CA2850040C - Method for producing a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal - Google Patents
Method for producing a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal Download PDFInfo
- Publication number
- CA2850040C CA2850040C CA2850040A CA2850040A CA2850040C CA 2850040 C CA2850040 C CA 2850040C CA 2850040 A CA2850040 A CA 2850040A CA 2850040 A CA2850040 A CA 2850040A CA 2850040 C CA2850040 C CA 2850040C
- Authority
- CA
- Canada
- Prior art keywords
- sodium
- sodium metal
- current collector
- metal
- dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 100
- 239000011734 sodium Substances 0.000 title claims abstract description 100
- 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 title claims abstract description 96
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 54
- -1 imide salt Chemical class 0.000 claims abstract description 45
- 239000011230 binding agent Substances 0.000 claims abstract description 26
- 239000011261 inert gas Substances 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 25
- 239000002923 metal particle Substances 0.000 claims description 8
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 abstract description 23
- 239000002932 luster Substances 0.000 abstract description 13
- 238000000151 deposition Methods 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 26
- 239000011889 copper foil Substances 0.000 description 22
- 239000010408 film Substances 0.000 description 21
- 238000002156 mixing Methods 0.000 description 17
- 239000002612 dispersion medium Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000012188 paraffin wax Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 230000001747 exhibiting effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 150000003385 sodium Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
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- 239000003273 ketjen black Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
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- 238000004381 surface treatment Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical class [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
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- 238000004528 spin coating Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/325—Processes or devices for cleaning the bath
-
- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/106—Coating with metal alloys or metal elements only
-
- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
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- 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
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
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- 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
- H01M4/043—Processes of manufacture in general involving compressing or compaction
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
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- H01M4/00—Electrodes
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- 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
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Abstract
A current collector is covered with sodium metal through: (1) a step of applying a sodium dispersion containing sodium metal and at least one substance selected from the group consisting of an imide salt and a binder, on a current collector in an inert gas environment (with an oxygen concentration of not more than 0.01% and a dew point of not more than -10°C), followed by heating and drying; (2) a step of pressure bonding a piece of solid sodium metal having a surface which exhibits a metallic luster onto a current collector in the aforementioned inert gas environment; (3) a step of vapor-depositing sodium metal on a current collector in a reduced pressure environment; or (4) a step of immersing a current collector having a surface fired at a temperature ranging from 150 to 300°C in molten sodium metal after removing a coating film which is generated on a surface and formed from impurities, in the aforementioned inert gas environment.
Description
METHOD FOR PRODUCING A NEGATIVE ELECTRODE
FOR USE IN A SODIUM SECONDARY BATTERY
IN WHICH A SURFACE OF A CURRENT COLLECTOR
IS COVERED WITH SODIUM METAL
[Background Art]
FOR USE IN A SODIUM SECONDARY BATTERY
IN WHICH A SURFACE OF A CURRENT COLLECTOR
IS COVERED WITH SODIUM METAL
[Background Art]
[0002]
Although the demand for lithium-ion batteries has been increasing in various fields such as mobile phones, automobiles, and storage batteries, because the ore source of lithium to become the negative electrode material thereof is ubiquitous worldwide, there is a growing concern about the global supply in recent years. On the other hand, sodium chloride which serves as a raw material of sodium is contained abundantly in seawater and bedded salt and is distributed globally. Accordingly, development of a sodium ion secondary battery using sodium in place of lithium has been desired.
Although the demand for lithium-ion batteries has been increasing in various fields such as mobile phones, automobiles, and storage batteries, because the ore source of lithium to become the negative electrode material thereof is ubiquitous worldwide, there is a growing concern about the global supply in recent years. On the other hand, sodium chloride which serves as a raw material of sodium is contained abundantly in seawater and bedded salt and is distributed globally. Accordingly, development of a sodium ion secondary battery using sodium in place of lithium has been desired.
[0003]
Although sodium-sulfur (NaS) batteries have been put into practical use as the battery using sodium as a raw material, NaS batteries require a temperature of 300 C or higher to drive, and thus are limited to the specific applications of power storage and have not been put into practical use for general applications. In addition, although molten sodium is used as a negative electrode active material and negative electrodes are configured using a mesh made of SUS, steel wool, or the like as a current collector in the NaS batteries, because sodium metal is used in the form of liquid with high activity, there is a disadvantage in that sodium metal easily flows into the positive electrode chamber side to cause short circuit in those cases where the solid electrolyte breaks down.
Although sodium-sulfur (NaS) batteries have been put into practical use as the battery using sodium as a raw material, NaS batteries require a temperature of 300 C or higher to drive, and thus are limited to the specific applications of power storage and have not been put into practical use for general applications. In addition, although molten sodium is used as a negative electrode active material and negative electrodes are configured using a mesh made of SUS, steel wool, or the like as a current collector in the NaS batteries, because sodium metal is used in the form of liquid with high activity, there is a disadvantage in that sodium metal easily flows into the positive electrode chamber side to cause short circuit in those cases where the solid electrolyte breaks down.
[0004]
In sodium secondary batteries, in order not to make sodium move to positive electrode side, it is required to adhere sodium to a current collector to prevent the break down of electrical connection therewith, thereby suppressing the flow of sodium. Accordingly, for example, those that are joined by adhering sodium metal or a sodium compound onto the surface of a current collector in layers so as to provide electrical conductivity have been used as the negative electrodes of sodium secondary batteries.
In sodium secondary batteries, in order not to make sodium move to positive electrode side, it is required to adhere sodium to a current collector to prevent the break down of electrical connection therewith, thereby suppressing the flow of sodium. Accordingly, for example, those that are joined by adhering sodium metal or a sodium compound onto the surface of a current collector in layers so as to provide electrical conductivity have been used as the negative electrodes of sodium secondary batteries.
[0005]
As a method of coating the surface of a support with sodium metal, for example, a method of producing a sodium metal-coated body has been known, which is characterized in that sodium metal is dissolved in liquid ammonia and the resulting solution is brought into contact with a support having good air permeability and a large surface area, followed by the volatilization of ammonia (for example, see Patent Document 1).
In addition, in the methods of producing sodium secondary batteries, a method of producing a negative electrode has been known, in which an appropriate amount of N-methyl pyrrolidone is added and mixed with a mixture prepared by mixing a negative electrode active material and polyvinylidene fluoride at a ratio of 95 ; 5 to obtain a coating material-like slurry; a masking tape is adhered onto a part of copper foil with a thickness of 10 [tm; the aforementioned slurry is coated onto the surface using a doctor blade, followed by drying to form a coating film;
then, a similar coating film is formed on the opposite surface side, followed by application of a roll press, thereby preparing an electrode having a width of about 55 mm, length of about 330 mm, and thickness of about 230 m to form a negative electrode;
and the metallic sodium cut out into a width of 5 mm, length of 20 mm, and thickness of 200 tun is further pressure bonded onto one end of that negative electrode (for example, see Patent Document 2). As an improved method of this method for producing a negative electrode, a method has been known, in which a negative electrode is immersed in a solution prepared by dissolving sodium metal in liquid ammonia which is placed in a vessel cooled to about -40 C, before the negative electrode is pressure bonded with sodium metal, and is then taken out and charged into a vacuum chamber at room temperature to carry out the removal of ammonia, thereby producing a negative electrode predoped with sodium ions (for example, see Patent Document 3).
[Citation List]
[Patent Documents]
As a method of coating the surface of a support with sodium metal, for example, a method of producing a sodium metal-coated body has been known, which is characterized in that sodium metal is dissolved in liquid ammonia and the resulting solution is brought into contact with a support having good air permeability and a large surface area, followed by the volatilization of ammonia (for example, see Patent Document 1).
In addition, in the methods of producing sodium secondary batteries, a method of producing a negative electrode has been known, in which an appropriate amount of N-methyl pyrrolidone is added and mixed with a mixture prepared by mixing a negative electrode active material and polyvinylidene fluoride at a ratio of 95 ; 5 to obtain a coating material-like slurry; a masking tape is adhered onto a part of copper foil with a thickness of 10 [tm; the aforementioned slurry is coated onto the surface using a doctor blade, followed by drying to form a coating film;
then, a similar coating film is formed on the opposite surface side, followed by application of a roll press, thereby preparing an electrode having a width of about 55 mm, length of about 330 mm, and thickness of about 230 m to form a negative electrode;
and the metallic sodium cut out into a width of 5 mm, length of 20 mm, and thickness of 200 tun is further pressure bonded onto one end of that negative electrode (for example, see Patent Document 2). As an improved method of this method for producing a negative electrode, a method has been known, in which a negative electrode is immersed in a solution prepared by dissolving sodium metal in liquid ammonia which is placed in a vessel cooled to about -40 C, before the negative electrode is pressure bonded with sodium metal, and is then taken out and charged into a vacuum chamber at room temperature to carry out the removal of ammonia, thereby producing a negative electrode predoped with sodium ions (for example, see Patent Document 3).
[Citation List]
[Patent Documents]
[0006]
[Patent Document 1] Japanese Unexamined Patent Application, First Publication No. Sho 61-074641 [Patent Document 2] Japanese Unexamined Patent Application, First Publication No. 2010-272492 [Patent Document 3] Japanese Unexamined Patent Application, First Publication No. 2011-009202 [Summary of Invention]
[Technical Problem]
[Patent Document 1] Japanese Unexamined Patent Application, First Publication No. Sho 61-074641 [Patent Document 2] Japanese Unexamined Patent Application, First Publication No. 2010-272492 [Patent Document 3] Japanese Unexamined Patent Application, First Publication No. 2011-009202 [Summary of Invention]
[Technical Problem]
[0007]
It is difficult to handle sodium because sodium exhibits higher activity than lithium, is easily deactivated by the moisture in the air, and also reacts violently with water. In particular, sodium hardly forms an alloy with metals such as copper, and thus there is a problem in that it is difficult to adhere sodium on the surface of a current collector in those cases where metal foils such as copper foils are used as a current collector.
In addition, there was a problem of complicated operation with the methods described in Patent Documents 1 and 3 because of the use of liquid ammonia.
Further, there is no description of specific method in Patent Document 2, and depending on the type of substrate, there was also a problem in that the obtained laminates were not necessarily satisfactory.
It is difficult to handle sodium because sodium exhibits higher activity than lithium, is easily deactivated by the moisture in the air, and also reacts violently with water. In particular, sodium hardly forms an alloy with metals such as copper, and thus there is a problem in that it is difficult to adhere sodium on the surface of a current collector in those cases where metal foils such as copper foils are used as a current collector.
In addition, there was a problem of complicated operation with the methods described in Patent Documents 1 and 3 because of the use of liquid ammonia.
Further, there is no description of specific method in Patent Document 2, and depending on the type of substrate, there was also a problem in that the obtained laminates were not necessarily satisfactory.
[0008]
The present invention has an object of providing a method for producing a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal in which sodium metal is deposited strongly and also in layers on the surface of a current collector; and a sodium dispersion composition used in the aforementioned production method.
[Solution to Problem]
The present invention has an object of providing a method for producing a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal in which sodium metal is deposited strongly and also in layers on the surface of a current collector; and a sodium dispersion composition used in the aforementioned production method.
[Solution to Problem]
[0009]
A first mode of the present invention relates to a method for producing a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal including any one of steps selected from the group consisting of the following steps (1) to (4):
(1) a step of applying a sodium dispersion containing sodium metal and at least one substance selected from the group consisting of an imide salt and a binder, on a current collector in an inert gas environment having an oxygen concentration of not more than 0.01% and a dew point of not more than -10 C, followed by heating and drying;
(2) a step of pressure bonding a piece of solid sodium metal having a surface which exhibits a metallic luster onto a current collector in an inert gas environment having an oxygen concentration of not more than 0.01% and a dew point of not more than -
A first mode of the present invention relates to a method for producing a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal including any one of steps selected from the group consisting of the following steps (1) to (4):
(1) a step of applying a sodium dispersion containing sodium metal and at least one substance selected from the group consisting of an imide salt and a binder, on a current collector in an inert gas environment having an oxygen concentration of not more than 0.01% and a dew point of not more than -10 C, followed by heating and drying;
(2) a step of pressure bonding a piece of solid sodium metal having a surface which exhibits a metallic luster onto a current collector in an inert gas environment having an oxygen concentration of not more than 0.01% and a dew point of not more than -
10 C;
(3) a step of vapor-depositing sodium metal on a current collector in a reduced pressure environment; and (4) a step of immersing a current collector having a surface fired at a temperature from 150 to 300 C in molten sodium metal after removing a coating film which is generated on a surface and formed from impurities, in an inert gas environment having an oxygen concentration of not more than 0.01% and a dew point of not more than -10 C.
The aforementioned production method preferably includes the aforementioned step (1).
The electrode covered with sodium metal which is obtained by the aforementioned step (1) is preferably further subjected to a pressure molding process.
The aforementioned sodium dispersion used in the aforementioned step (1) preferably contains an imide salt and sodium metal.
The aforementioned imide salt is preferably at least one substance selected from the group consisting of a bisfluorosulfonylimide sodium salt and a bisfluorosulfonylimide potassium salt.
[0010]
A second mode of the present invention relates to a sodium dispersion composition including sodium metal and an imide salt.
The aforementioned imide salt is preferably at least one substance selected from the group consisting of a bisfluorosulfonylimide sodium salt and a bisfluorosulfonylimide potassium salt.
[Advantageous Effects of Invention]
(3) a step of vapor-depositing sodium metal on a current collector in a reduced pressure environment; and (4) a step of immersing a current collector having a surface fired at a temperature from 150 to 300 C in molten sodium metal after removing a coating film which is generated on a surface and formed from impurities, in an inert gas environment having an oxygen concentration of not more than 0.01% and a dew point of not more than -10 C.
The aforementioned production method preferably includes the aforementioned step (1).
The electrode covered with sodium metal which is obtained by the aforementioned step (1) is preferably further subjected to a pressure molding process.
The aforementioned sodium dispersion used in the aforementioned step (1) preferably contains an imide salt and sodium metal.
The aforementioned imide salt is preferably at least one substance selected from the group consisting of a bisfluorosulfonylimide sodium salt and a bisfluorosulfonylimide potassium salt.
[0010]
A second mode of the present invention relates to a sodium dispersion composition including sodium metal and an imide salt.
The aforementioned imide salt is preferably at least one substance selected from the group consisting of a bisfluorosulfonylimide sodium salt and a bisfluorosulfonylimide potassium salt.
[Advantageous Effects of Invention]
[0011]
By using the present invention, it is possible to produce an electrode in which the surface of a current collector is covered uniformly and also firmly with sodium metal.
[Brief Description of Drawings]
By using the present invention, it is possible to produce an electrode in which the surface of a current collector is covered uniformly and also firmly with sodium metal.
[Brief Description of Drawings]
[0012]
FIG. 1 is an image of a laminate obtained in Example 1.
FIG. 2 is an image of a laminate obtained in Comparative Example 1.
FIG. 3 is an image of a laminate obtained in Example 2.
FIG. 4 is an image of a laminate obtained in Comparative Example 3.
FIG. 5 is an image of a laminate obtained in Example 3.
FIG. 6 is an electron microscope image of sodium particles which are bonded onto a copper foil in Example 4 (magnification: 1,000-fold).
FIG. 7 is an electron microscope image of sodium particles which are bonded onto a copper foil in Example 5 (magnification: 1,000-fo1d).
[Description of Embodiments]
FIG. 1 is an image of a laminate obtained in Example 1.
FIG. 2 is an image of a laminate obtained in Comparative Example 1.
FIG. 3 is an image of a laminate obtained in Example 2.
FIG. 4 is an image of a laminate obtained in Comparative Example 3.
FIG. 5 is an image of a laminate obtained in Example 3.
FIG. 6 is an electron microscope image of sodium particles which are bonded onto a copper foil in Example 4 (magnification: 1,000-fold).
FIG. 7 is an electron microscope image of sodium particles which are bonded onto a copper foil in Example 5 (magnification: 1,000-fo1d).
[Description of Embodiments]
[0013]
The inventors of the present invention have found that by suppressing the formation of oxides or the like on the surface of sodium metal, the adhesion of the sodium metal to the current collector improves. The present invention has been accomplished as a result of further investigation based on this finding.
The inventors of the present invention have found that by suppressing the formation of oxides or the like on the surface of sodium metal, the adhesion of the sodium metal to the current collector improves. The present invention has been accomplished as a result of further investigation based on this finding.
[0014]
<Production method of a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal>
A first mode of the present invention relates to a production method of an electrode in which the surface of a current collector is covered with sodium metal.
In the production method of the present mode, by depositing sodium metal with no impurities such as oxides onto a current collector, the sodium metal can be deposited onto the current collector with unprecedentedly sufficient strength.
<Production method of a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal>
A first mode of the present invention relates to a production method of an electrode in which the surface of a current collector is covered with sodium metal.
In the production method of the present mode, by depositing sodium metal with no impurities such as oxides onto a current collector, the sodium metal can be deposited onto the current collector with unprecedentedly sufficient strength.
[0015]
In the present invention and in the present description, an inert gas is a gas capable of suppressing the oxidation of sodium metal. Examples of the inert gas include nitrogen gas, helium gas, and argon gas.
The method for making the inside of the reaction system an inert gas atmosphere is not particularly limited, and examples thereof include a method of sufficiently purging the inside of the reaction system with an inert gas, and a method of repeating an operation several times in which the inside of the reaction system is degassed using a pump and then returned to normal pressure with an inert gas.
In the inert gas environment, the oxygen concentration is not more than 0.01%, and the dew point is not more than -10 C, and preferably not more than -40 C.
On the other hand, the lower limit of the oxygen concentration is 0% and the lower limit of the dew point is, but not limited to, -76 C.
In the present invention and in the present description, an inert gas is a gas capable of suppressing the oxidation of sodium metal. Examples of the inert gas include nitrogen gas, helium gas, and argon gas.
The method for making the inside of the reaction system an inert gas atmosphere is not particularly limited, and examples thereof include a method of sufficiently purging the inside of the reaction system with an inert gas, and a method of repeating an operation several times in which the inside of the reaction system is degassed using a pump and then returned to normal pressure with an inert gas.
In the inert gas environment, the oxygen concentration is not more than 0.01%, and the dew point is not more than -10 C, and preferably not more than -40 C.
On the other hand, the lower limit of the oxygen concentration is 0% and the lower limit of the dew point is, but not limited to, -76 C.
[0016]
In the present invention, the current collector to be covered with sodium metal is not particularly limited, and is, for example, a foil, film, thin film, wire, fiber, plate, net, cloth, or porous material which is formed from copper, nickel, aluminum, titanium, stainless steel, carbons such as graphite and amorphous carbon, or a conductive rubber or resin, and which is subjected to no surface treatment or is subjected to a heat treatment. Among these, the aforementioned current collector is preferably a copper foil. The aforementioned copper foil is preferably an oxygen-free copper foil, more preferably a copper foil whose surface is heated and fired with a gas burner or the like, and even more preferably a copper foil which is surface-treated by being heated to a temperature equal to or higher than room temperature but not more than 300 C with a butane burner or the like.
[00171 In those cases where solid sodium metal is used, it is possible to produce a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal by a step of pressure bonding a piece of solid sodium metal whose surface exhibits a metallic luster onto a current collector in an inert gas environment with an oxygen concentration of not more than 0.01%
and a dew point of not more than -10 C, and preferably not more than -40 C. The aforementioned piece of solid sodium metal having a surface with a metallic luster can be obtained by removing a coating film which is usually formed on the surface of solid sodium metal and formed from impurities, and more specifically, a coating film formed from peroxides, superoxides, oxides, hydroxides, or a mixture thereof (hereinafter, referred to as a coating film of oxides or the like) in the aforementioned inert gas environment. The piece of solid sodium metal prepared in this manner is immediately pressure bonded onto a current collector in the same inert gas environment.
[0018]
In an inert gas environment with an oxygen concentration of not more than 0.01% and a dew point of not more than -10 C, the activity of sodium metal can be suppressed, and the formation of oxides or the like can be suppressed. For this reason, in this environment, it is possible to pressure bond a piece of solid sodium metal exhibiting a metallic luster onto the surface of a current collector before the coating film of oxides or the like is formed on the surface.
[0019]
The method of pressure bonding a piece of solid sodium metal with a current collector is not particularly limited, and examples thereof include a method of rolling both of them with a roller and a method of pressing both of them with a pressing machine.
The pressure at the time of pressure bonding a piece of solid sodium metal and a current collector is not particularly limited as long as the force is at least sufficient enough to adhere the two, and, for example, it is possible to pressure bond the two by applying an external force which is at least sufficient enough to break the surface of the sodium particles, while the piece of solid sodium metal and the current collector are superposed.
[0020]
In the case of using sodium vapor, it is possible to produce a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal through a process in which sodium metal is vapor-deposited onto a current collector under a reduced pressure environment. The aforementioned reduced pressure environment is preferably one that is obtained by reducing the pressure in the aforementioned inert gas environment. Since the outside air is strictly blocked and the dew point is also lowered, in such a reduced pressure environment, an atmosphere is achieved in which degradation of the surface of solid sodium metal is suppressed. Under this atmosphere, it is possible to adhere sodium metal onto the current collector with no impurities involved by heating sodium metal and vapor-depositing the generated sodium vapor onto the current collector.
[0021]
The method of depositing the sodium vapor onto a current collector is not particularly limited. For example, the sodium vapor may be deposited electrostatically onto a current collector, the sodium vapor may be sprayed and deposited onto a current collector, or the sodium vapor may be condensed and deposited onto a cooled current collector. It is preferable to vapor-deposit the sodium vapor onto a current collector which is heated to about 881 C or less.
[0022]
In the case of using molten (liquid) sodium metal, it is possible to produce a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal through a process in which a current collector whose surface is fired at a temperature ranging from 150 to 300 C with a burner or the like is immersed in a molten sodium metal immediately after the coating film of oxides or the like which is present on the liquid surface is removed therefrom, in an inert gas environment with an oxygen concentration of not more than 0.01% and a dew point of not more than -10 C, and preferably not more than -40 C. By removing a coating film of oxides or the like from the molten sodium metal in advance, it is possible to adhere sodium metal containing no impurities such as oxides onto the current collector.
[0023]
As a current collector to be immersed in molten sodium metal, those having a surface with no dirt or the like attached thereon are used, and more specifically, a current collector fired from 150 to 300 C with a gas burner or the like is used. This current collector is immersed in molten sodium metal and then pulled out to solidify as it is, thereby forming a thin layer of sodium metal on the surface of the current collector.
[0024]
By applying a sodium dispersion containing sodium metal and at least one substance selected from the group consisting of an imide salt and a binder onto a current collector in the aforementioned inert gas environment (with an oxygen concentration of not more than 0.01% and a dew point of not more than -10 C, and preferably not more than -40 C) and subjecting the resultant to heating and drying (preferably heating and drying under reduced pressure), it is possible to produce a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal. The aforementioned sodium dispersion is in the form of, for example, an emulsion or suspension in which the sodium metal particles are dispersed (uniformly suspended) or in the form of a precipitating dispersion.
The aforementioned sodium dispersion preferably contains no impurities such as oxides. For this reason, as the aforementioned sodium metal, a piece of metal which is cut out from solid sodium metal in the aforementioned inert gas environment, and in which the entire surface exhibits a metallic luster, or molten sodium metal is preferably used.
[0025]
As the aforementioned imide salt, it is preferable to use at least one substance selected from the group consisting of a bisfluorosulfonylimide sodium salt and a bisfluorosulfonylimide potassium salt.
When the aforementioned sodium dispersion contains an imide salt, since the surface of the sodium metal particles is coated with the imide salt, the formation of oxides or the like on the surface of the sodium metal particles is further suppressed, which is preferred.
[0026]
As a binder, for example, those can be used which are selected appropriately from amongst the binders used together with an electrode active material, when preparing the electrodes of sodium secondary batteries or lithium secondary batteries.
[0027]
More specifically, examples of the binders include (meth)acrylic acid-based resins, (meth)acrylamide-based resins, styrene-based resins, polybutadiene resins, epoxy resins, vinyl resins, polyvinyl alcohols, phenol resins, melamine resins, polyurethane resins, urea resins, polyamide resins, polyimide resins, and polyamideimide resins. Other than those, polysaccharides or the derivatives thereof such as starch, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, and nitrocellulose may be used. Further, the binder may be a polymer of a fluorine compound or may be a polymer formed from monomers containing no fluorine atom. Examples of the polymers of fluorine compounds include polyvinylidene fluoride. In addition, one type of binder may be used alone, or two or more types thereof may be used as a mixture. As the binder used in the present invention, (meth)acrylic acid-based resins, (meth)acrylamide-based resins, styrene-based resins, epoxy resins, vinyl resins, and polyvinyl alcohols are preferred, and (meth)acrylic acid-based resins such as sodium polyacrylate or styrene-butadiene-based resins are more preferred.
[0028]
A conductive agent can also be mixed if necessary, and specific examples thereof include conductive materials such as Ketjen black, carbon black, acetylene black, natural graphite, artificial graphite, carbon fibers, metal powders, metal fibers, and conductive ceramic materials. In the present invention, only one type of conductive agent may be used, or a mixture of two or more types thereof may be used. As the conductive agent used in the present invention, it is preferable to use one type of Ketjen black, carbon black, and acetylene black, or a mixture of two or more types thereof.
[0029]
The aforementioned sodium dispersion is prepared by adding and mixing sodium metal and at least one substance selected from the group consisting of an imide salt and a binder in an appropriate dispersion medium. The sodium metal, and the imide salt and/or binder may be added directly for preparation in one dispersion medium; each of a dispersion containing sodium metal and a solution containing an imide salt and/or a binder may be independently prepared, followed by mixing of the two for preparation; or each of a dispersion containing sodium metal and an imide salt and a solution containing a binder may be independently prepared, followed by mixing of the two for preparation. Here, in the case of preparing the aforementioned dispersion containing sodium metal, it is preferable either to load the aforementioned piece of solid sodium metal haying a surface with a metallic luster in a dispersion medium, followed by mixing and stirring while heating to a temperature equal to or higher than the melting point of sodium (97.8 C), or to add molten sodium metal to a dispersion medium followed by mixing and stirring. In addition, in the case of preparing a dispersion containing an imide salt, it is preferable to carry out the mixing and stirring while heating to a temperature equal to or higher than the melting point of the imide salt.
Further, in the case of preparing a dispersion containing sodium metal and an imide salt, it is preferable to carry out the mixing and stirring while heating to a temperature which is equal to or higher than the melting point of sodium and is also equal to or higher than the melting point of the imide salt. By preparing a sodium dispersion in this manner, the sodium metal particles in which the formation of oxides or the like is suppressed can be dispersed more uniformly within a dispersion medium, and a more uniform coating film of sodium metal can be formed on a current collector.
The aforementioned mixing method is not particularly limited, and can be performed by using a generally used dispersing machine such as a homogenizer, a ball mill, a sand mill, and a planetary mixer.
[0030]
Before mixing with sodium metal, it is preferable to remove contaminants and impurities such as water which react with sodium metal from the dispersion medium, imide salt and binder in advance. As a removal method, specific examples include a method in which, in the case of preparing a solution containing an imide salt and/or a binder followed by mixing with a dispersion containing sodium metal, a small amount of sodium metal, other than the sodium metal to be adhered onto a current collector, is added in advance to the solution containing an imide salt and/or a binder, thereby carrying out a dehydration reaction or the like in advance.
[0031]
The dispersion medium for dispersing sodium metal or the like is not particularly limited as long as it is a solvent which does not react with sodium metal. As the solvent, for example, hydrocarbon-based solvents are preferred, and specific examples thereof include fluid, paraffin-based hydrocarbons having 6 to 20 carbon atoms and aromatic hydrocarbons such as toluene and xylene. The paraffin-based hydrocarbon may be a linear normal paraffin or an isoparaffin having a branched chain, and a normal paraffin is more preferred. The dispersion medium may be composed solely of one type or a mixture of two or more types thereof may be used.
[0032]
The content of each of the components in the sodium dispersion containing sodium metal and an imide salt and/or a binder is not particularly limited as long as the amount is sufficient so that when this sodium dispersion is applied onto the surface of the current collector, eventually, an electrode covered with sodium metal is obtained. For example, in this sodium dispersion, the content of sodium metal is preferably not more than 30% by mass and not less than 0.5% by mass, and more preferably not more than 10% by mass and not less than 1% by mass. In addition, in this sodium dispersion, the content of the binder is preferably not more than 10%
by mass, and more preferably ranges from 3 to 5% by mass, relative to 100% by mass of the sodium metal content. Further in this sodium dispersion, the content of the imide salt is preferably not more than 5% by mass, and more preferably from 0.5 to 2% by mass, relative to 100% by mass of the sodium metal content.
[0033]
The aforementioned sodium dispersion is applied onto a current collector in an inert gas environment with an oxygen concentration of not more than 0.01%
and a dew point of not more than -10 C, and preferably not greater than -40 C. The method for applying the aforementioned sodium dispersion onto the current collector surface is not particularly limited, and examples thereof include a spin coating method, a bar coating method, a doctor blade method, a dipping method, and a direct rolling method.
[0034]
Thereafter, the current collector onto which the aforementioned sodium dispersion is applied is heated and dried in an inert gas environment with the same low oxygen concentration and the same low dew point as those described above.
Here, this heating and drying treatment is preferably carried out under a reduced pressure environment, because the outside air is strictly blocked and the dew point is lowered, and thereby, the formation of impurities such as oxides can be further suppressed. Due to this heating and drying treatment, the dispersion medium on the current collector is removed through evaporation, and the fine particles of sodium metal or the fine particles of sodium metal of which the surface is coated with a molten salt (ionic liquid) of the imide salt are deposited onto the current collector surface together with the binder. It should be noted that in order to remove the organic solvent more completely from the current collector surface, it is preferable to wash the current collector, after being heated and dried, with a volatile solvent which the organic solvent used as a dispersion medium can dissolve, followed by drying.
[0035]
The thus obtained electrode covered with sodium metal can be used as it is, but is preferably further subjected to a pressure molding process thereafter.
For example, by applying pressure using a pressing machine or the like to an electrode covered with sodium metal which is formed by applying a sodium dispersion onto the surface of a current collector, followed by drying, it is possible to further strengthen the joint between the coating film formed from sodium dispersion and the current collector. Moreover, it is possible to break down the surface coating film of fine particles of sodium metal which are adhered onto the current collector surface by pressurization, and to thereby expose a non-degraded, active surface, which is intrinsic to sodium metal. For example, when pressure is applied through, for instance, the rolling process using a roll press, gaps such as cracks are generated in the coating film of sodium metal. By using an electrode having cracks in the coating film of sodium metal, it is possible to form a sodium coating film with a higher sodium activity and a larger effective surface area.
[0036]
<Sodium dispersion composition containing sodium metal and imide salt>
A second mode of the present invention relates to a sodium dispersion composition containing sodium metal and an imide salt. The sodium dispersion composition of the present mode is used for enhancing the adhesion of sodium metal to the current collector, and is used in the aforementioned production method according to the first mode.
The aforementioned sodium dispersion composition is in the form of, for example, an emulsion or suspension in which the sodium metal particles are dispersed (uniformly suspended) or in the form of a precipitating dispersion.
[0037]
The aforementioned sodium metal is prepared by using those described in the aforementioned first mode, and preferably a piece of solid sodium metal with a surface exhibiting a metallic luster which is obtained by cutting off a coating film of oxides or the like from the surface of the piece of solid sodium metal in the aforementioned inert gas environment, or molten sodium metal.
[0038]
As the aforementioned imide salt, at least one substance selected from the group consisting of a bisfluorosulfonylimide sodium salt and a bisfluorosulfonylimide potassium salt is preferably used.
[0039]
The sodium dispersion composition according to the second mode of the present invention can, as in the first mode described above, contain a binder, a conductive agent, and/or a dispersion medium or the like, and it is preferable to at least contain a binder and a dispersion medium. For the aforementioned binder, conductive agent and dispersion medium, those described in the aforementioned first mode can be used.
[0040]
The sodium dispersion composition according to the second mode of the present invention is prepared by mixing sodium metal and an imide salt in the same method as in the aforementioned first mode. The aforementioned sodium dispersion composition is preferably prepared by adding, in one dispersion medium in the inert gas environment described above, the aforementioned piece of solid sodium metal with a surface exhibiting a metallic luster or molten sodium metal and an imide salt, followed by mixing and stirring. More preferably, the aforementioned sodium dispersion composition is prepared by charging the aforementioned piece of solid sodium metal with a surface exhibiting a metallic luster and an imide salt in a dispersion medium, followed by mixing and stirring while heating to a temperature which is equal to or higher than the melting point of sodium (97.8 C) and is also equal to or higher than the melting point of the imide salt. Because the surface of the sodium metal particles can be coated with an imide salt more efficiently when prepared in this manner, there is a tendency that the formation of oxides or the like on the surface of the sodium metal particles is
In the present invention, the current collector to be covered with sodium metal is not particularly limited, and is, for example, a foil, film, thin film, wire, fiber, plate, net, cloth, or porous material which is formed from copper, nickel, aluminum, titanium, stainless steel, carbons such as graphite and amorphous carbon, or a conductive rubber or resin, and which is subjected to no surface treatment or is subjected to a heat treatment. Among these, the aforementioned current collector is preferably a copper foil. The aforementioned copper foil is preferably an oxygen-free copper foil, more preferably a copper foil whose surface is heated and fired with a gas burner or the like, and even more preferably a copper foil which is surface-treated by being heated to a temperature equal to or higher than room temperature but not more than 300 C with a butane burner or the like.
[00171 In those cases where solid sodium metal is used, it is possible to produce a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal by a step of pressure bonding a piece of solid sodium metal whose surface exhibits a metallic luster onto a current collector in an inert gas environment with an oxygen concentration of not more than 0.01%
and a dew point of not more than -10 C, and preferably not more than -40 C. The aforementioned piece of solid sodium metal having a surface with a metallic luster can be obtained by removing a coating film which is usually formed on the surface of solid sodium metal and formed from impurities, and more specifically, a coating film formed from peroxides, superoxides, oxides, hydroxides, or a mixture thereof (hereinafter, referred to as a coating film of oxides or the like) in the aforementioned inert gas environment. The piece of solid sodium metal prepared in this manner is immediately pressure bonded onto a current collector in the same inert gas environment.
[0018]
In an inert gas environment with an oxygen concentration of not more than 0.01% and a dew point of not more than -10 C, the activity of sodium metal can be suppressed, and the formation of oxides or the like can be suppressed. For this reason, in this environment, it is possible to pressure bond a piece of solid sodium metal exhibiting a metallic luster onto the surface of a current collector before the coating film of oxides or the like is formed on the surface.
[0019]
The method of pressure bonding a piece of solid sodium metal with a current collector is not particularly limited, and examples thereof include a method of rolling both of them with a roller and a method of pressing both of them with a pressing machine.
The pressure at the time of pressure bonding a piece of solid sodium metal and a current collector is not particularly limited as long as the force is at least sufficient enough to adhere the two, and, for example, it is possible to pressure bond the two by applying an external force which is at least sufficient enough to break the surface of the sodium particles, while the piece of solid sodium metal and the current collector are superposed.
[0020]
In the case of using sodium vapor, it is possible to produce a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal through a process in which sodium metal is vapor-deposited onto a current collector under a reduced pressure environment. The aforementioned reduced pressure environment is preferably one that is obtained by reducing the pressure in the aforementioned inert gas environment. Since the outside air is strictly blocked and the dew point is also lowered, in such a reduced pressure environment, an atmosphere is achieved in which degradation of the surface of solid sodium metal is suppressed. Under this atmosphere, it is possible to adhere sodium metal onto the current collector with no impurities involved by heating sodium metal and vapor-depositing the generated sodium vapor onto the current collector.
[0021]
The method of depositing the sodium vapor onto a current collector is not particularly limited. For example, the sodium vapor may be deposited electrostatically onto a current collector, the sodium vapor may be sprayed and deposited onto a current collector, or the sodium vapor may be condensed and deposited onto a cooled current collector. It is preferable to vapor-deposit the sodium vapor onto a current collector which is heated to about 881 C or less.
[0022]
In the case of using molten (liquid) sodium metal, it is possible to produce a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal through a process in which a current collector whose surface is fired at a temperature ranging from 150 to 300 C with a burner or the like is immersed in a molten sodium metal immediately after the coating film of oxides or the like which is present on the liquid surface is removed therefrom, in an inert gas environment with an oxygen concentration of not more than 0.01% and a dew point of not more than -10 C, and preferably not more than -40 C. By removing a coating film of oxides or the like from the molten sodium metal in advance, it is possible to adhere sodium metal containing no impurities such as oxides onto the current collector.
[0023]
As a current collector to be immersed in molten sodium metal, those having a surface with no dirt or the like attached thereon are used, and more specifically, a current collector fired from 150 to 300 C with a gas burner or the like is used. This current collector is immersed in molten sodium metal and then pulled out to solidify as it is, thereby forming a thin layer of sodium metal on the surface of the current collector.
[0024]
By applying a sodium dispersion containing sodium metal and at least one substance selected from the group consisting of an imide salt and a binder onto a current collector in the aforementioned inert gas environment (with an oxygen concentration of not more than 0.01% and a dew point of not more than -10 C, and preferably not more than -40 C) and subjecting the resultant to heating and drying (preferably heating and drying under reduced pressure), it is possible to produce a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal. The aforementioned sodium dispersion is in the form of, for example, an emulsion or suspension in which the sodium metal particles are dispersed (uniformly suspended) or in the form of a precipitating dispersion.
The aforementioned sodium dispersion preferably contains no impurities such as oxides. For this reason, as the aforementioned sodium metal, a piece of metal which is cut out from solid sodium metal in the aforementioned inert gas environment, and in which the entire surface exhibits a metallic luster, or molten sodium metal is preferably used.
[0025]
As the aforementioned imide salt, it is preferable to use at least one substance selected from the group consisting of a bisfluorosulfonylimide sodium salt and a bisfluorosulfonylimide potassium salt.
When the aforementioned sodium dispersion contains an imide salt, since the surface of the sodium metal particles is coated with the imide salt, the formation of oxides or the like on the surface of the sodium metal particles is further suppressed, which is preferred.
[0026]
As a binder, for example, those can be used which are selected appropriately from amongst the binders used together with an electrode active material, when preparing the electrodes of sodium secondary batteries or lithium secondary batteries.
[0027]
More specifically, examples of the binders include (meth)acrylic acid-based resins, (meth)acrylamide-based resins, styrene-based resins, polybutadiene resins, epoxy resins, vinyl resins, polyvinyl alcohols, phenol resins, melamine resins, polyurethane resins, urea resins, polyamide resins, polyimide resins, and polyamideimide resins. Other than those, polysaccharides or the derivatives thereof such as starch, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, and nitrocellulose may be used. Further, the binder may be a polymer of a fluorine compound or may be a polymer formed from monomers containing no fluorine atom. Examples of the polymers of fluorine compounds include polyvinylidene fluoride. In addition, one type of binder may be used alone, or two or more types thereof may be used as a mixture. As the binder used in the present invention, (meth)acrylic acid-based resins, (meth)acrylamide-based resins, styrene-based resins, epoxy resins, vinyl resins, and polyvinyl alcohols are preferred, and (meth)acrylic acid-based resins such as sodium polyacrylate or styrene-butadiene-based resins are more preferred.
[0028]
A conductive agent can also be mixed if necessary, and specific examples thereof include conductive materials such as Ketjen black, carbon black, acetylene black, natural graphite, artificial graphite, carbon fibers, metal powders, metal fibers, and conductive ceramic materials. In the present invention, only one type of conductive agent may be used, or a mixture of two or more types thereof may be used. As the conductive agent used in the present invention, it is preferable to use one type of Ketjen black, carbon black, and acetylene black, or a mixture of two or more types thereof.
[0029]
The aforementioned sodium dispersion is prepared by adding and mixing sodium metal and at least one substance selected from the group consisting of an imide salt and a binder in an appropriate dispersion medium. The sodium metal, and the imide salt and/or binder may be added directly for preparation in one dispersion medium; each of a dispersion containing sodium metal and a solution containing an imide salt and/or a binder may be independently prepared, followed by mixing of the two for preparation; or each of a dispersion containing sodium metal and an imide salt and a solution containing a binder may be independently prepared, followed by mixing of the two for preparation. Here, in the case of preparing the aforementioned dispersion containing sodium metal, it is preferable either to load the aforementioned piece of solid sodium metal haying a surface with a metallic luster in a dispersion medium, followed by mixing and stirring while heating to a temperature equal to or higher than the melting point of sodium (97.8 C), or to add molten sodium metal to a dispersion medium followed by mixing and stirring. In addition, in the case of preparing a dispersion containing an imide salt, it is preferable to carry out the mixing and stirring while heating to a temperature equal to or higher than the melting point of the imide salt.
Further, in the case of preparing a dispersion containing sodium metal and an imide salt, it is preferable to carry out the mixing and stirring while heating to a temperature which is equal to or higher than the melting point of sodium and is also equal to or higher than the melting point of the imide salt. By preparing a sodium dispersion in this manner, the sodium metal particles in which the formation of oxides or the like is suppressed can be dispersed more uniformly within a dispersion medium, and a more uniform coating film of sodium metal can be formed on a current collector.
The aforementioned mixing method is not particularly limited, and can be performed by using a generally used dispersing machine such as a homogenizer, a ball mill, a sand mill, and a planetary mixer.
[0030]
Before mixing with sodium metal, it is preferable to remove contaminants and impurities such as water which react with sodium metal from the dispersion medium, imide salt and binder in advance. As a removal method, specific examples include a method in which, in the case of preparing a solution containing an imide salt and/or a binder followed by mixing with a dispersion containing sodium metal, a small amount of sodium metal, other than the sodium metal to be adhered onto a current collector, is added in advance to the solution containing an imide salt and/or a binder, thereby carrying out a dehydration reaction or the like in advance.
[0031]
The dispersion medium for dispersing sodium metal or the like is not particularly limited as long as it is a solvent which does not react with sodium metal. As the solvent, for example, hydrocarbon-based solvents are preferred, and specific examples thereof include fluid, paraffin-based hydrocarbons having 6 to 20 carbon atoms and aromatic hydrocarbons such as toluene and xylene. The paraffin-based hydrocarbon may be a linear normal paraffin or an isoparaffin having a branched chain, and a normal paraffin is more preferred. The dispersion medium may be composed solely of one type or a mixture of two or more types thereof may be used.
[0032]
The content of each of the components in the sodium dispersion containing sodium metal and an imide salt and/or a binder is not particularly limited as long as the amount is sufficient so that when this sodium dispersion is applied onto the surface of the current collector, eventually, an electrode covered with sodium metal is obtained. For example, in this sodium dispersion, the content of sodium metal is preferably not more than 30% by mass and not less than 0.5% by mass, and more preferably not more than 10% by mass and not less than 1% by mass. In addition, in this sodium dispersion, the content of the binder is preferably not more than 10%
by mass, and more preferably ranges from 3 to 5% by mass, relative to 100% by mass of the sodium metal content. Further in this sodium dispersion, the content of the imide salt is preferably not more than 5% by mass, and more preferably from 0.5 to 2% by mass, relative to 100% by mass of the sodium metal content.
[0033]
The aforementioned sodium dispersion is applied onto a current collector in an inert gas environment with an oxygen concentration of not more than 0.01%
and a dew point of not more than -10 C, and preferably not greater than -40 C. The method for applying the aforementioned sodium dispersion onto the current collector surface is not particularly limited, and examples thereof include a spin coating method, a bar coating method, a doctor blade method, a dipping method, and a direct rolling method.
[0034]
Thereafter, the current collector onto which the aforementioned sodium dispersion is applied is heated and dried in an inert gas environment with the same low oxygen concentration and the same low dew point as those described above.
Here, this heating and drying treatment is preferably carried out under a reduced pressure environment, because the outside air is strictly blocked and the dew point is lowered, and thereby, the formation of impurities such as oxides can be further suppressed. Due to this heating and drying treatment, the dispersion medium on the current collector is removed through evaporation, and the fine particles of sodium metal or the fine particles of sodium metal of which the surface is coated with a molten salt (ionic liquid) of the imide salt are deposited onto the current collector surface together with the binder. It should be noted that in order to remove the organic solvent more completely from the current collector surface, it is preferable to wash the current collector, after being heated and dried, with a volatile solvent which the organic solvent used as a dispersion medium can dissolve, followed by drying.
[0035]
The thus obtained electrode covered with sodium metal can be used as it is, but is preferably further subjected to a pressure molding process thereafter.
For example, by applying pressure using a pressing machine or the like to an electrode covered with sodium metal which is formed by applying a sodium dispersion onto the surface of a current collector, followed by drying, it is possible to further strengthen the joint between the coating film formed from sodium dispersion and the current collector. Moreover, it is possible to break down the surface coating film of fine particles of sodium metal which are adhered onto the current collector surface by pressurization, and to thereby expose a non-degraded, active surface, which is intrinsic to sodium metal. For example, when pressure is applied through, for instance, the rolling process using a roll press, gaps such as cracks are generated in the coating film of sodium metal. By using an electrode having cracks in the coating film of sodium metal, it is possible to form a sodium coating film with a higher sodium activity and a larger effective surface area.
[0036]
<Sodium dispersion composition containing sodium metal and imide salt>
A second mode of the present invention relates to a sodium dispersion composition containing sodium metal and an imide salt. The sodium dispersion composition of the present mode is used for enhancing the adhesion of sodium metal to the current collector, and is used in the aforementioned production method according to the first mode.
The aforementioned sodium dispersion composition is in the form of, for example, an emulsion or suspension in which the sodium metal particles are dispersed (uniformly suspended) or in the form of a precipitating dispersion.
[0037]
The aforementioned sodium metal is prepared by using those described in the aforementioned first mode, and preferably a piece of solid sodium metal with a surface exhibiting a metallic luster which is obtained by cutting off a coating film of oxides or the like from the surface of the piece of solid sodium metal in the aforementioned inert gas environment, or molten sodium metal.
[0038]
As the aforementioned imide salt, at least one substance selected from the group consisting of a bisfluorosulfonylimide sodium salt and a bisfluorosulfonylimide potassium salt is preferably used.
[0039]
The sodium dispersion composition according to the second mode of the present invention can, as in the first mode described above, contain a binder, a conductive agent, and/or a dispersion medium or the like, and it is preferable to at least contain a binder and a dispersion medium. For the aforementioned binder, conductive agent and dispersion medium, those described in the aforementioned first mode can be used.
[0040]
The sodium dispersion composition according to the second mode of the present invention is prepared by mixing sodium metal and an imide salt in the same method as in the aforementioned first mode. The aforementioned sodium dispersion composition is preferably prepared by adding, in one dispersion medium in the inert gas environment described above, the aforementioned piece of solid sodium metal with a surface exhibiting a metallic luster or molten sodium metal and an imide salt, followed by mixing and stirring. More preferably, the aforementioned sodium dispersion composition is prepared by charging the aforementioned piece of solid sodium metal with a surface exhibiting a metallic luster and an imide salt in a dispersion medium, followed by mixing and stirring while heating to a temperature which is equal to or higher than the melting point of sodium (97.8 C) and is also equal to or higher than the melting point of the imide salt. Because the surface of the sodium metal particles can be coated with an imide salt more efficiently when prepared in this manner, there is a tendency that the formation of oxides or the like on the surface of the sodium metal particles is
17 further suppressed, and that the uniform adhesion of sodium metal to the current collector is further enhanced.
[0041]
As in the first mode described above, with respect to the constituents of the sodium dispersion composition other than the sodium metal, such as the dispersion medium and the imide salt described above, it is preferable to remove the contaminants and impurities such as water which react with sodium metal in advance, before mixing with sodium metal.
[0042]
The content of sodium metal in the sodium dispersion composition according to the second mode of the present invention is not particularly limited, but is preferably not more than 30% by mass and not less than 0.5% by mass, and more preferably not more than 10% by mass and not less than 1% by mass. In addition, the content of the imide salt in the sodium dispersion composition according to the second mode of the present invention is preferably not more than 5% by mass, and more preferably ranges from 0.5 to 2% by mass, relative to 100% by mass of the sodium metal content.
[Examples]
[0043]
Hereinafter, the present invention is described in detail, based on a series of examples. It should be understood that the scope of the present invention is in no way limited by the following examples.
[0044]
[Example 1] Preparation of laminate using solid sodium metal First, a solid sodium metal obtained by collecting the molten sodium metal following the solidification in a mold was transferred into a glove box under a 4N
grade nitrogen atmosphere with a dew point of not more than -10 C and an oxygen concentration of not more than 0.01%. The surface of the solid sodium metal was
[0041]
As in the first mode described above, with respect to the constituents of the sodium dispersion composition other than the sodium metal, such as the dispersion medium and the imide salt described above, it is preferable to remove the contaminants and impurities such as water which react with sodium metal in advance, before mixing with sodium metal.
[0042]
The content of sodium metal in the sodium dispersion composition according to the second mode of the present invention is not particularly limited, but is preferably not more than 30% by mass and not less than 0.5% by mass, and more preferably not more than 10% by mass and not less than 1% by mass. In addition, the content of the imide salt in the sodium dispersion composition according to the second mode of the present invention is preferably not more than 5% by mass, and more preferably ranges from 0.5 to 2% by mass, relative to 100% by mass of the sodium metal content.
[Examples]
[0043]
Hereinafter, the present invention is described in detail, based on a series of examples. It should be understood that the scope of the present invention is in no way limited by the following examples.
[0044]
[Example 1] Preparation of laminate using solid sodium metal First, a solid sodium metal obtained by collecting the molten sodium metal following the solidification in a mold was transferred into a glove box under a 4N
grade nitrogen atmosphere with a dew point of not more than -10 C and an oxygen concentration of not more than 0.01%. The surface of the solid sodium metal was
18 removed with a knife in this glove box, and by using a roller, a piece of sodium metal in a state of maintaining a metallic luster was immediately rolled, pressure bonded, and joined to a copper foil which had not been subjected to a surface treatment (oxygen-free copper was used, and the same applies hereinafter), thereby producing a sodium metal laminate. The thus obtained sodium metal laminate is shown in FIG. 1. Sodium was deposited on the produced sodium metal laminate with sufficient strength and did not detach therefrom.
[0045]
[Comparative Example 1]
A sodium metal laminate was prepared in the same manner as in Example 1 with the exception that the surface of the sodium metal was not removed in the glove box. As shown in FIG. 2, the sodium metal in which the surface was not removed did not adhere to the copper foil and detached therefrom.
[0046]
[Example 2] Preparation of laminate using molten sodium metal After heating a stainless steel container charged with solid sodium metal using a heating device to melt the sodium metal in a glove box under the same conditions as in Example 1, the coating film of oxides or the like which was generated on the surface was removed from the obtained molten sodium metal. A
copper film prepared by firing the surface at 150 C using a burner was immersed in a molten sodium metal which exhibited a metallic luster immediately after the removal of the surface coating film, and was then immediately pulled out. The sodium metal deposited onto the copper foil was solidified as it is, thereby producing a sodium metal laminate with a smooth surface. The thus obtained sodium metal laminate is shown in FIG. 3. Sodium was deposited on the produced sodium metal laminate with sufficient strength and did not detach therefrom.
[0047]
[Comparative Example 2]
A sodium metal laminate was prepared in the same manner as in Example 2
[0045]
[Comparative Example 1]
A sodium metal laminate was prepared in the same manner as in Example 1 with the exception that the surface of the sodium metal was not removed in the glove box. As shown in FIG. 2, the sodium metal in which the surface was not removed did not adhere to the copper foil and detached therefrom.
[0046]
[Example 2] Preparation of laminate using molten sodium metal After heating a stainless steel container charged with solid sodium metal using a heating device to melt the sodium metal in a glove box under the same conditions as in Example 1, the coating film of oxides or the like which was generated on the surface was removed from the obtained molten sodium metal. A
copper film prepared by firing the surface at 150 C using a burner was immersed in a molten sodium metal which exhibited a metallic luster immediately after the removal of the surface coating film, and was then immediately pulled out. The sodium metal deposited onto the copper foil was solidified as it is, thereby producing a sodium metal laminate with a smooth surface. The thus obtained sodium metal laminate is shown in FIG. 3. Sodium was deposited on the produced sodium metal laminate with sufficient strength and did not detach therefrom.
[0047]
[Comparative Example 2]
A sodium metal laminate was prepared in the same manner as in Example 2
19 with the exception that molten sodium metal in which the liquid surface was covered with oxides or the like was used. As a result, sodium deposited onto the copper foil was in an uneven manner and sodium did not deposit uniformly.
[0048]
[Comparative Example 3]
A sodium metal laminate was prepared in the same manner as in Example 2 with the exception that a copper foil with no firing treatment conducted on the surface and with contaminants deposited thereon was used. As a result, the wettability of the copper foil and liquid sodium was deteriorated, and as shown in FIG. 4, sodium did not deposit uniformly onto the copper foil.
[0049]
[Example 3] Preparation of laminate using sodium metal vapor After placing sodium metal and a copper foil each in a vacuum pressure vessel which could be heated separately in a glove box under the same conditions as in Example 1, the lid was placed thereon, and heating was carried out while reducing the pressure. Sodium metal was vapor-deposited onto the copper foil in this container, thereby obtaining a sodium metal laminate. The thus obtained sodium metal laminate is shown in FIG. 5. In the produced sodium metal laminate, sodium did not detach and was deposited uniformly.
[0050]
[Example 4] Preparation of laminate using sodium dispersion A piece of sodium metal with a surface exhibiting a metallic luster was obtained by cutting from solid sodium metal in a glove box under the same conditions as in Example 1, and the thus obtained piece of sodium metal was placed in a four-necked flask with normal paraffin so that the content of sodium metal was 10% by mass. This mixture of normal paraffin and sodium metal was heated to a temperature equal to or higher than the melting point of sodium while stirring with a homogenizer to disperse sodium, and was then cooled to room temperature, thereby obtaining a gray colored sodium dispersion (hereinafter, referred to as a dispersion A). Separate from this, a combined preparation containing a binder was prepared by dispersing, mixing and stirring, at a ratio of, 9 g of a styrene-butadiene-based resin, 90 g of normal paraffin and 1 g of Ketjen black. 10 g of the aforementioned dispersion A and 3 g of the combined preparation containing a binder was sufficiently stirred and applied onto a copper foil, and then normal paraffin was removed by heating and drying under reduced pressure, to thereby obtain a sodium laminate in which a uniform sodium dispersion was bonded to the copper foil, as shown in FIG. 6.
[0051]
[Example 5] Preparation of laminate using sodium dispersion composition 8 g of sodium, 0.4 g of an equimolar mixture of a bisfluorosulfonylimide sodium salt and a bisfluorosulfonylimide potassium salt, and 72 g of normal paraffin were placed in a four-necked flask under the same conditions as in Example 4, and they were then heated to a temperature which was equal to or higher than the melting point of sodium and was also equal to or higher than the melting point of the imide salt, and stirred and dispersed collectively, thereby obtaining a dispersion with a black surface (hereinafter referred to as a dispersion B). A sodium dispersion composition prepared by mixing 0.3 g of the combined preparation containing a binder which was described in Example 4 and 1 g of the aforementioned dispersion B was applied onto a copper foil and heated and dried under reduced pressure, thereby forming a coating film formed from the sodium particles which were uniformly bonded to the surface of the copper foil, as shown in FIG. 7. The sodium laminate obtained in this manner had a large effective surface area while maintaining the activity of sodium.
[0052]
[Example 6]
The sodium laminate prepared in Example 5 was rolled with a pressing machine. As a result, a sodium laminate in which cracks were present on the surface of the sodium particles was obtained.
[Industrial Applicability]
[0053]
According to the present invention, it is possible to produce an electrode in which the periphery of the current collector is covered uniformly and also firmly with sodium metal, by use of the present invention.
[0048]
[Comparative Example 3]
A sodium metal laminate was prepared in the same manner as in Example 2 with the exception that a copper foil with no firing treatment conducted on the surface and with contaminants deposited thereon was used. As a result, the wettability of the copper foil and liquid sodium was deteriorated, and as shown in FIG. 4, sodium did not deposit uniformly onto the copper foil.
[0049]
[Example 3] Preparation of laminate using sodium metal vapor After placing sodium metal and a copper foil each in a vacuum pressure vessel which could be heated separately in a glove box under the same conditions as in Example 1, the lid was placed thereon, and heating was carried out while reducing the pressure. Sodium metal was vapor-deposited onto the copper foil in this container, thereby obtaining a sodium metal laminate. The thus obtained sodium metal laminate is shown in FIG. 5. In the produced sodium metal laminate, sodium did not detach and was deposited uniformly.
[0050]
[Example 4] Preparation of laminate using sodium dispersion A piece of sodium metal with a surface exhibiting a metallic luster was obtained by cutting from solid sodium metal in a glove box under the same conditions as in Example 1, and the thus obtained piece of sodium metal was placed in a four-necked flask with normal paraffin so that the content of sodium metal was 10% by mass. This mixture of normal paraffin and sodium metal was heated to a temperature equal to or higher than the melting point of sodium while stirring with a homogenizer to disperse sodium, and was then cooled to room temperature, thereby obtaining a gray colored sodium dispersion (hereinafter, referred to as a dispersion A). Separate from this, a combined preparation containing a binder was prepared by dispersing, mixing and stirring, at a ratio of, 9 g of a styrene-butadiene-based resin, 90 g of normal paraffin and 1 g of Ketjen black. 10 g of the aforementioned dispersion A and 3 g of the combined preparation containing a binder was sufficiently stirred and applied onto a copper foil, and then normal paraffin was removed by heating and drying under reduced pressure, to thereby obtain a sodium laminate in which a uniform sodium dispersion was bonded to the copper foil, as shown in FIG. 6.
[0051]
[Example 5] Preparation of laminate using sodium dispersion composition 8 g of sodium, 0.4 g of an equimolar mixture of a bisfluorosulfonylimide sodium salt and a bisfluorosulfonylimide potassium salt, and 72 g of normal paraffin were placed in a four-necked flask under the same conditions as in Example 4, and they were then heated to a temperature which was equal to or higher than the melting point of sodium and was also equal to or higher than the melting point of the imide salt, and stirred and dispersed collectively, thereby obtaining a dispersion with a black surface (hereinafter referred to as a dispersion B). A sodium dispersion composition prepared by mixing 0.3 g of the combined preparation containing a binder which was described in Example 4 and 1 g of the aforementioned dispersion B was applied onto a copper foil and heated and dried under reduced pressure, thereby forming a coating film formed from the sodium particles which were uniformly bonded to the surface of the copper foil, as shown in FIG. 7. The sodium laminate obtained in this manner had a large effective surface area while maintaining the activity of sodium.
[0052]
[Example 6]
The sodium laminate prepared in Example 5 was rolled with a pressing machine. As a result, a sodium laminate in which cracks were present on the surface of the sodium particles was obtained.
[Industrial Applicability]
[0053]
According to the present invention, it is possible to produce an electrode in which the periphery of the current collector is covered uniformly and also firmly with sodium metal, by use of the present invention.
Claims (7)
1. A production method for producing a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal comprising any one of steps selected from the group consisting of the following steps (1) and (2):
(1) a step of applying a sodium dispersion containing sodium metal and at least one substance selected from the group consisting of an imide salt and a binder, on a current collector in an inert gas environment having an oxygen concentration of not more than 0.01% and a dew point of not more than -10°C, followed by heating and drying; and (2) a step of immersing a current collector having a surface fired at a temperature ranging from 150 to 300°C in molten sodium metal after removing a coating film which is generated on a surface of molten sodium metal and formed from impurities, from the surface of the molten sodium metal, in an inert gas environment having an oxygen concentration of not more than 0.01% and a dew point of not more than -10°C.
(1) a step of applying a sodium dispersion containing sodium metal and at least one substance selected from the group consisting of an imide salt and a binder, on a current collector in an inert gas environment having an oxygen concentration of not more than 0.01% and a dew point of not more than -10°C, followed by heating and drying; and (2) a step of immersing a current collector having a surface fired at a temperature ranging from 150 to 300°C in molten sodium metal after removing a coating film which is generated on a surface of molten sodium metal and formed from impurities, from the surface of the molten sodium metal, in an inert gas environment having an oxygen concentration of not more than 0.01% and a dew point of not more than -10°C.
2. The production method according to claim 1, comprising said step (1).
3. The production method according to claim 2, further comprising a pressure molding step.
4. The production method according to claim 2 or 3, wherein said sodium dispersion comprises said imide salt and sodium metal.
5. The production method according to claim 4, wherein said imide salt is at least one substance selected from the group consisting of a bisfluorosulfonylimide sodium salt and a bisfluorosulfonylimide potassium salt.
6. A sodium dispersion composition for forming a negative electrode of a sodium secondary battery comprising sodium metal and an imide salt, wherein a surface of the sodium metal particles is coated with the imide salt.
7. The sodium dispersion composition according to claim 6, wherein said imide salt is at least one substance selected from the group consisting of a bisfluorosulfonylimide sodium salt and a bisfluorosulfonylimide potassium salt.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011213624 | 2011-09-29 | ||
| JP2011-213624 | 2011-09-29 | ||
| PCT/JP2012/074882 WO2013047657A1 (en) | 2011-09-29 | 2012-09-27 | Method for producing electrode covered with sodium metal |
Publications (2)
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|---|---|
| CA2850040A1 CA2850040A1 (en) | 2013-04-04 |
| CA2850040C true CA2850040C (en) | 2016-01-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CA2850040A Active CA2850040C (en) | 2011-09-29 | 2012-09-27 | Method for producing a negative electrode for use in a sodium secondary battery in which a surface of a current collector is covered with sodium metal |
Country Status (8)
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| US (1) | US9647258B2 (en) |
| EP (1) | EP2763216B1 (en) |
| JP (1) | JP5689976B2 (en) |
| KR (1) | KR101678748B1 (en) |
| CN (1) | CN103828095B (en) |
| CA (1) | CA2850040C (en) |
| TW (1) | TWI462382B (en) |
| WO (1) | WO2013047657A1 (en) |
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| DE102014208047A1 (en) * | 2014-04-29 | 2015-10-29 | Mahle International Gmbh | Anode and electrolyte for a metal-air battery |
| TWI597887B (en) * | 2014-11-13 | 2017-09-01 | 日本曹達股份有限公司 | Negative electrode composition for power storage device, negative electrode including the same, and power storage device, and method for producing negative electrode for power storage device |
| KR101711437B1 (en) * | 2015-10-21 | 2017-03-02 | 한국화학연구원 | Binder for negative-electrode material for secondary battery |
| WO2018014164A1 (en) * | 2016-07-18 | 2018-01-25 | 宁德时代新能源科技股份有限公司 | Method for supplementing sodium ion battery with sodium and electrode sheet and battery obtained by preparation |
| WO2018014165A1 (en) * | 2016-07-18 | 2018-01-25 | 宁德时代新能源科技股份有限公司 | Sodium ion battery electrode sheet, preparation method therefor, and sodium ion battery having electrode sheet |
| DE102017208218A1 (en) * | 2017-05-16 | 2018-11-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | A method of making an alkali metal coated substrate by means of a mediator layer and a mediator layer, and a coated substrate |
| WO2021134782A1 (en) * | 2020-01-03 | 2021-07-08 | 南京大学 | Method for preparing sodium interface and method for preparing sodium optical structure device |
| CN116130584A (en) * | 2022-09-08 | 2023-05-16 | 陈本 | Sodium metal negative electrode with solid polymer protective coating, preparation method of sodium metal negative electrode and battery containing negative electrode |
| CN115295792B (en) * | 2022-09-15 | 2026-04-14 | 溧阳紫宸新材料科技有限公司 | Composite metal sodium negative electrode material, preparation method thereof and sodium metal battery |
| CN117810578B (en) * | 2023-12-11 | 2024-07-09 | 三一红象电池有限公司 | Sodium ion battery reference electrode, preparation method thereof and three-electrode battery |
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| JPS6174641A (en) | 1984-09-20 | 1986-04-16 | Tatsuo Ido | Method for manufacturing metal sodium coating |
| US6090506A (en) * | 1996-08-02 | 2000-07-18 | Fuji Photo Film Co. Ltd. | Nonaqueous secondary battery |
| US6645675B1 (en) * | 1999-09-02 | 2003-11-11 | Lithium Power Technologies, Inc. | Solid polymer electrolytes |
| JP2001185140A (en) * | 1999-12-22 | 2001-07-06 | Sony Corp | Method for producing negative electrode material, method for producing negative electrode, and method for producing nonaqueous electrolyte battery |
| US6589299B2 (en) * | 2001-02-13 | 2003-07-08 | 3M Innovative Properties Company | Method for making electrode |
| JP3913490B2 (en) | 2001-03-28 | 2007-05-09 | 三洋電機株式会社 | Method for producing electrode for lithium secondary battery |
| US10122014B2 (en) * | 2008-02-04 | 2018-11-06 | Sumitomo Chemical Company, Limited | Mixed metal oxide and sodium secondary battery |
| JP5493301B2 (en) * | 2008-06-30 | 2014-05-14 | 住友化学株式会社 | Sodium secondary battery |
| JP2010020987A (en) * | 2008-07-09 | 2010-01-28 | Sumitomo Chemical Co Ltd | Non-aqueous electrolyte secondary battery |
| JP2010027538A (en) * | 2008-07-24 | 2010-02-04 | Kyushu Univ | Sodium secondary battery |
| JP2010102917A (en) * | 2008-10-23 | 2010-05-06 | Sumitomo Chemical Co Ltd | Sodium secondary battery |
| JP2010272492A (en) | 2009-05-25 | 2010-12-02 | Sumitomo Chemical Co Ltd | Sodium secondary battery manufacturing method and sodium secondary battery |
| JP5550988B2 (en) * | 2009-05-25 | 2014-07-16 | 住友化学株式会社 | Sodium secondary battery manufacturing method and sodium secondary battery |
| JP5707698B2 (en) * | 2009-12-24 | 2015-04-30 | 住友化学株式会社 | Electrode manufacturing method, electrode paste manufacturing method, and sodium secondary battery |
| JP2011150958A (en) * | 2010-01-25 | 2011-08-04 | Sony Corp | Nonaqueous electrolyte and nonaqueous electrolyte battery |
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- 2012-09-27 CN CN201280046266.9A patent/CN103828095B/en not_active Expired - Fee Related
- 2012-09-27 CA CA2850040A patent/CA2850040C/en active Active
- 2012-09-27 EP EP12836312.4A patent/EP2763216B1/en not_active Not-in-force
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- 2012-09-27 JP JP2013536379A patent/JP5689976B2/en not_active Expired - Fee Related
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| CN103828095B (en) | 2016-06-22 |
| EP2763216A4 (en) | 2015-06-10 |
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| CA2850040A1 (en) | 2013-04-04 |
| TWI462382B (en) | 2014-11-21 |
| US9647258B2 (en) | 2017-05-09 |
| US20140230688A1 (en) | 2014-08-21 |
| EP2763216B1 (en) | 2017-06-07 |
| KR101678748B1 (en) | 2016-11-23 |
| EP2763216A1 (en) | 2014-08-06 |
| WO2013047657A1 (en) | 2013-04-04 |
| TW201320452A (en) | 2013-05-16 |
| CN103828095A (en) | 2014-05-28 |
| JP5689976B2 (en) | 2015-03-25 |
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