CN103379972B - 稳定化的纯锂金属粉末和其制备方法 - Google Patents
稳定化的纯锂金属粉末和其制备方法 Download PDFInfo
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- CN103379972B CN103379972B CN201180056945.XA CN201180056945A CN103379972B CN 103379972 B CN103379972 B CN 103379972B CN 201180056945 A CN201180056945 A CN 201180056945A CN 103379972 B CN103379972 B CN 103379972B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 62
- 239000000843 powder Substances 0.000 title claims abstract description 26
- 230000006641 stabilisation Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 fatty acid ester Chemical class 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000002161 passivation Methods 0.000 claims abstract description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000000194 fatty acid Substances 0.000 claims abstract description 8
- 229930195729 fatty acid Natural products 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000012442 inert solvent Substances 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 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 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
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- 238000000576 coating method Methods 0.000 claims description 7
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 4
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
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- 238000009835 boiling Methods 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229940070765 laurate Drugs 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
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- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 2
- 239000003960 organic solvent Substances 0.000 claims 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 claims 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims 1
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 claims 1
- 235000021319 Palmitoleic acid Nutrition 0.000 claims 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 claims 1
- 235000021313 oleic acid Nutrition 0.000 claims 1
- 150000003626 triacylglycerols Chemical group 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 34
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000000428 dust Substances 0.000 description 14
- 238000003860 storage Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VZDFGYYBKPOHLT-UHFFFAOYSA-N FN(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F Chemical compound FN(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VZDFGYYBKPOHLT-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- YZAZXIUFBCPZGB-QZOPMXJLSA-N (z)-octadec-9-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O YZAZXIUFBCPZGB-QZOPMXJLSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0408—Light metal alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C24/00—Alloys based on an alkali or an alkaline earth metal
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Powder Metallurgy (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Lubricants (AREA)
Abstract
本发明涉及稳定化的锂金属粉末以及其制备方法，其中该稳定化的纯锂金属粉末在有机惰性溶剂中在分散条件下用相应于通式（I）R-COORˊ的脂肪酸或脂肪酸酯钝化，其中R表示C10-C29基团和Rˊ表示H或C1-C8基团。
Description
本发明涉及稳定化的锂金属粉末以及通过在脂肪酸或脂肪酸酯的存在下分散在有机惰性溶剂中制备稳定化的纯锂金属粉末的方法。
锂属于碱金属。正如第一主族的较重元素同系物，它的特点是相对于多种材料来说强的反应能力。因此，它与水、醇及其它含有质子氢的其它物质剧烈地反应，往往出现燃烧的情况。它在空气中不稳定，并与氧气、氮气和二氧化碳反应。因此，它通常在惰性气体（稀有气体，例如氩气）下操作，并储存在石蜡油保护层中。
此外，它与许多官能化的溶剂反应，即使这些溶剂不含有质子氢。例如，环状醚（如THF）开环裂解，酯和羰基化合物通常被锂化和/或被还原。通常，提到的化学品和/或环境材料之间的反应是通过水来催化的。因此，锂金属在干燥的空气中可以储存较长时间并进行操作，因为它形成了在一定程度上稳定的钝化层而阻止了进一步的腐蚀。类似的情况适用于官能化的溶剂例如N-甲基-2-吡咯烷酮,它以无水的形式基本上对于锂，比起例如水含量>几百ppm的情况，有实质上较低的反应性。
为了提高锂金属的储存能力和加工时的安全性，开发了一系列减少腐蚀的涂层方法。例如在US5，567，474和US5，776，369中已知，用CO2来处理熔化的锂金属。对于该涂层，通常将液态锂在惰性的烃中与0.3%CO2接触/结合至少1分钟。然而，对于许多应用由此起作用的保护是不够的，特别是对电池的电极材料在N-甲基-2-吡咯烷酮（NMP）悬浮液中的预锂化。
稳定锂金属的另一种方法是，将其加热至超过它的熔点，搅拌熔化的锂，并使其与氟化剂接触，例如全氟戊胺（WO2007/005983A2）。缺点在于，氟化剂往往是有毒或腐蚀性的，因此在工业实践应用中不受欢迎。
用于锂金属的保护性表面处理的另一种方法是，将其用蜡层（例如聚乙烯蜡）涂覆（WO2008/045557A1）。缺点在于，消耗了相对大量的涂层剂。在上述专利申请的实施例中约1%。
US2008/0283155A1描述了稳定锂金属的方法，其特征在于以下步骤：a）将锂金属粉末加热超过其熔点，以便产生熔化的锂金属，b）分散熔化的锂金属；和c）将熔化的锂金属与含磷物质接触，以便在锂金属粉末上产生基本上连续的磷酸锂保护层。通常和特别是在锂金属的存在下使用酸性、腐蚀性的物质（磷酸）操作是不利的：这两种物质在接触时相互非常剧烈反应并释放出大量的热量。此外，在锂金属和磷酸反应时产生爆炸危险的氢气。
最后，在US2009/0061321中建议，用基本上连续的聚合物涂层制备稳定化的锂金属粉末。该聚合物可以选在聚氨酯、PTFE、PVC、聚苯乙烯等。该方法的缺点是，被保护的锂金属获得不确定的有机物质表面涂层，这可能会干扰锂金属的后续应用，例如对于电极材料的预锂化。
本发明的目的在于，提供制备具有钝化性覆盖层的锂金属粉末的方法，
·其可以不用使用气态或酸性的、腐蚀性或毒性的钝化剂，
·其不会导致形成不确定的有机物，特别是有机聚合物，和
·其在锂表面上形成由无机难溶盐膜组成的钝化保护层，和
·其表面涂层不会干扰例如作为阳极材料的预锂化剂的使用。
这样的锂金属粉末应该在极性、反应性溶剂（正如在制备电极涂层中使用的，例如NMP）的存在下至少在约50℃在几天时间里是稳定的。
本发明的目的是通过使用相应于下列通式I的饱和和/或不饱和脂肪酸和/或脂肪酸酯作为钝化剂来实现的：
R-COOR'（I）
其中R表示C10-C29基团和R'表示H或C1-C8基团。作为锂源使用纯的，即特别是贫钠品质。令人惊奇地发现，使用贫钠的锂金属可以得到非常特别稳定的、可安全操作的产品。
首先，将锂在惰性气体（稀有气体，例如干燥的氩气）在有机惰性溶剂或溶剂混合物（通常是基于烃的）加热到超过熔点温度（180.5℃）。在使用沸腾温度＞180℃的溶剂（例如十一烷、十二烷或相应的市售的矿物油混合物，例如Shellsol）时，可以在常压下进行该方法。与此相反，如果使用了较易挥发性的烃，例如己烷、庚烷、辛烷、癸烷、甲苯、乙苯或异丙基苯，则在密闭的容器中在压力条件下进行该熔化过程。
在完全熔化之后，加入钝化剂，并运转用于制备分散体的搅拌器（通常是分散圆盘）。准确的分散参数（即主要是转动速度和分散时间）取决于所想要的颗粒大小。此外，它还取决于分散溶剂的粘度以及每个搅拌元件的几何形状参数（例如直径、准确位置和齿圈的大小）。本领域的技术人员可以容易地通过相应的试验精细地调节分散方法来制备所想要的颗粒分布。
如果制备的锂颗粒的粒径在5-100μm的范围，则搅拌频率通常在1000-25000upm，优选2000-20000upm。分散时间，即分散装置以全功率运行的时间，为1-30分钟，优选2-15分钟。
可以在加热阶段开始之前已经与金属和容易一起加入了钝化剂。但是，优选在金属熔化之后，即在＞180℃的温度才加入钝化剂。可以在分散过程中不加控制地（即以一份的形式）加入。但是，优选经过约5-1000s，特别优选30-500s的时间加入钝化剂。作为钝化剂使用脂肪酸或脂肪酸酯。这些助剂的优点在于商业上可以得到并且没有毒性，没有明显的蒸汽压，并在金属表面形成不会干扰的是由元素氧、碳和氢组成的薄膜。优选的钝化剂例如有：油酸（油酸）、硬脂酸、棕榈酸、月桂酸、肉豆蔻酸、十七烷酸、橄榄油酸、亚油酸、亚麻酸以纯的形式或者以它们的混合物的形式。此外，可以使用它们的酯，例如脂肪酸甘油酯或与一元醇的酯，例如乙醇酯(ethylate)、丙醇酯(propanolate)或丁醇酯(butylate)。特别优选也可以使用天然产物，例如油菜籽油、橄榄油、葵花籽油或亚麻子油。通常每kg锂金属使用0.1-50g上述的钝化剂。优选每kg锂金属使用1-10g钝化剂。准确的量取决于钝化剂中官能团的浓度（它是例如羧酸基团或羧酸酯基团），以及取决于待产生的金属粉末的精细度：其越精细，其比表面越大，相应地对钝化剂的需求越大。
以纯的形式使用锂金属，即总的金属杂质必须少于500ppm。特别是钠含量限制在最多200ppm。钠含量优选＜100ppm和特别优选＜50ppm。这种品质的贫钠的锂金属粉末是按照上述方法借助脂肪酸或脂肪酸酯钝化的，令人惊奇地证明在与反应性、极性溶剂（例如N-甲基-2-吡咯烷酮）接触时是非常特别稳定的。
本发明的金属粉末的平均颗粒大小为最大200μm，优选最大100μm和特别优选最大50μm。
在本发明的范围，也可以通过附加涂层将用脂肪酸或脂肪酸酯钝化的金属粉末更加稳定化。合适的涂层剂例如有含磷化合物（如磷酸、三（草酸根合）磷酸锂）、氟化剂（例如全氟戊胺）、蜡（例如聚乙烯蜡）或聚合物涂层（例如具有PU，PTFE，PVC或聚苯乙烯）。在烃溶剂中在低于锂熔点的温度（即＜180.5℃）进行该附加钝化作用。
当在N-甲基-2-吡咯烷酮（水含量<约200ppm）的悬浮液中在50℃和特别优选在100℃储存至少15小时，本发明的锂金属粉末在DSC测试中没有显示出显着的放热效应，尤其是没有“跑开现象”。借助下列实施例阐述其行为。
接下来，借助实施例、比较例和五张附图进一步阐述本发明，而不应该由此限制所要求的实施方式的范围。
其中：
图1：将按照实施例1的金属粉末在NMP中在80℃和100℃的烘箱温度（-）和样品温度（+，△）的储存过程中的热行为
图2：将按照对比例1的金属粉末在NMP中在50℃的烘箱温度（-）和样品温度（+）的储存过程中的热行为
图3：将按照实施例1得到的金属粉末（Na含量为17ppm）在水含量为1%的NMP中在烘箱温度（-）和样品温度（+，△）的储存过程中的热行为
图4：将按照实施例1得到的Na含量为55ppm的金属粉末在50和100℃的烘箱温度（-）和样品温度（+，x）在NMP（水含量为148ppm）的储存过程中的热行为
图5：将按照实施例1得到的Na含量为55ppm的金属粉末在80℃的烘箱温度（-）和样品温度（+）在NMP（水含量为200ppm）的储存过程中的热行为。
实施例1：用亚麻籽油钝化的贫钠的锂金属粉末的制备
在干燥的用氩气惰性化的带有分散搅拌器的2L不锈钢双外壳反应器中加入399gShellsolD100和19.4g锂金属条段。该锂具有17ppm的钠含量。在非常慢的搅拌下（约50rpm），通过外壳加热将内部温度提高到205℃。然后用注射器加入0.05g亚麻籽油。将搅拌频率提高到3600rpm，并保持6分钟。然后停止搅拌，并将悬浮液冷却至室温。
将该悬浮液在玻璃吸滤瓶上放干，将过滤残余物多次用己烷冲洗至不含油并然后真空干燥。
产率：15.6g（理论值的80%）
平均颗粒大小：约50μm（REM图片估测）。
对比例1：用亚麻籽油钝化的富钠的锂金属粉末的制备
在干燥的用氩气惰性化的带有分散搅拌器的2L不锈钢双外壳反应器中加入525gShellsolD100/32.3g锂金属条段和0.11g钠。该锂具有17ppm的钠含量。在非常慢的搅拌下（约50rpm），通过外壳加热将内部温度提高到205℃。然后用注射器加入0.09g亚麻籽油。将搅拌频率提高到3600rpm，并保持6分钟。然后停止搅拌，并将悬浮液冷却至室温。
将该悬浮液在玻璃吸滤瓶上放干，将过滤残余物多次用己烷冲洗至不含油并然后真空干燥。
产率：27.3g（理论值的84%）
平均颗粒大小：约50μm（REM图片评估）
Na含量（FES）：0.3%。
实施例2：将本发明的按照实施例1的金属粉末在NMP中在80和100℃储存（DSC-测试）
DSC测试（“差示扫描量热法”）使用了公司Systag，瑞士（Radex系统）的仪器。在样品容器中，在保护气体氛围下称重约2g的NMP和0.1g锂金属粉末。在一定的温度下储存该样品15小时。对比例2：将不是本发明的按照对比例1的金属粉末在NMP中在50℃储存（DSC-测试）
实施例2和比较例2证明了，本发明的锂金属粉末在与NMP接触时具有显著改善的稳定性：本发明的产物在80和100℃的储存下没有引起任何显著的放热效应（样品温度在整个观察时间保持在明显低于烘箱温度），而不是本发明的金属粉末在50℃的储存下已经发生明显的放热反应。这可以根据样品温度明显超过烘箱温度而确认。
实施例3：将本发明的按照实施例1的金属粉末（Na含量为17ppm）在水含量为1%的NMP中储存（DSC-测试）
特别优选的Na含量为17ppm的Li金属粉末甚至在水分多的NMP中被证明是动力学稳定的。
实施例4：将按照本发明制备的Na含量为55ppm的锂金属粉末在50和100℃在NMP（水含量为148ppm）中储存（DSC-测试）
实施例5：将按照本发明制备的Na含量为55ppm的锂金属粉末在80℃在NMP（水含量为200ppm）中储存（DSC-测试）
具有钠含量为55ppm的金属粉末在储存温度为50℃和80℃下是稳定的，然而在100℃下其显示出放热，但不是跑开(run-away)现象。在100℃的DSC实验之后仍有73%的使用的锂以金属的形式存在。
Claims (13)
1.稳定化的锂金属粉末，其特征在于，其钠含量＜200ppm且平均颗粒大小为最大200μm，并且在有机惰性溶剂中在分散条件下用相应于下列通式I的脂肪酸或脂肪酸酯将其钝化，
R-COOR'（I），
其中R表示C10-C29基团和R'表示H或C1-C8基团。
2.根据权利要求1的稳定化的锂金属粉末，其特征在于，它的钠含量＜100ppm。
3.根据权利要求1的稳定化的纯锂金属粉末，其特征在于，它的钠含量＜50ppm。
4.根据权利要求1-3中的任一项的稳定化的锂金属粉末，其特征在于，它的平均颗粒大小为最大100μm。
5.根据权利要求1-3中的任一项的稳定化的锂金属粉末，其特征在于，它的平均颗粒大小为最大50μm。
6.稳定化的锂金属粉末的制备方法，其特征在于，钠含量＜200ppm的锂金属在180℃以上在分散条件下与含有相应于下列通式I的一种或多种脂肪酸和/或一种或多种脂肪酸酯的用量为每kg锂金属0.1-50g的钝化剂在惰性有机溶剂中反应，
R-COOR'（I），
其中R表示C10-C29基团和R'表示H或C1-C8基团。
7.根据权利要求6的稳定化的锂金属粉末的制备方法，其特征在于，作为钝化剂以纯的形式或其混合物的形式使用选自油酸、硬脂酸、棕榈酸、月桂酸、肉豆蔻酸、十七烷酸、棕榈油酸、亚油酸、亚麻酸的不饱和脂肪酸，或者使用它们的酯，或使用选自油菜籽油、橄榄油、葵花籽油或亚麻子油的天然油。
8.根据权利要求7的方法，其特征在于，所述酯为甘油三酯、乙醇酯、丙醇酯或丁醇酯。
9.根据权利要求6－8中的任一项的方法，其特征在于，所述钝化剂的使用量为1-10g/kg锂金属。
10.根据权利要求6－8中的任一项的方法，其特征在于，作为惰性的有机溶剂以纯的形式或以混合物的形式使用选自己烷、庚烷、辛烷、癸烷、十一烷、十二烷、甲苯、乙苯、异丙基苯的以市售的沸腾馏分的形式的烃类。
11.根据权利要求6－8的任一项的方法，其特征在于，在＜180.5℃的温度实施附加涂覆。
12.根据权利要求1的钝化的锂金属在预锂化电化学活性材料中的应用。
13.根据权利要求12的应用，其特征在于，所述电化学活性材料为锂电池的石墨-、合金-或转化阳极。
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| CN106537666B (zh) * | 2014-07-14 | 2020-02-28 | 住友金属矿山株式会社 | 包覆锂-镍复合氧化物粒子和包覆锂-镍复合氧化物粒子的制造方法 |
| CN104157463A (zh) * | 2014-08-15 | 2014-11-19 | 万星光电子(东莞)有限公司 | 负极片及其制备方法、锂离子超级电容器 |
| CN105762328B (zh) * | 2014-12-15 | 2019-03-29 | 比亚迪股份有限公司 | 一种钝化锂粉及其制备方法、添加该钝化锂粉的正极材料及电池 |
| DE102015202612A1 (de) | 2015-02-13 | 2016-08-18 | Rockwood Lithium GmbH | Stabilisierte (teil)lithiierte Graphitmaterialien, Verfahren zu deren Herstellung und Verwendung für Lithiumbatterien |
| CN104835652A (zh) * | 2015-03-24 | 2015-08-12 | 中航锂电（洛阳）有限公司 | 锂超级电容电池用嵌锂负极片及制备方法、锂超级电容电池 |
| CN106001585A (zh) * | 2015-03-31 | 2016-10-12 | Tdk株式会社 | 稳定化锂粉和使用其的锂离子二次电池 |
| CN107058761B (zh) * | 2016-12-19 | 2019-06-11 | 天齐锂业股份有限公司 | 金属锂或锂合金中降除氮化物的方法 |
| CN106756105B (zh) * | 2016-12-19 | 2018-10-30 | 天齐锂业股份有限公司 | 金属锂或锂合金中氮化物的降除方法 |
| KR20190106639A (ko) | 2018-03-09 | 2019-09-18 | 주식회사 엘지화학 | 리튬 이차전지 |
| CN108923046B (zh) * | 2018-07-03 | 2021-08-31 | 江苏乐能电池股份有限公司 | 一种纳米多孔富锂磷酸铁锂材料的制备方法 |
| CN115249787A (zh) | 2021-04-28 | 2022-10-28 | 株式会社村田制作所 | 一种锂离子二次电池负极、其制备方法及锂离子二次电池 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101295788A (zh) * | 2007-04-27 | 2008-10-29 | Tdk株式会社 | 活性物质、电极、电池、活性物质的制造方法 |
| CN101522343A (zh) * | 2006-10-13 | 2009-09-02 | Fmc公司-锂部 | 用于锂离子用途的稳定化锂金属粉末、组合物和方法 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5776369A (en) | 1993-02-18 | 1998-07-07 | Fmc Corporation | Alkali metal dispersions |
| WO1994019100A1 (en) * | 1993-02-18 | 1994-09-01 | Fmc Corporation | Alkali metal dispersions |
| JPH0811694B2 (ja) * | 1994-01-27 | 1996-02-07 | リチウム コーポレーション オブ アメリカ | 結晶アンチモン酸の製法 |
| WO1997006910A1 (en) * | 1995-08-15 | 1997-02-27 | Fmc Corporation | Alkali metal dispersions |
| US20050130043A1 (en) * | 2003-07-29 | 2005-06-16 | Yuan Gao | Lithium metal dispersion in electrodes |
| US7588623B2 (en) * | 2005-07-05 | 2009-09-15 | Fmc Corporation Lithium Division | Stabilized lithium metal powder for li-ion application, composition and process |
| US8021496B2 (en) * | 2007-05-16 | 2011-09-20 | Fmc Corporation | Stabilized lithium metal powder for Li-ion application, composition and process |
| US20090061321A1 (en) * | 2007-08-31 | 2009-03-05 | Fmc Corporation, Lithium Division | Stabilized lithium metal powder for li-ion application, composition and process |
| CN101418406A (zh) * | 2008-11-18 | 2009-04-29 | 天津中能锂业有限公司 | 一种纯化锂及纯化方法 |
-
2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101522343A (zh) * | 2006-10-13 | 2009-09-02 | Fmc公司-锂部 | 用于锂离子用途的稳定化锂金属粉末、组合物和方法 |
| CN101295788A (zh) * | 2007-04-27 | 2008-10-29 | Tdk株式会社 | 活性物质、电极、电池、活性物质的制造方法 |
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| KR101919329B1 (ko) | 2018-11-19 |
| EP2621650B1 (de) | 2020-12-09 |
| JP5882335B2 (ja) | 2016-03-09 |
| EP2621650A2 (de) | 2013-08-07 |
| CA2811941A1 (en) | 2012-04-26 |
| KR20130128389A (ko) | 2013-11-26 |
| WO2012052265A2 (de) | 2012-04-26 |
| JP2013545886A (ja) | 2013-12-26 |
| WO2012052265A3 (de) | 2013-05-30 |
| DE112011103269A5 (de) | 2013-09-12 |
| US20130181160A1 (en) | 2013-07-18 |
| US11021797B2 (en) | 2021-06-01 |
| US10655229B2 (en) | 2020-05-19 |
| US20170268110A1 (en) | 2017-09-21 |
| CA2811941C (en) | 2020-10-20 |
| CN103379972A (zh) | 2013-10-30 |
| BR112013007687A2 (pt) | 2016-08-09 |
| US20200240020A1 (en) | 2020-07-30 |
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