WO2016042728A1 - MSix(Mは第3~9族元素から選択される少なくとも一元素。ただし、1/3≦x≦3)含有シリコン材料およびその製造方法 - Google Patents
MSix(Mは第3~9族元素から選択される少なくとも一元素。ただし、1/3≦x≦3)含有シリコン材料およびその製造方法 Download PDFInfo
- Publication number
- WO2016042728A1 WO2016042728A1 PCT/JP2015/004505 JP2015004505W WO2016042728A1 WO 2016042728 A1 WO2016042728 A1 WO 2016042728A1 JP 2015004505 W JP2015004505 W JP 2015004505W WO 2016042728 A1 WO2016042728 A1 WO 2016042728A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- msix
- silicon material
- containing silicon
- calcium silicide
- polysilane
- Prior art date
Links
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910015861 MSix Inorganic materials 0.000 claims abstract description 219
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 49
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- 229910021346 calcium silicide Inorganic materials 0.000 claims description 78
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 39
- 229910001416 lithium ion Inorganic materials 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 239000007773 negative electrode material Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 19
- 229910008484 TiSi Inorganic materials 0.000 claims description 13
- 229910005347 FeSi Inorganic materials 0.000 claims description 10
- 229910005329 FeSi 2 Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010309 melting process Methods 0.000 claims description 3
- 239000011575 calcium Substances 0.000 description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- 238000002441 X-ray diffraction Methods 0.000 description 27
- 239000000203 mixture Substances 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 24
- 229910052791 calcium Inorganic materials 0.000 description 20
- 239000010936 titanium Substances 0.000 description 20
- 239000010410 layer Substances 0.000 description 19
- 229910004706 CaSi2 Inorganic materials 0.000 description 18
- 239000011149 active material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- -1 hexafluoroarsenic acid Chemical compound 0.000 description 16
- 229910052719 titanium Inorganic materials 0.000 description 16
- 239000013078 crystal Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 12
- 239000011889 copper foil Substances 0.000 description 11
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910018557 Si O Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910016006 MoSi Inorganic materials 0.000 description 3
- 239000004962 Polyamide-imide Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000002482 conductive additive Substances 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920002312 polyamide-imide Polymers 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920013683 Celanese Polymers 0.000 description 2
- 229910019974 CrSi Inorganic materials 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 229910013275 LiMPO Inorganic materials 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- OMQHDIHZSDEIFH-UHFFFAOYSA-N 3-Acetyldihydro-2(3H)-furanone Chemical compound CC(=O)C1CCOC1=O OMQHDIHZSDEIFH-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QGLBZNZGBLRJGS-UHFFFAOYSA-N Dihydro-3-methyl-2(3H)-furanone Chemical compound CC1CCOC1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 description 1
- 108010022355 Fibroins Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910015868 MSiO Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229930183415 Suberin Natural products 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910006249 ZrSi Inorganic materials 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000728 ammonium alginate Substances 0.000 description 1
- 235000010407 ammonium alginate Nutrition 0.000 description 1
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 235000013490 limbo Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical group O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- 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
- C01B33/021—Preparation
-
- 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
- C01B33/04—Hydrides of 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
- C01B33/06—Metal silicides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements 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
- H01M4/58—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a silicon material containing MSix (M is at least one element selected from Group 3 to 9 elements, provided that 1/3 ⁇ x ⁇ 3), and a method for producing the same.
- Silicon materials are known to be used as components of semiconductors, solar cells, secondary batteries and the like, and research on silicon materials has been actively conducted in recent years.
- Non-Patent Document 1 describes that CaSi 2 is reacted with an acid to synthesize a layered polysilane.
- Patent Document 1 describes that CaSi 2 is reacted with an acid to synthesize a layered polysilane, and it is described that a lithium ion secondary battery having the layered polysilane as an active material exhibits a suitable capacity. ing.
- Patent Document 2 describes an alloy composed of silicon, aluminum, iron, and titanium, and a lithium ion secondary battery using the alloy as a negative electrode active material.
- Patent Document 3 CaSi 2 is reacted with an acid to synthesize a layered polysilane, the layered polysilane is heated at 300 ° C. or higher to produce a nanosilicon material from which hydrogen is released, and the nanosilicon material It is described that the lithium ion secondary battery which comprises as an active material shows a suitable capacity maintenance rate.
- Patent Document 4 an alloy composed of silicon, calcium and copper was produced, and a silicon material was produced using the alloy as a raw material.
- the present invention has been made in view of such circumstances, and an object thereof is to provide a new silicon material and a method of manufacturing the same.
- the inventor of the present invention has intensively examined trial and error repeatedly to provide a new silicon material. Then, when the molten metal produced by heating Ca, Ti and Si was cooled, needle-like TiSi 2 was dispersed in the CaSi 2 matrix instead of the three-component compound obtained in Patent Document 4 I found that I could get And the present inventors completed the present invention based on such a discovery.
- the silicon material of the present invention MSix (M is at least one element selected from the group 3 to 9 elements, provided that 1/3 ⁇ x ⁇ 3) is characterized by containing MSix in the silicon matrix.
- the method for producing the MSix-containing silicon material of the present invention is Melting process in which Ca, M (M is at least one element selected from Group 3 to 9 elements) and Si are heated to form a molten metal; Cooling the molten metal to obtain MSix-containing calcium silicide containing MSix (where 1/3 ⁇ x ⁇ 3) in a calcium silicide matrix, Reacting the MSix-containing calcium silicide with an acid to obtain MSix-containing polysilane containing MSix in a polysilane matrix, Heating the MSix-containing polysilane at 300 ° C. or higher; It is characterized by including.
- the MSix-containing silicon material of the present invention can be a suitable silicon material.
- FIG. 5 is a scanning electron microscope image of a cross section of MSix-containing calcium silicide particles of Example 1.
- FIG. 8 is a scanning electron microscope image of a cross section of MSix containing calcium silicide particles of Example 4.
- 8 is a scanning electron microscope image of a cross section of MSix containing calcium silicide particles of Example 5.
- 8 is a scanning electron microscope image of a cross section of MSix containing calcium silicide particles of Example 6.
- FIG. 6 is an X-ray diffraction chart of MSix-containing calcium silicide of Examples 1 to 3 and calcium silicide of Comparative Example 1.
- FIG. FIG. 6 is an X-ray diffraction chart of MSix-containing calcium silicide of Examples 4 to 6.
- 7 is an X-ray diffraction chart of MSix-containing calcium silicide of Examples 7 to 8.
- 3 is an X-ray diffraction chart of the MSix-containing silicon material of Examples 1 to 3 and the silicon material of Comparative Example 1;
- 7 is an X-ray diffraction chart of the MSix-containing silicon material of Examples 4 to 6.
- 18 is an X-ray diffraction chart of the MSix-containing silicon material of Example 7.
- 7 is a scanning electron microscope image of the MSix-containing silicon material of Example 5.
- 7 is a scanning electron microscope image of the MSix-containing silicon material of Example 7. It is the scanning electron microscope image which expanded FIG. 15 is a scanning electron microscope image of the MSix-containing silicon material of Example 9. It is a graph of the relationship between the number of cycles and the capacity retention rate in Evaluation Example 7.
- the numerical range “x to y” described in the present specification includes the lower limit x and the upper limit y within the range. Then, the upper limit value and the lower limit value, and the numerical values listed in the examples can be combined arbitrarily to constitute a numerical range. Further, numerical values arbitrarily selected from within the numerical value range can be used as upper limit and lower limit numerical values.
- the MSix (M is at least one element selected from Group 3-9 elements, provided that 1/3 ⁇ x ⁇ 3) -containing silicon material of the present invention is characterized by containing MSix in a silicon matrix.
- the method for producing the MSix-containing silicon material of the present invention is Melting process in which Ca, M (M is at least one element selected from Group 3 to 9 elements) and Si are heated to form a molten metal; Cooling the molten metal to obtain MSix-containing calcium silicide containing MSix (where 1/3 ⁇ x ⁇ 3) in a calcium silicide matrix, Reacting the MSix-containing calcium silicide with an acid to obtain MSix-containing polysilane containing MSix in a polysilane matrix, Heating the MSix-containing polysilane at 300 ° C. or higher; It is characterized by including.
- Ca, M is at least one element selected from Group 3 to 9 elements
- Si are heated to form a molten metal
- Ca, M, and Si used at a molten metal process an element single-piece
- Ca, M and Si may contain unavoidable impurities and other elements and compounds within the range that does not inhibit the formation of molten Ca, M and Si. The amounts of Ca, M and Si used may be determined in accordance with the composition ratio of MSix-containing calcium silicide obtained in the next step.
- Ca, M and Si may be individually melted and then mixed to form a molten metal, or may be mixed and melted and then the remaining one may be mixed to form a molten metal, The three may be mixed and melted.
- the melting point of Ca is 842 ° C.
- the melting point of Si is 1410 ° C.
- the melting point of M is higher than the melting points of Ca and Si. Since Ca has a boiling point of 1484 ° C., it is preferable to melt Ca and Si after melting Si and M in order to suppress scattering of Ca.
- the heating temperature may be a temperature at which a mixture of Ca, M and Si can be a molten metal.
- the molten metal means a liquid-like state of a mixture of Ca, M and Si.
- the heating temperature is preferably in the range of 1000 ° C. to 1800 ° C., more preferably in the range of 1050 ° C. to 1500 ° C., and still more preferably in the range of 1100 ° C. to 1400 ° C.
- the molten metal is generated by the following mechanism.
- ⁇ Si and M dissolve in molten Ca to form molten metal ⁇ Ca diffuses in solid Si and solid M in molten Ca, and the melting point of Si and M gradually decreases to form molten metal ⁇ Solid M Si diffuses into it, and the melting point of M gradually falls and becomes a molten metal. Therefore, it is considered that a heating temperature higher than the melting point of each of Ca, M and Si is not necessarily required in the molten metal process.
- a high frequency induction heating device an electric furnace, or a gas furnace can be used as a heating device for the molten metal process.
- the molten metal process may be performed under pressure or reduced pressure conditions, or under an inert gas atmosphere such as argon.
- the cooling rate is not particularly limited. If the cooling rate is slow, the precipitated MSix will be relatively large fibrous particles, and if the cooling rate is fast, the precipitated MSix will be relatively small particles.
- the shape of MSix in this step is reflected in the shape of MSix in the subsequent polysilane and silicon material.
- MSix has a higher strength and a higher Young's modulus than silicon, and therefore has a role of buffering stress due to expansion and contraction of silicon. It is estimated to be responsible for Then, in order to effectively block the stress due to expansion and contraction of silicon, the shape of MSix is preferably fibrous.
- c is the fiber length in the fibrous MSix and a is a width perpendicular to the fiber length direction
- 1 ⁇ c / a ⁇ 1000 is preferable
- 3 ⁇ c / A ⁇ 100 is more preferable
- 5 ⁇ c / a ⁇ 50 is more preferable.
- c is preferably in the range of 0 ⁇ c ⁇ 1000 ⁇ m, more preferably in the range of 0.01 ⁇ c ⁇ 500 ⁇ m, still more preferably in the range of 0.1 ⁇ c ⁇ 200 ⁇ m, and in the range of 1 ⁇ c ⁇ 100 ⁇ m Particularly preferred.
- As a preferable cooling rate for forming a suitable MSix shape 100 to 10000 ° C./sec can be exemplified.
- MSix containing calcium silicide in the composition formula becomes Ca d M e Si f (0.5 ⁇ d ⁇ 1,0 ⁇ e ⁇ 0.5,1 ⁇ f ⁇ 3).
- inevitable impurities and the like are not considered.
- the fibrous state of MSix in the matrix of CaSi 2 may not be maintained, and a silicon material containing MSix to be described later is used as the negative electrode of a secondary battery.
- a silicon material containing MSix to be described later is used as the negative electrode of a secondary battery.
- MSix When used as an active material, MSix itself has a weak or no effect as an active material, and thus the capacity of the secondary battery may be reduced.
- f If the value of f is too small, the state in which MSix exists in the matrix of CaSi 2 may not be maintained, and a silicon material containing MSix described later will be used as a negative electrode active material of a secondary battery. When used, the capacity of the secondary battery is reduced. If the value of f is too large, the amount of Si alone may be too large, which may adversely affect the stability of MSix-containing calcium silicide and the reactivity of the next step.
- d, e and f 0.6 ⁇ d ⁇ 0.99, 0.7 ⁇ d ⁇ 0.98, 0.75 ⁇ d ⁇ 0.97, 0 ⁇ e ⁇ 0.4, 0 ⁇
- the obtained MSix-containing calcium silicide may be ground or further classified.
- the step of reacting the MSix-containing calcium silicide with an acid to obtain MSix-containing polysilane containing MSix in a polysilane matrix will be described.
- Si forms a Si—H bond while Ca in the layered CaSi 2 constituting the MSix-containing calcium silicide is replaced with H of the acid.
- the MSix-containing polysilane has a layered structure because the basic skeleton of the CaSi 2 -based Si layer of the raw material MSix-containing calcium silicide is maintained.
- hydrofluoric acid hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, methanesulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluoroarsenic acid And fluoroantimonic acid, hexafluorosilicic acid, hexafluorogermanic acid, hexafluorotin (IV) acid, trifluoroacetic acid, hexafluorotitanic acid, hexafluorozirconic acid, trifluoromethanesulfonic acid and fluorosulfonic acid.
- these acids may be used alone or in combination.
- an acid capable of generating a fluorine anion it may be preferable to adopt an acid capable of generating a fluorine anion.
- the acid it is possible to reduce Si—O bonds that can occur in the MSix-containing polysilane and bonds between Si and anions of other acids (for example, in the case of hydrochloric acid, Si—Cl bonds). If Si-O bonds or Si-Cl bonds exist in the MSix-containing polysilane, there may be cases where Si-O bonds or Si-Cl bonds exist in the MSix-containing silicon material even after the next step.
- the acid is preferably used in excess in molar ratio to Ca contained in MSix-containing calcium silicide.
- the process may be carried out without a solvent, it is preferable to use water as a solvent from the viewpoint of separation of the target substance and removal of by-products such as CaCl 2 and the like.
- the reaction conditions in the same step are preferably reduced pressure conditions such as vacuum or under an inert gas atmosphere, and it is preferable to set temperature conditions below room temperature such as an ice bath. The reaction time of the same process may be set appropriately.
- Si 6 H 6 corresponds to an ideal polysilane.
- MSix-containing polysilane is represented by a composition formula, M e Si f H a (OH) b X c (X is an element or group derived from the acid anion, 0 ⁇ e ⁇ 0.5, 1 ⁇ f ⁇ 3, It becomes 0 ⁇ a ⁇ fxe, 0 ⁇ b ⁇ fxe, 0 ⁇ c ⁇ fxe, and x ⁇ e + a + b + c ⁇ f.
- composition formula of only M and Si in the MSix-containing polysilane is Me e Si f (0 ⁇ e ⁇ 0.5, 1 ⁇ f ⁇ 3).
- e and f 0 ⁇ e ⁇ 0.4, 0 ⁇ e ⁇ 0.3, 0 ⁇ e ⁇ 0.25, 1.3 ⁇ f ⁇ 2.7, 1.5 ⁇ f ⁇ 2. 5, 1.7 ⁇ f ⁇ 2.3 can be exemplified.
- the MSix-containing polysilane actually used in the heating step is M e Si f H a (OH) b X c (X is an element or group derived from the acid anion, 0 ⁇ e ⁇ 0.5, 1 ⁇ f ⁇ 3 , 0 ⁇ a ⁇ f ⁇ x e, 0 ⁇ b ⁇ f xe, 0 ⁇ c ⁇ f xe, x ⁇ e + a + b + c ⁇ f), and further contains unavoidable impurities to order, MSIX containing silicon material actually obtained, M e Si f H p O q X r (X is an anion derived from an element or group of acid, 0 ⁇ e ⁇ 0.5,1 ⁇ f ⁇ 3,0 ⁇ p ⁇ a, 0 ⁇ q ⁇ b, 0 ⁇ r ⁇ c, x ⁇ e + 3 H 2 ⁇
- X is an element or group derived
- q is preferably in the range of 0 ⁇ q ⁇ 0.7, more preferably in the range of 0 ⁇ q ⁇ 0.5, and still more preferably in the range of 0 ⁇ q ⁇ 0.3.
- the range of 0 ⁇ q ⁇ 0.2 is particularly preferable.
- r is preferably in the range of 0 ⁇ r ⁇ 0.7, more preferably in the range of 0 ⁇ r ⁇ 0.5, and still more preferably in the range of 0 ⁇ r ⁇ 0.3.
- the range of 0 ⁇ r ⁇ 0.2 is particularly preferred.
- the composition formula of only M and Si in the MSix-containing silicon material is M e Si f (0 ⁇ e ⁇ 0.5, 1 ⁇ f ⁇ 3).
- e and f 0 ⁇ e ⁇ 0.4, 0 ⁇ e ⁇ 0.3, 0 ⁇ e ⁇ 0.25, 1.3 ⁇ f ⁇ 2.7, 1.5 ⁇ f ⁇ 2. 5, 1.7 ⁇ f ⁇ 2.3 can be exemplified.
- the heating step is preferably carried out under a non-oxidizing atmosphere having a lower oxygen content than under normal atmosphere.
- a non-oxidizing atmosphere a reduced pressure atmosphere including vacuum and an inert gas atmosphere can be exemplified.
- the heating temperature is preferably in the range of 350 ° C. to 950 ° C., and more preferably in the range of 400 ° C. to 800 ° C. If the heating temperature is too low, hydrogen may not be sufficiently released, and if the heating temperature is too high, energy is wasted.
- the heating time may be set appropriately according to the heating temperature. It is preferable to determine the heating time while measuring the amount of hydrogen and the like that escapes from the reaction system.
- the ratio of amorphous silicon and silicon crystallite contained in the manufactured MSix-containing silicon material and the size of silicon crystallite can also be adjusted.
- the heating temperature and the heating time it is also possible to prepare the shape of a nano-level thick layer including amorphous silicon and silicon crystallite contained in the manufactured MSix-containing silicon material.
- the size of the silicon crystallite is preferably nano-sized.
- the silicon crystallite size is preferably in the range of 0.5 nm to 300 nm, more preferably in the range of 1 nm to 100 nm, still more preferably in the range of 1 nm to 50 nm, particularly preferably in the range of 1 nm to 10 nm preferable.
- the silicon crystallite size is calculated from X-ray diffraction measurement (XRD measurement) on a silicon material, and from the Scheller equation using the half value width of the diffraction peak of the Si (111) plane of the obtained XRD chart.
- a MSix-containing silicon material having a structure in which a plurality of plate-like silicon bodies are stacked in the thickness direction can be obtained.
- MSix can be present in an orderly or disorderly manner.
- MSix is fibrous
- the MSix-containing silicon material can be obtained in a state in which the fibrous MSix is oriented in a direction intersecting the plate-like surface of the plate-like silicon body.
- a MSix-containing silicon material is obtained with the fibrous MSix being disposed across the plurality of layers of the plate-like silicon body.
- MSix-containing silicon materials can be obtained in a state where MSix is dispersed.
- the above plate-like silicon body has a thickness of 10 nm or more for efficient insertion and desorption reaction of charge carriers such as lithium ions.
- the range of 100 nm is preferable, and the range of 20 nm to 50 nm is more preferable.
- the length of the plate-like silicon body in the long axis direction is preferably in the range of 0.1 ⁇ m to 50 ⁇ m.
- the plate-like silicon body preferably has a (longitudinal direction length) / (thickness) in the range of 2 to 1,000.
- the size of fibrous MSix in the MSix-containing silicon material is preferably 1 ⁇ c / a ⁇ 1000, where c is the fiber length and a is the width perpendicular to the fiber length direction when observed by SEM. 3 ⁇ c / a ⁇ 100 is more preferable, and 5 ⁇ c / a ⁇ 50 is more preferable.
- c is preferably in the range of 0 ⁇ c ⁇ 1000 ⁇ m, more preferably in the range of 0.01 ⁇ c ⁇ 500 ⁇ m, still more preferably in the range of 0.1 ⁇ c ⁇ 200 ⁇ m, and in the range of 1 ⁇ c ⁇ 100 ⁇ m Particularly preferred.
- the obtained MSix-containing silicon material may be crushed or further classified.
- the average particle diameter (D50) is in the range of 1 to 30 ⁇ m.
- the average particle size (D50) is in the range of 1 to 10 ⁇ m.
- the MSix-containing silicon material of the present invention can be used as a negative electrode active material of a storage battery such as a secondary battery such as a lithium ion secondary battery, an electric double layer capacitor, and a lithium ion capacitor.
- a storage battery such as a secondary battery such as a lithium ion secondary battery, an electric double layer capacitor, and a lithium ion capacitor.
- the MSix-containing silicon material of the present invention can also be used as, for example, a material such as a CMOS, a semiconductor memory, a solar cell, or a photocatalytic material.
- the lithium ion secondary battery of the present invention comprises an MSix-containing silicon material as a negative electrode active material.
- the lithium ion secondary battery of the present invention comprises a positive electrode, a negative electrode provided with a MSix-containing silicon material as a negative electrode active material, an electrolytic solution, and a separator.
- the positive electrode has a current collector and a positive electrode active material layer bonded to the surface of the current collector.
- the current collector refers to a chemically inert electron conductor for keeping current flowing to the electrode during discharge or charge of the lithium ion secondary battery.
- As the current collector at least one selected from silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum, stainless steel, etc. A metal material can be illustrated.
- the current collector may be coated with a known protective layer. What processed the surface of a collector by a well-known method may be used as a collector.
- the current collector can take the form of a foil, a sheet, a film, a line, a rod, a mesh or the like. Therefore, as the current collector, for example, metal foils such as copper foil, nickel foil, aluminum foil, and stainless steel foil can be suitably used.
- the thickness is preferably in the range of 1 ⁇ m to 100 ⁇ m.
- the positive electrode active material layer contains a positive electrode active material and, if necessary, a conductive aid and / or a binder.
- a positive electrode active material spinel such as LiMn 2 O 4 and a solid solution composed of a mixture of spinel and layered compound, LiMPO 4 , LiMVO 4 or Li 2 MSiO 4 (M in the formula is Co, Ni, Mn, Polyanionic compounds represented by (at least one of Fe) and the like can be mentioned.
- tavorite compound (the M a transition metal) LiMPO 4 F, such as LiFePO 4 F represented by, Limbo 3 such LiFeBO 3 (M is a transition metal) include borate-based compound represented by be able to.
- any metal oxide used as a positive electrode active material may have the above composition formula as a basic composition, and one obtained by substituting a metal element contained in the basic composition with another metal element can also be used as a positive electrode active material .
- a positive electrode active material a positive electrode active material containing no lithium ion contributing to charge and discharge, for example, a simple substance of sulfur, a compound of sulfur and carbon, a metal sulfide such as TiS 2 , V 2 O 5 , MnO Oxides such as 2 , polyaniline and anthraquinone, and compounds containing these aromatics in the chemical structure, conjugated materials such as conjugated diacetic acid organic substances, and other known materials can also be used.
- a compound having a stable radical such as nitroxide, nitronyl nitroxide, galvinoxyl, phenoxyl or the like may be adopted as the positive electrode active material.
- a positive electrode active material containing no lithium it is necessary to add ions to the positive electrode and / or the negative electrode by a known method.
- a metal or a compound containing the ions may be used.
- a conductive aid is added to enhance the conductivity of the electrode. Therefore, the conductive additive may be optionally added when the conductivity of the electrode is insufficient, and may not be added when the conductivity of the electrode is sufficiently excellent.
- the conductive auxiliary agent may be any chemically active high electron conductor, and carbon black particles such as carbon black, graphite, acetylene black, ketjen black (registered trademark), vapor grown carbon fiber (vapor grown carbon) Fiber (VGCF), and various metal particles are exemplified. These conductive assistants can be added to the active material layer singly or in combination of two or more.
- the binder plays the role of anchoring the active material and the conductive aid to the surface of the current collector and maintaining the conductive network in the electrode.
- the binder may, for example, be a fluorine-containing resin such as polyvinylidene fluoride, polytetrafluoroethylene or fluororubber, a thermoplastic resin such as polypropylene or polyethylene, an imide resin such as polyimide or polyamideimide, an alkoxysilyl group-containing resin, Examples of acrylic resins such as acrylic acid, styrene-butadiene rubber (SBR), alginates such as carboxymethylcellulose, sodium alginate and ammonium alginate, water-soluble cellulose ester cross-linked product, starch-acrylic acid graft polymer it can. These binders may be used alone or in combination.
- the blending ratio of the binder in the active material layer is, in mass ratio, preferably active material: binder 1: 0.001 to 1: 0.3, 1: 0.005 to 1: 0 It is more preferably 0.2, and more preferably 1: 0.01 to 1: 0.15.
- the negative electrode includes a current collector and a negative electrode active material layer bonded to the surface of the current collector.
- As the current collector one described for the positive electrode may be appropriately adopted appropriately.
- the negative electrode active material layer contains a negative electrode active material and, if necessary, a conductive aid and / or a binder.
- an MSix-containing silicon material may be used, and only the MSix-containing silicon material may be adopted, or the MSix-containing silicon material and a known negative electrode active material may be used in combination. What coated MSix containing silicon material with carbon may be used as a negative electrode active material.
- those described for the positive electrode may be appropriately adopted at the same mixing ratio.
- an active material layer on the surface of a current collector current collection can be performed using conventionally known methods such as roll coating, die coating, dip coating, doctor blade method, spray coating, and curtain coating.
- the active material may be applied to the surface of the body.
- the active material, the solvent, and, if necessary, the binder and / or the conductive auxiliary agent are mixed to prepare a slurry.
- the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone and water.
- the slurry is applied to the surface of a current collector and then dried. The dried one may be compressed to increase the electrode density.
- the electrolytic solution contains a non-aqueous solvent and an electrolyte dissolved in the non-aqueous solvent.
- cyclic esters examples include ethylene carbonate, propylene carbonate, butylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone and gamma valerolactone.
- chain ester examples include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, ethyl methyl carbonate, alkyl propionic acid ester, malonic acid dialkyl ester, acetic acid alkyl ester and the like.
- ethers tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane can be exemplified.
- non-aqueous solvent a compound in which part or all of hydrogens in the chemical structure of the above specific solvent is substituted with fluorine may be adopted.
- Examples of the electrolyte include lithium salts such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , and LiN (CF 3 SO 2 ) 2 .
- electrolyte solution 0.5 mol / L to 1.7 mol of lithium salts such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 and the like in nonaqueous solvents such as ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate and the like
- LiClO 4 LiPF 6
- LiBF 4 LiCF 3 SO 3
- nonaqueous solvents such as ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate and the like
- a solution dissolved at a concentration of about / L can be exemplified.
- the separator separates the positive electrode and the negative electrode, and allows lithium ions to pass while preventing a short circuit due to the contact of the both electrodes.
- synthetic resins such as polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, polyaramid (Aromatic polyamide), polyester, polyacrylonitrile, etc., polysaccharides such as cellulose and amylose, natural substances such as fibroin, keratin, lignin and suberin Examples thereof include porous bodies, non-woven fabrics, and woven fabrics using one or more kinds of electrically insulating materials such as polymers and ceramics.
- the separator may have a multilayer structure.
- a separator is sandwiched between the positive electrode and the negative electrode as necessary to form an electrode body.
- the electrode body may be any of a laminated type in which the positive electrode, the separator and the negative electrode are stacked, or a wound type in which the positive electrode, the separator and the negative electrode are wound.
- the shape of the lithium ion secondary battery of the present invention is not particularly limited, and various shapes such as cylindrical, square, coin, and laminate types can be adopted.
- the lithium ion secondary battery of the present invention may be mounted on a vehicle.
- the vehicle may be a vehicle using electric energy from a lithium ion secondary battery for all or part of its power source, and may be, for example, an electric vehicle, a hybrid vehicle, or the like.
- a lithium ion secondary battery is mounted on a vehicle, a plurality of lithium ion secondary batteries may be connected in series to form a battery pack.
- various household appliances driven by a battery such as a personal computer and a mobile communication apparatus, as well as a vehicle, an office apparatus, an industrial apparatus and the like can be mentioned.
- the lithium ion secondary battery of the present invention can be used in wind power generation, solar power generation, hydroelectric power generation, storage devices and power smoothing devices for electric power systems, power sources for power and / or accessories of ships, etc., aircraft, Power supply source for power of spacecraft and / or accessories, auxiliary power supply for vehicles not using electricity as power source, power supply for mobile home robots, power supply for system backup, power supply for uninterruptible power supply, You may use for the electrical storage apparatus which stores temporarily the electric power required for charge in the charge station etc. for electric vehicles.
- Example 1 As described below, MSix-containing calcium silicide, MSix-containing polysilane, and MSix-containing silicon materials of Example 1 were produced.
- Step of Obtaining MSix-Containing Calcium Silicide The molten metal was poured into a predetermined mold and cooled to obtain a TiSi 2 -containing calcium silicide containing TiSi 2 in a calcium silicide matrix. The obtained TiSi 2 -containing calcium silicide was ground in a mortar and sieved with an opening of 53 ⁇ m. The TiSi 2 -containing calcium silicide that passed through a mesh with a mesh size of 53 ⁇ m was used as the MSix-containing calcium silicide in Example 1. When the MSix-containing calcium silicide in Example 1 is represented by a composition formula, it becomes Ca 0.95 Ti 0.05 Si 2 .
- Step 8 g of the MSix-containing polysilane of Example 1 was heated at 500 ° C. for 1 hour in an argon gas atmosphere to obtain the MSix-containing silicon material of Example 1.
- Example 2 MSix-containing calcium silicide, MSix-containing polysilane, and MSix-containing according to Example 2 in the same manner as in Example 1 except that the molar ratio of Ca, Ti and Si in the smelting step was 0.87: 0.13: 2. Obtained silicon material. Note that when representing the MSix containing calcium silicide of Example 2 by the composition formula, the Ca 0.87 Ti 0.13 Si 2.
- Example 3 MSix-containing calcium silicide, MSix-containing polysilane, and MSix-containing of Example 3 in the same manner as in Example 1 except that the molar ratio of Ca, Ti and Si in the smelting step was 0.78: 0.22: 2. Obtained silicon material. Note that when representing the MSix containing calcium silicide in Example 3 a composition formula, the Ca 0.78 Ti 0.22 Si 2.
- Example 4 In the same manner as in Example 1, except that Ca, Fe and Si were used at a molar ratio of 0.95: 0.03: 2 instead of Ca, Ti and Si in the molten metal process. MSix-containing calcium silicide, MSix-containing polysilane and MSix-containing silicon material were obtained. When the MSix-containing calcium silicide in Example 4 is represented by a composition formula, it becomes Ca 0.95 Fe 0.03 Si 2 .
- Example 5 was prepared in the same manner as in Example 1 except that Ca, Fe and Si were used at a molar ratio of 0.84: 0.13: 2 in place of Ca, Ti and Si in the melting step. MSix-containing calcium silicide, MSix-containing polysilane and MSix-containing silicon material were obtained. Note that when representing the MSix containing calcium silicide of Example 5 by the composition formula, the Ca 0.84 Fe 0.13 Si 2.
- Example 6 In the same manner as in Example 1, except that Ca, Fe and Si were used in the molar ratio of 0.72: 0.22: 2 instead of Ca, Ti and Si in the molten metal process. MSix-containing calcium silicide, MSix-containing polysilane and MSix-containing silicon material were obtained. Note that when representing the MSix containing calcium silicide of Example 6 by the composition formula, the Ca 0.72 Fe 0.22 Si 2.
- Example 7 Melt Process An Fe-containing CaSi 2 was prepared. Twenty grams of the CaSi 2 was placed in a carbon crucible. The carbon crucible was placed in a high frequency induction heating device, and heated at 1150 ° C. in an argon gas atmosphere to melt CaSi 2 . To the molten CaSi 2 was added 1.5 g of Ca to make a molten metal.
- Step of Obtaining MSix-Containing Calcium Silicide The molten metal was poured into a predetermined mold and cooled to obtain FeSix-containing calcium silicide containing FeSix in a calcium silicide matrix. The obtained FeSix-containing calcium silicide was ground in a mortar and sieved with an opening of 53 ⁇ m. The FeSix-containing calcium silicide that passed through a mesh with a mesh size of 53 ⁇ m was used as the MSix-containing calcium silicide in Example 7.
- the MSix-containing calcium silicide in Example 7 is represented by a composition formula as Ca 0.95 Fe 0.09 Si 2 .
- MSix-containing polysilane and MSix-containing silicon material of Example 7 were produced in the same manner as in Example 1.
- Example 8 An MSix-containing calcium silicide, MSix-containing polysilane, and MSix-containing silicon material of Example 8 were obtained in the same manner as in Example 7 except that the amount of Ca added in the melting step was 2 g. Note that when representing the MSix containing calcium silicide of Example 8 by the composition formula, the Ca 1.08 Fe 0.08 Si 1.9.
- Example 9 The same method as in Example 1 except that Ca, Fe and Si are used at a molar ratio of 32: 6: 62 instead of Ca, Ti and Si in the molten metal process, and the heating temperature is set to 900 ° C. in the heating process.
- MSix-containing calcium silicide, MSix-containing polysilane and MSix-containing silicon material of Example 9 were obtained.
- the MSix-containing calcium silicide in Example 9 is represented by a composition formula, it becomes Ca 32 Fe 6 Si 64 , that is, Ca 1 Fe 0.19 Si 2 .
- Comparative example 1 The calcium silicide, the polysilane and the silicon material of Comparative Example 1 were obtained by the same method as in Example 1 except that Ti and Ca and Si were employed at a molar ratio of 1: 2 in the melting step.
- the cross sections of the particles of MSix-containing calcium silicide of Examples 4 to 6 were observed by SEM, and further, analysis on Ca, Fe, and Si was performed by EDX.
- the obtained SEM images are shown in FIGS. From the results of EDX, in the SEM images of FIGS. 2 to 4, it is found that Si is present in the whole, the deepest color spot is Si alone, Fe is present in a white fibrous spot, Ca is fibrous And it has confirmed that it exists in places other than the deepest color. Therefore, it was confirmed that the MSix-containing calcium silicide of Examples 4 to 6 contained fibrous FeSi and FeSi 2 in a calcium silicide matrix.
- MSix-containing calcium silicides of Examples 4 to 6 were measured with a powder X-ray diffractometer. The obtained X-ray diffraction chart is shown in FIG. From the X-ray diffraction charts of the MSix-containing calcium silicides of Examples 4 to 6, the presence of CaSi 2 crystals, FeSi crystals and FeSi 2 crystals could be confirmed.
- MSix-containing calcium silicides of Examples 7 to 8 were measured with a powder X-ray diffractometer. The obtained X-ray diffraction chart is shown in FIG. The presence of CaSi 2 crystals and FeSi crystals could be confirmed from the X-ray diffraction charts of the MSix-containing calcium silicides of Examples 7 to 8.
- the peak present in the X-ray diffraction chart of the MSix-containing silicon material of Example 1 which is not present in the X-ray diffraction chart of the silicon material of Comparative Example 1 is the peak of the TiSi 2 crystal.
- a peak common to the X-ray diffraction chart of the MSix-containing silicon material of Example 1 and the X-ray diffraction chart of the silicon material of Comparative Example 1 is presumed to be derived from the layered polysilane.
- the X-ray diffraction of the MSix-containing silicon material of Examples 4 to 6 was measured with a powder X-ray diffractometer.
- the obtained X-ray diffraction chart is shown in FIG. From FIG. 9, it can be confirmed that FeSi crystals and FeSi 2 crystals are present in the MSix-containing silicon materials of Examples 4 to 6. Further, it can be confirmed from FIG. 9 that the MSix-containing silicon material of Examples 4 to 6 has a silicon crystallite having a nano size.
- X-ray diffraction of the MSix-containing silicon material of Example 7 was measured with a powder X-ray diffractometer.
- the obtained X-ray diffraction chart is shown in FIG. From FIG. 10, it can be confirmed that FeSi crystals and FeSi 2 crystals exist in the MSix-containing silicon material of Example 7. Further, it can be confirmed from FIG. 10 that, in the MSix-containing silicon material of Example 7, silicon crystallite having a nano size is present.
- Si was present in both the plate-like lateral laminate and the fiber body orthogonal to the laminate. Further, it was found that Fe was present in the above-mentioned fiber body. It can be said that in the MSix-containing silicon material of Example 5 and Example 7, a plate-like laminate containing Si and a fiber body containing FeSi and / or FeSi 2 orthogonal to the laminate exist.
- the MSix-containing silicon material of Example 9 was observed by SEM, and further analysis was performed on Fe and Si by EDX. The obtained SEM image is shown in FIG. From the results of EDX analysis, it was found that Si is present in the entire plate-like laminate in the SEM image of FIG. Further, it was found that Fe was dispersed in the form of dots on the particles having the above-mentioned laminate.
- Example A-1 Using the MSix-containing silicon material of Example 1, a lithium ion secondary battery of Example A-1 was produced as follows.
- Example 1 45 parts by mass of the MSix-containing silicon material of Example 1 as a negative electrode active material, 40 parts by mass of graphite as a negative electrode active material, 10 parts by mass of polyamideimide as a binder, 5 parts by mass of acetylene black as a conductive aid, An appropriate amount of N-methyl-2-pyrrolidone was mixed to form a slurry.
- An electrolytic copper foil having a thickness of 20 ⁇ m was prepared as a current collector.
- the slurry was applied onto the surface of the copper foil in the form of a film using a doctor blade.
- the copper foil coated with the slurry was dried at 80 ° C. for 20 minutes to remove N-methyl-2-pyrrolidone by volatilization.
- a copper foil having a negative electrode active material layer formed on the surface was obtained.
- the copper foil was compressed with a roll press so that the thickness of the negative electrode active material layer was 20 ⁇ m, to obtain a bonded product.
- the joined product was dried by heating under reduced pressure at 200 ° C. for 2 hours to obtain an electrode of Example A-1.
- the negative electrode active material layer was disposed at 2 mg / cm 2 on the current collector, and the density of the negative electrode active material layer was 1 g / cm 3 .
- Example A-1 The electrode of Example A-1 was cut to a diameter of 11 mm and used as an evaluation electrode.
- the lithium metal foil was cut to a diameter of 13 mm to form a counter electrode.
- a glass filter (Hoechst Celanese) and celgard 2400 (Polypore Co., Ltd.) which is a single-layer polypropylene were prepared as a separator. It was also prepared an electrolyte solution obtained by dissolving LiPF 6 at 1 mol / L in a solvent obtained by mixing 50 parts by volume of ethylene carbonate and diethyl carbonate 50 parts by volume. The two types of separators were sandwiched between the counter electrode and the evaluation electrode in the order of the counter electrode, the glass filter, celgard 2400, and the evaluation electrode to form an electrode body.
- the electrode body was housed in a coin-type battery case CR2032 (Housen Co., Ltd.), and an electrolyte was further injected to obtain a coin-type battery.
- the resultant was used as a lithium ion secondary battery of Example A-1.
- Example A-2 A lithium ion catalyst of Example A-2 was prepared in the same manner as Example A-1, except that the MSix containing silicon material of Example 2 was used instead of the MSix containing silicon material of Example 1 as the negative electrode active material. The following battery was manufactured.
- Example A-3 A lithium ion catalyst of Example A-3 was prepared in the same manner as Example A-1, except that the MSix containing silicon material of Example 3 was employed instead of the MSix containing silicon material of Example 1 as the negative electrode active material. The following battery was manufactured.
- Example A-4 A lithium ion catalyst of Example A-4 was prepared in the same manner as Example A-1, except that the MSix containing silicon material of Example 4 was employed instead of the MSix containing silicon material of Example 1 as the negative electrode active material. The following battery was manufactured.
- Example A-5 A lithium ion catalyst of Example A-5 was prepared in the same manner as Example A-1, except that the MSix containing silicon material of Example 5 was employed instead of the MSix containing silicon material of Example 1 as the negative electrode active material. The following battery was manufactured.
- Example A-6 A lithium ion catalyst of Example A-6 was prepared in the same manner as Example A-1, except that the MSix containing silicon material of Example 6 was employed instead of the MSix containing silicon material of Example 1 as the negative electrode active material. The following battery was manufactured.
- Comparative Example A-1 A lithium ion secondary battery of Comparative Example A-1 was prepared in the same manner as Example A-1, except that the silicon material of Comparative Example 1 was used instead of the MSix-containing silicon material of Example 1 as the negative electrode active material. Manufactured.
- Evaluation Example 6 occluding Li in the evaluation electrode is referred to as discharge, and releasing Li from the evaluation electrode is referred to as charging.
- the capacity retention rate of the lithium ion secondary batteries of Examples A-1 to A-6 was superior to the capacity retention rate of the lithium ion secondary battery of Comparative Example 2. This result indicates that MSix of the MSix-containing silicon material used in the lithium ion secondary batteries of Examples A-1 to A-6 efficiently blocked stress concentration due to expansion and contraction of silicon, thereby making it possible to use the negative electrode active material. Is considered to have been able to suppress the collapse of the It was confirmed that the MSix-containing silicon material of the present invention is suitable.
- Example A-7 The MSix-containing silicon material of Example 7 was crushed and coated with carbon and then washed with water to produce the carbon-coated MSix-containing silicon material of Example 7. 75 parts by mass of the carbon-coated MSix-containing silicon material of Example 7 as a negative electrode active material, 10 parts by mass of graphite as a negative electrode active material, 10 parts by mass of polyamideimide as a binder, and 5 parts by mass of acetylene black as a conductive aid Parts and an appropriate amount of N-methyl-2-pyrrolidone were mixed to form a slurry. An electrolytic copper foil having a thickness of 20 ⁇ m was prepared as a current collector.
- the slurry was applied onto the surface of the copper foil in the form of a film using a doctor blade.
- the copper foil coated with the slurry was dried at 80 ° C. for 20 minutes to remove N-methyl-2-pyrrolidone by volatilization.
- a copper foil having a negative electrode active material layer formed on the surface was obtained.
- the copper foil was compressed with a roll press so that the thickness of the negative electrode active material layer was 20 ⁇ m, to obtain a bonded product.
- the bonded product was dried under reduced pressure at 200 ° C. for 2 hours to form an electrode.
- the above electrode was cut into a diameter of 11 mm and used as an evaluation electrode.
- the lithium metal foil was cut to a diameter of 13 mm to form a counter electrode.
- a glass filter (Hoechst Celanese) and celgard 2400 (Polypore Co., Ltd.) which is a single-layer polypropylene were prepared as a separator. It was also prepared an electrolyte solution obtained by dissolving LiPF 6 at 1 mol / L in a solvent obtained by mixing 50 parts by volume of ethylene carbonate and diethyl carbonate 50 parts by volume. The two types of separators were sandwiched between the counter electrode and the evaluation electrode in the order of the counter electrode, the glass filter, celgard 2400, and the evaluation electrode to form an electrode body. The electrode body was housed in a coin-type battery case CR2032 (Housen Co., Ltd.), and an electrolyte was further injected to obtain a coin-type battery. The resultant was used as a lithium ion secondary battery of Example A-7.
- Example 7 The lithium ion secondary battery of Example A-7 was discharged at a 0.25 C rate until the voltage to the counter electrode of the evaluation electrode was 0.01 V, and the 0.25 C rate until the voltage to the counter electrode of the evaluation electrode was 1 V 50 cycles of charge and discharge cycles to charge the battery. The ratio of the charge capacity in each cycle to the initial charge capacity was taken as the capacity retention rate. A graph of the relationship between the number of cycles and the capacity retention rate is shown in FIG. In Evaluation Example 7, occluding Li in the evaluation electrode is referred to as discharge, and releasing Li from the evaluation electrode is referred to as charging. From FIG. 15, it can be seen that the lithium ion secondary battery of Example A-7 preferably maintains its capacity.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
Description
Ca、M(Mは第3~9族元素から選択される少なくとも一元素)及びSiを加熱して溶湯とする溶湯工程、
前記溶湯を冷却して、珪化カルシウムマトリックス中にMSix(ただし、1/3≦x≦3)を含有するMSix含有珪化カルシウムを得る工程、
前記MSix含有珪化カルシウムを酸と反応させて、ポリシランマトリックス中にMSixを含有するMSix含有ポリシランを得る工程、
前記MSix含有ポリシランを300℃以上で加熱する加熱工程、
を含むことを特徴とする。
Ca、M(Mは第3~9族元素から選択される少なくとも一元素)及びSiを加熱して溶湯とする溶湯工程、
前記溶湯を冷却して、珪化カルシウムマトリックス中にMSix(ただし、1/3≦x≦3)を含有するMSix含有珪化カルシウムを得る工程、
前記MSix含有珪化カルシウムを酸と反応させて、ポリシランマトリックス中にMSixを含有するMSix含有ポリシランを得る工程、
前記MSix含有ポリシランを300℃以上で加熱する加熱工程、
を含むことを特徴とする。
・溶融Ca中にSiやMが溶解して溶湯となる
・溶融Ca中で固体のSiや固体のMにCaが拡散し、徐々にSiやMの融点が下がり、溶湯となる
・固体のM中にSiが拡散し、徐々にMの融点が下がり、溶湯となる
そのため、溶湯工程においては、Ca、M及びSiの各単体の融点以上の加熱温度が必ずしも必要ではないと考えられる。
上記反応式において、Si6H6が理想的なポリシランに該当する。
ただし、加熱工程に実際に用いられるMSix含有ポリシランはMeSifHa(OH)bXc(Xは酸のアニオン由来の元素若しくは基、0<e≦0.5、1≦f≦3、0<a<f-x×e、0<b<f-x×e、0<c<f-x×e、x×e+a+b+c≦f)で表されるものであり、さらに不可避不純物も含有するため、実際に得られるMSix含有シリコン材料は、MeSifHpOqXr(Xは酸のアニオン由来の元素若しくは基、0<e≦0.5、1≦f≦3、0≦p<a、0≦q<b、0≦r≦c、x×e+p+q+r≦f、ただしa、b、cはMSix含有ポリシランの組成式で定義される。)で表され、さらに不可避不純物も含有するものとなる。
以下のとおり、実施例1のMSix含有珪化カルシウム、MSix含有ポリシラン、MSix含有シリコン材料を製造した。
Ca、Ti及びSiを0.95:0.05:2のモル比で炭素坩堝に秤量し、高周波誘導加熱装置にて、アルゴンガス雰囲気下、坩堝を1150℃で加熱してCa、Ti及びSiを溶湯とした。
前記溶湯を所定の鋳型に注湯して冷却し、珪化カルシウムマトリックス中にTiSi2を含有するTiSi2含有珪化カルシウムを得た。得られたTiSi2含有珪化カルシウムを乳鉢で粉砕し、目開き53μmの篩にかけた。目開き53μmの篩を通過したTiSi2含有珪化カルシウムを実施例1のMSix含有珪化カルシウムとした。実施例1のMSix含有珪化カルシウムを組成式で表わすと、Ca0.95Ti0.05Si2となる。
氷浴中の36質量%HCl水溶液100mLに、アルゴンガス気流中にて上記実施例1のMSix含有珪化カルシウム10gを加え、90分間撹拌した。反応液中に暗緑粉末が分散するのが確認できた。反応液を濾過し、残渣を蒸留水及びアセトンで洗浄し、さらに、室温で12時間以上減圧乾燥して8gのTiSi2含有ポリシランを得た。これを実施例1のMSix含有ポリシランとした。
上記実施例1のMSix含有ポリシラン8gをアルゴンガス雰囲気下、500℃で1時間加熱し、実施例1のMSix含有シリコン材料を得た。
溶湯工程のCa、Ti及びSiを0.87:0.13:2のモル比とした以外は、実施例1と同様の方法で、実施例2のMSix含有珪化カルシウム、MSix含有ポリシラン及びMSix含有シリコン材料を得た。なお、実施例2のMSix含有珪化カルシウムを組成式で表わすと、Ca0.87Ti0.13Si2となる。
溶湯工程のCa、Ti及びSiを0.78:0.22:2のモル比とした以外は、実施例1と同様の方法で、実施例3のMSix含有珪化カルシウム、MSix含有ポリシラン及びMSix含有シリコン材料を得た。なお、実施例3のMSix含有珪化カルシウムを組成式で表わすと、Ca0.78Ti0.22Si2となる。
溶湯工程において、Ca、Ti及びSiに換えて、Ca、Fe及びSiを0.95:0.03:2のモル比で用いた以外は、実施例1と同様の方法で、実施例4のMSix含有珪化カルシウム、MSix含有ポリシラン及びMSix含有シリコン材料を得た。なお、実施例4のMSix含有珪化カルシウムを組成式で表わすと、Ca0.95Fe0.03Si2となる。
溶湯工程において、Ca、Ti及びSiに換えて、Ca、Fe及びSiを0.84:0.13:2のモル比で用いた以外は、実施例1と同様の方法で、実施例5のMSix含有珪化カルシウム、MSix含有ポリシラン及びMSix含有シリコン材料を得た。なお、実施例5のMSix含有珪化カルシウムを組成式で表わすと、Ca0.84Fe0.13Si2となる。
溶湯工程において、Ca、Ti及びSiに換えて、Ca、Fe及びSiを0.72:0.22:2のモル比で用いた以外は、実施例1と同様の方法で、実施例6のMSix含有珪化カルシウム、MSix含有ポリシラン及びMSix含有シリコン材料を得た。なお、実施例6のMSix含有珪化カルシウムを組成式で表わすと、Ca0.72Fe0.22Si2となる。
・溶湯工程
Feを含有するCaSi2を準備した。当該CaSi220gを炭素坩堝に入れた。当該炭素坩堝を高周波誘導加熱装置に配置して、アルゴンガス雰囲気下、1150℃で加熱し、CaSi2を溶融した。溶融したCaSi2に、Ca1.5gを添加し、溶湯とした。
前記溶湯を所定の鋳型に注湯して冷却し、珪化カルシウムマトリックス中にFeSixを含有するFeSix含有珪化カルシウムを得た。得られたFeSix含有珪化カルシウムを乳鉢で粉砕し、目開き53μmの篩にかけた。目開き53μmの篩を通過したFeSix含有珪化カルシウムを実施例7のMSix含有珪化カルシウムとした。実施例7のMSix含有珪化カルシウムを組成式で表わすと、Ca0.95Fe0.09Si2である。
溶湯工程で添加したCaの量を2gとした以外は、実施例7と同様の方法で、実施例8のMSix含有珪化カルシウム、MSix含有ポリシラン及びMSix含有シリコン材料を得た。なお、実施例8のMSix含有珪化カルシウムを組成式で表わすと、Ca1.08Fe0.08Si1.9となる。
溶湯工程にて、Tiを用いず、Ca及びSiを1:2のモル比で採用した以外は、実施例1と同様の方法で、比較例1の珪化カルシウム、ポリシラン及びシリコン材料を得た。
実施例1のMSix含有珪化カルシウムの粒子の断面につき、走査型電子顕微鏡(SEM)で観察し、さらに、エネルギー分散型X線分析法(EDX)でCa、Ti及びSiを対象とした分析を行った。得られたSEM画像を図1に示す。EDXの結果から、図1のSEM画像において、Siが全体に存在すること、最濃色箇所はSi単体であること、Tiは淡色の繊維状の箇所に存在すること、Caは繊維状及び最濃色以外の箇所に存在することが確認できた。
したがって、実施例1のMSix含有珪化カルシウムは、珪化カルシウムマトリックス中に繊維状のTiSi2を含有していることが裏付けられた。
したがって、実施例4~6のMSix含有珪化カルシウムは、珪化カルシウムマトリックス中に繊維状のFeSi及びFeSi2を含有していることが裏付けられた。
粉末X線回折装置にて、実施例1~3のMSix含有珪化カルシウム及び比較例1の珪化カルシウムのX線回折を測定した。得られたX線回折チャートをTiSi2結晶及びCaSi2結晶のX線回折チャートとともに図5に示す。
粉末X線回折装置にて、実施例1~3のMSix含有シリコン材料及び比較例1のシリコン材料のX線回折を測定した。得られたX線回折チャートをTiSi2結晶のX線回折チャートとともに図8に示す。
実施例1~6のMSix含有シリコン材料及び比較例1のシリコン材料の組成分析を、酸素については酸素窒素分析装置EMGA(株式会社堀場製作所)を用い、塩素についてはイオンクロマトグラフを用い、Ca、Ti及びFeについては誘導結合プラズマ発光分光法を用いて行った。結果を表1に示す。表中の数値は質量%である。なお、Siの値は100から他の元素の割合を減じて算出した。
実施例5のMSix含有シリコン材料につき、SEMで観察し、さらに、EDXでFe及びSiを対象とした分析を行った。得られたSEM画像を図11に示す。EDX分析の結果から、図11のSEM画像において、Siが板状の横方向の積層体と、当該積層体に対して直交する繊維体の両者の全体に存在することが判明した。また、Feは上記繊維体に存在することが判明した。
実施例7のMSix含有シリコン材料につき、SEMで観察し、さらに、EDXでFe及びSiを対象とした分析を行った。得られたSEM画像を図12に示し、その拡大図を図13に示す。EDX分析の結果から、図12及び図13のSEM画像において、Siが板状の横方向の積層体と、当該積層体に対して直交する繊維体の両者の全体に存在することが判明した。また、Feは上記繊維体に存在することが判明した。
実施例5及び実施例7のMSix含有シリコン材料には、Siを含む板状の積層体と、当該積層体に対して直交する、FeSi及び/又はFeSi2を含む繊維体が、存在するといえる。
実施例9のMSix含有シリコン材料につき、SEMで観察し、さらに、EDXでFe及びSiを対象とした分析を行った。得られたSEM画像を図14に示す。EDX分析の結果から、図14のSEM画像において、Siが板状の積層体の全体に存在することが判明した。また、Feは上記積層体を有する粒子に、点状に分散して存在することが判明した。
実施例1のMSix含有シリコン材料を用いて、以下のとおり、実施例A-1のリチウムイオン二次電池を製造した。
負極活物質として実施例1のMSix含有シリコン材料の代わりに、実施例2のMSix含有シリコン材料を採用した以外は、実施例A-1と同様の方法で、実施例A-2のリチウムイオン二次電池を製造した。
負極活物質として実施例1のMSix含有シリコン材料の代わりに、実施例3のMSix含有シリコン材料を採用した以外は、実施例A-1と同様の方法で、実施例A-3のリチウムイオン二次電池を製造した。
負極活物質として実施例1のMSix含有シリコン材料の代わりに、実施例4のMSix含有シリコン材料を採用した以外は、実施例A-1と同様の方法で、実施例A-4のリチウムイオン二次電池を製造した。
負極活物質として実施例1のMSix含有シリコン材料の代わりに、実施例5のMSix含有シリコン材料を採用した以外は、実施例A-1と同様の方法で、実施例A-5のリチウムイオン二次電池を製造した。
負極活物質として実施例1のMSix含有シリコン材料の代わりに、実施例6のMSix含有シリコン材料を採用した以外は、実施例A-1と同様の方法で、実施例A-6のリチウムイオン二次電池を製造した。
負極活物質として実施例1のMSix含有シリコン材料の代わりに比較例1のシリコン材料を採用した以外は、実施例A-1と同様の方法で、比較例A-1のリチウムイオン二次電池を製造した。
実施例A-1~A-6及び比較例A-1のリチウムイオン二次電池につき、対極に対する評価極の電圧が0.01Vになるまで0.25Cレートで放電を行い、対極に対する評価極の電圧が1Vになるまで0.25Cレートで充電を行う充放電サイクルを50サイクル行った。(50サイクル目の充電容量/初回充電容量)×100を容量維持率(%)として算出した。結果を表2に示す。
実施例7のMSix含有シリコン材料を粉砕し、炭素で被覆した後に水洗して、実施例7の炭素被覆MSix含有シリコン材料を製造した。
負極活物質として実施例7の炭素被覆MSix含有シリコン材料を75質量部、さらに負極活物質として黒鉛を10質量部、結着剤としてポリアミドイミドを10質量部、導電助剤としてアセチレンブラックを5質量部及び適量のN-メチル-2-ピロリドンを混合してスラリーとした。
集電体として厚さ20μmの電解銅箔を準備した。該銅箔の表面に、ドクターブレードを用いて上記スラリーが膜状になるように塗布した。スラリーが塗布された銅箔を80℃で20分間乾燥することでN-メチル-2-ピロリドンを揮発により除去し、その結果、表面に負極活物質層が形成された銅箔を得た。該銅箔を負極活物質層の厚みが20μmとなるように、ロールプレス機で圧縮して接合物を得た。この接合物を200℃で2時間減圧加熱乾燥し、電極とした。
上記電極を径11mmに裁断し、評価極とした。金属リチウム箔を径13mmに裁断し対極とした。セパレータとしてガラスフィルター(ヘキストセラニーズ社)及び単層ポリプロピレンであるcelgard2400(ポリポア株式会社)を準備した。また、エチレンカーボネート50容量部及びジエチルカーボネート50容量部を混合した溶媒にLiPF6を1mol/Lで溶解した電解液を準備した。対極、ガラスフィルター、celgard2400、評価極の順に、2種のセパレータを対極と評価極で挟持し電極体とした。この電極体をコイン型電池ケースCR2032(宝泉株式会社)に収容し、さらに電解液を注入して、コイン型電池を得た。これを実施例A-7のリチウムイオン二次電池とした。
実施例A-7のリチウムイオン二次電池につき、評価極の対極に対する電圧が0.01Vになるまで0.25Cレートで放電を行い、評価極の対極に対する電圧が1Vになるまで0.25Cレートで充電を行う充放電サイクルを50サイクル行った。初回の充電容量に対する各サイクルでの充電容量の比率を容量維持率とした。サイクル数と容量維持率との関係のグラフを図15に示す。なお、評価例7では、評価極にLiを吸蔵させることを放電といい、評価極からLiを放出させることを充電という。
図15から、実施例A-7のリチウムイオン二次電池は、好適に容量を維持しているのがわかる。
Claims (10)
- Ca、M(Mは第3~9族元素から選択される少なくとも一元素)及びSiを加熱して溶湯とする溶湯工程、
前記溶湯を冷却して、珪化カルシウムマトリックス中にMSix(ただし、1/3≦x≦3)を含有するMSix含有珪化カルシウムを得る工程、
前記MSix含有珪化カルシウムを酸と反応させて、ポリシランマトリックス中にMSixを含有するMSix含有ポリシランを得る工程、
前記MSix含有ポリシランを300℃以上で加熱する加熱工程、
を含むことを特徴とするシリコンマトリックス中にMSixを含有するMSix含有シリコン材料の製造方法。 - 前記MSixは、FeSi及び/又はFeSi2である、請求項1に記載のMSix含有シリコン材料の製造方法。
- 珪化カルシウムマトリックス中にMSix(Mは第3~9族元素から選択される少なくとも一元素。ただし、1/3≦x≦3)を含有することを特徴とするMSix含有珪化カルシウム。
- ポリシランマトリックス中にMSix(Mは第3~9族元素から選択される少なくとも一元素。ただし、1/3≦x≦3)を含有することを特徴とするMSix含有ポリシラン。
- シリコンマトリックス中にMSix(Mは第3~9族元素から選択される少なくとも一元素。ただし、1/3≦x≦3)を含有することを特徴とするMSix含有シリコン材料。
- 前記MSixは、FeSi及び/又はFeSi2である、請求項5に記載のMSix含有シリコン材料。
- 前記MSix含有シリコン材料は複数枚の板状シリコン体が厚さ方向に積層されてなる構造を有する粒子であり、
前記FeSi及び/又はFeSi2は繊維状であって、前記粒子における複数の層に亘って配置されている、請求項6に記載のMSix含有シリコン材料。 - 前記MSix含有シリコン材料は複数枚の板状シリコン体が厚さ方向に積層されてなる構造を有する粒子であり、
前記FeSi及び/またはFeSi2は、前記粒子に分散して配置されている、請求項6に記載のMSix含有シリコン材料。 - 前記MSixは、TiSi2である請求項5に記載のMSix含有シリコン材料。
- 請求項5~9のいずれかに記載のMSix含有シリコン材料を負極活物質として具備するリチウムイオン二次電池。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020177006779A KR101927009B1 (ko) | 2014-09-19 | 2015-09-04 | MSix (M 은 제 3 ∼ 9 족 원소에서 선택되는 적어도 한 원소. 단, 1/3 ≤ x ≤ 3) 함유 실리콘 재료 및 그 제조 방법 |
JP2016548548A JP6288285B2 (ja) | 2014-09-19 | 2015-09-04 | MSix(Mは第3〜9族元素から選択される少なくとも一元素。ただし、1/3≦x≦3)含有シリコン材料およびその製造方法 |
CN201580050308.XA CN107074559B (zh) | 2014-09-19 | 2015-09-04 | 含MSix硅材料及其制造方法 |
US15/511,746 US10135067B2 (en) | 2014-09-19 | 2015-09-04 | MSix-containing silicon material (M is at least one element selected from group 3 to 9 elements. ⅓<=x<=3) and method for producing same |
DE112015004276.8T DE112015004276T5 (de) | 2014-09-19 | 2015-09-04 | MSix-ENTHALTENDES SILICIUMMATERIAL (M IST ZUMINDEST EIN ELEMENT AUSGEWÄHLT AUS DEN GRUPPE 3 BIS 9 ELEMENTEN. 1/3 ≤ x ≤ 3) UND VERFAHREN ZUR HERSTELLUNG DAVON |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014190843 | 2014-09-19 | ||
JP2014-190843 | 2014-09-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016042728A1 true WO2016042728A1 (ja) | 2016-03-24 |
Family
ID=55532786
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/004505 WO2016042728A1 (ja) | 2014-09-19 | 2015-09-04 | MSix(Mは第3~9族元素から選択される少なくとも一元素。ただし、1/3≦x≦3)含有シリコン材料およびその製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10135067B2 (ja) |
JP (1) | JP6288285B2 (ja) |
KR (1) | KR101927009B1 (ja) |
CN (1) | CN107074559B (ja) |
DE (1) | DE112015004276T5 (ja) |
WO (1) | WO2016042728A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016199359A1 (ja) * | 2015-06-12 | 2016-12-15 | 株式会社豊田自動織機 | CaSi2含有組成物及びシリコン材料の製造方法 |
JP2017224499A (ja) * | 2016-06-15 | 2017-12-21 | 大同特殊鋼株式会社 | リチウムイオン電池用負極活物質およびリチウムイオン電池 |
WO2020166658A1 (ja) * | 2019-02-13 | 2020-08-20 | 三井金属鉱業株式会社 | 活物質 |
WO2020166655A1 (ja) * | 2019-02-13 | 2020-08-20 | 三井金属鉱業株式会社 | 活物質 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180179072A1 (en) * | 2015-06-12 | 2018-06-28 | Kabushiki Kaisha Toyota Jidoshokki | Silicon material and method for producing the same |
CN108063243A (zh) * | 2017-12-13 | 2018-05-22 | 盐城工学院 | 电池负极材料及其制备方法以及锂电池负极片、锂电池 |
CN108365186A (zh) * | 2018-01-11 | 2018-08-03 | 湖南立方新能源科技有限责任公司 | 一种硅基复合负极材料及其制备方法 |
CN109950542A (zh) * | 2019-04-03 | 2019-06-28 | 西安交通大学 | 一类含硅氧烷基团的接枝共聚物粘合剂及其应用以及基于其的二次电池 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012072046A (ja) * | 2010-09-03 | 2012-04-12 | Toyota Central R&D Labs Inc | 遷移金属シリサイド−Si複合粉末及びその製造方法、並びに、遷移金属シリサイド−Si複合粉末製造用CaSiy系粉末及びその製造方法 |
JP2013105655A (ja) * | 2011-11-15 | 2013-05-30 | Shin Etsu Chem Co Ltd | リチウムイオン電池用負極材 |
JP2014107132A (ja) * | 2012-11-28 | 2014-06-09 | Furukawa Electric Co Ltd:The | リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極、リチウムイオン二次電池、およびリチウムイオン二次電池用負極材料の製造方法 |
JP2014514683A (ja) * | 2011-02-07 | 2014-06-19 | シラ ナノテクノロジーズ インク | リチウムイオン電池負極の安定化 |
US20140234721A1 (en) * | 2011-08-04 | 2014-08-21 | Robert Bosch Gmbh | Mesoporous Silicon Compound used as Lithium-Ion Cell Negative Electrode Material and Preparation Method Thereof |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63185864A (ja) * | 1986-09-05 | 1988-08-01 | 株式会社日立製作所 | 複合セラミツクスおよびその製法 |
EP1833109A1 (en) * | 2005-06-03 | 2007-09-12 | Matsushita Electric Industrial Co., Ltd. | Rechargeable battery with nonaqueous electrolyte and process for producing negative electrode |
US7732095B2 (en) | 2005-12-01 | 2010-06-08 | 3M Innovative Properties Company | Electrode compositions based on an amorphous alloy having a high silicon content |
JP5471284B2 (ja) | 2009-10-20 | 2014-04-16 | 株式会社豊田中央研究所 | リチウム二次電池用電極及びそれを備えたリチウム二次電池 |
CN102502664B (zh) * | 2011-11-11 | 2013-01-23 | 武汉大学 | 一种SiO2纳米纤维束阵列的合成方法 |
DE112013005568T5 (de) | 2012-11-21 | 2015-09-17 | Kabushiki Kaisha Toyota Jidoshokki | Nanokristallines Siliciummaterial, Aktivmaterial für eine negative Elektrode, Herstellungsverfahren für das Material und elektrisches Speichergerät |
JP6318859B2 (ja) | 2014-05-29 | 2018-05-09 | 株式会社豊田自動織機 | 銅含有シリコン材料及びその製造方法と負極活物質及び二次電池 |
-
2015
- 2015-09-04 US US15/511,746 patent/US10135067B2/en active Active
- 2015-09-04 JP JP2016548548A patent/JP6288285B2/ja active Active
- 2015-09-04 CN CN201580050308.XA patent/CN107074559B/zh active Active
- 2015-09-04 WO PCT/JP2015/004505 patent/WO2016042728A1/ja active Application Filing
- 2015-09-04 KR KR1020177006779A patent/KR101927009B1/ko active IP Right Grant
- 2015-09-04 DE DE112015004276.8T patent/DE112015004276T5/de not_active Ceased
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012072046A (ja) * | 2010-09-03 | 2012-04-12 | Toyota Central R&D Labs Inc | 遷移金属シリサイド−Si複合粉末及びその製造方法、並びに、遷移金属シリサイド−Si複合粉末製造用CaSiy系粉末及びその製造方法 |
JP2014514683A (ja) * | 2011-02-07 | 2014-06-19 | シラ ナノテクノロジーズ インク | リチウムイオン電池負極の安定化 |
US20140234721A1 (en) * | 2011-08-04 | 2014-08-21 | Robert Bosch Gmbh | Mesoporous Silicon Compound used as Lithium-Ion Cell Negative Electrode Material and Preparation Method Thereof |
JP2013105655A (ja) * | 2011-11-15 | 2013-05-30 | Shin Etsu Chem Co Ltd | リチウムイオン電池用負極材 |
JP2014107132A (ja) * | 2012-11-28 | 2014-06-09 | Furukawa Electric Co Ltd:The | リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極、リチウムイオン二次電池、およびリチウムイオン二次電池用負極材料の製造方法 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016199359A1 (ja) * | 2015-06-12 | 2016-12-15 | 株式会社豊田自動織機 | CaSi2含有組成物及びシリコン材料の製造方法 |
JPWO2016199359A1 (ja) * | 2015-06-12 | 2018-04-26 | 株式会社豊田自動織機 | CaSi2含有組成物及びシリコン材料の製造方法 |
US10308515B2 (en) | 2015-06-12 | 2019-06-04 | Kabushiki Kaisha Toyota Jidoshokki | Method for producing CaSi2-containing composition and silicon material |
JP2017224499A (ja) * | 2016-06-15 | 2017-12-21 | 大同特殊鋼株式会社 | リチウムイオン電池用負極活物質およびリチウムイオン電池 |
WO2020166658A1 (ja) * | 2019-02-13 | 2020-08-20 | 三井金属鉱業株式会社 | 活物質 |
WO2020166655A1 (ja) * | 2019-02-13 | 2020-08-20 | 三井金属鉱業株式会社 | 活物質 |
Also Published As
Publication number | Publication date |
---|---|
US20170309901A1 (en) | 2017-10-26 |
JP6288285B2 (ja) | 2018-03-07 |
DE112015004276T5 (de) | 2017-06-22 |
US10135067B2 (en) | 2018-11-20 |
KR20170042331A (ko) | 2017-04-18 |
CN107074559A (zh) | 2017-08-18 |
KR101927009B1 (ko) | 2018-12-07 |
JPWO2016042728A1 (ja) | 2017-05-25 |
CN107074559B (zh) | 2019-11-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6288285B2 (ja) | MSix(Mは第3〜9族元素から選択される少なくとも一元素。ただし、1/3≦x≦3)含有シリコン材料およびその製造方法 | |
WO2016139957A1 (ja) | リチウムイオン二次電池用正極及びその製造方法並びにリチウムイオン二次電池 | |
JPWO2016031126A1 (ja) | 炭素被覆シリコン材料の製造方法 | |
WO2016199358A1 (ja) | シリコン材料およびその製造方法 | |
JP6926873B2 (ja) | Al及びO含有シリコン材料 | |
JP6724927B2 (ja) | シリコン材料の製造方法 | |
JP6436234B2 (ja) | CaSi2含有組成物及びシリコン材料の製造方法 | |
JP6252864B2 (ja) | シリコン材料の製造方法 | |
JP6376054B2 (ja) | シリコン材料及びその製造方法並びにシリコン材料を具備する二次電池 | |
JP6635292B2 (ja) | M含有シリコン材料(MはSn、Pb、Sb、Bi、In、Zn又はAuから選択される少なくとも一元素)およびその製造方法 | |
JP2018032602A (ja) | 負極材料の製造方法 | |
JP6642822B2 (ja) | MSix(Mは第3〜9族元素から選択される少なくとも一元素。ただし、1/3≦x≦3)含有シリコン材料およびその製造方法 | |
JP6852691B2 (ja) | 酸素含有シリコン材料及びその製造方法 | |
JP6859930B2 (ja) | Al含有シリコン材料 | |
JP6852689B2 (ja) | Al含有シリコン材料 | |
JP2016219354A (ja) | 結晶性シリコン粉末及び非晶質シリコン粉末を具備する負極 | |
JP2018058746A (ja) | 炭素被覆シリコン材料の製造方法 | |
JP2016141587A (ja) | 層状シリコン化合物及びシリコン材料の製造方法、並びに、シリコン材料を具備する二次電池 | |
WO2019053983A1 (ja) | Al含有シリコン材料を含む負極活物質 | |
WO2019053984A1 (ja) | Al含有シリコン材料を含む負極活物質 | |
JP2020102383A (ja) | 負極活物質 | |
WO2019064728A1 (ja) | 酸素含有シリコン材料を含む負極活物質及びその製造方法 | |
WO2019053985A1 (ja) | Al含有シリコン材料を含む負極活物質 | |
JP2019179718A (ja) | 正極活物質 | |
JP2017114742A (ja) | シリコン材料の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15842271 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016548548 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20177006779 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15511746 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 112015004276 Country of ref document: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15842271 Country of ref document: EP Kind code of ref document: A1 |