CN112673495B - 涂覆氧化物材料的方法 - Google Patents
涂覆氧化物材料的方法 Download PDFInfo
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- CN112673495B CN112673495B CN201980059114.4A CN201980059114A CN112673495B CN 112673495 B CN112673495 B CN 112673495B CN 201980059114 A CN201980059114 A CN 201980059114A CN 112673495 B CN112673495 B CN 112673495B
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- metal
- lithiated
- nickel cobalt
- pressure
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- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 23
- 239000011248 coating agent Substances 0.000 title claims abstract description 9
- 238000000576 coating method Methods 0.000 title claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- 239000011236 particulate material Substances 0.000 claims abstract description 26
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 21
- 150000001408 amides Chemical class 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 239000006182 cathode active material Substances 0.000 claims abstract description 10
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- ACKHWUITNXEGEP-UHFFFAOYSA-N aluminum cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Co+2].[Ni+2] ACKHWUITNXEGEP-UHFFFAOYSA-N 0.000 claims abstract description 8
- XEUFSQHGFWJHAP-UHFFFAOYSA-N cobalt(2+) manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Co++] XEUFSQHGFWJHAP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 27
- -1 alkyl compound Chemical class 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 230000001427 coherent effect Effects 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 230000000415 inactivating effect Effects 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 229910001507 metal halide Inorganic materials 0.000 abstract description 6
- 150000005309 metal halides Chemical class 0.000 abstract description 6
- 229910052987 metal hydride Inorganic materials 0.000 abstract description 6
- 150000004681 metal hydrides Chemical class 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 150000003624 transition metals Chemical class 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 108010062802 CD66 antigens Proteins 0.000 description 4
- RAURUSFBVQLAPW-DNIKMYEQSA-N clocinnamox Chemical compound N1([C@@H]2CC3=CC=C(C=4O[C@@H]5[C@](C3=4)([C@]2(CCC5=O)NC(=O)\C=C\C=2C=CC(Cl)=CC=2)CC1)O)CC1CC1 RAURUSFBVQLAPW-DNIKMYEQSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229960005235 piperonyl butoxide Drugs 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RGPSRYWDFHAWOT-UHFFFAOYSA-N CCCCCCCC[Mg]CCCC Chemical compound CCCCCCCC[Mg]CCCC RGPSRYWDFHAWOT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910016365 Ni0.33Co0.33Mn0.33 Inorganic materials 0.000 description 1
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 description 1
- 229910017246 Ni0.8Co0.1Mn0.1 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- WRMFBHHNOHZECA-UHFFFAOYSA-N butan-2-olate Chemical compound CCC(C)[O-] WRMFBHHNOHZECA-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- GRJJQCWNZGRKAU-UHFFFAOYSA-N pyridin-1-ium;fluoride Chemical compound F.C1=CC=NC=C1 GRJJQCWNZGRKAU-UHFFFAOYSA-N 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4417—Methods specially adapted for coating powder
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/442—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using fluidised bed process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract
本发明涉及一种涂覆氧化物材料的方法,所述方法包括以下步骤:(a)提供选自锂化镍钴铝氧化物、锂化钴锰氧化物和锂化层状镍钴锰氧化物的颗粒材料,(b)在比环境压力高5毫巴至1巴的压力下用金属醇盐或金属氨基化物或烷基金属化合物或金属卤化物或金属氢化物处理所述阴极活性材料,(c)在环境压力下用含有水分或HF的气体使由步骤(b)中获得的材料失活,其中步骤(b)在将混合能机械地引入颗粒材料中的混合器中进行,或者借助移动床或固定床进行。
Description
本发明涉及一种涂覆氧化物材料的方法,所述方法包括以下步骤:
(a)提供选自锂化镍钴铝氧化物、锂化钴锰氧化物和锂化层状镍钴锰氧化物的颗粒材料,
(b)在比环境压力高5毫巴至1巴的压力下用金属醇盐或金属氨基化物或烷基金属化合物或金属卤化物或金属氢化物处理所述阴极活性材料,
(c)在环境压力下用含有水分或HF的气体使步骤(b)中获得的材料失活,其中步骤(b)和(c)在将混合能机械地引入颗粒材料中的混合器中进行,或者借助移动床或固定床进行。
锂离子二次电池组是用于储存能量的现代设备。已经并且正在设想许多应用领域,从诸如移动电话和笔记本电脑的小型设备到汽车电池组和用于电动交通(e-mobility)的其他电池组。电池组的各种组分如电解质、电极材料和隔膜在电池组性能方面具有决定性作用。对阴极材料给予了特别的关注。已经提出了数种材料,例如磷酸铁锂、锂钴氧化物和锂镍钴锰氧化物。尽管已经进行了广泛的研究,但迄今为止发现的解决方案仍有待改进。
锂离子电池组的一个问题在于阴极活性材料表面上的不希望的反应。该反应可为电解质或溶剂或二者的分解。因此,已尝试了在不妨碍充放电期间的锂离子交换的情况下保护表面。实例是试图用例如氧化铝或氧化钙涂覆阴极活性材料的表面,参见例如US 8,993,051。
然而,该方法的效率可能仍有待改善。尤其是在颗粒具有附聚倾向的实施方案中,效率有时在反应时间和包覆颗粒的百分比以及颗粒的包覆百分比方面留有改进的空间。
因此,本发明的目的是提供一种方法,通过该方法可在不过长的反应时间的情况下涂覆颗粒材料,其中该颗粒材料具有形成附聚物的倾向。另一目的是提供一种用于实施该方法的反应器。
因此,已发现了开头所定义的方法,下文也称为本发明方法或根据本发明的方法。本发明方法是一种涂覆颗粒材料的方法。
在本发明上下文中获得的经涂覆的材料是指一批颗粒材料的至少80%的颗粒经涂覆,并且各颗粒的至少75%表面经涂覆,例如75-99.99%,优选80-90%。
该涂层的厚度可非常低,例如0.1-5nm。在其他实施方案中,厚度可为6-15nm。在其他实施方案中,该涂层的厚度为16-50nm。在该上下文中,厚度是指通过计算每个颗粒表面(以m2计)的金属醇盐或金属氨基化物或金属氢化物或烷基金属化合物或金属卤化物的量并假设步骤(b)和步骤(C)中的转化率为100%以数学方式测定的平均厚度。
不希望受任何理论束缚,据信由于颗粒的特定化学性质,例如由于化学反应性基团,例如但不限于羟基、具有化学约束的氧化物结构部分或吸附的水的密度,颗粒的未涂覆部分不反应。
在本发明的一个实施方案中,颗粒材料的平均粒径(D50)为3-20μm,优选为5-16μm。平均粒径可例如通过光散射或激光衍射测定。颗粒通常由初级颗粒的附聚物组成,并且上述粒径是指二次颗粒直径。
在本发明的一个实施方案中,颗粒材料具有0.1-1.5m2/g的比表面积,下文也为“BET表面积”。BET表面积可在将样品在200℃下脱气30分钟或更长后通过氮吸附并且此外根据DIN ISO 9277:2010来测定。
本发明方法包括三个步骤(a)、(b)和(c),在本发明的上下文中也称为步骤(a)、步骤(b)和步骤(c)。
步骤(a)包括提供选自锂化镍钴铝氧化物和锂化钴锰氧化物的颗粒材料。锂化层状钴锰氧化物的实例为Li1+x(CoeMnfM4 d)1-xO2。层状镍钴锰氧化物的实例为通式Li1+x(NiaCobMncM4 d)1-xO2的化合物,其中M4选自Mg、Ca、Ba、Al、Ti、Zr、Zn、Mo、Nb、V和Fe,其中其他变量定义如下:
0≤x≤0.2,
0.1≤a≤0.95,
0≤b≤0.5,
0.1≤c≤0.6,
0≤d≤0.1,且a+b+c+d=1。
在一个优选实施方案中,在通式(I)的化合物中:
Li(1+x)[NiaCobMncM4 d](1-x)O2 (I)
M4选自Ca、Mg、Al和Ba,
其他变量如上所定义。
在Li1+x(CoeMnfM4 d)1-xO2中,e为0.2-0.99,f为0.01-0.8,变量M4和d和x如上所定义,并且e+f+d=1。
锂化镍钴铝氧化物的实例为通式Li[NihCoiAlj]O2+r的化合物。r、h、i和j的典型值为:
h为0.8-0.95,
i为0.015-0.19,
j为0.01-0.08,和
r为0-0.4。
特别优选的是Li(1+x)[Ni0.33Co0.33Mn0.33](1-x)O2、Li(1+x)[Ni0.5Co0.2Mn0.3](1-x)O2、Li(1+x)[Ni0.6Co0.2Mn0.2](1-x)O2、Li(1+x)[Ni0.7Co0.2Mn0.1](1-x)O2和Li(1+x)[Ni0.8Co0.1Mn0.1](1-x)O2,各自具有如上所定义的x,以及Li[Ni0.88Co0.065Al0.055]O2和Li[Ni0.91Co0.045Al0.045]O2。
所述颗粒材料优选在不使用任何添加剂如导电碳或粘合剂下提供,而是作为自由流动的粉末提供。
在本发明的一个实施方案中,颗粒材料如锂化镍钴铝氧化物或层状锂过渡金属氧化物的颗粒分别是粘结的。这意指根据Geldart分组,颗粒材料难以流化,因此符合GeldartC区域的要求。然而,在本发明的过程中,并非在所有实施方案中都不需要机械搅拌。
粘结产品的其他实例是具有根据Jenike的流动性因子ffc≤7,优选1<ffc≤7(ffc=σ1/σc;σ1—主要主应力(major principle stress),σc—自由屈服强度)的那些,或具有Hausner比fH≥1.1,优选1.6≥fH≥1.1(fH=ρ振实/ρ堆积;ρ振实—在振动容积计中1250次行程后测得的振实密度,ρ堆积—根据DIN EN ISO 60的堆积密度)的那些。
在本发明方法的步骤(b)中,用金属醇盐或金属氨基化物或烷基金属化合物处理步骤(a)中提供的颗粒材料。所述处理将在下文更详细地描述。
本发明方法的步骤(b)和(c)在一个容器或至少两个容器的级联中进行,所述容器或级联—如果适用的话—在本发明的上下文中也称为反应器。优选地,步骤(b)和(c)在同一容器中进行。
在本发明方法的一个实施方案中,步骤(b)在15-1000℃,优选15-500℃,更优选20-350℃,甚至更优选150-200℃的温度下进行。优选在步骤(b)中选择金属醇盐或金属氨基化物或烷基金属化合物(视情况而定)处于气相中的温度。
步骤(b)在高于环境压力的压力下进行。因此,步骤(b)在比环境压力高5毫巴至1巴,优选比环境压力高10-150毫巴,更优选比环境压力高10-560毫巴的压力下进行。在本发明的上下文中,环境压力是指环境压力。在海平面上,环境压力为105Pa,但取决于实施本发明方法的位置的高度,环境压力可能会更低。在一个特别优选的实施方案中,在步骤(b)中,压力为比环境压力高5至350毫巴。
在本发明的一个优选实施方案中,烷基金属化合物或金属醇盐或金属氨基化物或金属氢化物或金属卤化物分别选自M1(R1)2、M2(R1)3、M3(R1)4-yHy、M1(OR2)2、M2(OR2)3、M3(OR2)4、M3[N(R2)2]4、M2H3、M3H4、M2X3、M3X4和M1或M2或M3与抗衡离子的组合的化合物,例如M1(R1)X、M2(R1)2X、M2R1X2、M3(R1)3X、M3(R1)2X2、M3R1X3,以及每分子具有两个金属原子的化合物,例如但不限于M3 2X6和甲基铝氧烷,其中:
R1不同或相同,并且选自氢(hydride)和直链或支化C1-C8烷基,
R2不同或相同,并且选自直链或支化C1-C4烷基,
M1选自Mg和Zn,
M2选自Al和B,
M3选自Si、Sn、Ti、Zr和Hf,其中优选Sn和Ti,
X选自相同或不同的卤离子(halide),其中优选氟离子,更优选氯离子,变量y选自0-4,尤其是0和1。
金属醇盐可选自如下的C1-C4醇盐:碱金属,优选钠和钾,碱土金属,优选镁和钙,铝,硅和过渡金属。优选的过渡金属为钛和锆。醇盐的实例为甲醇化物(下文也称为甲醇盐)、乙醇化物(下文也称为乙醇盐)、丙醇化物(下文也称为丙醇盐)和丁醇化物(下文也称为丁醇盐)。丙醇盐的具体实例为正丙醇盐和异丙醇盐。丁醇盐的具体实例为正丁醇盐、异丁醇盐、仲丁醇盐和叔丁醇盐。醇盐的组合也是可行的。
碱金属醇盐的实例为NaOCH3、NaOC2H5、NaO-异-C3H7、KOCH3、KO-异-C3H7和K-O-C(CH3)3。
金属C1-C4醇盐的优选实例为Si(OCH3)4、Si(OC2H5)4、Si(O-n-C3H7)4、Si(O-异-C3H7)4、Si(O-n-C4H9)4、Ti[OCH(CH3)2]4、Ti(OC4H9)4、Zn(OC3H7)2、Zr(OC4H9)4、Zr(OC2H5)4、Al(OCH3)3、Al(OC2H5)3、Al(O-n-C3H7)3、Al(O-异-C3H7)3、Al(O-仲-C4H9)3和Al(OC2H5)(O-仲-C4H9)2。
选自锂、钠和钾的碱金属的金属烷基化合物的实例,特别优选烷基锂化合物,例如甲基锂、正丁基锂和正己基锂。碱土金属的烷基化合物的实例为二正丁基镁和正丁基正辛基镁(“BOMAG”)。烷基锌化合物的实例为二甲基锌和二乙基锌。
烷基铝化合物的实例为三甲基铝、三乙基铝、三异丁基铝和甲基铝氧烷。
金属氨基化物有时也称为金属亚氨基化物(metal imide)。金属氨基化物的实例为Na[N(CH3)2]、Li[N(CH3)2]、Si[N(CH3)2]4和Ti[N(CH3)2]4。
M2X3和M3X4以及M1或M2或M3与抗衡离子的组合的化合物的实例为AlCl3、AlCl(CH3)2、AlCl2CH3、TiCl4、TiF4、ZrCl4、ZrF4、HfCl4、HfOCl2、SiH4、SiCl4、(CH3)3SiCl、SiO2、CH3SiCl3、Si2Cl6、SiH2Cl2、SnCl4和HwSi[N(CH3)2]4-w,其中w为1-4的数。
金属氢化物的实例是M3H4。金属氢化物的一个优选实例是Si2H6。合适金属氯化物的实例是M2Cl3和M3Cl4,例如TiCl4、SiCl4和AlCl3。
特别优选的化合物选自金属C1-C4醇盐和金属C1-C4烷基化合物,甚至更优选三甲基铝。
在本发明的一个实施方案中,金属醇盐或金属氨基化物或烷基金属化合物或金属卤化物的量为0.1-1g/kg颗粒材料。
优选地,金属醇盐或金属氨基化物或烷基金属化合物或金属卤化物的量分别经计算为颗粒材料上单分子层的80-200%的量。
在本发明的一个优选实施方案中,步骤(b)的持续时间为1秒钟至2小时,优选为1秒钟至10分钟。
在第三步骤(在本发明的上下文中,也称为步骤(c))中,在环境压力下用含有水分或HF的气体使步骤(b)中获得的材料失活。
在本发明的一个实施方案中,步骤(c)在50-250℃的温度下进行。
可将HF直接或通过加热在加热时释放HF的材料(例如HF的铵盐,例如NH4F或NH4F·HF或HF·吡啶)引入步骤(c)。
在本发明的一个实施方案中,在步骤(b)中,在比环境压力高5毫巴至1巴的压力下用金属醇盐或金属氨基化物或烷基金属化合物或金属氢化物或金属氯化物处理阴极活性材料,且在步骤(c)中,在环境压力下用含HF的气体使由步骤(b)获得的材料失活。
在本发明的上下文中,环境压力如在步骤(b)的上下文中所定义。
所述水分或HF可例如通过用水分或HF饱和的惰性气体,例如用水分或HF饱和的氮气或水分或HF饱和的稀有气体如氩气处理根据步骤(b)获得的材料来引入。饱和可指正常条件或步骤(c)中的反应条件。
在本发明的一个实施方案中,步骤(c)的持续时间为10秒钟至2小时,优选为1秒钟至10分钟。
步骤(b)和(c)的序列仅实施一次。
在本发明的一个优选实施方案中,步骤(c)在不含二氧化碳的气氛中进行。在本发明的上下文中,“不含二氧化碳”是指相应的气氛中的二氧化碳的含量为0.01至500重量ppm或甚至更低,优选为0.1至50重量ppm或甚至更低。CO2含量可通过例如使用红外光的光学方法测定。甚至更优选使用二氧化碳低于例如使用基于红外光的光学方法的检测限值的气氛。
本发明方法的步骤(b)和(c)可连续或间歇进行。
在本发明的一个实施方案中,在步骤(b)和(c)之间用惰性气体冲洗或吹扫进行本发明方法的反应器,例如用干燥氮气或用干燥氩气。合适的冲洗—或吹扫—时间为1秒钟至30分钟,优选为1-10分钟。优选惰性气体的量足以将反应器的内容物交换1-15次。通过该冲洗或吹扫,可避免产生副产物,例如金属醇盐或金属氨基化物或烷基金属化合物各自与水的反应产物的单独颗粒。在配对三甲基铝和水的情况下,该副产物是的甲烷和不沉积在颗粒材料上的氧化铝或三甲基铝,其中后者是不希望的副产物。
反应器设计的各种实施方案可实施本发明方法的步骤(b)和(c)。步骤(b)和(c)在将混合能机械地引入颗粒材料中的混合器中进行,例如强制混合器和自由下落混合器。自由下落混合器利用重力来移动颗粒,而强制混合器利用移动,特别是旋转安装在混合室中的混合元件来工作。在本发明的上下文中,混合室是反应器内部。强制混合器的实例为犁铧式混合器(在德国也称为混合器)、桨式混合器和铲式混合器。优选犁铧式混合器。犁铧式混合器可竖直或水平安装,术语水平或竖直分别是指混合元件围绕其旋转的轴。优选水平安装。优选地,本发明方法在根据投掷和旋转原理的犁铧式混合器中进行。
在本发明的另一实施方案中,本发明方法可在自由下落混合器中进行。自由下落混合器利用重力来实现混合。在一个优选实施方案中,本发明方法的步骤(b)和(c)在围绕其水平轴旋转的鼓或管形容器中进行。在一个更优选的实施方案中,本发明方法的步骤(b)和(c)在具有挡板的旋转容器中进行。
在本发明的一个实施方案中,容器或至少其部分以5-500转/分钟(“rpm”)的速度旋转,优选为5-60rpm。在使用自由下落混合器的实施方案中,更优选为5-25rpm,甚至更优选为5-10rpm。在使用犁铧式混合器的实施方案中,优选为50-400rpm,甚至更优选为100-250rpm。
在本发明的另一实施方案中,步骤(b)和(c)通过移动床或固定床进行。在固定床方法中,将步骤(a)中提供的颗粒材料置于多孔区域如筛板上。因此,步骤(a)中提供的颗粒材料形成床。在步骤(b)中,介质,尤其是含有金属醇盐或金属氨基化物或烷基金属化合物的惰性气体从顶部至底部地流动通过床,并且在步骤(c)中,水分(例如呈潮湿的氮气或潮湿的空气形式)从底部至顶部或从顶部至底部地流动通过床。
在移动床方法中,将步骤(a)中提供的颗粒材料引入管式反应器的顶部,从而自动形成颗粒床。含有金属醇盐或金属氨基化物或烷基金属化合物的气流从底部向上地流动通过所述床,其中气体速度不足以使颗粒床保持稳态。相反,颗粒床与气流逆流移动(步骤(b))。相应地进行步骤(c),但用水分或HF代替金属醇盐或金属酰胺或烷基金属。
在允许气动输送所述颗粒材料的本发明的一个优选方案中,施加至多4巴的压差。涂覆的颗粒可将从反应器中吹出或通过抽吸移除。
在本发明的一个实施方案中,入口压力高于但接近所需反应器压力。必须补偿气体入口和移动床或固定床(如果适用)的压降。
在本发明方法的过程中,由于反应器的形状而将强剪切力引入流化床中,附聚物中的颗粒经常交换,这允许整个颗粒表面的可接近性。通过本发明方法,可在短时间内涂覆颗粒材料,特别是可非常均匀地涂覆粘结颗粒。
在本发明的一个优选实施方案中,本发明方法包括通过气动对流(例如20-100m/s)从在其中进行步骤(b)和(c)的反应器中移除涂覆的材料的步骤。
在本发明的一个实施方案中,废气在高于环境压力,甚至更优选略低于进行步骤(b)和(c)的反应器中的压力,例如比环境压力高2毫巴至1巴,优选比环境压力高4-25毫巴的压力下用水处理。升高的压力有利于补偿废气管线中的压力损失。
将反应器和废气处理容器与环境分离所需的密封有利地配备有氮气冲洗。
在本发明的一个实施方案中,气体入口和出口位于用于本发明方法的容器的相对位置。
在本发明的一个实施方案中,使步骤(c)后获得的涂覆的氧化物材料经受后处理步骤(d),例如在100至500℃的温度和1毫巴至105Pa的压力下热后处理5分钟至5小时。
通过本发明方法,可在短时间内涂覆颗粒材料,特别是可非常均匀地涂覆粘结颗粒。本发明方法允许良好安全性,因为可容易地避免任何可燃性或者甚至爆炸性气氛。
可通过质谱法控制本发明方法的进展。
下面的工作实施例说明了本发明方法。环境压力:105Pa。
sccm:标准立方厘米/分钟
I.阴极活性材料
I.1.阴极活性材料的前体的制备
在搅拌釜反应器中填充去离子水。混合过渡金属氢氧化物前体的沉淀通过以1.9的流率比和导致停留时间为8小时的总流率同时供入过渡金属水溶液和碱性沉淀剂开始。过渡金属水溶液以6:2:2的摩尔比和1.65mol/kg的总过渡金属浓度含有Ni、Co和Mn(作为各自的硫酸盐)。碱性沉淀剂由重量比为25的25重量%的氢氧化钠溶液和25重量%的氨溶液组成。通过单独供入氢氧化钠水溶液将pH值保持在11.9。在粒度稳定后,将所得悬浮液由搅拌容器连续移除。通过过滤所得悬浮液,用蒸馏水洗涤,在空气中于120℃下干燥并筛分,获得混合过渡金属(TM)羟基氧化物前体。
I.2.阴极活性材料的制备
C-CAM.1(对比):将根据I.1获得的混合过渡金属羟基氧化物前体与Al2O3(平均粒径6nm)和LiOH单水合物混合,获得相对于Ni+Co+Mn+Al为0.3摩尔%的Al浓度和1.03的Li/(TM+Al)摩尔比。将该混合物加热至885℃并在氧气的强制流动下保持8小时,以获得电极活性材料C-CAM 1。
D50=9.5μm,使用激光衍射技术在来自Malvern Instruments的Mastersize 3000仪器中测定。铝含量由ICP分析测定并且对应于820ppm。250℃下的残留水分经测定为300ppm。
CAM.2(本发明):向具有外部加热夹套的流化床反应器中加入100g C-CAM.1,并在1030毫巴的平均压力下使C-CAM.1流化。将流化床反应器加热至180℃并在180℃下保持3小时。
步骤(b.1):将气态三甲基铝(TMA)通过打开通向含有液体形式的TMA并保持在50℃下的前体储罐的阀通过滤板引入流化床反应器中。用氮气作为载气稀释TMA。TMA和N2的气体流量为10sccm。在210秒的反应时段之后,将未反应的TMA通过氮气流移除,并且将反应器用氮气以30sccm的流量吹扫15分钟。
步骤(c.1):然后,将压力设定为环境压力(105Pa)。将气态的水通过打开通向含有保持在24℃下的液体水的储罐的阀引入流化床反应器中,流量为10sccm。在120秒的反应时段之后,通过氮气流移除未反应的水,并用氮气以30sccm吹扫反应器15分钟。获得本发明的涂覆氧化物材料CAM.2。
Claims (20)
1.一种制备涂覆氧化物材料的方法,所述方法包括以下步骤:
(a)提供选自锂化镍钴铝氧化物、锂化钴锰氧化物和锂化层状镍钴锰氧化物的颗粒阴极活性材料,
(b)在比环境压力高5毫巴至1巴的压力下用金属醇盐或金属氨基化物或烷基金属化合物处理所述阴极活性材料,
(c)在环境压力下用含有HF的气体使步骤(b)中获得的材料失活,其中步骤(b)在将混合能机械地引入颗粒材料中且选自强制混合器和自由下落混合器的混合器中进行,或者借助移动床或固定床进行,其中,步骤(b)借助移动床或固定床进行时,含有金属醇盐或金属氨基化物或烷基金属化合物的惰性气流从顶部向底部流动通过相应床。
2.根据权利要求1所述的方法,其中步骤(c)在不含二氧化碳的气氛中进行。
3.根据权利要求1所述的方法,其中烷基金属化合物或金属醇盐或金属氨基化物分别选自M1(R1)2、M2(R1)3、M3(R1)4-yHy、M1(OR2)2、M2(OR2)3、M3(OR2)4、M3[N(R2)2]4以及甲基铝氧烷,其中:
R1不同或相同,并且选自氢和直链或支化C1-C8烷基,
R2不同或相同,并且选自直链或支化C1-C4烷基,
M1选自Mg和Zn,
M2选自Al和B,
M3选自Si、Sn、Ti、Zr和Hf,
变量y选自0-4。
4.根据权利要求2所述的方法,其中烷基金属化合物或金属醇盐或金属氨基化物分别选自M1(R1)2、M2(R1)3、M3(R1)4-yHy、M1(OR2)2、M2(OR2)3、M3(OR2)4、M3[N(R2)2]4以及甲基铝氧烷,其中:
R1不同或相同,并且选自氢和直链或支化C1-C8烷基,
R2不同或相同,并且选自直链或支化C1-C4烷基,
M1选自Mg和Zn,
M2选自Al和B,
M3选自Si、Sn、Ti、Zr和Hf,
变量y选自0-4。
5.根据权利要求1所述的方法,其中锂化层状镍钴锰氧化物为通式(I)的材料:
Li(1+x)[NiaCobMncM4 d](1-x)O2 (I)
其中:
M4选自Mg、Ca、Ba、Al、Ti、Zr、Zn、Nb、Mo、V和Fe,
0≤x≤0.2,
0.1≤a≤0.8,
0≤b≤0.5,
0.1≤c≤0.6,
0≤d≤0.1,和
a+b+c+d=1。
6.根据权利要求2所述的方法,其中锂化层状镍钴锰氧化物为通式(I)的材料:
Li(1+x)[NiaCobMncM4 d](1-x)O2 (I)
其中:
M4选自Mg、Ca、Ba、Al、Ti、Zr、Zn、Nb、Mo、V和Fe,
0≤x≤0.2,
0.1≤a≤0.8,
0≤b≤0.5,
0.1≤c≤0.6,
0≤d≤0.1,和
a+b+c+d=1。
7.根据权利要求3所述的方法,其中锂化层状镍钴锰氧化物为通式(I)的材料:
Li(1+x)[NiaCobMncM4 d](1-x)O2 (I)
其中:
M4选自Mg、Ca、Ba、Al、Ti、Zr、Zn、Nb、Mo、V和Fe,
0≤x≤0.2,
0.1≤a≤0.8,
0≤b≤0.5,
0.1≤c≤0.6,
0≤d≤0.1,和
a+b+c+d=1。
8.根据权利要求4所述的方法,其中锂化层状镍钴锰氧化物为通式(I)的材料:
Li(1+x)[NiaCobMncM4 d](1-x)O2 (I)
其中:
M4选自Mg、Ca、Ba、Al、Ti、Zr、Zn、Nb、Mo、V和Fe,
0≤x≤0.2,
0.1≤a≤0.8,
0≤b≤0.5,
0.1≤c≤0.6,
0≤d≤0.1,和
a+b+c+d=1。
9.根据权利要求1-8中任一项所述的方法,其中在高于环境压力的压力下用水处理废气。
10.根据权利要求9所述的方法,其中在比环境压力高5毫巴至1巴的压力下用水处理废气。
11.根据权利要求1-8中任一项所述的方法,其中在步骤(b)中,压力为比环境压力高5毫巴至350毫巴。
12.根据权利要求10所述的方法,其中在步骤(b)中,压力为比环境压力高5毫巴至350毫巴。
13.根据权利要求1-8中任一项所述的方法,其中锂化镍钴铝氧化物或锂化层状镍钴锰氧化物的颗粒分别是粘结的。
14.根据权利要求12所述的方法,其中锂化镍钴铝氧化物或锂化层状镍钴锰氧化物的颗粒分别是粘结的。
15.根据权利要求1-8中任一项所述的方法,其中步骤(b)在15-350℃的温度下进行。
16.根据权利要求14所述的方法,其中步骤(b)在15-350℃的温度下进行。
17.根据权利要求1-8中任一项所述的方法,其中在步骤(b)和(c)之间用惰性气体冲洗在其中进行步骤(b)的反应器。
18.根据权利要求16所述的方法,其中在步骤(b)和(c)之间用惰性气体冲洗在其中进行步骤(b)的反应器。
19.根据权利要求1-8中任一项所述的方法,其包括通过气动对流从在其中进行步骤(b和(c)的反应器中移除涂覆材料的步骤。
20.根据权利要求18所述的方法,其包括通过气动对流从在其中进行步骤(b和(c)的反应器中移除涂覆材料的步骤。
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