JP6837439B2 - リチオ化されたケイ素/炭素複合材料及びそれを生産する方法 - Google Patents
リチオ化されたケイ素/炭素複合材料及びそれを生産する方法 Download PDFInfo
- Publication number
- JP6837439B2 JP6837439B2 JP2017539664A JP2017539664A JP6837439B2 JP 6837439 B2 JP6837439 B2 JP 6837439B2 JP 2017539664 A JP2017539664 A JP 2017539664A JP 2017539664 A JP2017539664 A JP 2017539664A JP 6837439 B2 JP6837439 B2 JP 6837439B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- arbitrary value
- powder
- assumed
- graphite
- 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
- 238000000034 method Methods 0.000 title claims description 20
- 229910052710 silicon Inorganic materials 0.000 title claims description 12
- 239000010703 silicon Substances 0.000 title claims description 10
- 150000001721 carbon Chemical class 0.000 title 1
- 229910052744 lithium Inorganic materials 0.000 claims description 64
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 239000002131 composite material Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 23
- 229910002804 graphite Inorganic materials 0.000 claims description 21
- 239000010439 graphite Substances 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 15
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011863 silicon-based powder Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 6
- -1 sulfur organic compounds Chemical class 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 230000002687 intercalation Effects 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000005586 carbonic acid group Chemical group 0.000 claims 1
- 150000001733 carboxylic acid esters Chemical class 0.000 claims 1
- 239000011247 coating layer Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 230000002123 temporal effect Effects 0.000 claims 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- GSSXLFACIJSBOM-UHFFFAOYSA-N 2h-pyran-2-ol Chemical compound OC1OC=CC=C1 GSSXLFACIJSBOM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000871495 Heeria argentea Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012803 optimization experiment Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/06—Metal silicides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Description
1.低く不可逆性の初期損失、
2.少なくとも500、好ましくは少なくとも1000Ah/kgの高い容量、及び
3.十分なサイクル安定性
を有する、ケイ素に主に基づく材料が求められる。
SixC 10 −xLiz
(式中、
xは1〜9の任意の値及びa=0.1〜1の任意の値で、z=a(4,4x+1/6(10−x))を想定することができる)を有する。したがって、複合材料中のリチウムの量は、化学量論的に最大に可能なリチウム吸収の10〜100モル%の範囲である(LiC6及びLi22Si5は熱力学的に安定的な相であり、室温でリチウムに最も富んでいる)。
・粉砕ボール対生成物混合物の重量比
・粉砕ボールのタイプ(例えば硬さ及び密度)
・粉砕の強度(粉砕プレートの回転の頻度)
・リチウム粉末の反応性(例えばコーティングのタイプ)
・Li:Cの重量比
・生成物特異的特性
・所望される粒子サイズなど
・コートされないリチウム黒鉛層間化合物LiC6(Li含有量=8.8%)Tonset=
130℃
・熱分解されないLi/Si/C−組成物Li3,9SiC2.7を備えた複合物(Li含有量=31%):Tonset=170℃
・150℃で4時間熱分解したLi/Si/C−組成物Li3,9SiC2.7を備えた複合
物(Li含有量=31%):Tonset=140℃
・250℃で10時間熱分解したLi/Si/C−組成物Li3,9SiC2.7を備えた複
合物(Li含有量=31%):Tonset=150℃。
)にもかかわらず、本発明に記載の材料は、EC/EMC混合物に比較して改善された熱安定性を有する。
未満、好ましくは1V未満である。
以下の:
・1.80gのSi粉末(供給業者Wacker、Si含有量89.4%、D50=58μm
・1.16gのLiの粉末(Rockwood lithium、コートされない、Li含有量>99%、D50=105μm
・3.00gの黒鉛粉末(Timcal社からのSLP 30)
からなる混合物を、
Arにより充填されたグローブボックス中のFritsch社からの酸化ジルコニウム粉砕カップを備えた遊星ボールミルPulverisette P 7中で、逆戻り操作で400rpmで26個のZr02ボール(直径3mm)と一緒に4時間粉砕した。
実施例1に従って生産された1.05gの混合物を、閉鎖スチールオートクレーブ中のAr保護ガス中で150℃で4時間熱分解する。続いて、以下の相:ケイ化リチウム、黒鉛及びSi(低減した強度)は、XRDによって同定することができる。金属リチウムは同定することができない。
実施例1に従って生産された1.16gの混合物を、閉鎖スチールオートクレーブ中のAr保護ガス中で250℃で10時間熱分解する。続いて、以下の相:ケイ化リチウム(上昇した強度)、黒鉛及びSi(大幅に低減した強度)は、XRDによって同定することができる。金属リチウムは同定することができない。
Claims (10)
- リチオ化または部分的にリチオ化された黒鉛またはグラフェン、1〜100μmの間の粒子サイズを備えた粉状シリコンを含む緻密な混合物からなるという点で特徴づけられる、経験式SixC10 -xLiZ
(式中、
xは1〜9の任意の値及びa=0.1〜1の任意の値で、z=a(4.4x+1/6(10−x))を想定することができる)
を備えた複合材料。 - 請求項1に記載の複合体であって、前記混合物が金属リチウムをさらに含む、複合体。
- 粉状のケイ化リチウム及び(部分的)リチオ化または非リチオ化の黒鉛またはグラフェンからなる緻密な混合物からなるという点で特徴づけられる、経験式SixC10 -xLiZ(式中、
xは1〜9の任意の値及びa=0.1〜1の任意の値で、z=a(4.4x+1/6(10−x))を想定することができる)
を備えた複合材料。 - 請求項1ないし3のいずれか一項に記載の複合材料が、1つまたは複数の気体または液体のコーティング手段による後処理によって適用される安定化コーティング層を含むという点で特徴づけられる、経験式SixC10 -xLiZを備えた安定化した複合材料。
- SiとCとLiがx:10−x:zのモル比であり、1〜100μmのグレインサイズを備えたケイ素粉末と5〜500μmのグレインサイズを備えたリチウム粉末ならびに黒鉛粉末及び/またはグラフェン粉末との混合物が、不活性ガス下または真空中で0〜120℃の温度範囲で、機械化学的に変換されるという点で特徴づけられる、経験式SixC10 -xLiZ
(式中、
xは1〜9の任意の値及びa=0.1〜1の任意の値で、z=a(4.4x+1/6(10−x))を想定することができる)
を備えた複合材料を生産する方法。 - 1〜100μmのグレインサイズを備えたケイ素粉末と5〜500μmのグレインサイズを備えたリチウム粉末ならびに黒鉛粉末及び/またはグラフェン粉末との混合物が、不活性ガス下または真空中で0〜120℃の温度範囲で、最初はSiとCとLiがx:10−x:zのモル比で、機械化学的に変換され、得られた混合物が、続いて150〜350℃の温度範囲で5分〜24時間熱分解相へさらされる、という点で特徴づけられる、経験式SixC10 -xLiZ
(式中、
xは1〜9の任意の値及びa=0.1〜1の任意の値で、z=a(4.4x+1/6(10−x))を想定することができる)
を備えたケイ化複合材料を生産する方法 - 粉状のコートされないLiC o (o=30〜6の層間化合物)と1〜100μmのグレインサイズを備えたケイ素粉末の混合物が、SiとCとLiがx:10−x:zのモル比で混合され、続いて130〜350℃の温度範囲で5分〜24時間熱分解相へさらされる、という点で特徴づけられる、経験式SixC10 -xLiZ
(式中、
xは1〜9の任意の値及びa=0.1〜1の任意の値で、z=a(4.4x+1/6(10−x))を想定することができる)を備えたケイ化複合材料を生産する方法。 - 請求項5〜7のうちのいずれか1つに記載の方法に従って生産された複合材料が、気体または液体のコーティング剤により続いて処理されるという点で特徴づけられる、経験式SixC10 -xLiZ
(式中、xは1〜9の任意の値及びa=0.1〜1の任意の値で、z=a(4.4x+1/6(10−x))を想定することができる)を備えた安定化されたケイ化複合材料を生産する方法。 - 気体コーティング剤が、N2,CO2,CO,O2,N2O,NO,NO2,HF,F2,PF3,PF5,POF3の群から選択され、液体コーティング剤が、炭酸エステル;有機溶媒中の溶液としてのリチウムキレートボレート(chelatoborate)溶液の群から選択され、好ましくは、酸素含有ヘテロ環、炭酸エステル、ニトリル、カルボン酸エステル及びケトン、硫黄有機化合物(サルファイト、スルホン、スルトン);N含有有機化合物、リン酸、有機リン含有化合物、フッ素含有の有機化合物及び無機化合物(部分的にフッ素化された炭化水素、BF3、LiPF6、LiBF4)、ケイ素含有化合物から選択される、という点で特徴づけられる、請求項8に記載の方法。
- 非水性電解質によるガルバーニ電池(例えばリチウム電池)中の陽極材料としての経験式SixC10 -xLiZ
(式中、
xは1〜9の任意の値及びa=0.1〜1の任意の値で、z=a(4.4x+1/6(10−x))を想定することができる)
を備えた複合材料の使用。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102015201461.4 | 2015-01-28 | ||
DE102015201461 | 2015-01-28 | ||
PCT/EP2016/051680 WO2016120313A1 (de) | 2015-01-28 | 2016-01-27 | Lithiierte silicium/kohlenstoff-kompositmaterialien und verfahren zu deren herstellung |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2018510111A JP2018510111A (ja) | 2018-04-12 |
JP2018510111A5 JP2018510111A5 (ja) | 2020-04-16 |
JP6837439B2 true JP6837439B2 (ja) | 2021-03-03 |
Family
ID=55273245
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2017539664A Active JP6837439B2 (ja) | 2015-01-28 | 2016-01-27 | リチオ化されたケイ素/炭素複合材料及びそれを生産する方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20180019463A1 (ja) |
EP (1) | EP3251160B1 (ja) |
JP (1) | JP6837439B2 (ja) |
KR (1) | KR102488906B1 (ja) |
DE (1) | DE102016201164A1 (ja) |
WO (1) | WO2016120313A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111525108B (zh) * | 2020-04-20 | 2022-06-14 | 南昌大学 | 一种碳包覆硅负极材料的合成方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2122770C (en) * | 1994-05-03 | 2000-10-03 | Moli Energy (1990) Limited | Carbonaceous host compounds and use as anodes in rechargeable batteries |
JPH09249407A (ja) * | 1996-03-14 | 1997-09-22 | Toyota Central Res & Dev Lab Inc | 黒鉛複合物およびその製造方法 |
US20040137327A1 (en) * | 2003-01-13 | 2004-07-15 | Gross Karl J. | Synthesis of carbon/silicon composites |
JP6284488B2 (ja) | 2012-01-13 | 2018-02-28 | ロックウッド リチウム ゲゼルシャフト ミット ベシュレンクテル ハフツングRockwood Lithium GmbH | 合金形成元素でコーティングされた安定化されたリチウム金属形状付与物及びその製造法 |
US20150000118A1 (en) | 2013-06-26 | 2015-01-01 | Xin Zhao | Method for manufacturing graphene-incorporated rechargeable li-ion battery |
-
2016
- 2016-01-27 US US15/546,746 patent/US20180019463A1/en not_active Abandoned
- 2016-01-27 EP EP16702383.7A patent/EP3251160B1/de active Active
- 2016-01-27 KR KR1020177020813A patent/KR102488906B1/ko active IP Right Grant
- 2016-01-27 JP JP2017539664A patent/JP6837439B2/ja active Active
- 2016-01-27 WO PCT/EP2016/051680 patent/WO2016120313A1/de active Application Filing
- 2016-01-27 DE DE102016201164.2A patent/DE102016201164A1/de not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
JP2018510111A (ja) | 2018-04-12 |
DE102016201164A1 (de) | 2016-07-28 |
KR102488906B1 (ko) | 2023-01-13 |
EP3251160B1 (de) | 2020-01-08 |
US20180019463A1 (en) | 2018-01-18 |
EP3251160A1 (de) | 2017-12-06 |
KR20170107457A (ko) | 2017-09-25 |
WO2016120313A1 (de) | 2016-08-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6768113B2 (ja) | 安定化された(部分)リチオ化グラファイト材料、その製造方法およびリチウム電池のための使用 | |
JP6738276B2 (ja) | ガルバニ電池および高められた容量を有する(部分)リチオ化リチウム電池のアノードおよび合成グラファイト層間化合物を製造するための方法 | |
KR101944154B1 (ko) | 재충전식 배터리용 음극 재료 및 이의 제조 방법 | |
US9601758B2 (en) | Negative electrode material for a rechargeable battery, and method for producing it | |
JP6244415B2 (ja) | 充電池用アノード材料としてのMSnxナノ粒子を製造する方法 | |
JP5835141B2 (ja) | 二次電池用負極活物質、その製造方法、二次電池用負極、二次電池、及びSi−酸化物固体電解質複合体 | |
US20230163281A1 (en) | Lithiated silicon/carbon composite materials and method for producing the same | |
JP4952080B2 (ja) | 二次電池用非水系電解液及び非水系電解液二次電池 | |
JP6837439B2 (ja) | リチオ化されたケイ素/炭素複合材料及びそれを生産する方法 | |
TW201628971A (zh) | 電解電池及具高容量的(部分)鋰化鋰電池陽極以及製造合成石墨夾層連接部的方法 | |
JP2018510111A5 (ja) | ||
TWI707823B (zh) | 穩定化(部分)鋰化的石墨材料,其製造方法及用於鋰電池的應用 | |
DE102015202612A1 (de) | Stabilisierte (teil)lithiierte Graphitmaterialien, Verfahren zu deren Herstellung und Verwendung für Lithiumbatterien |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190107 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20191121 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20191204 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20200304 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200305 |
|
A524 | Written submission of copy of amendment under article 19 pct |
Free format text: JAPANESE INTERMEDIATE CODE: A524 Effective date: 20200305 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200309 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200527 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200824 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20210127 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210209 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6837439 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |