JP2012129166A - リチウムイオン二次電池 - Google Patents
リチウムイオン二次電池 Download PDFInfo
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- JP2012129166A JP2012129166A JP2010282265A JP2010282265A JP2012129166A JP 2012129166 A JP2012129166 A JP 2012129166A JP 2010282265 A JP2010282265 A JP 2010282265A JP 2010282265 A JP2010282265 A JP 2010282265A JP 2012129166 A JP2012129166 A JP 2012129166A
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- oxide
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- 239000006104 solid solution Substances 0.000 claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910015645 LiMn Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 17
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 17
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 10
- 159000000002 lithium salts Chemical class 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 5
- 150000004715 keto acids Chemical class 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 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
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- UGNSMKDDFAUGFT-UHFFFAOYSA-N 4,4-dimethyl-2-phenyl-5h-1,3-oxazole Chemical compound CC1(C)COC(C=2C=CC=CC=2)=N1 UGNSMKDDFAUGFT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 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
- 239000006230 acetylene black Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000457 gamma-lactone group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
【解決手段】xLi2MnO3−(1−x)LiMnaCobNicO2(式中、0.2≦x≦0.5、0.3≦a≦0.5、0.1≦b≦0.3、0.3≦c≦0.5、a+b+c=1である。)で表される固溶体の表面の少なくとも一部が、Me(但し、Meは、Mn、Co及びNi以外の遷移金属を表す。)の酸化物又は酸化物リチウム塩により被覆されてなる正極活物質を含有する正極を備えるようにした。
【選択図】なし
Description
酢酸マンガン(II)4水和物、酢酸コバルト(II)6水和物、酢酸ニッケル(II)4水和物を下記表1に示すモル比で混合し、全遷移金属と0.8モル当量のクエン酸を1Lの水に入れ、全遷移金属換算で0.2mol/Lの均一な溶液とした。次に、アンモニア水溶液(29%)を加えてpH6に調整した後、1時間撹拌し沈殿物を生成させ、濾別、水洗し120℃で5時間の真空乾燥を行った。更に、得られた粉末に炭酸リチウムを添加しボールミルで6時間混合した。これを磁性るつぼに移して、電気炉にて大気雰囲気中900℃で3時間の焼成を行い、固溶体を得た。
・実施例11(酸化物の被覆)
固溶体50gに、酸化物(MoO3)を下記表2に記載の被覆量(mol%)添加して、ボールミルで3時間混合し、600℃で3時間の焼成を行い、酸化物で被覆した正極活物質を得た。
固溶体50gを水300mLに懸濁させて、そこへ酸化物リチウム塩(Li2MoO4、Li2CrO4又はLi2WO4)を下記表2に記載の被覆量(mol%)添加した。そして、ロータリーエバポレーターでこの懸濁液の水分を蒸発させた後、120℃で3時間の真空乾燥を行い、酸化物リチウム塩で被覆した正極活物質を得た。
酢酸マンガン(II)4水和物、酢酸コバルト(II)6水和物、酢酸ニッケル(II)4水和物を表1の比較例3に示すモル比で混合し、全遷移金属と0.8モル当量のクエン酸を1Lの水に入れ、全遷移金属換算で0.2mol/Lの均一な溶液とした。次に、アンモニア水溶液(29%)を加えてpH6に調整した。1時間撹拌し沈殿物を生成させ、濾別、水洗して固溶体正極の前駆体を得た。この前駆体を水に分散させ、そこにモリブデン酸リチウム(VI)を得られた前駆体に対して2mol%溶解させた後ロータリーエバポレーターで脱水し、120℃で5時間の真空乾燥を行った。更に、得られた粉末に炭酸リチウムを添加しボールミルで6時間混合した。これを磁性るつぼに移して、電気炉にて大気雰囲気中900℃で3時間の焼成を行い、比較例3の正極活物質を得た。
結着剤であるポリフッ化ビニリデン3重量部をN−メチル−2−ピロリドンに溶解し、得られた溶液に、下記表2に記載の正極活物質94質量部と、カーボンブラック3質量部とを加えてスラリー化した。得られた正極スラリーを厚み20μmのAl箔上に均一に塗布し、乾燥して正極とした。
作製したラミネート型リチウムイオン二次電池を、25℃で湿度50%の条件下において、定電流0.1Cで4.6Vまで充電した後、発生した酸素ガス量を測定した。酸素ガス量を測定するにあたっては、図1に示すようにサンプル電池を流動パラフィン中に沈め、充放電を行う前後の液面の差から発生した酸素ガス量(体積)を測定した。得られた結果は表2に示した。ラミネート電池を一旦開封し、再度真空シールしてラミネート中のガス抜きを行ったのち放電終始電圧2.0Vまで0.1C放電を実施して、1サイクル目の放電容量(初期放電容量)を測定した。
Claims (2)
- xLi2MnO3−(1−x)LiMnaCobNicO2(式中、0.2≦x≦0.5、0.3≦a≦0.5、0.1≦b≦0.3、0.3≦c≦0.5、a+b+c=1である。)で表される固溶体の表面の少なくとも一部が、Me(但し、Meは、Mn、Co及びNi以外の遷移金属を表す。)の酸化物又は酸化物リチウム塩により被覆されてなる正極活物質を含有する正極を備えていることを特徴とするリチウムイオン二次電池。
- 前記Meが、Cr、Mo及びWからなる群より選ばれる少なくとも1種の遷移金属であり、
前記Meの酸化物又は酸化物リチウム塩の被覆量が、前記固溶体に対しモル比で0.3〜6mol%である請求項1記載のリチウムイオン二次電池。
Priority Applications (2)
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JP2012156046A (ja) * | 2011-01-27 | 2012-08-16 | Asahi Glass Co Ltd | リチウムイオン二次電池用の正極活物質およびその製造方法 |
JP2014002933A (ja) * | 2012-06-19 | 2014-01-09 | Toyota Motor Corp | リチウムマンガン含有酸化物とその製造方法、リチウムイオン二次電池の正極活物質、およびリチウムイオン二次電池 |
JP2014078500A (ja) * | 2012-09-21 | 2014-05-01 | Nichia Chem Ind Ltd | 非水電解液二次電池用正極活物質及びそれを用いた非水電解液二次電池 |
WO2015004705A1 (ja) * | 2013-07-08 | 2015-01-15 | 株式会社 日立製作所 | リチウムイオン二次電池用正極活物質 |
WO2015006957A1 (en) * | 2013-07-18 | 2015-01-22 | Robert Bosch Gmbh | AN OXIDE COATED xLi2MnO3·(1-x)LiNiyCozMn1-y-zO2 CORE-SHELL STRUCTURED CATHODE MATERIALS |
CN106104861A (zh) * | 2014-03-21 | 2016-11-09 | 罗伯特·博世有限公司 | 用于锂电池的电极 |
JP2017033641A (ja) * | 2015-07-29 | 2017-02-09 | トヨタ自動車株式会社 | 非水電解質二次電池用正極活物質 |
JPWO2015025844A1 (ja) * | 2013-08-23 | 2017-03-02 | 日本電気株式会社 | リチウム鉄マンガン系複合酸化物およびそれを用いたリチウムイオン二次電池 |
JP2020511741A (ja) * | 2017-09-29 | 2020-04-16 | エルジー・ケム・リミテッド | リチウム過剰のリチウムマンガン系酸化物およびリチウム過剰のリチウムマンガン系酸化物上にリチウムタングステン化合物、または追加的にタングステン化合物をさらに含む正極活物質およびこれを含むリチウム二次電池用正極 |
JP2021022527A (ja) * | 2019-07-30 | 2021-02-18 | 株式会社Soken | リチウム二次電池 |
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JP2012156046A (ja) * | 2011-01-27 | 2012-08-16 | Asahi Glass Co Ltd | リチウムイオン二次電池用の正極活物質およびその製造方法 |
JP2014002933A (ja) * | 2012-06-19 | 2014-01-09 | Toyota Motor Corp | リチウムマンガン含有酸化物とその製造方法、リチウムイオン二次電池の正極活物質、およびリチウムイオン二次電池 |
JP2014078500A (ja) * | 2012-09-21 | 2014-05-01 | Nichia Chem Ind Ltd | 非水電解液二次電池用正極活物質及びそれを用いた非水電解液二次電池 |
WO2015004705A1 (ja) * | 2013-07-08 | 2015-01-15 | 株式会社 日立製作所 | リチウムイオン二次電池用正極活物質 |
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CN105556715A (zh) * | 2013-07-18 | 2016-05-04 | 罗伯特·博世有限公司 | 氧化物涂覆的xLi2MnO3·(1-x)LiNiyCozMn1-y-zO2核-壳结构的阴极材料 |
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JP2017509126A (ja) * | 2014-03-21 | 2017-03-30 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングRobert Bosch Gmbh | リチウムセル用の電極 |
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JP2020511741A (ja) * | 2017-09-29 | 2020-04-16 | エルジー・ケム・リミテッド | リチウム過剰のリチウムマンガン系酸化物およびリチウム過剰のリチウムマンガン系酸化物上にリチウムタングステン化合物、または追加的にタングステン化合物をさらに含む正極活物質およびこれを含むリチウム二次電池用正極 |
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US11289695B2 (en) | 2017-09-29 | 2022-03-29 | Lg Energy Solution, Ltd. | Positive electrode active material comprising lithium-rich lithium manganese-based oxide and further comprising lithium tungsten compound, or additionally tungsten compound on the lithium-rich lithium manganese-based oxide, and positive electrode for lithium secondary battery comprising the same |
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