JP6844014B2 - ケイ素粒子の改質方法 - Google Patents
ケイ素粒子の改質方法 Download PDFInfo
- Publication number
- JP6844014B2 JP6844014B2 JP2019542778A JP2019542778A JP6844014B2 JP 6844014 B2 JP6844014 B2 JP 6844014B2 JP 2019542778 A JP2019542778 A JP 2019542778A JP 2019542778 A JP2019542778 A JP 2019542778A JP 6844014 B2 JP6844014 B2 JP 6844014B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon particles
- particles
- strongly
- oxygen
- modified silicon
- 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
- 239000011856 silicon-based particle Substances 0.000 title claims description 150
- 238000000034 method Methods 0.000 title claims description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 39
- 239000001301 oxygen Substances 0.000 claims description 39
- 229910052760 oxygen Inorganic materials 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 39
- 150000003376 silicon Chemical class 0.000 claims description 39
- 239000000376 reactant Substances 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims description 19
- 238000011282 treatment Methods 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 4
- 238000004220 aggregation Methods 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims 2
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000976 ink Substances 0.000 description 35
- 239000000203 mixture Substances 0.000 description 25
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- 238000009472 formulation Methods 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 19
- 239000010703 silicon Substances 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229920002678 cellulose Chemical class 0.000 description 3
- 239000001913 cellulose Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- -1 alkali metal salts Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Chemical class 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001370 static light scattering Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052726 zirconium 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
- C01B33/02—Silicon
-
- 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
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- 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
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/13—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
-
- 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
- H01M4/386—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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Silicon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
このプロセスは、従来の反応器、例えば管状炉、回転管状炉、流動床反応器又は移動床反応器中で実施することができる。焼成炉及び回転管炉が特に好ましい。このプロセスは、連続的又は不連続的に行うことができる。
ジェットミルは、静的若しくは動的であり得る統合された空気分級機を含むことが好ましく、又は外部空気分級機で循環しながら操作される。
粒径分布の測定は、Mieモデルを使用し、水又はイソプロパノール中の非常に希釈された懸濁液中のHoriba LA 950を使用する静的レーザー回折によって行った。指定された平均粒径は体積加重である。
酸素含有量の測定は、Leco TCH−600分析器を用いて行った。分析は、不活性ガス雰囲気下でグラファイトるつぼ中で試料を溶融することによって行った。検出は赤外線により行った(3つの分析セル)。
改質ケイ素粒子の平均二酸化ケイ素層厚d(SiO2)の測定は、次式にしたがって行った:
d50(Si):「粒径の測定」の見出しで上記したように測定した、改質ケイ素粒子の体積加重粒度分布のd50値
O含有量:上記したように測定した改質ケイ素粒子の酸素含有量
M(SiO2):二酸化ケイ素の(SiO2)のモル質量:60.084g/mol
M(O2):酸素(O2)のモル質量:31.998g/モル
ケイ素及び二酸化ケイ素の密度は、両種について同一又は実質的に同一の値を有するので、ここでは無視することができる。
試料50mg(80℃での測定用)又は100mg(40℃での測定用)をGC Headspaceバイアル(22ml)に秤量し、5mlの水性酢酸リチウム緩衝液(pH7;0.1M)と混合し、バイアルを密封し、撹拌しながら40℃で60分間保持し/アルミニウムブロック中で80℃に30分間加熱した。
水素発生の測定を行った温度をそれぞれの実験の次に報告する。
Si粒子Aの製造(本発明でない):
従来技術にしたがって、流動床ジェットミル(Netzsch−Condux CGS16、粉砕気体として90m3/hの窒素を7バールで用いる)でソーラーシリコンの製造からの粗粉砕ケイ素を粉砕することにより、Si粒子Aを製造した。得られた粒子を不活性ガス下で容器に充填し、貯蔵した。空気中で粒子を除去した後、表1に報告する分析データを得た。
Si粒子A(151.90g)を、Heraeus(T6060)乾燥キャビネット中のガラス皿中で空気中、80℃で6時間加熱した。室温まで冷却した後、こうして得られた改質ケイ素粒子Bを取り出し、再秤量し(152.10g)、分析した。
水中でのケイ素粒子の安定性を、「水素発生(H2発生)」の見出しで特定されるように、GCによって分析した。得られた結果を表1に示す。
ケイ素粒子A(829.2g、表1参照)を蒸発皿に導入し、ThermoConcept KK480焼成炉に入れた。炉の内部を600℃に6時間加熱し、Si床への空気流を確実にした。
室温まで冷却した後、こうして得られた改質ケイ素粒子Cを除去し、再秤量(832.8g)し、分析した。水中でのケイ素粒子の安定性を、「水素発生(H2発生)」の見出しで特定されるように、GCによって分析した。得られた結果を表1に示す。
127.5gのそれぞれのケイ素粒子を、45.5gのグラファイト(Imerys製のKS6L)と、100gのLiPAAバインダー水溶液(LiOH及びポリアクリル酸(分子量450k、Sigma−Aldrich,項目番号181285)から製造)(4重量%、pH6.9)と、遊星ミキサー(PC Laborsystem LPV 1G2)で混合した。50rpmで60分間撹拌した後、さらに119.5gの上記LiPAAバインダー溶液を添加し、100rpmでさらに60分間撹拌した。H2発生の分析のために、5g(Si粒子A)又は15g(Si粒子B/C)のそれぞれのインクをヘッドスペースバイアル(総体積20ml)に充填し、室温で保存した。表2に報告した時間後にガス空間の組成を分析した。分析データを表2に要約する。
Si粒子Aを含む電極コーティングは、厳しい水素発生のために、コーティングの破裂、及びそれによる不均一なコーティングの傾向を有する。
Claims (12)
- 3.0μm〜7.0μmの直径パーセンタイルd50を有する体積加重粒度分布を有する非強凝集ケイ素粒子を、酸素含有ガスで80℃〜900℃で処理することによる、非強凝集改質ケイ素粒子の製造方法であって、非強凝集改質ケイ素粒子の酸素含有量が、ケイ素粒子の総重量を基準として、いずれの場合にも、反応物として使用される非強凝集ケイ素粒子の酸素含有量よりも0.05重量%〜0.6重量%高い、該方法。
- 前記酸素含有ガスが、前記酸素含有ガスの総体積を基準にして、1〜100体積%、特に5体積%以上の酸素を含有することを特徴とする、請求項1に記載の非強凝集改質ケイ素粒子の製造方法。
- 酸素含有ガスによる処理が400℃〜800℃で実施されることを特徴とする、請求項1又は2に記載の非強凝集改質ケイ素粒子の製造方法。
- 酸素含有ガスによる処理が80℃〜400℃で実施されることを特徴とする、請求項1又は2に記載の非強凝集改質ケイ素粒子の製造方法。
- 反応物として使用される非強凝集ケイ素粒子が、反応物として使用される非強凝集ケイ素粒子の総重量を基準にして2.0重量%以下の酸素を含有することを特徴とする、請求項1〜4のいずれか一項に記載の非強凝集改質ケイ素粒子の製造方法。
- 非強凝集改質ケイ素粒子が、非強凝集改質ケイ素粒子の総重量を基準として、0.1重量%〜3.0重量%の酸素を含有することを特徴とする、請求項1〜4のいずれか一項に記載の非強凝集改質ケイ素粒子の製造方法。
- 反応物として使用される非強凝集ケイ素粒子が、非弱凝集であることを特徴とする、請求項1〜6のいずれか一項に記載の非強凝集改質ケイ素粒子の製造方法。
- 表面において、非強凝集改質ケイ素粒子が、平均層厚が2〜50nmの酸化ケイ素層を有することを特徴とする、請求項1〜7のいずれか一項に記載の非強凝集改質ケイ素粒子の製造方法。
- 非強凝集改質ケイ素粒子が、3.0μm〜7.0μmの直径パーセンタイルd50を有する体積加重粒度分布を有することを特徴とする、請求項1〜8のいずれか一項に記載の非強凝集改質ケイ素粒子の製造方法。
- 反応物として使用される非強凝集ケイ素粒子、又は非強凝集改質ケイ素粒子が、0.2〜8.0m2/gのBET表面積(決定方法:窒素によるDIN 66131に従う)を有することを特徴とする、請求項1〜9のいずれか一項に記載の非強凝集改質ケイ素粒子の製造方法。
- 請求項1〜10のいずれか一項に記載の方法による生成物、及び1種以上のバインダーが、水と混合されることを特徴とする、水性インク製剤の製造方法。
- リチウムイオン電池用のアノードを製造するための、請求項1〜10のいずれか一項に記載の方法による生成物の使用。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2016/075682 WO2018077389A1 (de) | 2016-10-25 | 2016-10-25 | Verfahren zum modifizieren von siliziumpartikeln |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2019533634A JP2019533634A (ja) | 2019-11-21 |
JP6844014B2 true JP6844014B2 (ja) | 2021-03-17 |
Family
ID=57208280
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2019542778A Active JP6844014B2 (ja) | 2016-10-25 | 2016-10-25 | ケイ素粒子の改質方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US11597656B2 (ja) |
EP (1) | EP3532432B1 (ja) |
JP (1) | JP6844014B2 (ja) |
KR (1) | KR102224790B1 (ja) |
CN (1) | CN109843798A (ja) |
WO (1) | WO2018077389A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7030970B2 (ja) | 2018-07-25 | 2022-03-07 | ワッカー ケミー アクチエンゲゼルシャフト | シリコン粒子の熱処理 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4126715B2 (ja) * | 1999-11-22 | 2008-07-30 | ソニー株式会社 | 負極材料の製造方法および二次電池の製造方法 |
EP1313158A3 (en) | 2001-11-20 | 2004-09-08 | Canon Kabushiki Kaisha | Electrode material for rechargeable lithium battery, electrode comprising said electrode material, rechargeable lithium battery having said electrode , and process for the production thereof |
JP4033720B2 (ja) | 2002-06-19 | 2008-01-16 | 三洋電機株式会社 | リチウム二次電池用負極及びリチウム二次電池 |
JP4171904B2 (ja) * | 2003-08-05 | 2008-10-29 | 信越化学工業株式会社 | リチウムイオン二次電池負極材及びその製造方法 |
KR101451805B1 (ko) * | 2008-01-25 | 2014-10-16 | 삼성에스디아이 주식회사 | 리튬이차전지 전해질용 첨가제, 이를 포함하는 유기 전해액및 상기 전해액을 채용한 리튬 전지 |
JP5444984B2 (ja) * | 2009-09-16 | 2014-03-19 | 信越化学工業株式会社 | 非水電解質二次電池用負極材の製造方法及び非水電解質二次電池 |
US10181600B2 (en) * | 2010-06-29 | 2019-01-15 | Umicore | Submicron sized silicon powder with low oxygen content |
CN105378984B (zh) * | 2013-07-10 | 2017-07-07 | 尤米科尔公司 | 硅基粉末以及包含硅基粉末的电极 |
DE102013215257A1 (de) | 2013-08-02 | 2015-02-05 | Wacker Chemie Ag | Verfahren zum Zerkleinern von Silicium und Verwendung des zerkleinerten Siliciums in einer Lithium-Ionen-Batterie |
DE102014202156A1 (de) * | 2014-02-06 | 2015-08-06 | Wacker Chemie Ag | Si/G/C-Komposite für Lithium-Ionen-Batterien |
DE102015215415A1 (de) | 2015-08-12 | 2017-02-16 | Wacker Chemie Ag | Siliciumpartikel enthaltende Anodenmaterialien für Lithium-Ionen-Batterien |
DE102016203352A1 (de) * | 2016-03-01 | 2017-09-07 | Wacker Chemie Ag | Verfahren zur Verarbeitung von Elektrodenmaterialien für Batterien |
-
2016
- 2016-10-25 JP JP2019542778A patent/JP6844014B2/ja active Active
- 2016-10-25 CN CN201680090287.9A patent/CN109843798A/zh active Pending
- 2016-10-25 US US16/344,675 patent/US11597656B2/en active Active
- 2016-10-25 EP EP16787817.2A patent/EP3532432B1/de active Active
- 2016-10-25 KR KR1020197011355A patent/KR102224790B1/ko active IP Right Grant
- 2016-10-25 WO PCT/EP2016/075682 patent/WO2018077389A1/de active Search and Examination
Also Published As
Publication number | Publication date |
---|---|
JP2019533634A (ja) | 2019-11-21 |
CN109843798A (zh) | 2019-06-04 |
US20200055737A1 (en) | 2020-02-20 |
EP3532432A1 (de) | 2019-09-04 |
US11597656B2 (en) | 2023-03-07 |
KR102224790B1 (ko) | 2021-03-08 |
KR20190047097A (ko) | 2019-05-07 |
WO2018077389A1 (de) | 2018-05-03 |
EP3532432B1 (de) | 2022-09-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10115493B2 (en) | Surface-modified carbon hybrid particles, methods of making, and applications of the same | |
US10777807B2 (en) | Silicon particle-containing anode materials for lithium ion batteries | |
US20190088933A1 (en) | Method for processing electrode materials for batteries | |
JP2018530871A (ja) | リチウムイオン電池 | |
JP2022504094A (ja) | リチウムイオン電池用の活性アノード物質としての、特定の塩素含有率を有するシリコン粒子 | |
JP6844014B2 (ja) | ケイ素粒子の改質方法 | |
KR20190042700A (ko) | 리튬 이온 전지의 애노드 | |
US20230101574A1 (en) | Method for producing carbon-coated silicon particles | |
JP7030970B2 (ja) | シリコン粒子の熱処理 | |
KR20190112805A (ko) | 규소 입자 및 중합체를 기초로 한 재분산성 입자 | |
RU2818523C2 (ru) | Смешанный оксид лития и переходного металла, покрытый полученными пирогенным способом оксидами, содержащими цирконий | |
US20230299271A1 (en) | Carbon-coated silicon particles for lithium batteries | |
CN115133032A (zh) | 用于铅酸电池的基于红铅的核壳颗粒 | |
US20150318536A1 (en) | Production of a material based on li4ti5o12 with milling in the presence of carbon |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A529 | Written submission of copy of amendment under article 34 pct |
Free format text: JAPANESE INTERMEDIATE CODE: A529 Effective date: 20190621 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190621 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200713 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200728 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20201002 |
|
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: 20210126 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210224 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6844014 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |