JP5744313B2 - リチウム二次電池用負極活物質及びその製造方法 - Google Patents
リチウム二次電池用負極活物質及びその製造方法 Download PDFInfo
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- JP5744313B2 JP5744313B2 JP2014502488A JP2014502488A JP5744313B2 JP 5744313 B2 JP5744313 B2 JP 5744313B2 JP 2014502488 A JP2014502488 A JP 2014502488A JP 2014502488 A JP2014502488 A JP 2014502488A JP 5744313 B2 JP5744313 B2 JP 5744313B2
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- Prior art keywords
- negative electrode
- active material
- electrode active
- secondary battery
- lithium secondary
- Prior art date
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- 239000007773 negative electrode material Substances 0.000 title claims description 57
- 229910052744 lithium Inorganic materials 0.000 title claims description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000003575 carbonaceous material Substances 0.000 claims description 41
- 238000007747 plating Methods 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 229910045601 alloy Inorganic materials 0.000 claims description 24
- 239000000956 alloy Substances 0.000 claims description 24
- 229910052718 tin Inorganic materials 0.000 claims description 20
- 239000011247 coating layer Substances 0.000 claims description 19
- 229910018100 Ni-Sn Inorganic materials 0.000 claims description 17
- 229910018532 Ni—Sn Inorganic materials 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 15
- 239000008151 electrolyte solution Substances 0.000 claims description 14
- 229910021382 natural graphite Inorganic materials 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000009713 electroplating Methods 0.000 claims description 10
- 229910020816 Sn Pb Inorganic materials 0.000 claims description 9
- 229910020922 Sn-Pb Inorganic materials 0.000 claims description 9
- 229910008783 Sn—Pb Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910020888 Sn-Cu Inorganic materials 0.000 claims description 6
- 229910020994 Sn-Zn Inorganic materials 0.000 claims description 6
- 229910019204 Sn—Cu Inorganic materials 0.000 claims description 6
- 229910009069 Sn—Zn Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002931 mesocarbon microbead Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 3
- 229910020836 Sn-Ag Inorganic materials 0.000 claims description 3
- 229910020810 Sn-Co Inorganic materials 0.000 claims description 3
- 229910020988 Sn—Ag Inorganic materials 0.000 claims description 3
- 229910018757 Sn—Co Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 3
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- -1 Si and Sn Chemical compound 0.000 description 2
- 229910020830 Sn-Bi Inorganic materials 0.000 description 2
- 229910018728 Sn—Bi Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- 229920008712 Copo Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 108010000020 Platelet Factor 3 Proteins 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/387—Tin or alloys based on tin
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
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Description
カーボン系活物質上にNi‐Snをコーティングするため、めっき液(Ni‐Sn電解質溶液)を用意した。Ni‐Snめっき液は、0.5Mのピロリン酸カリウム(K2P2O2)水溶液に0.075Mの塩化ニッケル六水和物(NiCl2・6H2O)、0.175Mの塩化スズ二水和物(SnCl2・2H2O)、及び0.125Mのグリシン(NH2CH2COOH)を添加して製造し、めっき液のpH調節は26%のアンモニア水(NH4OH)を用いた。
上記のようにして製造した負極活物質、バインダーとしてSBR(スチレン‐ブタジエンゴム)、増粘剤としてCMC(カルボキシメチルセルロース)及び導電材としてアセチレンブラックを95:2:2:1の重量比で混合し、これらを溶媒である水(H2O)とともに混合して均一な負極スラリーを製造した。製造した負極スラリーを銅集電体の一面に65μmの厚さでコーティングし、乾燥及び圧延した後、必要な大きさで打ち抜いて(punching)負極を製造した。
負極活物質としてNi‐Sn合金がコーティングされていない球状天然黒鉛粒子を使用したことを除き、実施例2と同様の方法でコイン型のリチウム二次電池を製造した。
Ni‐Sn合金がコーティングされていない球状天然黒鉛粒子、及び実施例1で製造した負極活物質であるNi‐Sn合金がコーティングされた天然黒鉛粒子の表面をSEM写真を通じて観察し、それぞれ図2及び図3に示した。
実施例2及び比較例1によって製造された電池を使用して充放電特性を評価した。
Claims (10)
- リチウム二次電池用負極活物質であって、
炭素材と、及び
前記炭素材粒子の表面に形成され、平均直径が1μm以下の複数のSn系ドメインで形成されたコーティング層とを備えてなり、
前記コーティング層の密度が、2.2ないし5.9g・cm -3 であることを特徴とする、リチウム二次電池用負極活物質。 - 前記Sn系ドメインが、Sn、Sn合金またはこれらの混合物を含むことを特徴とする、請求項1に記載のリチウム二次電池用負極活物質。
- 前記Sn合金が、Snと、Mg、Al、Ca、Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Zr、Nb、Pd、Ag、Cd、In、Sb、Pt、Au、Hg、Pb及びBiからなる群より選択された金属との合金であることを特徴とする、請求項2に記載のリチウム二次電池用負極活物質。
- 前記炭素材が、天然黒鉛、人造黒鉛、メソカーボンマイクロビーズ(MCMB)、炭素繊維、及びカーボンブラックからなる群より選択される何れか一種または二種以上の混合物を含むことを特徴とする、請求項1〜3の何れか一項に記載のリチウム二次電池用負極活物質。
- 前記炭素材が、比表面積が10m2/g以下であることを特徴とする、請求項1〜4の何れか一項に記載のリチウム二次電池用負極活物質。
- 前記炭素材が、平均粒径が5ないし100μmであることを特徴とする、請求項1〜5の何れか一項に記載のリチウム二次電池用負極活物質。
- リチウム二次電池の負極であって、
集電体と、及び
前記集電体の少なくとも一面に形成されて負極活物質を含んでなる負極活物質層とを備えてなり、
前記負極活物質が請求項1〜6の何れか一項に記載の負極活物質であることを特徴とする、リチウム二次電池用負極。 - リチウム二次電池であって、
正極と、負極と、及び前記正極と前記負極との間に介在したセパレータとを備えてなり、
前記負極が請求項7に記載のリチウム二次電池用負極であることを特徴とする、リチウム二次電池。 - 電気めっき槽に対電極と主電極を配置し、めっき用電解液を入れる段階と、
前記めっき用電解液に炭素材を分散させた後、電流を流し、前記炭素材粒子の表面に複数のSn系ドメインでなるコーティング層を形成する段階とを含んでなる、請求項1〜6の何れか一項に記載のリチウム二次電池用負極活物質の製造方法。 - 前記めっき用電解液が、酸性系Ni‐Sn、Sn‐Zn、Sn‐Co、Sn‐Pbめっき液;硫酸系Snめっき液;塩酸系Snめっき液;スルホン酸系Sn、Sn‐Pb、Sn‐Biめっき液;シアン系Sn‐Cu、Sn‐Agめっき液;及びピロリン酸系Sn、Sn‐Cu、Sn‐Pb、Sn‐Znめっき液であることを特徴とする、請求項9に記載のリチウム二次電池用負極活物質の製造方法。
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