JP2009521792A - リチウム−イオン電池の電極に有用なシリコン含有合金 - Google Patents
リチウム−イオン電池の電極に有用なシリコン含有合金 Download PDFInfo
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- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 16
- 239000010703 silicon Substances 0.000 title claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 title description 14
- 239000000956 alloy Substances 0.000 title description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 11
- 239000000203 mixture Substances 0.000 claims abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 150000002739 metals Chemical class 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 239000010937 tungsten Substances 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 239000010955 niobium Substances 0.000 claims abstract description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021332 silicide Inorganic materials 0.000 claims abstract description 5
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000012071 phase Substances 0.000 abstract 2
- 239000007790 solid phase Substances 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 8
- 239000011135 tin Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002160 Celluloid Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 235000013912 Ceratonia siliqua Nutrition 0.000 description 1
- 240000008886 Ceratonia siliqua Species 0.000 description 1
- 229910000669 Chrome steel Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001546602 Horismenus Species 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013562 LiCo0.2Ni0.8O2 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000364021 Tulsa Species 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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Abstract
Description
本出願は、2005年12月23日出願の米国特許出願第60/743,075号に優先権を主張し、その明細書の開示は全体をもって参照として本明細書に組み入れる。
本発明はリチウムイオン電池に有用な電極組成物類、そのような組成物を作製する方法、及びそのような組成物を備えた電池に関する。
Claims (28)
- 式、SixSnqMyCzを有するリチウムイオン電池用電極組成物であって、式中、q、x、y、およびzは原子パーセント値を表し、且つ
(a)(q+x)>2y+zであり、
(b)xは0より大であり、
(c)q及びzの各々は独立して、0より大であるか又は0に等しく、並びに
(d)Mは、マンガン、モリブデン、ニオブ、タングステン、タンタル、鉄、銅、チタン、バナジウム、クロム、ニッケル、コバルト、ジルコニウム、イットリウム、又はそれらの組み合わせから選択される1種以上の金属であり、
該組成物中、Si、Sn、M、及びC元素は、
(i)シリコンを含む非晶質相と、
(ii)金属シリサイドを含むナノ結晶相と、
(iii)z>0場合でシリコンカーバイドを含む相と、
(iv)q>0の場合でSnを含む非晶質相と、を含む多相のミクロ組織形態で配置される、電極組成物。 - Mは、コバルト、ニッケル、鉄、チタン、モリブデン、タングステン、又はそれらの組み合わせから選択される1種以上の金属である、請求項1に記載の電極組成物。
- x≧60である、請求項1に記載の電極組成物。
- z>0である、請求項1に記載の電極組成物。
- z≧10である、請求項1に記載の電極組成物。
- z≧15である、請求項1に記載の電極組成物。
- x≧60であり、且つMはコバルト、ニッケル、鉄、チタン、モリブデン、又はそれらの組み合わせから選択される1種以上の金属である、請求項1に記載の電極組成物。
- z>0である、請求項7に記載の電極組成物。
- z≧10である、請求項7に記載の電極組成物。
- MはCoを含む、請求項1に記載の電極組成物。
- z>0である、請求項10に記載の電極組成物。
- x≧60である、請求項10に記載の電極組成物。
- アノードと、
カソードと、
電解質と、
を含むリチウムイオン電池であって、該アノードは式、SixSnqMyCzを有する組成物を含み、式中、q、x、y、及びzは原子パーセント値を表し、且つ、
(a)(q+x)>2y+zであり、
(b)qは0より大であるか又は0に等しく、
(c)zは0より大であるか又は0に等しく、及び
(d)Mは、マンガン、モリブデン、ニオブ、タングステン、タンタル、鉄、銅、チタン、バナジウム、クロム、ニッケル、コバルト、ジルコニウム、イットリウム、又はそれらの組み合わせから選択される1種以上の金属であり、
該組成物中、Si、Sn、M及びC元素は、
(i)シリコンを含む非晶質相と、
(ii)金属シリサイドを含むナノ結晶相と、
(iii)z>0の場合でシリコンカーバイドを含む相と、
(iv)q>0の場合でSnを含む非晶質相と、を含む多相のミクロ組織形態で配置される、組成物のアノードを含むリチウムイオン電池。 - Mは、コバルト、ニッケル、鉄、チタン、モリブデン、タングステン、又はそれらの組み合わせから選択される1種以上の金属である、請求項13に記載されるリチウムイオン電池。
- x≧60である、請求項13に記載のリチウムイオン電池。
- z>0である、請求項13に記載のリチウムイオン電池。
- z≧10である、請求項13に記載のリチウムイオン電池。
- z≧15である、請求項13に記載のリチウムイオン電池。
- x≧60であり、且つMはコバルト、ニッケル、鉄、チタン、モリブデン、又はそれらの組み合わせから選択される1種以上の金属である、請求項13に記載のリチウムイオン電池。
- z>0である、請求項19に記載のリチウムイオン電池。
- z≧10である、請求項19に記載のリチウムイオン電池。
- MはCoを含む、請求項13に記載のリチウムイオン電池。
- z>0である、請求項22に記載のリチウムイオン電池。
- x≧60である、請求項22に記載のリチウムイオン電池。
- 前記アノードはバインダー及び導電性希釈剤をさらに含む、請求項13に記載のリチウムイオン電池。
- 前記バインダーはポリイミドを含む、請求項25に記載のリチウムイオン電池。
- 前記導電性希釈剤はカーボンブラックを含む請求項25に記載のリチウムイオン電池。
- 前記電解質はフルオロエチレンカーボネートを含む、請求項13に記載のリチウムイオン電池。
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US11/469,561 US7906238B2 (en) | 2005-12-23 | 2006-09-01 | Silicon-containing alloys useful as electrodes for lithium-ion batteries |
PCT/US2006/062305 WO2007120347A2 (en) | 2005-12-23 | 2006-12-19 | Silicon-containing alloys useful as electrodes for lithium-ion batteries |
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US10505184B2 (en) | 2014-12-17 | 2019-12-10 | Nissan Motor Co., Ltd. | Negative electrode active material for electric device and electric device using the same |
WO2017195071A1 (ja) * | 2016-05-12 | 2017-11-16 | 株式会社半導体エネルギー研究所 | 蓄電装置用負極、蓄電装置、および電気機器 |
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CN101341612A (zh) | 2009-01-07 |
US8071238B2 (en) | 2011-12-06 |
EP1974408A2 (en) | 2008-10-01 |
EP1974408A4 (en) | 2010-01-20 |
EP1974408B1 (en) | 2017-06-21 |
KR101323974B1 (ko) | 2013-10-31 |
US7906238B2 (en) | 2011-03-15 |
EP3249722A1 (en) | 2017-11-29 |
WO2007120347A2 (en) | 2007-10-25 |
US20070148544A1 (en) | 2007-06-28 |
TWI397206B (zh) | 2013-05-21 |
TW200746520A (en) | 2007-12-16 |
KR20080081283A (ko) | 2008-09-09 |
WO2007120347A3 (en) | 2007-12-27 |
US20110117449A1 (en) | 2011-05-19 |
JP5356826B2 (ja) | 2013-12-04 |
CN101341612B (zh) | 2012-02-08 |
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