manganese oxide in an aqueous medium and setting the temperature to 50 ° C or higher. A more preferred temperature is 100 ° C or higher, an even more preferred temperature is in the range of 100 to 250 ° C, and a most preferred temperature is in the range of 100 to 180 ° C. .
- the lithium compound and manganese oxide When performing the reaction at a temperature of 100 ° C or more, put the lithium compound and manganese oxide in an autoclave and add saturated water. Hydrothermal treatment is preferably performed under a vapor pressure or a pressurized condition.
- the lithium compound and manganese oxide are mixed in an aqueous medium, and the aqueous medium is heated, dried and solidified (evaporated to dryness) while evaporating the aqueous medium at a temperature of 50 ° C or higher. Accordingly, the concentration of the lithium compound in the aqueous medium becomes higher, and the lithium compound reacts with the manganese oxide to easily form a lithium manganate precursor, which is preferable.
- step (3) it is preferable to react while supplying the oxidizing agent batchwise or continuously, since the reactivity with the lithium compound is improved. What is a batch type?
- the continuous method is a method in which the reaction level of a manganese oxide and a lithium compound is measured, and an oxidizing agent is continuously supplied to the reaction system so that the reaction reaches a target reaction level.
- the continuous method is an economically preferable method for performing the reaction on an industrial scale.
- the oxidizing agent it is preferable to react with at least one selected from the group consisting of air, oxygen, ozone, aqueous hydrogen peroxide and peroxodisulfate as an oxidizing agent, because the reactivity between the lithium compound and manganese oxide is improved.
- the peroxodisulfate for example, potassium peroxodisulfate can be used.
- step 3 In order to supply the oxidizing agent batchwise by performing the above step 3 by hydrothermal treatment, air, oxygen, ozone is blown into the mixture of lithium compound and manganese oxide prior to hydrothermal treatment, or Hydrogen peroxide solution and peroxodisulfate are added, and oxygen can be further supplied.
- the temperature may be temporarily lowered during the hydrothermal treatment, and air, oxygen, or ozone may be blown into the air, or hydrogen peroxide or peroxodisulfate may be added to supply oxygen.
- oxygen gas is The hydrothermal treatment is performed while continuously supplying with.
- the amount of reaction between the manganese oxide and the lithium compound can be determined by taking a small amount of the reaction solution and measuring the alkali concentration of the liquid from which the solid has been separated by neutralization titration.
- Air, oxygen, or ozone may be blown into the solution containing the lithium manganate precursor obtained in the above step 3, or hydrogen peroxide or peroxodisulfate may be added for further oxidation. Further, if necessary, it may be filtered, washed, or dried.
- the drying temperature can be appropriately set as long as the temperature is below the temperature at which the lithium manganate precursor becomes lithium manganate, and a temperature of 50 to 200 ° C is appropriate.
- Step (2) is a step of heating and firing the lithium manganate precursor obtained in step (3) to obtain lithium manganate.
- the heating and firing temperature ranges from the temperature at which the precursor becomes lithium manganate to the temperature at which the specific surface area of the obtained lithium manganate becomes lm 2 / g or less. It is considered that the temperature of the heating and firing may vary depending on the composition, particle size, firing atmosphere, and the like of the precursor, but is generally in the range of 250 to 800 ° C, and is fine and has good crystallinity. In order to obtain lithium manganate, the range is preferably from 280 to 700 ° C, more preferably from 300 to 600 ° C. In order to obtain lithium manganate having a large particle diameter, the range is preferably from 65 to 80 ° C. If the heating and firing temperature is higher than the above range, the lithium in the produced lithium manganate evaporates and becomes brittle.
- the firing atmosphere is not particularly limited as long as it is an oxygen-containing atmosphere such as in the air, and the oxygen partial pressure
- the present invention is a positive electrode for a lithium battery using the above-mentioned lithium manganate as a positive electrode active material, and further a lithium battery using the positive electrode.
- a lithium battery in the present invention is a primary battery using lithium metal for the negative electrode, a rechargeable secondary battery using lithium metal for the negative electrode, a carbon material, a tin compound, lithium titanate, etc. for the negative electrode.
- the lithium manganate powder of the present invention may be added to a carbon-based conductive agent such as acetylene black, carbon, or graphite powder, or a polytetrafluoroethylene resin. It can be obtained by adding a binder such as polyvinylidene fluoride, kneading, and pelletizing. Further, when used for a cylindrical or rectangular battery, the lithium manganate powder of the present invention may contain other than these additives. An organic solvent such as N-methylpyrrolidone is also added to the mixture, kneaded to form a paste, applied on a metal current collector such as aluminum foil, and dried.
- lithium ions are dissolved in a polar organic solvent that is electrochemically stable, that is, is not oxidized or reduced in a wider range than the potential range that operates as a lithium ion battery.
- a polar organic solvent propylene carbonate, ethylene carbonate, getyl carbonate, dimethoxetane, tetrahydrofuran, acetyl lactone and the like or a mixture thereof can be used.
- As a solute serving as a lithium ion source lithium perchlorate / lithium hexafluorophosphate, lithium tetrafluoroborate, or the like can be used.
- Raw polypropylene film or polyethylene film will be arranged as a temporary separation.
- Battery types include a separator between the positive and negative electrodes in the form of pellets, pressure bonding to a sealed can with a gasket made of polypropylene, injection of electrolyte, and a sealed coin-type battery, or a positive electrode material. And a negative electrode material coated on a metal current collector, wound around a separator, inserted into a battery can with a gasket, injected with an electrolyte, and sealed, and the like.
- the performance of lithium manganate as a positive electrode material can be evaluated by constructing a lithium battery by the above-described method and charging and discharging the battery with an appropriate potential and current to measure its electric capacity. In addition, it is possible to judge whether the cycle characteristics are good or not from the change in the electric capacity due to repeated charging and discharging.
- the temperature of the slurry containing the obtained manganese hydroxide was raised to 60 ° C, and air was blown for 1 hour to oxidize in the aqueous medium, and then switched to nitrogen gas and aged for 1 hour. Filtered and washed. The filter cake was dried at 110 C for 12 hours and subjected to gas phase oxidation to obtain manganese oxide.
- the manganese oxide was mainly composed specific surface area, the void content is greater 2 Myuitaomikuron ⁇ Mn_ ⁇ 2.
- the obtained manganese oxide (240 g in terms of Mn) was dispersed in water to form a slurry. To this slurry was added 0.920 liters of lithium hydroxide at a concentration of 3.206 mol / liter and pure water to make a liquid volume of 2.40 liters, and the mixture was charged into a 3 liter glass reaction vessel and heated at 80 ° C. The reaction was allowed to proceed for 3 hours while blowing air. After replenishing the amount of evaporated water, a portion was taken and the alkali concentration in the solution was measured. As a result, it was found that 18.8% by weight of the added lithium had reacted with manganese oxide.
- This slurry was charged into an autoclave and subjected to hydrothermal treatment at a temperature of 130 ° C for 2 hours. After cooling the temperature to 80 ° C, the alkali concentration in the solution was measured in the same manner, and it was found that 57.1% by weight of the added lithium had reacted with the manganese oxide. After air was blown into the slurry for 2 hours, hydrothermal treatment was again performed at 130 ° C. for 2 hours to obtain a slurry of a lithium manganate precursor (sample a) by a batch method.
- the alkali concentration in the solution was measured by the same method, and it was found that 74.1% by weight of the added lithium had reacted with the manganese oxide.
- the molar ratio on L of sample a to Mn was 0.50.
- manganese Sanli lithium precursor sample a is a mixture containing 2 ⁇ ⁇ Mn0 2 and L i 2 0 ⁇ ⁇ ⁇ Mn0 2 solid solution, and L iMn 2 0 4 and L iMn0 2 mainly Being I understood.
- a manganese hydroxide was obtained in the same manner as in Example 1.
- the obtained manganese oxide (240 g in terms of Mn) was dispersed in water to form a slurry. To this slurry was added 0.870 liters of lithium hydroxide at a concentration of 3.206 mol / liter and pure water to make a liquid volume of 2.40 liters. The mixture was charged into a 3 liter glass reaction vessel and heated to 80 ° C. The temperature was raised and the reaction was carried out for 3 hours while blowing air. When the amount of evaporated water was replenished and a portion was taken and the alkali concentration in the solution was measured, it was found that 16.4% by weight of the added lithium had reacted with manganese oxide.
- This slurry was charged into an autoclave and subjected to hydrothermal treatment at a temperature of 150 ° C for 2 hours. After cooling the temperature to 80 ° C, the alkali concentration in the solution was measured by the same method, and it was found that 61.1% by weight of the added lithium reacted with manganese oxide. . Air was blown into the slurry for 2 hours, and then subjected to hydrothermal treatment again at 150 ° C. for 2 hours to obtain a slurry of a lithium manganate precursor (sample b) by a batch method.
- lithium manganate of the present invention (sample B) was obtained.
- a manganese hydroxide was obtained in the same manner as in Example 1.
- the obtained manganese oxide (186.5 g in terms of 1 ⁇ 11) was dispersed in water to form a slurry.
- a slurry To this slurry, 0.746 liters of lithium hydroxide having a concentration of 3,000 mol / liter and pure water were added, and the liquid volume was adjusted to 2.40 liters. The reaction was allowed to proceed for 3 hours while blowing air. After replenishing the amount of evaporated water, a portion was taken and the concentration of aluminum in the liquid was measured. As a result, it was found that 13.8% by weight of the added lithium had reacted with manganese oxide. .
- This slurry was charged into a autoclave and subjected to a hydrothermal treatment at 180 ° C. for 2 hours.
- the alkali concentration in the solution was measured in the same manner, and it was found that 55.5% by weight of the added lithium was reacting with manganese oxide.
- the slurry was again subjected to hydrothermal treatment at 180 ° C. for 2 hours to obtain a slurry of a lithium manganate precursor (sample c) by a batch method.
- the alkali concentration in the solution was measured in the same manner, and it was found that 79.1% by weight of the added lithium had reacted with manganese oxide.
- the molar ratio of Li to Mn in sample c was 0.52.
- a manganese hydroxide was obtained in the same manner as in Example 1. 'Synthesis of oxide)
- the temperature of the slurry containing the obtained manganese hydroxide was raised to 60 ° C, and air was blown for 1 hour to oxidize in the aqueous medium, and then switched to nitrogen gas and aged for 1 hour. Filtered and washed. The filter cake was dried at 200 ° C for 12 hours and subjected to gas phase oxidation to obtain manganese oxide.
- the manganese oxide was mainly composed specific surface area, the void content is greater 2 Myuitaomikuron ⁇ Mn_ ⁇ 2.
- the obtained manganese oxide (186.5 g in terms of Mn) was dispersed in water to form a slurry.
- To this slurry add 0.004 liters of lithium hydroxide and a pure water with a concentration of 3,000 mol / l and pure water to make a liquid volume of 2.40 liters, and charge the autoclave for 2 hours at 180 ° C.
- Hydrothermal treatment was performed. After cooling the temperature to 80 ° C, a portion was sampled and the alkali concentration in the solution was measured. As a result, it was found that 31.9% by weight of the added lithium had reacted with manganese oxide. did. After air was blown into the slurry for 2 hours, hydrothermal treatment was again performed at 180 ° C for 2 hours.
- the alkali concentration in the solution was measured in the same manner, and it was found that 56.6% by weight of the added lithium had reacted with the manganese oxide.
- hydrothermal treatment was again performed at 180 ° C for 2 hours, and a slurry of a lithium manganate precursor (sample d) was obtained by a batch method.
- the alkali concentration in the solution was measured in the same manner, and it was found that 75.8% by weight of the added lithium had reacted with the manganese oxide.
- the molar ratio of Li to Mn in sample d was 0.50.
- Manganese chloride tetrahydrate (MnC l 2 '99 wt% containing as 4H 2 0) 1 146 g was dissolved in water to 7.153 liters. This manganese chloride aqueous solution is charged into a 10-liter glass reaction vessel, and while stirring, the temperature is maintained at 15 ⁇ 5 ° C, under a nitrogen atmosphere, 6.209 mol / L sodium hydroxide 1 solution is added. 847 liters were dispersed and added over 1 hour to obtain a manganese hydroxide.
- the temperature of the obtained slurry containing manganese hydroxide was raised to 60 ° C, and air was blown in for 7 hours to oxidize in an aqueous medium, followed by filtration, washing and repulping to obtain a manganese oxide slurry.
- This manganese oxide was mainly composed of 2MnO • MnO 2 having a large specific surface area and a large void volume.
- a manganese hydroxide was obtained in the same manner as in Example 1.
- Sample h was pulverized finely using a small pulverizer, and then calcined in the air at 750 ° C. for 3 hours to obtain lithium manganate of the present invention (sample H).
- a manganese hydroxide was obtained in the same manner as in Example 1.
- a manganese oxidized product was obtained in the same manner as in Example 1.
- the obtained manganese oxide (324 g in terms of Mn) was dispersed in water to form a slurry.
- a lithium hydroxide solution having a concentration of 3.655 mol / liter and pure water to make a liquid volume of 2.40 l, which was charged into a 3 l glass reaction vessel.
- the temperature was raised to 90 ° C while blowing at liter / minute, and the reaction was carried out for 13 hours to obtain a lithium manganate precursor (sample i).
- a portion was taken and the alkali concentration in the solution was measured. As a result, it was found that 89.4% by weight of the added lithium had reacted with manganese oxide.
- the molar ratio of Li to Mn in Sample i was 0.54.
- Example 8 The obtained precursor slurry was filtered. No washing was performed. The filter cake was dried at 110 ° C, and calcined at 750 ° C in the air for 3 hours to obtain lithium manganate of the present invention (sample I).
- Example 8
- a manganese hydroxide was obtained in the same manner as in Example 1.
- the temperature of the slurry containing the obtained manganese hydroxide was raised to 60 ° C.
- the pH of this slurry was 8.3.
- Oxygen gas was blown into the slurry at a rate of 2 liters / minute to oxidize in the liquid until the pH reached 6.
- Bow I While adding oxygen gas continuously, adjust the pH to 9 by adding a 2 mol / liter sodium hydroxide solution, raise the temperature to 90 ° C, and ripen for 2 hours while maintaining the pH at 9. Filtered and washed.
- the filter cake thus obtained was dispersed in pure water to obtain a slurry having a concentration of 100 g / liter in terms of Mn.
- the pH of this slurry showed 10.7.
- the manganese oxide was composed mainly of specific surface area, 2 ⁇ ⁇ Mn0 2 void volume is large.
- the obtained manganese oxide (312 g in terms of Mn) was dispersed in water to form a slurry.
- a lithium hydroxide solution at a concentration of 3.655 mol / liter and pure water to make a liquid volume of 2.40 liters, charge a 3 liter glass reactor, and add oxygen gas to the reactor.
- the temperature was raised to 90 ° C while blowing at liter / minute, and the reaction was carried out for 6 hours to obtain a lithium manganate precursor (sample j). After replenishing the amount of evaporated water, a portion was taken and the alkali concentration in the solution was measured. As a result, it was found that 89.8% by weight of the added lithium had reacted with the manganese oxide.
- the molar ratio of Li to Mn in sample j was 0.51.
- Example J The obtained precursor slurry was filtered. No washing was performed. The filter cake was dried at 110 ° C, and calcined at 750 ° C for 3 hours in the atmosphere to obtain lithium manganate of the present invention (sample J).
- the 815 g (86 wt% containing as MnS_ ⁇ 4) manganese sulfate was dissolved in water 6.179 liters. This manganese sulfate aqueous solution was charged into a 10-liter glass reaction vessel, and the temperature was increased to 60 ° C under stirring and under a nitrogen atmosphere. While maintaining the temperature at 60 ° C., 2.321 liters of sodium hydroxide having a concentration of 4 mol / liter was dispersed and added thereto over 1 hour to obtain a manganese hydroxide.
- the pH of the slurry containing the obtained manganese hydroxide was 8.3.
- the slurry was oxidized in liquid until the pH reached 6 while oxygen gas was blown into the slurry at 2 liters / minute, and the slurry was washed with filtered water.
- This filter cake was dispersed in pure water to form a slurry of 100 g / liter in terms of Mn, charged into a 5-liter glass reaction vessel, and heated to 60 ° C.
- the obtained manganese oxide (312 g in terms of Mn) was dispersed in water to form a slurry.
- 0.841 l of a lithium hydroxide solution having a concentration of 3.655 mol / l and pure water was added to the slurry.
- the temperature was raised to 90 ° C while blowing at a rate of 1 liter / minute, and the reaction was carried out for 1 hour. After replenishing the amount of evaporated water, a portion was taken and the alkali concentration in the solution was measured. As a result, it was found that 55.6% by weight of the added lithium had reacted with manganese oxide.
- This slurry was charged into an autoclave and subjected to hydrothermal treatment at a temperature of 130 ° C for 3 hours. After cooling to a temperature of 90 ° C, the concentration of aluminum in the solution was measured in the same manner, and it was found that 76.9% by weight of the added lithium had reacted with the manganese oxide. did.
- the slurry was reacted at 90 ° C. for 2 hours while blowing oxygen gas at 1 liter / minute to obtain a slurry of a lithium manganate precursor (sample k). Alkali concentration in liquid in the same way As a result, it was found that 93.7% by weight of the added lithium had reacted with the manganese oxide.
- the molar ratio of Li to Mn in sample k was 0.51.
- Manganese dioxide reagent were mixed (Kanto Chemical, Mn0 2 as 95 wt% content) 50 g lithium hydroxide monohydrate in L i / Mn molar ratio 0.505 to become as well a small type pulverizer After mixing and grinding, the mixture was placed in an alumina crucible and calcined in air at 750 ° C for 3 hours to obtain a comparative sample, lithium manganate (Sample L).
- a manganese hydroxide was obtained in the same manner as in Example 1.
- Lithium hydroxide monohydrate was mixed with the obtained manganese oxide (50 g in terms of Mn) so as to have a Li / Mn molar ratio of 0.505, and then pulverized and mixed well with a small pulverizer.
- the physical properties of the samples A to M thus obtained were examined and are shown in Table 1.
- the particle shape of the lithium manganate of the present invention was confirmed to be cubic by observation with an electron microscope (for example, scanning electron microscope photographs of Samples A and C are shown in FIGS. 3 and 4). Some samples contained amorphous particles, but the amount of amorphous particles was very small.
- the sample M of the comparative example had a very high proportion of the same irregular shaped particles as the sample of the comparative example L, although the sample M partially contained a cubic shape.
- a spot-shaped diffraction image was obtained by electron diffraction (for example, an electron diffraction photograph of Sample A is shown in Fig.
- the specific surface area was measured by the BET method, and the void volume was measured by nitrogen adsorption. Bell Soap 28 manufactured by Bell Japan was used to measure the void volume. Table 1 shows the measurement results. From Table 1, it was found that all of Samples A to K had preferable specific surface areas, and that all had voids in the particles.
- metallic lithium having a thickness of 0.5 mm was formed into a circular shape having a diameter of 14 mm, sandwiched between metallic nickel meshes, and pressed to obtain a negative electrode.
- a 0.1-mm-thick lithium metal foil was wrapped around a nickel metal wire to the extent that rice grains were large, and this was used as a reference electrode.
- a non-aqueous electrolyte a mixed solution of 1,2-dimethoxyethane and propylene carbonate (1: 1 by volume) in which lithium perchlorate was dissolved at a concentration of 1 mol / liter was used.
- the electrodes were arranged in the order of a positive electrode, a reference electrode, and a negative electrode, and a porous polypropylene film was placed between them as a separator.
- the charge / discharge cycle was measured at a constant current with the voltage range set from 4.3 V to 3.5 V and the charge / discharge current set at 0.26 mA (about 1 cycle / day).
- Table 1 shows the initial discharge capacity, the discharge capacity at the 10th cycle, and the capacity retention ratio at that time.
- the capacity is Table 1
- the lithium manganate according to the present invention exhibited a high initial discharge capacity of at least 95 mAh / g and also had excellent cycle characteristics.
- Lithium manganate synthesized by the conventional dry method tends to have defects in the crystal structure, which causes repeated charge and discharge to deteriorate the crystallinity and decrease the cycle capacity.
- Lithium manganate has already been used as a positive electrode active material for lithium ion secondary batteries.
- the diffusion coefficient of lithium ions is smaller than that of lithium cobaltate, which has a layered rock salt structure and is practically used.
- the lithium manganate of the present invention has a cubic particle shape, has voids in the particles, and is excellent in crystallinity. In other words, conditions favorable for lithium insertion are provided, which is preferable for improving current density.
- the lithium manganate of the present invention has a cubic particle shape and has voids in the particles, a lithium battery using this as a positive electrode material exhibits a high initial discharge capacity, It has excellent characteristics. Further, the production method of the present invention is a method capable of advantageously producing lithium manganate having the above characteristics.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU16850/99A AU741721B2 (en) | 1997-12-22 | 1998-12-22 | Lithium manganate, method of producing the same, and lithium cell produced by the method |
BR9814384-0A BR9814384A (pt) | 1997-12-22 | 1998-12-22 | Manganato de lìtio, processo para a produção do mesmo, eletrodo positivo para baterias de lìtio, e, bateria de lìtio |
EP98961467A EP0969537B1 (en) | 1997-12-22 | 1998-12-22 | Lithium manganate, method of producing the same, and lithium cell produced by the method |
US09/367,285 US6334993B1 (en) | 1997-12-22 | 1998-12-22 | Lithium manganate, method of producing the same, and lithium cell produced by the method |
CA002314950A CA2314950C (en) | 1997-12-22 | 1998-12-22 | Lithium manganate, process for producing the same, and lithium battery using the same |
JP53237799A JP3489685B2 (ja) | 1997-12-22 | 1998-12-22 | マンガン酸リチウム及びその製造方法ならびにそれを用いてなるリチウム電池 |
KR10-2000-7006550A KR100506575B1 (ko) | 1997-12-22 | 1998-12-22 | 리튬 망가네이트, 그것의 제조 방법, 및 그 방법에 의해제조된 리튬 전지 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9/365563 | 1997-12-22 | ||
JP9365563A JPH11180717A (ja) | 1997-12-22 | 1997-12-22 | マンガン酸リチウム及びその製造方法ならびにそれを用いてなるリチウム電池 |
Publications (1)
Publication Number | Publication Date |
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WO1999033128A1 true WO1999033128A1 (fr) | 1999-07-01 |
Family
ID=18484576
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1998/005798 WO1999033128A1 (fr) | 1997-12-22 | 1998-12-22 | Manganate de lithium, procede de production, et pile au lithium produite d'apres ce procede |
Country Status (10)
Country | Link |
---|---|
US (1) | US6334993B1 (ja) |
EP (1) | EP0969537B1 (ja) |
JP (2) | JPH11180717A (ja) |
KR (1) | KR100506575B1 (ja) |
CN (1) | CN1148821C (ja) |
AU (1) | AU741721B2 (ja) |
BR (1) | BR9814384A (ja) |
CA (1) | CA2314950C (ja) |
TW (1) | TW565531B (ja) |
WO (1) | WO1999033128A1 (ja) |
Cited By (2)
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CN111333115A (zh) * | 2020-03-10 | 2020-06-26 | 中国石油大学(北京) | 一种二维多孔活性氧化锰及其制备方法和含有其的固化剂 |
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- 1998-12-22 CA CA002314950A patent/CA2314950C/en not_active Expired - Fee Related
- 1998-12-22 EP EP98961467A patent/EP0969537B1/en not_active Expired - Lifetime
- 1998-12-22 WO PCT/JP1998/005798 patent/WO1999033128A1/ja active IP Right Grant
- 1998-12-22 CN CNB988125560A patent/CN1148821C/zh not_active Expired - Fee Related
- 1998-12-22 US US09/367,285 patent/US6334993B1/en not_active Expired - Lifetime
- 1998-12-22 JP JP53237799A patent/JP3489685B2/ja not_active Expired - Fee Related
- 1998-12-22 KR KR10-2000-7006550A patent/KR100506575B1/ko not_active IP Right Cessation
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016071968A (ja) * | 2014-09-26 | 2016-05-09 | 旭化成株式会社 | リチウム含有金属酸化物 |
CN111333115A (zh) * | 2020-03-10 | 2020-06-26 | 中国石油大学(北京) | 一种二维多孔活性氧化锰及其制备方法和含有其的固化剂 |
Also Published As
Publication number | Publication date |
---|---|
CA2314950C (en) | 2009-07-14 |
BR9814384A (pt) | 2001-10-16 |
CN1283313A (zh) | 2001-02-07 |
US6334993B1 (en) | 2002-01-01 |
TW565531B (en) | 2003-12-11 |
JP3489685B2 (ja) | 2004-01-26 |
AU1685099A (en) | 1999-07-12 |
KR100506575B1 (ko) | 2005-08-08 |
EP0969537B1 (en) | 2012-02-15 |
JPH11180717A (ja) | 1999-07-06 |
EP0969537A4 (en) | 2006-06-14 |
KR20010033168A (ko) | 2001-04-25 |
EP0969537A1 (en) | 2000-01-05 |
CA2314950A1 (en) | 1999-07-01 |
AU741721B2 (en) | 2001-12-06 |
CN1148821C (zh) | 2004-05-05 |
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