JP7219756B2 - 固体材料へのチタンの均一導入 - Google Patents
固体材料へのチタンの均一導入 Download PDFInfo
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- JP7219756B2 JP7219756B2 JP2020511164A JP2020511164A JP7219756B2 JP 7219756 B2 JP7219756 B2 JP 7219756B2 JP 2020511164 A JP2020511164 A JP 2020511164A JP 2020511164 A JP2020511164 A JP 2020511164A JP 7219756 B2 JP7219756 B2 JP 7219756B2
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- Prior art keywords
- metal
- solid material
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- aqueous
- titanium
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- 239000011343 solid material Substances 0.000 title claims description 69
- 239000010936 titanium Substances 0.000 title claims description 62
- 229910052719 titanium Inorganic materials 0.000 title claims description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 32
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 25
- 239000002738 chelating agent Substances 0.000 claims description 23
- 229910021645 metal ion Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 20
- 229910052748 manganese Inorganic materials 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 229910010298 TiOSO4 Inorganic materials 0.000 claims description 10
- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000007858 starting material Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000007772 electrode material Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000006138 lithiation reaction Methods 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 239000011572 manganese Substances 0.000 description 23
- 239000011777 magnesium Substances 0.000 description 19
- 239000011734 sodium Substances 0.000 description 15
- 238000000975 co-precipitation Methods 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000001788 irregular Effects 0.000 description 11
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 235000002639 sodium chloride Nutrition 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000012798 spherical particle Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 150000004679 hydroxides Chemical class 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 235000012501 ammonium carbonate Nutrition 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 239000003637 basic solution Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 102220076495 rs200649587 Human genes 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 102220042174 rs141655687 Human genes 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- -1 Ti2O Inorganic materials 0.000 description 1
- 229910009973 Ti2O3 Inorganic materials 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000385 transition metal sulfate Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/06—Carbonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
- H01M10/3918—Sodium-sulfur cells characterised by the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、固体材料の沈殿方法、本発明の方法により製造された固体材料ならびに請求項の固体材料から二次電池用の陽極電極材料を製造する方法に関する。
石油・ガスの貯蔵量が限られていることと、CO2の排出量を削減しようとする尽力が増えていることは、電気エネルギーの生産量を再生可能な形のエネルギーにシフトさせるだけでなく、自動車産業における代替駆動系の研究を増加させる結果となっている。さらに、消費者エレクトロニクスおよびテレコミュニケーション内の耐久性高出力記憶媒体の需要の増加は、効率、コスト削減および安全性を主眼とした既存のエネルギー貯蔵システムの改善および新しいエネルギー貯蔵システムの開発の両方を促進する。
本発明は、固体材料の沈殿のための方法に関するものであり、当該方法は以下のものを含む:
- 金属イオン水溶液を提供すること、ここで、金属イオン溶液は、TiOSO4および金属Mの金属イオンを含み、Mは1つ以上の以下の元素:Mg、Co、Cu、Ni、Mn、Feであり;
- 炭酸塩水溶液を提供すること;ならびに、
- 前記金属イオン水溶液および前記炭酸塩水溶液を混合することにより、チタンおよび前記金属M(複数可)を含む金属炭酸塩を含む固体材料を提供し、ここで、前記チタンは固体材料内に均一に分布する。
以下に、いくつかの例を挙げる。各例は実験を記述する。実施例では、特定のモル濃度、温度およびCSTRパラメータが示されているが、実験は、モル濃度、温度およびCSTRパラメータの変動で同様の材料を合成することを可能にする、より大きなプロセスの枠を示しているので、これらは本発明を制限するものと見なすべきではない。
オキシ硫酸チタニウム(IV)および硫酸金属の炭酸塩による沈殿
本発明の実施形態
NiaMnbMgcTi1-a-b-c(CO3)x(OH)2-2x(0<a+b+c<1および0<x≦1)の提案式を有する材料は、連続攪拌槽反応器(CSTR)における水性共沈法によって合成することができ、これは別稿で述べ、図解されている[Schmidt、Lanny D。(1998).The Engineering of Chemical Reactions.New York: Oxford University Press]。
炭酸塩による硫酸金属の沈殿
比較例
NiaMnbMg1-a-b(CO3)x(OH)2-2x(0<a+b<1および0<x≦1)の提案式を有する材料を、連続攪拌槽反応器(CSTR)における水性共沈法によって合成することができる[参考として例1参照]。
例1および例2に記載されているTiOSO4の有無による共沈によって作製された2つの材料のX線回折図を比較した。比較は、この発明に関連する2つの重要な発見を明らかにした。第一は、TiOSO4との共沈によって作られた材料は、TiOSO4に関連した如何なる回折ピークも見られなかったことであり、共沈Tiが非常に小さいまたは非晶質結晶子の形であることを意味する。第二には、回折図で観察される金属炭酸塩結晶子(Rhodochrositeに一致するピーク)が、Tiを有する材料では、Tiを持たない材料よりも非常に広く、顕著ではないことである。これは、金属炭酸塩相の結晶ドメインが、Tiを持たない材料と比較して、Tiを持つ材料で非常に小さいことを意味する。これら2つの発見は、本発明で達成できるチタンの均一分布を保障するのに役立つ。
オキシ硫酸チタン(IV)および硫酸金属塩の水酸化物による沈殿
比較例
NiaMnbMgcTi1-a-b-c(OH)2(0<a+b+c<1)の提案式を有する材料は、連続攪拌槽反応器(CSTR)における水性共沈法によって合成することができる(詳細については例1を参照のこと)。
塩化チタン(III)および金属硝酸塩の炭酸塩による沈殿
比較例
NiaMnbMgcTi1-a-b-c(CO3)x(OH)2-2x(0<a+b+c<1および0<x≦1)の提案式を有する材料は、連続攪拌槽反応器(CSTR)で水性共沈法により合成できる[詳細は例1を参照のこと]。
NA-IONバッテリー用の陽性電子材料の製造
本発明の実施形態
本発明のさらなる態様を説明するために、それらの電気化学的性能を比較するために、例1および例2から得られた固体材料を用いて、Naイオン電池用の2つの陽極電極材料を製造した。
Claims (13)
- 固体材料の沈殿のための方法であって、前記方法は以下を含む:
- 金属イオン水溶液を提供すること、ここで、金属イオン溶液は、TiOSO4および金属Mの金属イオンを含み、MはMnおよび以下の元素:Mg、Co、Cu、Ni、Feの1つ以上であり;
- 炭酸塩水溶液を提供すること;ならびに、
- 前記金属イオン水溶液および前記炭酸塩水溶液を混合することにより、チタン、および前記金属Mを含む金属炭酸塩を含む固体材料を提供し、ここで、前記チタンは固体材料内に均一に分布する。 - 前記金属イオン溶液が、Mg2+イオンおよび金属M’の金属イオンを含み、ここでM’が以下の元素:Co、Cu、Ni、Feの1つ以上である、請求項1に記載の方法。
- MがNi、MnおよびMgを含む、請求項1に記載の方法。
- 前記金属イオン溶液が硫酸塩、硝酸塩または酢酸塩から製造される、請求項1~3のいずれかに記載の方法。
- キレート剤を使用せずに前記方法を実施する、請求項1~4のいずれかに記載の方法。
- 固体材料を沈殿させ、凝集粒子に凝集させ、ここで、凝集粒子のD50が1~50μmの間である、請求項1~5のいずれかに記載の方法。
- 前記凝集粒子が本質的に球形である、請求項6に記載の方法。
- 前記凝集粒子が、0.90より高い平均円形度、および同時に1.50未満の平均アスペクト比によって特徴づけられる、請求項6または7に記載の方法。
- 金属イオン水溶液と炭酸水溶液の混合物のpH値が7.5<pH<10.0である、請求項1~8のいずれかに記載の方法。
- 以下の工程をさらに含む、請求項1~9のいずれかに記載の方法:
-NaOH溶液を供給し、NaOH溶液を金属イオン水溶液および炭酸水溶液と混合する。 - 前記固体材料が、チタンと前記金属Mとの間の原子比Ti:Mが0<Ti:M≦0.2となるような全体組成を有する、請求項1~10のいずれかに記載の方法。
- 以下の工程を含む、請求項1~11に記載の固体材料の沈殿のための方法から製造される固体材料から二次電池用の陽極材料を製造する方法:
-チタンならびに金属炭酸塩を含む固体材料と、LiまたはNaを含む出発材料とを混合し、
-固体材料および出発材料を焼結し、それによって、前記固体材料および、LiまたはNaを含む前記出発材料を部分的または完全に分解する。 - 請求項1~11に記載の固体材料の沈殿のための方法から製造される固体材料のリチウム化またはナトリウム化後の二次電池用の陽極電極材料の製造のための前駆体としての、固体材料の使用。
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