IL127707A - Method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cells - Google Patents
Method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cellsInfo
- Publication number
- IL127707A IL127707A IL12770797A IL12770797A IL127707A IL 127707 A IL127707 A IL 127707A IL 12770797 A IL12770797 A IL 12770797A IL 12770797 A IL12770797 A IL 12770797A IL 127707 A IL127707 A IL 127707A
- Authority
- IL
- Israel
- Prior art keywords
- electrode material
- amorphous
- metal oxide
- active
- negative electrode
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910001935 vanadium oxide Inorganic materials 0.000 title description 27
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 23
- 229910052744 lithium Inorganic materials 0.000 title description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 56
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 55
- -1 vanadium metal oxide Chemical class 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000007774 positive electrode material Substances 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 14
- 239000007773 negative electrode material Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910015916 LixMyVzO Inorganic materials 0.000 claims 2
- 150000001447 alkali salts Chemical class 0.000 claims 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 abstract description 12
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical class [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 abstract description 7
- 230000001376 precipitating effect Effects 0.000 abstract description 6
- 229910003206 NH4VO3 Inorganic materials 0.000 abstract description 4
- 229910013720 M(NO3)n Inorganic materials 0.000 abstract 1
- 229910019501 NaVO3 Inorganic materials 0.000 abstract 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 45
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000009830 intercalation Methods 0.000 description 11
- 230000002687 intercalation Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000001351 cycling effect Effects 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000000137 annealing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000005280 amorphization Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229960002380 dibutyl phthalate Drugs 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910003006 LixMy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- WOJOYDJUXWPJES-UHFFFAOYSA-N [V]O[Ni] Chemical compound [V]O[Ni] WOJOYDJUXWPJES-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241000370685 Arge Species 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910001194 LixV2O5 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FLAMVRNMRAHFGQ-UHFFFAOYSA-N [O-2].[V+5].[Ni+2] Chemical class [O-2].[V+5].[Ni+2] FLAMVRNMRAHFGQ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/80—Compounds containing cobalt, with or without oxygen or hydrogen, and containing one or more other elements
- C01G51/82—Compounds containing cobalt, with or without oxygen or hydrogen, and containing two or more other elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
- C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/02—Amorphous compounds
-
- 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
- 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
- C01P2006/40—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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
Abstract
A method for preparing an amorphous ternary lithiated vanadium metal oxide of the formula LixMyVz O(x+5z+ny)/2, where M is a metal, 0lxo3, 0lyo3, 1ozo4, and n=2 or 3 characterized in that (a) an aqueous solution is prepared of (1) at least one metavanadate salt selected from the group consisting of NH4VO3 and NaVO3, (2) a nitrate salt of the formula M(NO3)n, where M is said metal, and (3) an excess of a lithium salt; (b) the resulting solution is heated; and (c) a sufficient amount of a base is added to the heated solution to obtain a pH suitable for precipitating the amorphous lithiated vanadium metal oxide.
Description
127707/2 rjffi ΝΛΙ swtYMa S oi>™ ¾> ο>_ηινβ o»fiiittN avptpuc tnsn ηυ>¾> mm fi3 vol? a*j*i iii ai»_n» A method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cells Telcordia Technologies, Inc.
C.115095 A METHOD FOR PREPARING MIXED AMORPHOUS VANADIUM OXIDES AND THEIR USE AS ELECTRODES IN RECHARGEABLE LITHIUM CELLS BACKGROUND OF THE INVENTION (1) Field of the Invention This invention relates to a novel method for syr.thesizin an -amorphous ternary lithiated vanadium-me al- oxide-of— he— formula LixMyV20,x+5:.,ny) /2 - where M is a metal, 0 < x < 3, 0 < < 3, 1 < z < 4, and n = 2 or 3 to a novel method for preparin an amorphous binary non-lithiated vanadium metal oxide of the formula .V,0(52..ny) 2. where M is a metal, 0 < y < 3, 1 < z < 4 and n = 2 or 3; and to a rechargeable lithiat;ed intercalation battery cell comprising a positive electrode, a negative electrode, and an electrolyte, wherein the active material of the negative electrode is an amorphous ternary lithiated (Li-V-0) vanadium metal oxide of the formula LixMy jO^s-^y) /2 or a amorphous binary non-lithiated (M-V-0) vanadium metal oxide c the formula yV20(52+ny) 2< prepared according to the methods o the present invention. (2) Description of Related Art Lithium ion secondary ceils represent an economically important sector of the battery market. One commercially significant -embodiment of such secondary cells employs a lithiated intercalation metal oxide as the positive electrode and a carbonaceous material as the negative electrode. Typical such cells are described in U.S. Patent No. 5,460,904, which is incorporated herein by reference. Commonly employed iithiated metal oxides include LiCo02, LiNiC2, and LiMn20 . of which LiCo02 is the most widely employed material. A common feature of ail these Iithiated metal oxides is that only about 0.5 iithium atoms per transition metal can be practically used in the charge/discharge cycles of the cells. Research investigations continue in a search for better, cheaper, and more efficient electrode materials.
Attempts to increase~~the capacity^f-such" cells are primarily focused in four areas: (1) improving the existing cobalt-, nickel-, or manganese-based oxides; (2) searching fo new iithiated metal oxides appropriate for use in Iithiated intercalation cells; (3) enhancing the electrochemical characteristics of the carbonaceous negative electrode; and i finding alternative materials to substitute for the carbonaceous negative electrode in Iithiated intercalation ceils .
Various researchers have sought, with limited success, t improve the reversible capacity of .the carbonaceous material i a iithiated intercalation ceil. J. Dahn et al. attempted to improve the electrochemical characteristics of the carbonacecu material by means of pyroiytic processing of organic material to obtain a carbonaceous electrode material. J. Dahn et al., Lithium batteries. (1994). F. Disma et al. has explored mechanical processing of the negative electrode material so a to augment its electrochemical capacity. Unfortunately, these approaches have not proved significantly successful.
Recently, Yoshio et al . in Japanese patent application J? 106542/92 and Guyomard et al . , C.R. Acad. Sci. Paris, 320, 523 (1995) , suggested a possible new approach :in negative electrode technology. These two research groups discovered that some iithiated vanadium oxide-based electrodes (initially sought as potential candidates for positive electrode materials) , when discharged to voltages lower than about 0.2 V, could reversibly intercalate lithium ions in amounts up to about 7 lithium atoms per transition metal atom.
However, these disclosures indicated that such Iithiated vanadium oxide-based were problematic when employed as electrodes. Guyomard et al. produced its Iithiated vanadium oxides by means of an initial crystallization, a process which severely limits its suitability as an electrode material in commercial ceils. Yoshio et al. disclosed lithium metal oxide compounds that had been manufactured by means of a method which required calcination and annealing at temperatures greater than 500°C for a period of a several days. Further, the compounds of Yoshio had also undergone an initial crystallization, as well as containing large numbers of diverse metallic elements that tend to become amorphous upon initial discharge. Thus, there remains a need for an efficient and effective synthesis of amorphous Iithiated and non-lithiated vanadium oxide materials which are suitable for use as tne active material in negative electrodes of commercial significant iithiated intercalation secondary cells.
SUMMARY OF THE T VSMTTfwj Accordingly, an object of the present invention is to provide a novel method for synthesizing an amorphous ternary iithiated vanadium metal oxide of the formula Lixl^.VzO(X+521.ny) /2. where M is a metal, 0 < x ≤ 3, 0 < y < 3, 1 < z < 4, and n = 2 or 3, which yields the ternary Iithiated vanadium metal oxide in an amorphous form by means of a simple, efficient synthesis.
It is another object of_ the present invention to provide a novel method for preparing an amorphous binary non- Iithiated vanadium metal oxide of the formula Μ^ν,Ο^,.^,,,, where M is a metal, 0 < y < 3, 1 z < 4, and n = 2 or 3 , which yields the binary non- Iithiated vanadium metal oxide in an amorphous form by means of a simple, efficient synthesis.
It is a still further object of the present invention to provide a rechargeable Iithiated intercalation battery ceil comprising a positive electrode, a negative electrode, and an electrolyte, wherein the active material of the negative electrode is an amorphous ternary iithiated vanadium metal oxide of the formula LixMyvz0(x+52+ny) /2 or an amorphous binary ncn-Iithiated vanadium metal oxide of the formula MyVs0(5z+ny) /2 , prepared according to the methods of the present invention.
These objects, among others, have been achieved by means of a method for preparing an amorphous ternary Iithiated vanadium metal oxide of the formula /2 > where M is a metal, 0" < x 3 , 0 < y < 3, 1 < z ≤ 4, and n = 2 or 3 , comprising the steps of creating an aqueous solution of at least one metavanadate salt selected from the group consisting of NH4VO3 and NaV03, and a nitrate salt of the formula M(N03)-., containing a large excess of a lithium salt; heating the solution; adding a sufficient amount of a base to obtain a pH greater than 8; and precipitating the amorphous ithiated vanadium metal oxide.
In addition, these objects, among others, have been achieved by means of a method for preparing an amorphous bir.ar non-lithiated vanadium metal oxide of the formula . ·, where M is a metal, 0 < y < 3, 1 < z < 4, and n = 2 or 3 , comprising the steps of creating an aqueous solution of at__ieas one metavanadate salt selected from the group consisting of NHV03 and NaV03, and a nitrate salt of the formula (N03):1; heating the solution; adding a sufficient amount of an acid t obtain a suitable pK for dissolution; adding a sufficient amount of a base to obtain a suitable pH for precipitating th amorphous binary non-lithiated vanadium metal oxide.
Still further, these objects, among others, have beer-achieved by means of a non-aqueous secondary cell comprising a active negative electrode material, an active positive electrode material and an non-aqueous electrolyte, wherei sai active negative electrode material' is an amorphous ternary lithiated vanadium metal oxide of the formula Lix ./V20(x+.5z<.ny) 2 where M is a metal, 0 < x < 3, 0 < y < 3, 1 ≤ z < 4, and n = or 3, said amorphous ternary lithiated vanadium metal oxide prepared by a process comprising the steps of creating an aqueous solution of at least one metavanadate salt selected from the group consisting of NH4V03 and NaV03, and a nitrate salt of the formula M(NC3)n, containing a large excess of a lithium salt; heating the solution; adding a sufficient amount of a base to obtain a pH greater than 3; and precipitating the amorphous lithiated vanadium metal oxide.
Additionally, these objects, among others, have been achieved by means of a non-aqueous secondary cell comprising an active negative electrode material, an active positive electrode material and an non-aqueous electrolyte, wherein said active negative electrode material is an amorphous binary non-lithiated vanadium metal oxide of the formula MyV20(52+ny) /2 , where M is a metal, 0 < y < 3, 1 < z < 4, and n = 2 or 3 , said amorphous binary non-lithiated vanadium_metal_oxide_prepared by-a process comprising the steps of creating an aqueous solution of at least one metavanadate salt selected from the group consisting of NH4V03 and NaV03, and a nitrate salt of the formula Μ{Ν03)ηί where n = 2 or 3 ; heating the solution; adding a sufficient amount of an acid to obtain a suitable pH for dissolution; and adding a sufficient amount of a base to obtain a pH suitable for precipitating the amorphous binary non-lithiated vanadium metal oxide.
BRIEF DESCRIPTION OF THE DRAWING A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same become better understood by reference to the following detailed description when considered in connection with the accompanying drawing, wherein: FIG. 1 depicts the respective X-ray diffraction traces of amorphous and crystalline LixNiV04 prepared according to the present invention; FIG.s 2 and 3 respectively depict the voltage/lithiun content curve and the capacity/cycle number curve of a cell employing amorphous LixNiV04 as the active positive electrode material v. Li; FIG.s 4 and 5 respectively depict the voltage/lithium content curve and the capacity/cycle number curve of a cell employing crystalline LixNiV04 as the active positive electrode material v. Li; FIG.s δ and 7 respectively depict the voltage/lithium content curve and the capacity/cycle number curve of a cell employing LixNiV0 , re-amorphized by mechanical grinding, as the active positive electrode material v. Li; FIG. 8 depicts the respective X-ray diffraction traces of amorphous and crystalline InV0 prepared according to the present invention; FIG.s 9 and 10 depict the voltage versus lithium content curves for cells employing InV04 as the active positive electrode material v. Li and cycled, respectively, with varying relaxation times; and FIG. 11 depicts the voltage versus lithium content curve for a Li-ion cell employing InV04 prepared according to the present invention as the active negative electrode material v ..
Substituting vanadium oxides for graphite as the negative electrode in rechargeable lithium ion cells results in a reduction of cell output voltage. The average voltage at which these vanadium oxide-based materials intercalate lithium ions is about 1.4 , as compared an intercalation voltage of about 0.3 V for a conventional graphite negative electrode.
Nevertheless, vanadium oxides can reversibiy intercalate up to about 7 lithium ions per unit formula, resulting in energy densities of about 800 to 900 Ah/kg, which, is about-.wo to two-and-one-half times greater than the energy density of the conventional graphite electrodes. Because of this greater electrochemical capacity of the iithiated vanadium oxides, the energy density of a rechargeable lithium ion cell employing a vanadium oxide as the negative electrode is equivalent to that achieved with a graphite negative electrode, within ± 5%.
One peculiar feature of the vanadium oxide-based materials is a propensity to become amorphous upon lithium ir.tercalation/deintercalation, as previously demonstrated by Delmas et al., J. Power Sources, 34, 103 (1991). Here, upon discharging an electrochemical cell employing V20s below 1 V, a substantial change was observed in the electrochemical potential relative to the lithium content in LixV205 between the first and second discharge. Specifically, a stepwise voltage variation was seen during the initial discharge, while a smooth and continuous variation in voltage relative to lithium content was found with the second discharge. metal oxides to become amorphous upon first discharge is a direct result of the characteristics of vanadium. More specifically, it is suggested that this amorphization is a result of -the tendency of a vanadium ion to alter its coordination sphere upon reduction. For instance, in Li iVO. vanadium is in the +5 oxidation state and possesses a tetrahedrai geometry. Upon reduction to the V*4 oxidation state the V ion prefers an octahedral coordination sphere as a result of crystal field stabilization. This shift in coordination geometry results in local structural modification It is believed that the amorphization observed during electrochemical cycling results from such changes in coordination geometry, associated with the reduction in the vanadium oxidation state.
The identical problem regarding amorphization observed with V205, was also found with the new class of lithiated vanadium metal oxides , as disclosed by Guyomard et al . Upon initial discharge of a cell employing a LiNiV04 electrode, th vanadium electrode became amorphous, resulting in a significantly different voltage/ lithium content curve between the first and second discharges.
In addition, it is noted that, upon the cycling of ceils the capacity of LiMV04-based electrodes (where M is a metal selected from the group of cadmium, cobalt, zinc, nickel, copper, and magnesium) increases significantly, in amounts cf up to about 150 percent, making the balancing of lithium ion cells quite difficult. This increase in capacity upon cycling which is also observed with other cell systems, results from mechanical processing of the electrode material upon cycling.
Because of these concerns regarding the balancing of lithiated vanadium metal oxide cells, it is preferred to prepare the lithiated vanadium metal oxide compositions in an amorphous state. Conventionally, these materials had been prepared by reacting stoichiometric amounts of lithium carbonate (Li2C03), NH4V03 and M(N03)2. (where M is a metal selected from the group of cadmium, cobalt, zinc, nickel, copper, and magnesium) at 500°C for 48 hours. Alternatively, some synthetic methods provided crystalline lithiated vanadium metal oxide compositions, which had to be further processed by means of an amorphization step. Such syntheses are time-consuming, ..energy-inefficient,..and labor-intensive.. There remains a need for an efficient and effective method preparing amorphous LiMV0 .
Because lithiated vanadium metal oxides have generated such significant enthusiasm and widespread research interest regarding their use in lithiated intercalation cells, researchers have focused their attention on the developmen < effective techniques for manufac uring these compounds.
Conventional fabrication of lithiated vanadium oxides requin calcination and annealing at temperatures greater than 500°C f a period of a several days, a technique which is costly and inefficient.
A new method for producing lithiated vanadium metal oxides of controlled morphology and grain size was sought so to improve the electrochemical performance of the oxides. Th has been attained by a novel process, in which an aqueous solution of at least one metavanadate salt selected from the group consisting of NH4V03 and NaV03, and a nitrate salt of t: formu a 3 n, conta n ng a arge excess o a t um sa t s constructed; the solution is heated; a sufficient amount of a base is added to obtain a pH greater than 8; and the amorphous lithiated vanadium metal oxide is spontaneously precipitated, providing fine particles of amorphous mixed lithiated vanadium metal oxides, which particles have a relatively large surface area.
In their attempts to provide a simple and effective method for producing non-li hiated vanadium metal oxides of controlled morphology and grain size, various aqueous solution methods were explored by the' present inventors. One approach employed vanadium pentoxide and the nitrate salt of iron as starting materials. This method failed when attempts were made to extend it to other elements. A second approach used ammonium metavanadate and the nitrate salt of a metal, both of which were dissolved in concentrated nitric acid. This method produced vanadium metal oxides whose degree of crystallinety was difficult to control, prompting a search for a new method of synthesis .
Moreover, attempts to prepare lithiated vanadium metal oxides by these methods were completely unsuccessful. It is now believed that these methods failed to account for the importance of the pH and the dissociation constant of the precursors. Upon discovering the present methods, however, the inventors were able to synthesize amorphous lithiated vanadium oxides of well-controlled morphology and non-lithiated vanadiu oxides of well-controlled morphology.
Initial attempts to synthesize LiNiV0 by means of solution chemistry were not successful. A solution of NHV03 was mixed with solutions of Ni(N03)2 and LiN03. Stoichiometric amounts of the components of LixNiyV20(JC+52+ny) /2 , where 0 < χ < 3, 0 < y ≤ 3, 1 < z ≤ 4, and n = 2 did not result in the expected mixed vanadium metal oxide but, rather, in two different non-lithiated nickel vanadium oxides. The present inventors now believe that, while the chemistry of the various transition metals is quite similar, the chemistry of transition metals and that of alkali metals, such as lithium and sodium, are quice dissimilar, perhaps as a result of the large difference in their respective electronegativities.
To entice the lithium ions to combine with the transition metal ions, the reaction was carried out with a large excess of lithium. However, as this large excess of lithium was added in the form of LiOK, the resultant solution was basic, having a pH greater than 7. Precipitation of amorphous LiNiV0 was then obtained by further adjusting the pH to a value in the range of about 8.0 to about 9.0, preferably to about 8.5, by the addition of an appropriate base such as H40H or organic bases. Suitable bases include ammonia; amines; alkali hydroxides, including lithium hydroxide. These bases can be added directly or as aqueous solutions of the base.
The present inventors have discovered that amorphous LiNiV04 can be prepared by a method which does not require calcination and annealing at temperatures greater than 500°C for a period of a several days. They have found that amorphous 11 hiated vanadium metal oxides can be prepared by means of a low temperature synthesis, comprising creating an aqueous solution of at least one metavanadate salt selected from the group consisting of H4V03 and NaV03,. and a nitrate salt of the formula M(N03)n, containing a large excess of a lithium salt; heating the solution; adding a sufficient amount of a base to obtain a pH greater than 8; and precipi ating the amorphous lithiated vanadium metal oxide.
Moreover, this method is not limited to amorphous lithiated vanadium metal oxides, but, rather, can be used to prepare amorphous vanadium oxide-based compounds.
Still further, the present inventors discovered that an amorphous binary non-lithiated vanadium metal oxide of the formula M,,Vz0(5z*ny> n · wh«re M is a metal, 0 < y < 3, 1 < z < 4 and n = 2 or 3 , can be prepared by means of a synthesis comprising the steps of creating an aqueous solution of at leas one etavanadate salt selected from the group consisting of NH4VO3 and NaV03, and a nitrate salt of the formula M(N03)n, where n = 2 or 3 ; heating the solution; adding a sufficient amount of a base to obtain a suitable pH for dissolution; and precipitating the amorphous binary non-lithiated vanadium meta oxid .
Other features of the invention will become apparent in the course of the following descriptions of exemplary embodiments which are given for illustration of the invention and are not intended to be limi ing" thereof .
Example 1 Ammonium metavanadate (NH4V03) was initially dissolved in water by heating and stirring to yield a solution of about 2.5 x 10-: M. A separate solution of Ni (N03) 2/LiN03 in the ratio of about 1:15 was prepared such that the separate solution had a concentrat on of Ni(N03)2 o about . x 10'2 M. and a concentration of LiN03 of about 0.7 M. When ail the H4V03 had dissolved, the cold solution of nitrate salts was added. The pH of the resultant solution was 5 and no precipitation occurred. While the solution was heated (80°C to 90°C) and stirred, the pH was adjusted to 8.5 by means of a 3 N ammoniacal solution. A yellow precipitate appeared spontaneously. The mixture continued to be stirred and heated for about 10 minutes.
Filtration of the precipitate was carried out with a 0.1 urn filter. In an alternate embodiment of the present invention, the precipitate can be separated from the filtrate by means of centrifugation . The solid precipitate, which was yellow-green in color, was then washed sequentially with water and ethanoi to entrain and remove NH3. The precipitate was then dried in a 50°C oven for about 12 hours. X-ray diffraction analysis of the solid indicated that the lithiated vanadium metal oxide was amorphous, as shown by the relatively featureless trace 12 in FIG . 1. The sample was then heated at 300°C for about 10 hours during which crystallization developed, as was confirmed in trace 16 of subsequent room temperature X-ray analysis. 3y carrying out a series of annealings at 50°C increments over a temperature range from 300°C to 800°C, continuous growth of diffraction peaks was observed under X-ray analysis. The amorphous mixture was additionally confirmed by means of differential thermal analysis. After annealing at 800°C, at which it crystallized as a perfect crystal, the solid was identified as LiNiV04 by X-ray analysis (JCFDS 38-1395) . To verify the stoichiometry of the compound, determination of the Li/Ni/V ratio was carried out by means of atomic absorption spectroscopy (AAS) analysis of the redissolved precipitate. The results confirmed the LiNiV04 formula. The observed data is consistent with the phase diagram of LiNiV0 provided in Chem. Bull. Soc. Jap.. 11, 1483 (1979) .
The specific surface area of both the amorphous lithiated vanadium nickel oxide and the crystallized lithiated vanadium nickel oxide were measured, with the amorphous material havina a specific surface area of about 30 to 36 m2/g and the crystalline material (annealed at 700°C) having a specific surface area of about 3 to 4 m2/g.
Example 2 A rechargeable lithium cell using the amorphous lithiated vanadium oxide LiNiV04 of Example 1 as the active material of the positive electrode and lithium metal as the active material of the negative electrode was constructed in a Swagelock-type assembly. The positive electrode was prepared from a 0.3 mm thick film of 6 parts by weight of carbon black and 56 parts of LiNiV04 intimately dispersed in a binder matrix of 16 parts of an 88:12 vinyiidene fluoride : hexafluoropropylene (PVDF:HFP) copolymer and 16 parts of compatible dibutylphthalate (DBP) piasticizer. A disk of 1 cm2 was cut from the film and immersed in diethyl ether to extract substantially all the DBP piasticizer from the electrode composition. The DBP-free positive electrode disk, after drying under vacuum for 1 hour, was placed in a dry box under a helium atmosphere.
The negative electrode of the same size was prepared from a lithium metal foil pasted onto a nickel disk. The positive and negative electrodes were electrically isolated by a separator disk cut from a silica fiber mat, and soaked in an electrolyte solution of 1 M LiPF6 in an solvent mixture of 1/3 dimethyl carbonate and 2/3 ethylene carbonate. The cell assembly was then inserted into Swagelock hardware where physical contact between the cell components was ensured by spring pressure while the cell was maintained air-tight by stainless steel plungers . The cell was then removed from the dry box for electrochemical testing over a number of charge/discharge cycles between 0.05 V and 3 V by means of a MacPile system operating in a galvanostatic mode. FIG.s 2 and 3 respectively depict the voltage/ lithium content curve and the capacity/cycle number curve for the amorphous Lix iV04 cell.
Example 3 A cell was similarly prepared employing the crystalline rather than the amorphous Lix iV0 material of Example 1 as the active positive electrode component. FIG.s 4 and 5 respectively illustrate the vol age/lithium content curve and the capacity/ cycle number of the ceil. With both cells, about 7 lithium ions per unit formula can be reversibly intercalated. However, the initial capacity achieved with amorphous LixNiV0 is larger than that obtained with crystalline Lix iV04/ resulting in capacities for cells employing amorphous LixNiV04 as large as 920 mAh/g, about 2.5 times, greater that obtained with a conventional graphite electrode.
Further, with the method of the present invention, it is net necessary to slowly transform the crystallized phase into an unordered amorphous phase. Thus, the desired ternary lithiated vanadium metal oxide is produced directly in an efficienc and effective synthesis, in contrast to the time-consuming, energy-inefficient, and labor-intensive conventional process. Moreover, these graphs indicate that the amorphous phase can reversibiy intercalate as many lithium ions as the crystallized phase, but at a faster rate.
As noted, it is possible to transform the initial amorphous stage into the corresponding crystallized phase by annealing at 800°C. It is also possible to re-amorphize the crystallized phase by means of mechanical processing, e.g., using a Spex 3000 impact ball mill, for use in a rechargeable cell, as is shown in the following example. gxample 4 Two stainless steel balls were placed with 1 g of the crystalline LixNiV0 material of Example 1 in a 25 cm3 airtight, sealed ceil. The cell was mounted onto a Spex 8000 apparatus and ball-milled for 80 hours. The crystalline LixNiV04 was re-amorphized in this operation and the resulting material was substituted for the active positive electrode material of Example 2 in preparing a test cell. FIG.s 6 and 7 respectively depict the voltage/lithium content curve and the capacity/cycle number curve for the resulting cell.
The slight increase in the irreversible loss of capacity observed between the first discharge and first charge of a eel-containing the re-amorphized LixNiV^ is consistent with the small increase in specific surface area observed with the re-amorphized sampie (6 m2/g) relative to the specific surface area of the crystallized sample (3 m2/g) . Further, the irreversible loss of capacity between the first discharge and the first charge supports the hypochesis that such capacity loss occurs by means of a catalytic decomposition of the electrolyte on the surface of the metal oxide. It is also to be noted that the first discharge voltage is greater for the amorphous phase than for the crystallized phase. This observation is again consistent with the larger degree of amorphization. As the degree of disorder in the structure increases, the Fermi level rises in energy, resulting in an increase in the intercalation voltage.
Further, upon cycling, the observed capacity of the amorphous Lix iV04-based cell remains__more constant than, the capacity of the crystalline LixNiV0 -based cell. Moreover, the capacity does not increase as had previously been observed with the crystalline lithiated vanadium oxides. It is believed that this constant capacity is a direct result of the initial amorphous character of the lithiated vanadium metal oxide produced by the process of the present invention, in contrast to the cycling that is required with the conventional syntheses of the crystalline lithiated vanadium oxide to achieve the proper degree of amorphization.
EXAM LE; 5 A process analogous to that of Example 1 was employed in the synthesis of LiCoV04. Ammonium metavanadate (NHV03) was initially dissolved in water with heating and stirring to yield a solution of about 2.5 x 10"2 M. A separate solution of Co (N03) 2/LiN03 in a ratio of about 1:20 was prepared such that the separate solution had a Co(N03)2 concentration of about 4.5 x 10~2 M and a LiN03 concentration of about 0.7 M. When the K4V03 had been completely dissolved, the cold solution of nitrate salts was added. The pH of the resultant mixture was 5 and no precipitation occurred. While the solution was heated to a temperature of about 80°C to 90°C and stirred, the pH was adjusted to 8.5 by addition of aiiqucts of a 3 N ammoniacal solution. An orange precipitate appeared spontaneously. The mixture continued to be stirred and heated for about 10 minutes. The amorphous LiCoV0 phase was recovered by centrifugation. and washed with water and ethanol to entrain and remove K3. The precipitate was then dried in a 50°C oven for a few hours. X-ray-diffraction analysis of the solid indicated that the lithiated vanadium metal oxide was amorphous. Upon heating the amorphous powder, LiCoV0 appeared to be the predominant component .
The analogous approach can be employed in the synthesis of other amorphous LixMy zO(x+52J.ny) /2. where M is a metal selected from the group of manganese, cobalt, iron, nickel, copper, cadmium, chromium, magnesium, aluminum, and indium, 0 x < 3 , 0 < y < 3 , 1 < z < 4 , and n = 2 or 3.
Employing molar proportions of Ni:V:Li :: 1:1:1, non-lithiated amorphous vanadium oxides have been synthesized.
These compounds were later obtained in their stoichiometric conditions, without employing LiN03 as reagent.
At a pH of 8.5, the analogous vanadium oxide Ni3(V04)2 obtained when the Li/Ni ratio was zero or insufficient.
Therefore, the structures are different for LiNiV04 and Ni3(V04)2.
When the pH was reduced below the preferred range, Ni2V:G was obtained. The pH of the solution containing Ni(N03)2 a d NH4VO3 must be initially decreased to 2 by means of concentrated acid, for example K 03. Afterwards, the pH is raised to a range of about 4 to about 5 so as to induce precipitation. During the initial pH adjustment from about 5 to about 2, the solution remained translucent. After washing and filtration. X-ray diffraction analysis of the resultant solid indicated that the solid phase was amo phous. Successive annealings of the solid precipitate did not progress towards crystallization as clearly as with Ni3 (V04)2 and LiNiV04.
Under stoichiometric conditions, Ni:V :: 3:2 for Ni3(V04)-_aad_Ni.:.y__:_:__l-:-l—for- i2V207 , the corresponding vanadium oxides were obtained.
Binary non-lithiated vanadium oxides of the formula 'iiyVz0(5Z+ny) 2< where M is a metal selected from the group of manganese, cobalt, iron, nickel, copper, cadmium, chromium, magnesium, aluminum, and indium, 0 < y < 3, 1 ≤ 2 ≤ 4, and n = 2 or 3; MV04, can be obtained by analogous aqueous syntheses.
A solution of about 2.5 x 10"2 M NH4V03 was mixed with a solution of about 4.5 x 10"2 M In(N03)3-5H;0. The pH of the resultant solution was about 2 to about 2.5. Instantaneously upon mixing, a precipitate was observed. To ensure complete reaction, the precipitate was redissolved by lowering the pH cf the solution to about 1 with the addition of aliquots of 3 N KNO3. The pK of the solution was then raised to about 4 by gently adding- 3 N NH40H, at which pH the amorphous InV0 precipitated. At a pH greater than about 4, In(0H)3 was observed, while at a pK lower than about 4, vanadium oxide (V205) or its ammoniacai salt (NH4V03) appeared. Thermal analysis of the resulting amorphous phase at a rate of 1C°C per minute indicated an approximate structural sequence in which, with increasing temperature, an initial amorphous InV04 · 2.6H->0 is transformed into amorphous InV04 which, in turn, at a temperature of about 550°C is transformed into mcnoclinic InV04, which is then transformed into orthorhombic InV04 at a temperature of about 73C°C. As in Example 1, X-ray diffraction analysis, depicted respectively in traces 82 and 86 of FIG. 8, confirmed the structures of the amorphous and monoclinic phases .
Swagelock test ceils were prepared as in Example 2 employing the amorphous InV0 as the active positive electrode material. Resulting ceils were likewise tested in the MacPile system at a C/4 rate with a variation in relaxation time between charge and discharge cycles of 0.003 hours and 0.25 hours. The voltage/ li hium content curves for such cell tests over the first 10 cycles are shown, respectively, in FIG.s 9 and 10. In both cases an irreversible component of self-discharge corresponding to about 3 lithium atoms per formula unit and a reversible component of self-discharge of about 6 lithium atoms per formula unit were observed. These results correlate with an initial capacity of about 900 mAh/g and represent the first time that lithium intercalation into an amorphous non-lithiated vanadium oxide has been achieved.
EXAMPLE 7 In the foregoing examples, the ability of the prepared amorphous vanadium oxides to intercalate large amounts of lithium at low voltages was shown through the simpler expedient of electrolytic cells comprising negative electrodes of lithium metal and positive electrodes incorporating the vanadium oxide. These latter materials, however, are no less effective in the role of active negative electrode components which are particularly useful in the more desirable Li-ion cells described, for example, in U.S. Patent 5,460,904. Electrodes for such an exemplary cell were prepared in the described manner using as the negative electrode a film of LiNiV0 composition according to Example 2, above. A positive electrode was prepared as described in the noted patent in the form of a 0.2 mm thick film of 56 parts by weight-oi—finely-divided —- LiMn20 , 6 parts of carbon black, 15 parts of the PVdF : KF? copolymer, and 23 parts of DBP plasticizer. An electrolyte/ separator film according to the patent was formed as a 85|jm thick film of the copolymer mixed with equal parts of DBP. The films were then assembled with the separator between the electrode components and the assembly was laminated with heat and pressure. A 1 cm2 disk was cut from the laminate and immersed in diethyl ether to extract a substantial portion of the DBP plasticizer, and the disk was then immersed in the electrolyte solution of Example 2 which was absorbed into the copolymer matrix to activate the cell. The cell was then mounted in a Swagelok apparatus and tested in cycling between 4.5 V and 2 V with a current density of 350 mA/cm2. The results of such cycling are shown in FIG. 11.
It is expected that other embodiments and variations of the present invention will be apparent to the skilled practitioner in light of the above teachings, and such embodiments and variations are nonetheless considered to be within the scope of the appended claims.
Claims (13)
1. A method for preparing an amorphous ternary lithiated vanadium metal oxide of the formula LixMyV2 O(x+5z+ny)/2, where M is a metal, 0
2. A method according to claim 1 characterized in that said aqueous solution is — -^" prepared by mixing a) a first aqueous solution comprising said metavanadaie salt; and b) a second aqueous solution comprising said nitrate and lithium salts.
3. A method according to claim 1 wherein said base is selected from the group consisting of ammonia, amines, alkali hydroxides, alkaline earth hydroxides, alkali salts of alcohols, and alkali salts of carboxylic acids.
4. A method according to claim 1 wherein said base is added in the form of an aqueous solution of said base.
5. A method according to claim 1 wherein said lithium salt is selected from the group consisting of LiN03, LiOH, LiOH · H:0, and Li2C03.
6. A method according to claim 1 wherein said heating comprises hearing the solution to a temperature in the range of about 80e C. to 95' C.
7. A method according to claim 1 wherein said metal is at least one metal selected from the group consisting of manganese, cobalt, iron, copper, cadmium, nickel, chromium, indium, aluminum, and magnesium.
8. A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and an non-aqueous electrolyte characterized in that said active positive electrode material is an amorphous vanadium metal oxide selected from the group consisting of: a) ternary lithiated vanadium metal oxides of the formula where M is a metal, 0
9. A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and a non-aqueous electrolyte characterized in that said active positive electrode material is an amorphous vanadium metal oxide consisting of a ternary lithiated vanadium metal oxide of the formula LixMyVzO(X+JZ+oyy2, where M is a metal, 0
10. A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and a non-aqueous electrolyte characterized in that said active positive electrode material is a binary non-lithiated vanadium metal oxide of the formula Μ?νΙ0(5ι+η>)β, where M is a metal, 0
11. 1 1. A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and an non-aqueous electrolyte characterized in that said active negative electrode material is an amorphous vanadium metal oxide selected from the group consisting of: a) ternary lithiated vanadium metal oxides of the formula Li MyVzO(X*5Z»ny y:, where M is a metal, 0
12. A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and a non-aqueous electrolyte characterized in that said active negative electrode material is a ternary lithiated vanadium metal oxide of the formula LixMyVzO(x+5z+nyv2» where M is a metal, 0
13. A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and a non-aqueous electrolyte characterized in that said active negative electrode material is a binary non-lithiated vanadium metal oxide of the formula MyVzO(jz+nyy2. where M is a metal, 0
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/678,210 US5700598A (en) | 1996-07-11 | 1996-07-11 | Method for preparing mixed amorphous vanadium oxides and their use as electrodes in reachargeable lithium cells |
| PCT/US1997/011285 WO1998002929A1 (en) | 1996-07-11 | 1997-06-27 | A method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cells |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL127707A0 IL127707A0 (en) | 1999-10-28 |
| IL127707A true IL127707A (en) | 2002-05-23 |
Family
ID=24721854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL12770797A IL127707A (en) | 1996-07-11 | 1997-06-27 | Method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cells |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5700598A (en) |
| EP (1) | EP0913007A1 (en) |
| JP (2) | JP2000503622A (en) |
| AU (1) | AU715258B2 (en) |
| CA (1) | CA2259590C (en) |
| ID (1) | ID17594A (en) |
| IL (1) | IL127707A (en) |
| MY (1) | MY133690A (en) |
| TW (1) | TW362296B (en) |
| WO (1) | WO1998002929A1 (en) |
Families Citing this family (39)
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|---|---|---|---|---|
| US6277521B1 (en) | 1997-05-15 | 2001-08-21 | Fmc Corporation | Lithium metal oxide containing multiple dopants and method of preparing same |
| ZA983867B (en) * | 1997-05-16 | 1998-11-13 | Henkel Corp | Lithium and vanadium containing sealing composition and process therewith |
| DE69827700T2 (en) * | 1997-05-22 | 2005-10-06 | Matsushita Electric Industrial Co., Ltd., Kadoma | Secondary battery with non-aqueous electrolyte |
| US6017654A (en) * | 1997-08-04 | 2000-01-25 | Carnegie Mellon University | Cathode materials for lithium-ion secondary cells |
| US6517974B1 (en) * | 1998-01-30 | 2003-02-11 | Canon Kabushiki Kaisha | Lithium secondary battery and method of manufacturing the lithium secondary battery |
| US5980855A (en) * | 1998-05-26 | 1999-11-09 | Rentech, Inc. | Method for preparing lithiated metal oxides |
| US5939043A (en) * | 1998-06-26 | 1999-08-17 | Ga-Tek Inc. | Process for preparing Lix Mn2 O4 intercalation compounds |
| US6267943B1 (en) | 1998-10-15 | 2001-07-31 | Fmc Corporation | Lithium manganese oxide spinel compound and method of preparing same |
| DK1137598T3 (en) | 1998-11-13 | 2003-08-18 | Fmc Corp | Layered lithium metal oxides free of local cubic spinel-like structural phases and processes for making the same |
| EP1135334B1 (en) | 1998-11-20 | 2002-10-09 | Fmc Corporation | Multiple doped lithium manganese oxide compounds and methods of preparing same |
| US6322928B1 (en) * | 1999-09-23 | 2001-11-27 | 3M Innovative Properties Company | Modified lithium vanadium oxide electrode materials and products |
| AU1951601A (en) | 1999-12-10 | 2001-06-18 | Fmc Corporation | Lithium cobalt oxides and methods of making same |
| EP1251575A1 (en) * | 2000-04-19 | 2002-10-23 | Japan Storage Battery Co., Ltd. | Positive electrode active material for secondary cell, method for producing the same and nonaqueous electrolyte secondary cell comprising the same |
| EP1164649A1 (en) * | 2000-06-13 | 2001-12-19 | Japan Storage Battery Company Limited | Positive active material for secondary battery, process for preparation thereof and non-aqueous secondary battery comprising same |
| DE10296692T5 (en) * | 2002-03-28 | 2004-04-29 | Council Of Scientific And Industrial Research | Combustion process for the production of LiCoVO4 |
| US20030235761A1 (en) * | 2002-04-26 | 2003-12-25 | Prabaharan S.R. Sahaya | Rechargeable lithium-containing battery employing brannerite type LiVMoO5.5 cathode and method of preparing same |
| US20040048157A1 (en) * | 2002-09-11 | 2004-03-11 | Neudecker Bernd J. | Lithium vanadium oxide thin-film battery |
| US8026003B2 (en) * | 2003-08-21 | 2011-09-27 | Samsung Sdi Co., Ltd. | Negative active material for a non-aqueous electrolyte battery, and a non-aqueous electrolyte battery comprising the same |
| US7682746B2 (en) * | 2005-03-31 | 2010-03-23 | Panasonic Corporation | Negative electrode for non-aqueous secondary battery |
| US7399457B2 (en) * | 2005-04-12 | 2008-07-15 | Conocophillips Company | Process for the removal of heavy metals from gases, and compositions therefor and therewith |
| KR100759410B1 (en) * | 2006-11-20 | 2007-09-19 | 삼성에스디아이 주식회사 | Anode active material for lithium secondary battery, manufacturing method thereof and lithium secondary battery comprising same |
| KR100778450B1 (en) * | 2006-11-22 | 2007-11-28 | 삼성에스디아이 주식회사 | Anode active material for lithium secondary battery, preparation method thereof and lithium secondary battery comprising same |
| KR100814880B1 (en) * | 2006-11-22 | 2008-03-18 | 삼성에스디아이 주식회사 | Anode active material for lithium secondary battery, preparation method thereof and lithium secondary battery comprising same |
| JP5270089B2 (en) * | 2006-12-18 | 2013-08-21 | 三星エスディアイ株式会社 | Method for producing negative electrode material for non-aqueous secondary battery and method for producing non-aqueous secondary battery using the same |
| EP1935850A3 (en) * | 2006-12-18 | 2008-07-02 | Samsung SDI Co., Ltd. | Composition for negative electrodes and non-aqueous rechargeable battery prepared using Same |
| KR100805123B1 (en) * | 2007-02-15 | 2008-02-21 | 삼성에스디아이 주식회사 | Lithium secondary battery |
| KR100953615B1 (en) * | 2007-04-13 | 2010-04-20 | 삼성에스디아이 주식회사 | Anode active material for lithium secondary battery, manufacturing method thereof and lithium secondary battery comprising same |
| JP5511128B2 (en) * | 2007-06-07 | 2014-06-04 | 三星エスディアイ株式会社 | Anode material for non-aqueous secondary battery and non-aqueous secondary battery |
| KR100918048B1 (en) | 2007-09-07 | 2009-09-22 | 삼성에스디아이 주식회사 | Lithium secondary battery |
| KR100898291B1 (en) * | 2007-09-12 | 2009-05-18 | 삼성에스디아이 주식회사 | Lithium secondary battery |
| TW201002623A (en) * | 2008-05-30 | 2010-01-16 | Basf Se | Process for preparing lithium vanadium oxides and their use as cathode material |
| KR101208910B1 (en) | 2010-09-29 | 2012-12-06 | 전자부품연구원 | Manufacturing method of negative composition for Lithium secondary battery using lithium vanadium oxide substituted other metal |
| RU2453014C1 (en) * | 2010-11-23 | 2012-06-10 | Государственное образовательное учреждение высшего профессионального образования Самарский государственный технический университет | Electrolyte for chemical current source |
| KR101418060B1 (en) * | 2012-02-20 | 2014-07-10 | 경북대학교 산학협력단 | Preparation method of a positive active for a lithium secondary battery |
| US10297855B2 (en) | 2012-05-29 | 2019-05-21 | Nutech Ventures | Rechargeable multi-cell battery |
| CN103268964B (en) * | 2013-05-09 | 2015-08-05 | 西安交通大学 | A kind of method of sodium vanadate assembling aqueous solution lithium ion battery |
| ES2974780T3 (en) * | 2020-02-26 | 2024-07-01 | Lg Energy Solution Ltd | Irreversible additive, positive electrode including the irreversible additive, and secondary lithium battery including the positive electrode |
| JP2024055325A (en) * | 2022-10-07 | 2024-04-18 | 日本ケミコン株式会社 | Method for producing lithium vanadium oxide crystal, lithium vanadium oxide crystal, electrode material and power storage device |
| KR102907969B1 (en) * | 2023-11-28 | 2026-01-02 | 경북대학교 산학협력단 | Vanadium oxide-based negative electrode active material and method for manufacturing the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4675260A (en) * | 1984-11-12 | 1987-06-23 | Nippon Telegraph And Telephone Corporation | Lithium battery including vanadium pentoxide base amorphous cathode active material |
| IT1231750B (en) * | 1989-05-12 | 1991-12-21 | Consiglio Nazionale Ricerche | HIGH ENERGY AND POWER LITHIUM ACCUMULATORS AND RELATED PRODUCTION METHOD |
| US5284721A (en) * | 1990-08-01 | 1994-02-08 | Alliant Techsystems Inc. | High energy electrochemical cell employing solid-state anode |
| FR2685129B1 (en) * | 1991-12-13 | 1994-03-25 | Centre Nal Etudes Spatiales | USE OF VANADIUM OXIDE BRONZES WITH IRON AND / OR ALUMINUM AS CATHODE MATERIAL IN ELECTROCHEMICAL GENERATORS. |
| US5334334A (en) * | 1993-03-30 | 1994-08-02 | Valence Technology, Inc. | Method of preparing lithium battery electrode compositions |
| JPH07122275A (en) * | 1993-05-25 | 1995-05-12 | Wilson Greatbatch Ltd | Cathode for electrochemical cell, method for its preparation and electrochemical cell |
-
1996
- 1996-07-11 US US08/678,210 patent/US5700598A/en not_active Expired - Lifetime
-
1997
- 1997-06-27 WO PCT/US1997/011285 patent/WO1998002929A1/en not_active Ceased
- 1997-06-27 IL IL12770797A patent/IL127707A/en not_active IP Right Cessation
- 1997-06-27 AU AU36443/97A patent/AU715258B2/en not_active Ceased
- 1997-06-27 CA CA002259590A patent/CA2259590C/en not_active Expired - Fee Related
- 1997-06-27 JP JP10506049A patent/JP2000503622A/en active Pending
- 1997-06-27 EP EP97933196A patent/EP0913007A1/en not_active Withdrawn
- 1997-07-08 MY MYPI97003089A patent/MY133690A/en unknown
- 1997-07-10 ID IDP972381A patent/ID17594A/en unknown
- 1997-07-11 TW TW086109800A patent/TW362296B/en active
-
2002
- 2002-08-22 JP JP2002242077A patent/JP2003142096A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US5700598A (en) | 1997-12-23 |
| CA2259590C (en) | 2005-10-25 |
| EP0913007A1 (en) | 1999-05-06 |
| WO1998002929A1 (en) | 1998-01-22 |
| JP2000503622A (en) | 2000-03-28 |
| AU715258B2 (en) | 2000-01-20 |
| CA2259590A1 (en) | 1998-01-22 |
| AU3644397A (en) | 1998-02-09 |
| MY133690A (en) | 2007-11-30 |
| TW362296B (en) | 1999-06-21 |
| ID17594A (en) | 1998-01-15 |
| JP2003142096A (en) | 2003-05-16 |
| IL127707A0 (en) | 1999-10-28 |
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