JP2013032283A - 無機化合物 - Google Patents
無機化合物 Download PDFInfo
- Publication number
- JP2013032283A JP2013032283A JP2012242348A JP2012242348A JP2013032283A JP 2013032283 A JP2013032283 A JP 2013032283A JP 2012242348 A JP2012242348 A JP 2012242348A JP 2012242348 A JP2012242348 A JP 2012242348A JP 2013032283 A JP2013032283 A JP 2013032283A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- cooling
- present
- metal oxide
- lithium metal
- 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
- 150000002484 inorganic compounds Chemical class 0.000 title 1
- 229910010272 inorganic material Inorganic materials 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 103
- 238000001816 cooling Methods 0.000 claims abstract description 45
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000011572 manganese Substances 0.000 description 56
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 38
- 239000000047 product Substances 0.000 description 37
- 239000002245 particle Substances 0.000 description 31
- 229910052744 lithium Inorganic materials 0.000 description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 24
- 239000002994 raw material Substances 0.000 description 18
- 229910052759 nickel Inorganic materials 0.000 description 16
- 229910017052 cobalt Inorganic materials 0.000 description 15
- 239000010941 cobalt Substances 0.000 description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 15
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 13
- 238000000634 powder X-ray diffraction Methods 0.000 description 13
- 238000010304 firing Methods 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 9
- 239000011164 primary particle Substances 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 229910015118 LiMO Inorganic materials 0.000 description 7
- 229910013716 LiNi Inorganic materials 0.000 description 6
- 150000002697 manganese compounds Chemical class 0.000 description 6
- 229910052596 spinel Inorganic materials 0.000 description 6
- 239000011029 spinel Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 229910013733 LiCo Inorganic materials 0.000 description 3
- 229910014689 LiMnO Inorganic materials 0.000 description 3
- 229910013825 LiNi0.33Co0.33Mn0.33O2 Inorganic materials 0.000 description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- 229910016366 Ni0.33Co0.33Mn0.33(OH)2 Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011236 particulate material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910011669 LiNi0.7Co0.2Mn0.1O2 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000004590 computer program Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000499 gel 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
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- 240000007651 Rubus glaucus Species 0.000 description 1
- 235000011034 Rubus glaucus Nutrition 0.000 description 1
- 235000009122 Rubus idaeus Nutrition 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- BTFOWJRRWDOUKQ-UHFFFAOYSA-N [Si]=O.[Sn] Chemical compound [Si]=O.[Sn] BTFOWJRRWDOUKQ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010325 electrochemical charging Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 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
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- 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
-
- 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
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06Q—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
- G06Q99/00—Subject matter not provided for in other groups of this subclass
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Physics & Mathematics (AREA)
- General Business, Economics & Management (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
【解決手段】実質的に単相で、六方晶層状結晶構造を有し、実質的に局所的な立方晶スピネル類似構造相を有しない化合物の製造方法であって、当該製造方法は、化学式LiXNiaCobMncО2で表されるリチウム金属酸化物(ただし、上記式中、a、b及びcはそれぞれ独立に0.05以上0.8以下の数であり、0.95≦a+b+c≦1.02、0.98≦x≦1.05、x+a+b+c=2である)を600℃以上に加熱する加熱工程と、当該加熱された化合物を冷却する冷却工程とから成り、当該冷却工程が、T=f*EXP(−R*t)で示される関数に基づいて冷却される(ただし、上記式中、Tは温度(℃)、fは係数、Rは冷却速度、tは冷却時間を示し、f=600〜1000℃、R=0.0009〜0.01、且つ関数は非線形である)ことを特徴とする化合物の製造方法。
【選択図】なし
Description
タップ密度1.74g/cm3の粉末Ni0.33Co0.33Mn0.33(OH)23150gと粒径57μm未満の粉末炭酸リチウム(LiCO3)1362gとを乾燥混合した。得られた混合物を5等分し、300L/時のガス流量で、1000mbаrの圧力下、860℃で20時間焼成した。
市販のLiNi0.5Co0.2Mn0.3O2を860℃で1時間焼成し、焼成炉中の焼成物を加熱ゾーンから室温でステンレススチールの皿上に直接広げて冷却し、サンプル3を得た。冷却速度は22℃/分であった。また、温度と時間との記録より、300℃までの冷却はT=823.85*EXP(−0.0401*t)の式に従っていることを確認した。
Claims (8)
- 実質的に単相で、六方晶層状結晶構造を有し、実質的に局所的な立方晶スピネル類似構造相を有しない化合物の製造方法であって、当該製造方法は、化学式LiXNiaCobMncО2で表されるリチウム金属酸化物(ただし、上記式中、a、b及びcはそれぞれ独立に0.05以上0.8以下の数であり、0.95≦a+b+c≦1.02、0.98≦x≦1.05、x+a+b+c=2である)を600℃以上に加熱する加熱工程と、当該加熱された化合物を冷却する冷却工程とから成り、当該冷却工程が、T=f*EXP(−R*t)で示される関数に基づいて冷却される(ただし、上記式中、Tは温度(℃)、fは係数、Rは冷却速度、tは冷却時間を示し、f=600〜1000℃、R=0.0009〜0.01、且つ関数は非線形である)ことを特徴とする化合物の製造方法。
- f=750〜850℃、R=0.001〜0.009である請求項2に記載の製造方法。
- R=0.002〜0.005である請求項2又は3に記載の製造方法。
- R=0.003〜0.0044である請求項1〜3の何れかに記載の製造方法。
- LiXNiaCobMncО2で表される化合物を600℃以上に加熱する加熱工程を含む請求項1〜4の何れかに記載の製造方法。
- 冷却工程がLiXNiaCobMncО2で表される化合物を均一に冷却する工程を含む請求項1〜5の何れかに記載の製造方法。
- LiXNiaCobMncО2で表される化合物が600℃以上の温度で合成される工程を含む請求項1〜6の何れかに記載の製造方法。
- LiXNiaCobMncО2で表される化合物を予め合成し、さらに、600℃以上の温度で加熱する工程を含む請求項1〜7の何れかに記載の製造方法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05013925 | 2005-06-28 | ||
EP05013925.2 | 2005-06-28 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2008518686A Division JP2008544468A (ja) | 2005-06-28 | 2006-06-23 | 無機化合物 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013032283A true JP2013032283A (ja) | 2013-02-14 |
JP5716002B2 JP5716002B2 (ja) | 2015-05-13 |
Family
ID=34937695
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2008518686A Pending JP2008544468A (ja) | 2005-06-28 | 2006-06-23 | 無機化合物 |
JP2012242348A Active JP5716002B2 (ja) | 2005-06-28 | 2012-11-02 | 無機化合物 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2008518686A Pending JP2008544468A (ja) | 2005-06-28 | 2006-06-23 | 無機化合物 |
Country Status (8)
Country | Link |
---|---|
US (1) | US8377412B2 (ja) |
EP (1) | EP1900046B1 (ja) |
JP (2) | JP2008544468A (ja) |
KR (1) | KR101284413B1 (ja) |
CN (1) | CN101283464B (ja) |
CA (1) | CA2613182C (ja) |
TW (1) | TW200715632A (ja) |
WO (1) | WO2007000286A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015056384A (ja) * | 2013-09-13 | 2015-03-23 | Jx日鉱日石金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、及び、リチウムイオン電池 |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100816206B1 (ko) * | 2007-07-16 | 2008-03-28 | 삼성에스디아이 주식회사 | 리튬 이차 전지의 양극 활물질, 그 형성 방법 및 리튬 이차전지 |
DE102007039471A1 (de) * | 2007-08-21 | 2009-02-26 | H.C. Starck Gmbh | Pulverförmige Verbindungen, Verfahren zu deren Herstellung sowie deren Verwendung in Lithium-Sekundärbatterien |
KR101363229B1 (ko) | 2009-03-31 | 2014-02-12 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | 리튬 이온 전지용 정극 활물질 |
US8993160B2 (en) | 2009-12-18 | 2015-03-31 | Jx Nippon Mining & Metals Corporation | Positive electrode for lithium ion battery, method for producing said positive electrode, and lithium ion battery |
WO2011077932A1 (ja) | 2009-12-22 | 2011-06-30 | Jx日鉱日石金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極及びそれを用いたリチウムイオン電池、並びに、リチウムイオン電池用正極活物質前駆体 |
EP2533333B1 (en) | 2010-02-05 | 2018-09-12 | JX Nippon Mining & Metals Corporation | Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery |
CN102792496B (zh) | 2010-02-05 | 2016-03-23 | Jx日矿日石金属株式会社 | 锂离子电池用正极活性物质、锂离子电池用正极和锂离子电池 |
WO2011108389A1 (ja) | 2010-03-04 | 2011-09-09 | Jx日鉱日石金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、及び、リチウムイオン電池 |
EP2544270A4 (en) * | 2010-03-04 | 2014-06-11 | Jx Nippon Mining & Metals Corp | POSITIVE ACTIVE ELECTRODE MATERIAL FOR A LITHIUM ION BATTERY, POSITIVE ELECTRODE FOR A LITHIUM ION BATTERY AND LITHIUM ION BATTERY |
CN102782909B (zh) | 2010-03-04 | 2015-01-14 | Jx日矿日石金属株式会社 | 锂离子电池用正极活性物质、锂离子电池用正极及锂离子电池 |
US9216913B2 (en) | 2010-03-04 | 2015-12-22 | Jx Nippon Mining & Metals Corporation | Positive electrode active substance for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery |
EP2544272B1 (en) | 2010-03-04 | 2017-07-19 | JX Nippon Mining & Metals Corporation | Positive electrode active substance for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery |
EP2544280B1 (en) | 2010-03-05 | 2018-06-06 | JX Nippon Mining & Metals Corporation | Positive-electrode active material for lithium ion battery, positive electrode for lithium battery, and lithium ion battery |
EP2648251B1 (en) | 2010-12-03 | 2018-04-25 | JX Nippon Mining & Metals Corporation | Positive electrode active material for lithium-ion battery, a positive electrode for lithium-ion battery, and lithium-ion battery |
WO2012098724A1 (ja) | 2011-01-21 | 2012-07-26 | Jx日鉱日石金属株式会社 | リチウムイオン電池用正極活物質の製造方法及びリチウムイオン電池用正極活物質 |
KR101373963B1 (ko) | 2011-03-29 | 2014-03-12 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | 리튬 이온 전지용 정극 활물질의 제조 방법 및 리튬 이온 전지용 정극 활물질 |
WO2012133434A1 (ja) | 2011-03-31 | 2012-10-04 | Jx日鉱日石金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、及び、リチウムイオン電池 |
US8992794B2 (en) * | 2011-06-24 | 2015-03-31 | Basf Corporation | Process for synthesis of a layered oxide cathode composition |
JP6292739B2 (ja) | 2012-01-26 | 2018-03-14 | Jx金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、及び、リチウムイオン電池 |
JP6292738B2 (ja) | 2012-01-26 | 2018-03-14 | Jx金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、及び、リチウムイオン電池 |
US9911518B2 (en) | 2012-09-28 | 2018-03-06 | Jx Nippon Mining & Metals Corporation | Cathode active material for lithium-ion battery, cathode for lithium-ion battery and lithium-ion battery |
KR102632660B1 (ko) | 2015-10-14 | 2024-02-01 | 바스프 에스이 | 세라믹 매트릭스 복합재를 포함하는 열투과성 튜브 |
JP6613952B2 (ja) * | 2016-02-23 | 2019-12-04 | Tdk株式会社 | 正極活物質、及びそれを用いた正極ならびにリチウムイオン二次電池 |
KR102561971B1 (ko) * | 2019-04-26 | 2023-07-31 | 유미코아 | 충전식 리튬 이온 전지용 양극 재료의 제조 방법 |
BR112022019431A2 (pt) | 2020-03-27 | 2022-12-06 | Univ Texas | Materiais de cátodo de alta energia com baixo cobalto e sem cobalto para baterias de lítio |
WO2023242092A1 (en) | 2022-06-13 | 2023-12-21 | Umicore | Positive electrode active material and method for manufacturing a positive electrode active material |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001357850A (ja) * | 2000-06-15 | 2001-12-26 | Toyota Central Res & Dev Lab Inc | リチウム二次電池正極活物質用リチウム遷移金属複合酸化物およびそれを用いたリチウム二次電池 |
WO2002086993A1 (fr) * | 2001-04-20 | 2002-10-31 | Yuasa Corporation | Matiere active anodique et son procede de production, anode pour pile secondaire a electrolyte non aqueux et pile secondaire a electrolyte non aqueux |
US20040234854A1 (en) * | 2003-03-14 | 2004-11-25 | The University Of Chicago | Layered Li1+XNialphaMnbetaAgammaO2 cathode materials for Li-ion rechargeable batteries and methods of manufacturing the same |
WO2005008812A1 (ja) * | 2003-07-17 | 2005-01-27 | Yuasa Corporation | 正極活物質及びその製造方法、並びに、これを用いたリチウム二次電池用正極及びリチウム二次電池 |
JP2005327644A (ja) * | 2004-05-17 | 2005-11-24 | Shin Kobe Electric Mach Co Ltd | リチウム二次電池用正極材の製造方法、正極材及びリチウム二次電池 |
JP2006151707A (ja) * | 2004-11-25 | 2006-06-15 | Mitsubishi Chemicals Corp | リチウム遷移金属複合酸化物製造用水酸化リチウム無水物、並びにその製造方法、およびそれを用いたリチウム遷移金属複合酸化物の製造方法 |
JP2006202678A (ja) * | 2005-01-24 | 2006-08-03 | Gs Yuasa Corporation:Kk | 正極活物質及びその製造方法、並びに、それを用いた非水電解質電池 |
JP2006252865A (ja) * | 2005-03-09 | 2006-09-21 | Gs Yuasa Corporation:Kk | 正極活物質及びその製造方法 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69819395T2 (de) * | 1997-04-15 | 2004-09-09 | Sanyo Electric Co., Ltd., Moriguchi | Positivelektrodenmaterialf für Verwendung nichtwässriger Elektrolyt enthaltender Batterie und Verfahren zur seiner Herstellung und nichtwässriger Elektrolyt enthaltende Batterie |
JP3524762B2 (ja) | 1998-03-19 | 2004-05-10 | 三洋電機株式会社 | リチウム二次電池 |
JP2000133262A (ja) | 1998-10-21 | 2000-05-12 | Sanyo Electric Co Ltd | 非水系電解液二次電池 |
JP4183374B2 (ja) | 2000-09-29 | 2008-11-19 | 三洋電機株式会社 | 非水電解質二次電池 |
WO2002073718A1 (fr) * | 2001-03-14 | 2002-09-19 | Yuasa Corporation | Matiere active pour electrode positive et accumulateur a electrolyte non aqueux comportant ladite matiere |
JP4510331B2 (ja) * | 2001-06-27 | 2010-07-21 | パナソニック株式会社 | 非水電解質二次電池 |
JP2003059490A (ja) * | 2001-08-17 | 2003-02-28 | Tanaka Chemical Corp | 非水電解質二次電池用正極活物質及びその製造方法 |
WO2003044882A1 (fr) | 2001-11-20 | 2003-05-30 | Tdk Corporation | Materiau actif d'electrode, electrode, element d'accumulateur au lithium-ion, procede de production de materiau actif d'electrode et procede de production d'element d'accumulateur au lithium-ion |
US7393476B2 (en) * | 2001-11-22 | 2008-07-01 | Gs Yuasa Corporation | Positive electrode active material for lithium secondary cell and lithium secondary cell |
JP2003197256A (ja) | 2001-12-25 | 2003-07-11 | Yuasa Corp | 非水電解質二次電池 |
WO2003081698A1 (fr) * | 2002-03-27 | 2003-10-02 | Yuasa Corporation | Substance active pour electrode positive et batterie a electrolyte non aqueuse renfermant ladite substance |
CN1331267C (zh) * | 2003-08-15 | 2007-08-08 | 比亚迪股份有限公司 | 一种锂离子二次电池及其制备方法 |
US7556655B2 (en) * | 2003-03-14 | 2009-07-07 | 3M Innovative Properties Company | Method of producing lithium ion cathode materials |
US7776603B2 (en) * | 2003-04-01 | 2010-08-17 | Cabot Corporation | Methods of specifying or identifying particulate material |
US7314682B2 (en) * | 2003-04-24 | 2008-01-01 | Uchicago Argonne, Llc | Lithium metal oxide electrodes for lithium batteries |
JP4216669B2 (ja) | 2003-08-07 | 2009-01-28 | 日鉱金属株式会社 | リチウム・ニッケル・マンガン・コバルト複合酸化物並びにそれを正極活物質として用いたリチウムイオン二次電池 |
-
2006
- 2006-06-23 JP JP2008518686A patent/JP2008544468A/ja active Pending
- 2006-06-23 KR KR1020077030165A patent/KR101284413B1/ko active IP Right Grant
- 2006-06-23 CA CA2613182A patent/CA2613182C/en active Active
- 2006-06-23 WO PCT/EP2006/006063 patent/WO2007000286A1/en active Application Filing
- 2006-06-23 EP EP06754526.9A patent/EP1900046B1/en active Active
- 2006-06-23 CN CN2006800231048A patent/CN101283464B/zh active Active
- 2006-06-23 US US11/922,414 patent/US8377412B2/en active Active
- 2006-06-27 TW TW095123052A patent/TW200715632A/zh unknown
-
2012
- 2012-11-02 JP JP2012242348A patent/JP5716002B2/ja active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001357850A (ja) * | 2000-06-15 | 2001-12-26 | Toyota Central Res & Dev Lab Inc | リチウム二次電池正極活物質用リチウム遷移金属複合酸化物およびそれを用いたリチウム二次電池 |
WO2002086993A1 (fr) * | 2001-04-20 | 2002-10-31 | Yuasa Corporation | Matiere active anodique et son procede de production, anode pour pile secondaire a electrolyte non aqueux et pile secondaire a electrolyte non aqueux |
US20040234854A1 (en) * | 2003-03-14 | 2004-11-25 | The University Of Chicago | Layered Li1+XNialphaMnbetaAgammaO2 cathode materials for Li-ion rechargeable batteries and methods of manufacturing the same |
WO2005008812A1 (ja) * | 2003-07-17 | 2005-01-27 | Yuasa Corporation | 正極活物質及びその製造方法、並びに、これを用いたリチウム二次電池用正極及びリチウム二次電池 |
JP2005327644A (ja) * | 2004-05-17 | 2005-11-24 | Shin Kobe Electric Mach Co Ltd | リチウム二次電池用正極材の製造方法、正極材及びリチウム二次電池 |
JP2006151707A (ja) * | 2004-11-25 | 2006-06-15 | Mitsubishi Chemicals Corp | リチウム遷移金属複合酸化物製造用水酸化リチウム無水物、並びにその製造方法、およびそれを用いたリチウム遷移金属複合酸化物の製造方法 |
JP2006202678A (ja) * | 2005-01-24 | 2006-08-03 | Gs Yuasa Corporation:Kk | 正極活物質及びその製造方法、並びに、それを用いた非水電解質電池 |
JP2006252865A (ja) * | 2005-03-09 | 2006-09-21 | Gs Yuasa Corporation:Kk | 正極活物質及びその製造方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015056384A (ja) * | 2013-09-13 | 2015-03-23 | Jx日鉱日石金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、及び、リチウムイオン電池 |
Also Published As
Publication number | Publication date |
---|---|
US20090299922A1 (en) | 2009-12-03 |
EP1900046B1 (en) | 2013-11-06 |
EP1900046A1 (en) | 2008-03-19 |
JP5716002B2 (ja) | 2015-05-13 |
WO2007000286A1 (en) | 2007-01-04 |
JP2008544468A (ja) | 2008-12-04 |
KR20080035522A (ko) | 2008-04-23 |
CN101283464A (zh) | 2008-10-08 |
CA2613182C (en) | 2014-04-15 |
CA2613182A1 (en) | 2007-01-04 |
CN101283464B (zh) | 2010-12-08 |
TW200715632A (en) | 2007-04-16 |
KR101284413B1 (ko) | 2013-07-09 |
US8377412B2 (en) | 2013-02-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5716002B2 (ja) | 無機化合物 | |
Pimenta et al. | Synthesis of Li-rich NMC: a comprehensive study | |
Purwanto et al. | NCA cathode material: Synthesis methods and performance enhancement efforts | |
Jo et al. | A new high power LiNi0. 81Co0. 1Al0. 09O2 cathode material for lithium‐ion batteries | |
TW515778B (en) | Layered lithium metal oxides free of localized cubic spinel-like structural phases and methods of making same | |
Chebiam et al. | Structural instability of delithiated Li1− x Ni1− y Co y O2 cathodes | |
CN109715562B (zh) | 用于锂离子电池的表面稳定阴极材料及其合成方法 | |
Lee et al. | Improved rate capability and thermal stability of LiNi0. 5Co0. 2Mn0. 3O2 cathode materials via nanoscale SiP2O7 coating | |
Meng et al. | Combining ab initio computation with experiments for designing new electrode materials for advanced lithium batteries: LiNi1/3Fe1/6Co1/6Mn1/3 O 2 | |
JP2018503238A (ja) | リチウムイオン電池用の傾斜構造を有する多成分材料、その調製方法、リチウムイオン電池の正極及びリチウムイオン電池 | |
Lu et al. | Single-crystal nickel-based cathodes: fundamentals and recent advances | |
Lee et al. | Cation Ordering and Electrochemical Properties of the Cathode Materials LiZn x Mn2-x O4, 0< x≤ 0.5: A 6Li Magic-Angle Spinning NMR Spectroscopy and Diffraction Study | |
Alcantara et al. | New LiNi y Co1− 2y Mn1+ y O 4 Spinel Oxide Solid Solutions as 5 V Electrode Material for Li Ion Batteries | |
Lee et al. | Lithiated Spinel LiCo1–x Al x O2 as a Stable Zero-Strain Cathode | |
Liang et al. | Process engineering to increase the layered phase concentration in the immediate products of flame spray pyrolysis | |
Yan et al. | Recent advances on the understanding of structural and composition evolution of LMR cathodes for Li-ion batteries | |
CN115763799A (zh) | 一种通过氟化物包覆改性提高单晶型高镍三元正极材料电化学性能的方法 | |
Xu et al. | Correlating morphological and structural evolution with the electrochemical performance of nickel-rich cathode materials: From polycrystal to single crystal | |
KR101134474B1 (ko) | 급속 충방전이 가능한 리튬 이차전지용 고용량 음극소재 및 그 제조 방법 | |
CN112751021A (zh) | 锂复合氧化物 | |
Tahmasebi et al. | Quantitative Measurement of Compositional Inhomogeneity in NMC Cathodes by X-ray Diffraction | |
JP7048944B2 (ja) | チタン及び/又はゲルマニウム置換リチウムマンガン系複合酸化物及びその製造方法 | |
Habibi et al. | Solution combustion synthesis of the nanocrystalline NCM oxide for lithium-ion battery uses | |
Zhang et al. | Research Development on Spinel Lithium Manganese Oxides Cathode Materials for Lithium-Ion Batteries | |
JPH11329432A (ja) | リチウム二次電池用正極材料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140603 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20140901 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20140904 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140918 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150309 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150316 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5716002 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R157 | Certificate of patent or utility model (correction) |
Free format text: JAPANESE INTERMEDIATE CODE: R157 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |