WO2015012086A1 - 複合粒子及びその製造方法並びに電極及び非水電解質二次電池 - Google Patents
複合粒子及びその製造方法並びに電極及び非水電解質二次電池 Download PDFInfo
- Publication number
- WO2015012086A1 WO2015012086A1 PCT/JP2014/067918 JP2014067918W WO2015012086A1 WO 2015012086 A1 WO2015012086 A1 WO 2015012086A1 JP 2014067918 W JP2014067918 W JP 2014067918W WO 2015012086 A1 WO2015012086 A1 WO 2015012086A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- silicon phase
- powder
- particles
- composite
- Prior art date
Links
- 239000011246 composite particle Substances 0.000 title claims abstract description 104
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 130
- 239000002245 particle Substances 0.000 claims abstract description 117
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 95
- 239000010703 silicon Substances 0.000 claims abstract description 95
- 238000010438 heat treatment Methods 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 17
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 46
- 239000011812 mixed powder Substances 0.000 claims description 38
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 239000007833 carbon precursor Substances 0.000 claims description 22
- 239000011149 active material Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 16
- 239000007773 negative electrode material Substances 0.000 abstract description 15
- 229910045601 alloy Inorganic materials 0.000 description 98
- 239000000956 alloy Substances 0.000 description 98
- 239000012071 phase Substances 0.000 description 88
- 229910052751 metal Inorganic materials 0.000 description 34
- 239000011300 coal pitch Substances 0.000 description 33
- 239000002184 metal Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 20
- 230000014759 maintenance of location Effects 0.000 description 18
- 239000008151 electrolyte solution Substances 0.000 description 15
- 238000010298 pulverizing process Methods 0.000 description 14
- 238000000227 grinding Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 229910021332 silicide Inorganic materials 0.000 description 9
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 238000007712 rapid solidification Methods 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 229910021382 natural graphite Inorganic materials 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910015861 MSix Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 229940105329 carboxymethylcellulose Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000011856 silicon-based particle Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000009689 gas atomisation Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012073 inactive phase Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000011301 petroleum pitch Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013562 LiCo0.2Ni0.8O2 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- 229910005881 NiSi 2 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 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
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910010069 TiCo Inorganic materials 0.000 description 1
- 229910008484 TiSi Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 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
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 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
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
Definitions
- the present invention relates to composite particles and a method for producing the same.
- the present invention also relates to an electrode obtained from the composite particles and a non-aqueous electrolyte secondary battery.
- the silicon-containing particles are coated with a carbon material using a CVD method.
- CVD method See, for example, JP-A-2005-235589, JP-A-2004-047404, JP-A-10-32226, etc.
- JP 2005-235589 A Japanese Patent Laid-Open No. 2004-047404 Japanese Patent Laid-Open No. 10-32226
- An object of the present invention is to provide a negative electrode active material capable of improving charge / discharge cycle characteristics of a nonaqueous electrolyte secondary battery in which silicon-containing particles are used as a negative electrode active material, and a method for producing the same.
- the method for producing composite particles according to the present invention includes a mixing step and a heat treatment step.
- the mixing step particles containing silicon phase (hereinafter referred to as “silicon phase-containing particles”) and thermoplastic organic powder are mixed to prepare a mixed powder.
- the “silicon phase-containing particles” mentioned here may be “silicon particles formed only from a silicon phase” or “the silicon phase is dispersed in a lithium inert phase (for example, a metal silicide phase). Alloy particles ”.
- the “thermoplastic organic powder” referred to here is, for example, petroleum-based pitch powder, coal-based pitch powder, thermoplastic resin powder, and the like.
- the mixing method is preferably dry mixing.
- the mixed powder is heat treated. And the composite particle which concerns on this invention is obtained after this heat processing process.
- a negative electrode active material capable of improving charge / discharge cycle characteristics of a non-aqueous electrolyte secondary battery is prepared by using a relatively small amount of thermoplastic organic powder. can do. For this reason, in this composite particle manufacturing method, it is possible to prepare such a negative electrode active material while suppressing raw material costs more than before.
- the ratio of the mass of the silicon phase-containing particles to the sum of the mass of the silicon phase-containing particles and the mass of the thermoplastic organic powder is in the range of 85% to 99%.
- the mixed powder is preferably prepared by mixing the silicon phase-containing particles and the thermoplastic organic powder so that This is because the charge / discharge cycle characteristics of the nonaqueous electrolyte secondary battery can be improved without significantly reducing the charge / discharge capacity.
- the silicon phase-containing particles and the heat are controlled so that the ratio of the mass of the silicon phase-containing particles to the sum of the mass of the silicon phase-containing particles and the mass of the thermoplastic organic powder is in the range of 90% to 99%.
- the mixed powder is prepared by mixing the plastic organic powder. The ratio is more preferably in the range of 92% to 98%.
- the mixed powder in the heat treatment step, is preferably heat treated at a temperature within a range of 300 ° C. or higher and 900 ° C. or lower. This is because the charge / discharge cycle characteristics of the nonaqueous electrolyte secondary battery can be further improved while reducing the energy used in the production of the electrode active material.
- the mixed powder it is more preferable that the mixed powder is heat treated at a temperature in the range of 300 ° C. or more and 700 ° C. or less.
- the composite particle according to the present invention includes a particle portion containing a silicon phase (hereinafter referred to as “silicon phase-containing particle portion”) and a binding portion.
- the “silicon phase-containing particle part” mentioned here may be “a silicon particle part formed only from a silicon phase” or “a silicon phase in a lithium inert phase (for example, a metal silicide phase, etc.). May be an alloy particle portion in which is dispersed.
- the binding portion contains at least one of non-graphitic carbon and a carbon precursor as a main component.
- a binder has as a main component at least a carbon precursor of non-graphitic carbon and a carbon precursor. And this binding part binds a silicon phase content particle part.
- the composite particles according to the present invention are useful as an electrode active material of a non-aqueous electrolyte secondary battery (for example, a lithium ion secondary battery), particularly as a negative electrode active material.
- the ratio of the mass of the silicon phase-containing particle part to the sum of the mass of the silicon phase-containing particle part and the mass of the binding part is in the range of 92% to 99.5%. Is preferred. The ratio is more preferably in the range of 95% to 99.5%. The ratio is more preferably in the range of 95% to 99%.
- the composite particle according to the present invention it is preferable that at least a part of the silicon phase-containing particle portion is exposed to the outside.
- the maximum particle size of the silicon phase is preferably 1000 nm or less. In the present composite particle, the maximum particle size of the silicon phase is more preferably 500 nm or less.
- the specific surface area value is preferably in the range of 0.5 m 2 / g to 16 m 2 / g. In the present composite particle, the specific surface area value is more preferably in the range of 1 m 2 / g to 11 m 2 / g.
- FIG. 1 is a schematic cross-sectional view of composite particles according to an embodiment of the present invention.
- 5 is a high-angle scattering annular dark-field scanning transmission microscope image (white portion indicates silicon and black portion indicates carbon) of the composite particles according to Example 1 of the present invention, and elemental analysis charts at points +1 to 6.
- FIG. FIG. 2 is a high-angle scattering annular dark-field scanning transmission microscope image (white portion indicates silicon and black portion indicates carbon) of the composite particle according to Example 1 of the present invention, in which the silicon phase-containing particle portion is exposed and bound. The presence of
- the composite particles according to the embodiment of the present invention are formed by binding a plurality of silicon phase-containing particles via a binding portion. That is, the composite particle 100 is mainly composed of a silicon phase-containing particle part 110 and a binding part 120 as shown in FIG.
- the specific surface area value of the composite particles 100 is preferably in the range of less than 0.5 m 2 / g or more 16m 2 / g, it is more preferably in the range of less than 1 m 2 / g or more 11m 2 / g.
- the silicon phase-containing particle part 110 and the binding part 120 will be described in detail, and the method for producing the composite particle 100 will be described in detail.
- Silicon phase-containing particle part may be “silicon particles” composed only of a silicon phase, or “alloy particle part in which a silicon phase is dispersed in a lithium inert phase. It may be.
- the ratio of the mass of the silicon phase-containing particle portion to the sum of the mass of the silicon phase-containing particle portion and the mass of the binding portion is preferably in the range of 92% to 99.5%.
- the silicon phase is mainly formed from silicon atoms.
- the silicon phase is preferably formed only from silicon atoms. In this silicon phase, strain (dislocation) is introduced so as not to be completely crystalline.
- the maximum particle size of the silicon phase is preferably in the range of more than 0 nm to 1000 nm or less, more preferably in the range of more than 0 nm to 700 nm or less, still more preferably in the range of more than 0 nm to 500 nm or less, and 0 nm It is particularly preferably within the range of more than 300 nm and most preferably within the range of more than 0 nm and not more than 200 nm.
- the maximum particle diameter of the silicon phase refers to the maximum value among the major diameters of the silicon phase crystal grains in the field of view in observation with a transmission electron microscope (TEM).
- the lithium inactive phase is a phase that does not substantially absorb lithium ions.
- a metal silicide phase is preferred as the lithium inert phase.
- the metal silicide phase is formed from silicon atoms and at least one metal atom.
- the metal silicide phase may be an intermetallic compound.
- strain (dislocation) is introduced into the metal silicide phase so as not to be completely crystalline.
- This metal silicide phase preferably has a composition of mainly MSix.
- M is one or more metal elements, Si is silicon, and x is a value greater than 0 and less than 2.
- M is aluminum (Al), iron (Fe), nickel (Ni), titanium (Ti), copper (Cu), cobalt (Co), chromium (Cr), vanadium (V), manganese (Mn), Zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), indium (In), At least one metal selected from the group consisting of hafnium (Hf), tantalum (Ta), tungsten (W), platinum (Pt), lanthanum (La), cerium (Ce), praseodymium (Pr), and neodymium (Nd). Preferably it is an element.
- the metal silicide phase may contain a structure other than MSix such as TiSi 2 , Ni 4 Ti 4 Si 7, and NiSi 2 as long as the gist of the present invention is not impaired.
- the MSix content in the metal silicide phase is preferably 20% by volume or more, and more preferably 30% by volume or more.
- lithium inert phase examples include Al 2 Cu, NiAl 3 , Ni 2 Al 3 , Al 3 Ce, Mn 3 Sn, Ti 6 Sn 5 , compounds containing Al and Sn elements, TiCo 2 , Cu 4 Ti, An intermetallic compound by a combination of transition elements such as Fe 2 Ti and Co 2 NiV may be used.
- (A) Metal melting step In the metal melting step, a plurality of metal raw materials containing silicon (Si) are melted to prepare a specific molten metal. In such a case, silicon (Si) is added to the metal raw material so that a silicon phase is precipitated. The amount of silicon (Si) added can be easily determined using an equilibrium diagram. Note that the metal raw materials are not necessarily melted at the same time, and may be melted in stages.
- the metal raw material is usually brought into a molten state by heating.
- the metal raw material is preferably heated and melted in an inert gas or vacuum atmosphere.
- the heating method includes high frequency induction heating, arc discharge heating (arc melting), plasma discharge heating (plasma melting), resistance heating, and the like. In this step, it is important to form a compositionally uniform molten metal.
- (B) Rapid solidification step In the rapid solidification step, the specific alloy melt is rapidly solidified to produce a specific alloy solidified product.
- the specific alloy molten metal is preferably rapidly solidified at a cooling rate of 100 K / second or more, and more preferably the specific alloy molten metal is rapidly solidified at a cooling rate of 1,000 K / second or more. .
- rapid solidification method examples include a gas atomizing method, a roll rapid cooling method, a plate casting method, a rotating electrode method, a liquid atomizing method, and a melt spinning method.
- the molten metal in the tundish is caused to flow out from the pores at the bottom of the tundish, and a high-pressure inert gas such as argon (Ar), nitrogen (N 2 ), and helium (He) is supplied to the fine stream of the molten metal.
- a high-pressure inert gas such as argon (Ar), nitrogen (N 2 ), and helium (He) is supplied to the fine stream of the molten metal.
- the roll rapid cooling method is a method in which a molten metal is dropped on a single roll or a double roll rotating at high speed, or a thin cast slab is obtained by pulling up the molten metal with a roll.
- the obtained thin cast slab is pulverized to an appropriate size in a pulverization process which is a subsequent process.
- the flat plate casting method is a method of casting a molten metal into a flat plate mold so that the thickness of the ingot is thin, and the cooling rate is faster than that of the block shape ingot.
- the obtained flat plate-like ingot is pulverized to an appropriate size in a pulverization step which is a subsequent step.
- the specific alloy solidified product is pulverized to form the specific alloy powder.
- This pulverization step is preferably carried out in a non-oxidizing atmosphere. This is because, in the pulverization step, when the specific alloy solidified product is pulverized, a new surface is formed and the specific surface area is increased. Note that an inert gas atmosphere is preferable as the non-oxidizing atmosphere, but there is no particular problem even if oxygen of about 2 to 5% by volume is contained.
- the specific alloy powder is subjected to a mechanical grinding treatment (hereinafter referred to as “MG treatment”) to produce the alloy particles described above.
- MG treatment a mechanical grinding treatment
- the specific alloy powder subjected to MG treatment preferably has an average particle size of 5 mm or less, more preferably 1 mm or less, even more preferably 500 ⁇ m or less, more preferably 100 ⁇ m. More preferably, it has the following average particle size.
- the MG treatment In the MG treatment, a compressive force and a shear force are applied to the powder as the material to be treated, and the powder is repeatedly disintegrated and granulated while being crushed. As a result, the original structure of the powder is collapsed, and particles having a structure in which the phase existing before the processing is ultrafinely dispersed on the nanometer order are formed. However, the type and content of the phase constituting the fine structure are substantially the same as before the treatment, and no new phase is formed by the treatment. Due to the characteristics of this MG treatment, when the alloy particles according to the present invention are used as a negative electrode material for a nonaqueous electrolyte secondary battery, the negative electrode exhibits a stable discharge capacity. This is different from the MA method (mechanical alloying method) in which an alloying reaction between elements occurs and the content of the phase is changed by the treatment. In the process of MG treatment, local mechanical alloying may occur in a very small part of the alloy powder.
- MA method mechanical alloying method
- the particles after pulverization retain the structure before pulverization. That is, in the pulverization, only the particle diameter is reduced, and the structure is not refined.
- the MG process in which the structure is crushed and broken during processing and the structure becomes finer is different from pulverization in this respect.
- MG treatment can be carried out by any pulverizer capable of grinding the material.
- a pulverizer using a ball-shaped pulverizing medium that is, a ball mill type pulverizer is preferable.
- the ball mill type grinder is simple in structure, the balls of the grinding media are easily available in various materials, and grinding / grinding occurs at the contact point between the balls, so it can be uniformly ground in many places. And the like (which is particularly important from the viewpoint of high uniformity of reaction, that is, product stability), and is particularly suitable for use in the present invention.
- ball mill-type pulverizers not only simply rotating the pulverizing cylinder, but also a vibrating ball mill with increased pulverization energy by applying vibrations, and a rotating rod forcing the balls to be crushed and grinding media
- An attritor that stirs and a planetary ball mill in which grinding energy is increased by rotational force and centrifugal force are preferred.
- the MG treatment is preferably performed in an inert gas atmosphere such as argon in order to prevent oxidation of the material being treated.
- the material may be subjected to MG treatment in an air atmosphere.
- the metal particles after the MG treatment preferably have an oxygen concentration of 7.0% by mass or less, and more preferably 5.0% by mass or less.
- the oxygen concentration of the metal particles after MG treatment is 7.0% by mass or less, when the metal particles are used as an electrode material for a non-aqueous electrolyte secondary battery, the irreversible capacity is relatively small and the charge / discharge efficiency is good. This is because it can be maintained.
- the pulverizer is provided with a cooling mechanism. In such a case, the MG process is performed while the system is cooled.
- the binder part has at least one of non-graphitic carbon and a carbon precursor as a main component, and binds the silicon phase-containing particle part.
- a binder has as a main component at least a carbon precursor of non-graphitic carbon and a carbon precursor. This is because decomposition of the electrolyte solvent can be stably suppressed by using the carbon precursor as a main component.
- Non-graphitic carbon is at least one of amorphous carbon and turbostratic carbon.
- amorphous carbon means that it has short-range order (several atoms to several tens of atoms order) but does not have long-range order (several hundreds to thousands of atoms order).
- the “turbulent structure carbon” herein refers to carbon composed of carbon atoms having a turbulent structure parallel to the hexagonal plane direction but having no crystallographic regularity in the three-dimensional direction. This turbostratic carbon is preferably confirmed by a transmission electron microscope (TEM) or the like.
- TEM transmission electron microscope
- this non-graphitic carbon is obtained by firing a thermoplastic organic material such as a thermoplastic resin.
- the thermoplastic resin is, for example, petroleum pitch, coal pitch, synthetic thermoplastic resin, natural thermoplastic resin, and a mixture thereof.
- pitch powder is particularly preferable. This is because the pitch powder is melted and carbonized in the temperature rising process, and as a result, the silicon phase-containing particles 110 can be suitably bound to each other. Pitch powder is preferable from the viewpoint of low irreversible capacity even when fired at low temperature.
- the carbon precursor is a carbon-rich substance before the thermoplastic organic material is converted to non-graphitic carbon when the thermoplastic organic material is heated.
- this binding part may contain other components such as graphite, conductive carbonaceous fine particles, and tin particles as long as the gist of the present invention is not impaired.
- the graphite may be either natural graphite or artificial graphite, but is preferably natural graphite.
- As the graphite a mixture of natural graphite and artificial graphite may be used.
- the graphite is preferably a spherical graphite granulated product formed by aggregating a plurality of scaly graphites.
- scale-like graphite natural graphite, artificial graphite, mesophase calcined carbon (bulk mesophase) made from tar pitch, coke (raw coke, green coke, pitch coke, needle coke, petroleum coke, etc.), etc.
- Graphitized, etc. and those granulated using a plurality of natural graphites having high crystallinity are particularly preferable.
- the conductive carbonaceous fine particles are directly attached to the graphite.
- the conductive carbonaceous fine particles are, for example, carbon black such as ketjen black, furnace black, acetylene black, carbon nanotube, carbon nanofiber, carbon nanocoil and the like. Of these conductive carbonaceous fine particles, acetylene black is particularly preferred.
- the conductive carbonaceous fine particles may be a mixture of different types of carbon black and the like.
- the composite particles according to the embodiment of the present invention are manufactured through a mixing process and a heat treatment process.
- silicon phase-containing particles (powder) and thermoplastic organic powder are solid-phase mixed to prepare a mixed powder.
- the ratio of fine powder may be reduced by classifying the silicon phase-containing particles (powder). Thereby, a specific surface area becomes smaller, the decomposition reaction of the electrolyte solution which occurs at the time of the first charge is suppressed, and the negative electrode material has an effect of improving the initial efficiency.
- the mixed powder has a temperature in the range of 300 ° C. or higher and 1200 ° C. or lower, preferably in the range of 300 ° C. or higher and 1000 ° C. or lower in a non-oxidizing atmosphere (inert gas atmosphere, vacuum atmosphere, etc.) More preferably, the temperature is in the range of 300 ° C. or higher and 900 ° C. or lower, more preferably the temperature is in the range of 300 ° C. or higher and 800 ° C. or lower, particularly preferably the temperature is in the range of 300 ° C. or higher and 700 ° C. or lower, and most preferably 400 ° C. Heat treatment is performed at a temperature in the range of 700 ° C. or lower.
- thermoplastic organic powder is softened to bind the silicon phase-containing particles (powder) to each other, and the thermoplastic organic powder is converted into at least one of non-graphitic carbon and a carbon precursor.
- the heating temperature By setting the heating temperature to 900 ° C. or lower, the growth of the silicon phase particle size can be suppressed, so that the charge / discharge cycle characteristics can be improved.
- the heating temperature By setting the heating temperature to 300 ° C. or higher, it is possible to obtain a stable binding between the silicon phase-containing particles via the thermoplastic organic material.
- the electrode excellent in charging / discharging cycling characteristics can be formed as heating temperature is the said range.
- the electrode which concerns on embodiment of this invention can be formed from the above-mentioned composite particle.
- an appropriate binder is mixed into the composite particles, and an appropriate conductive powder is mixed as necessary to improve conductivity, thereby preparing an electrode mixture.
- a solvent for dissolving the binder is added to the electrode mixture, and if necessary, the mixture is sufficiently stirred using a homogenizer and glass beads to form a slurry.
- a slurry kneader combining a rotation motion and a revolution motion may be used.
- this slurry-like electrode mixture is applied to an electrode substrate (current collector) such as rolled copper foil or copper electrodeposited copper foil using a doctor blade or the like, dried, and then consolidated by roll rolling or the like, An electrode for a water electrolyte secondary battery is obtained.
- This electrode is usually used as a negative electrode.
- water-insoluble resins such as polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), and polytetrafluoroethylene (PTFE) (however, those that are insoluble in the solvent used for the non-aqueous electrolyte of the battery) ), Water-soluble resins such as carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA), and aqueous dispersion type binders such as styrene-butadiene rubber (SBR).
- an organic solvent such as N-methylpyrrolidone (NMP) or dimethylformamide (DMF) or water can be used depending on the binder.
- Examples of the conductive powder include carbon materials (eg, carbon black, graphite) and metals (eg, Ni). Among these, carbon materials are preferable. Since the carbon material can occlude Li ions between the layers, the carbon material can contribute to the capacity of the negative electrode in addition to the conductivity, and also has excellent liquid retention. Among these carbon materials, acetylene black is particularly preferable.
- the nonaqueous electrolyte secondary battery according to the embodiment of the present invention is manufactured using the above-described negative electrode.
- the nonaqueous electrolyte secondary battery is, for example, a lithium ion secondary battery.
- the composite particles and electrodes described above are suitable as a negative electrode active material and a negative electrode for a lithium ion secondary battery.
- the composite particles and electrodes according to the present embodiment can theoretically be applied to other nonaqueous electrolyte secondary batteries.
- the nonaqueous electrolyte secondary battery includes a negative electrode, a positive electrode, a separator, and a nonaqueous electrolyte as a basic structure.
- a negative electrode the one manufactured according to the present invention as described above is used.
- the positive electrode, the separator and the electrolyte known materials or materials developed in the future may be appropriately used.
- the nonaqueous electrolyte may be liquid, solid, or gel.
- the solid electrolyte include polymer electrolytes such as polyethylene oxide, polytetrafluoroethylene, fluorine-containing copolymers, and combinations thereof.
- the liquid electrolyte include ethylene carbonate, diethyl carbonate, propylene carbonate, and combinations thereof.
- the electrolyte is provided with a lithium electrolyte salt. Suitable salts include, for example, lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium perchlorate (LiClO 4 ), and the like.
- suitable cathode compositions include lithium cobaltate (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), and LiCo 0.2 Ni 0.8 O 2 .
- the melt was rapidly solidified by bringing it into contact with a copper water-cooled roll rotating at a peripheral speed of 90 m / min to obtain a flaky slab (strip casting (SC) method).
- the cooling rate at this time is estimated to be about 500 to 2,000 ° C./second.
- the cast slab thus obtained was pulverized and classified with a 63 ⁇ m sieve to produce a primary powder having an average particle size of 25 to 30 ⁇ m.
- the primary powder was put into a high-speed ball mill (volume: 5 liters) together with stearic acid (amount of 1% by mass with respect to the primary powder), and the primary powder was subjected to mechanical grinding treatment (hereinafter referred to as “rotation speed 300 rpm”) for 15 hours.
- An alloy powder (hereinafter, one alloy powder may be referred to as “alloy particles”) was prepared by abbreviating as “MG treatment”. At this time, 450 g of SUJ2 balls having a diameter of about 8 mm ⁇ were added to 10 g of the primary powder.
- the alloy powder with respect to the sum of the mass of the above-described alloy powder and the mass of the coal-based pitch powder softening point 86 ° C., average particle size 20 ⁇ m, residual carbon ratio after heating at 1000 ° C. 50%
- the mixed powder was prepared by charging the alloy powder and the coal-based pitch powder into a rocking mixer (manufactured by Aichi Electric Co., Ltd.) so that the mass ratio of the steel was 96.0%.
- Electrode preparation CMC (Carboxymethylcellulose sodium) powder and acetylene black (Denka Black, powdered product manufactured by Denki Kagaku Kogyo Co., Ltd.) are mixed with the composite particles described above. After adding an aqueous dispersion of SBR (styrene-butadiene rubber), the mixture was stirred to obtain an electrode mixture slurry.
- SBR styrene-butadiene rubber
- CMC and SBR are binders.
- the compounding ratio of the composite particles, CMC, acetylene black and SBR was 75.0: 5.0: 15.0: 5.0 by mass ratio.
- this electrode mixture slurry was applied onto a copper foil (current collector) having a thickness of 17 ⁇ m by the doctor blade method (the coating amount was 2.5 to 3.5 mg / cm 2 ). After drying the coating solution to obtain a coating film, the coating film was punched into a disk shape having a diameter of 13 mm.
- (3-2) Battery Preparation An electrode assembly was prepared by disposing the above electrode and a counter Li metal foil on both sides of a polyolefin separator. And the electrolyte solution was inject
- dedoping (corresponding to detachment of lithium ions from the electrode and discharging of the lithium ion secondary battery) is performed at a constant current of 0.56 mA / cm 2 until the potential difference becomes 1.2 V, and the dedoping capacity is measured. did.
- the doping capacity and the dedoping capacity at this time correspond to the charging capacity (mAh / g) and discharging capacity (mAh / g) when this electrode is used as the negative electrode of the lithium ion secondary battery.
- the discharge capacity The initial charge and discharge efficiency (%) was obtained by dividing “discharge capacity at the first cycle of dedoping” by “charge capacity at the first cycle of doping” and multiplying by 100.
- the dope and dedope were repeated 20 times under the same conditions as described above. Then, the capacity retention rate (%) was obtained by dividing "discharge capacity at the time of dedoping at the 20th cycle" by "discharge capacity at the time of dedoping at the first cycle” and multiplying by 100.
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell according to this example was 87.9%, and the capacity retention rate was 60.3% (see Table 1).
- the maximum reaction electricity amount (mAh / g) among the reaction electricity amounts at the plurality of potential differences was used as an indicator of the electrolyte decomposability.
- the electrolytic solution decomposability according to this example was 2.1 mAh / g.
- the target composite particles were obtained in the same manner as in Example 1 except that in “(3) Heat treatment of mixed powder”, heating was performed at a temperature of 200 ° C. for 1 hour and then further heating at a temperature of 500 ° C. for 1 hour. In the same manner, the characteristics of the composite particles were evaluated. In this composite particle, the ratio of the mass of the alloy powder to the sum of the mass of the alloy powder and the mass of the material derived from the coal-based pitch powder (presumably a carbon precursor) was 98.0% (see Table 1). ).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 261 nm, and the BET specific surface area was 4.5 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 87.8%, and the capacity retention rate was 69.7% (see Table 1).
- the electrolytic solution decomposability was 2.0 mAh / g (see Table 1).
- the target composite particles were obtained in the same manner as in Example 1 except that in “(3) Heat treatment of mixed powder”, heating was performed at a temperature of 200 ° C. for 1 hour, followed by further heating at a temperature of 600 ° C. for 1 hour. In the same manner, the characteristics of the composite particles were evaluated. In this composite particle, the ratio of the mass of the alloy powder to the sum of the mass of the alloy powder and the mass of the material derived from the coal-based pitch powder (presumably a carbon precursor) was 98.0% (see Table 1). ).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 368 nm, and the BET specific surface area was 9.7 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 89.4%, and the capacity retention rate was 61.1% (see Table 1).
- the electrolytic solution decomposability was 2.2 mAh / g (see Table 1).
- the target composite particles were obtained in the same manner as in Example 1 except that in “(3) Heat treatment of mixed powder”, heating was performed at a temperature of 200 ° C. for 1 hour and then further heated at a temperature of 700 ° C. for 1 hour. In the same manner, the characteristics of the composite particles were evaluated. In this composite particle, the ratio of the mass of the alloy powder to the sum of the mass of the alloy powder and the mass of the material derived from the coal-based pitch powder (presumably non-graphitic carbon) was 98.0% (Table 1). reference).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 500 nm, and the BET specific surface area was 10.9 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 89.8%, and the capacity retention rate was 72.6% (see Table 1).
- the electrolyte decomposability was 2.6 mAh / g (see Table 1).
- the target composite particles were obtained in the same manner as in Example 1 except that in “(3) Heat treatment of mixed powder”, heating was performed at a temperature of 200 ° C. for 1 hour and then further heating at a temperature of 300 ° C. for 1 hour. In the same manner, the characteristics of the composite particles were evaluated. In this composite particle, the ratio of the mass of the alloy powder to the sum of the mass of the alloy powder and the mass of the material derived from the coal-based pitch powder (presumably a carbon precursor) was 96.6% (see Table 1). ).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 143 nm, and the BET specific surface area was 1.2 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 85.3%, and the capacity retention rate was 30.2% (see Table 1).
- the electrolytic solution decomposability was 5.5 mAh / g (see Table 1).
- the target composite particles were obtained in the same manner as in Example 1 except that, in “(3) Heat treatment of mixed powder”, heating was performed at a temperature of 200 ° C. for 1 hour and then further heated at a temperature of 350 ° C. for 1 hour. In the same manner, the characteristics of the composite particles were evaluated. In this composite particle, the ratio of the mass of the alloy powder to the sum of the mass of the alloy powder and the mass of the material derived from the coal-based pitch powder (presumably a carbon precursor) was 96.6% (see Table 1). ).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 155 nm, and the BET specific surface area was 1.7 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 86.5%, and the capacity retention rate was 51.6% (see Table 1).
- the electrolyte decomposability was 3.8 mAh / g (see Table 1).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 190 nm, and the BET specific surface area was 3.1 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 87.9%, and the capacity retention rate was 49.7% (see Table 1).
- the electrolytic solution decomposability was 1.8 mAh / g (see Table 1).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 190 nm, and the BET specific surface area was 2.8 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 87.9%, and the capacity retention rate was 60.0% (see Table 1).
- the electrolytic solution decomposability was 2.1 mAh / g (see Table 1).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 190 nm, and the BET specific surface area was 1.2 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 86.6%, and the capacity retention rate was 81.0% (see Table 1).
- the electrolyte decomposability was 3.2 mAh / g (see Table 1).
- the target composite particles were obtained in the same manner as in Example 1 except that in “(3) Heat treatment of mixed powder”, heating was performed at a temperature of 200 ° C. for 1 hour and then further heated at a temperature of 800 ° C. for 1 hour. In the same manner, the characteristics of the composite particles were evaluated. In this composite particle, the ratio of the mass of the alloy powder to the sum of the mass of the alloy powder and the mass of the material derived from the coal-based pitch powder (presumably non-graphitic carbon) was 98.0% (Table 1). reference).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 640 nm, and the BET specific surface area was 13.3 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 89.8%, and the capacity retention rate was 75.1% (see Table 1).
- the electrolyte solution decomposability was 2.7 mAh / g (see Table 1).
- the target composite particles were obtained in the same manner as in Example 1 except that, in “(3) Heat treatment of mixed powder”, heating was performed at a temperature of 200 ° C. for 1 hour and then further heated at a temperature of 900 ° C. for 1 hour. In the same manner, the characteristics of the composite particles were evaluated. In this composite particle, the ratio of the mass of the alloy powder to the sum of the mass of the alloy powder and the mass of the material derived from the coal-based pitch powder (presumably non-graphitic carbon) was 98.0% (Table 1). reference).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 860 nm, and the BET specific surface area was 15.7 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 90.3%, and the capacity retention rate was 77.7% (see Table 1).
- the electrolytic solution degradability was 2.8 mAh / g (see Table 1).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 190 nm, and the BET specific surface area was 2.2 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 88.4%, and the capacity retention rate was 69.2% (see Table 1).
- Electrolytic solution degradability was 2.5 mAh / g (see Table 1).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 190 nm, and the BET specific surface area was 1.8 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 88.2%, and the capacity retention rate was 73.2% (see Table 1).
- the electrolyte solution decomposability was 2.7 mAh / g (see Table 1).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 190 nm, and the BET specific surface area was 1.5 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 87.5%, and the capacity retention rate was 76.6% (see Table 1).
- the electrolytic solution degradability was 2.9 mAh / g (see Table 1).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 190 nm, and the BET specific surface area was 0.6 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 86.2%, and the capacity retention rate was 86.9% (see Table 1).
- the electrolyte decomposability was 3.6 mAh / g (see Table 1).
- the maximum particle size (major axis) of the silicon phase in the alloy particles obtained as described above was 100 nm, and the BET specific surface area was 3.7 m 2 / g (see Table 1).
- the initial charge / discharge efficiency of the coin-type non-aqueous test cell was 88.8%, and the capacity retention rate was 20.3% (see Table 1).
- the electrolytic solution decomposability was 10.6 mAh / g (see Table 1).
- the composite particles according to the present invention are useful as a negative electrode active material for a non-aqueous electrolyte secondary battery.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
110 ケイ素相含有粒子部
120 結着部
(1)ケイ素相含有粒子部
ケイ素相含有粒子部は、ケイ素相のみから構成される「ケイ素粒子」であってもよいし、「リチウム不活性相中にケイ素相が分散している合金粒子部」であってもよい。この複合粒子において、ケイ素相含有粒子部の質量と結着部の質量との和に対するケイ素相含有粒子部の質量の割合は92%以上99.5%以下の範囲内であることが好ましく、95%以上99.5%以下の範囲内であることがより好ましく、95%以上99%以下の範囲内であることがさらに好ましく、96%以上98.5%以下の範囲内であることが特に好ましい。ケイ素相含有粒子部の少なくとも一部が外部に露出していることが好ましい。
ケイ素相は、主としてケイ素原子から形成される。ケイ素相は、ケイ素原子のみから形成されるのが好ましい。このケイ素相には、完全な結晶質とは言い難いほど、歪(転位)が導入されている。
リチウム不活性相は、リチウムイオンを実質的に吸収しない相である。リチウム不活性相としては、金属ケイ化物相が好ましい。金属ケイ化物相は、ケイ素原子および少なくとも一種の金属原子から形成される。なお、金属ケイ化物相は、金属間化合物であってもよい。また、この金属ケイ化物相には、完全な結晶質とは言い難いほど、歪(転位)が導入されている。
ケイ素相含有粒子部が合金粒子部である場合、その合金粒子は、金属溶融工程、急冷凝固工程、粉砕工程およびメカニカルグラインディング工程を経て製造される。以下、各工程について詳述する。
金属溶融工程では、ケイ素(Si)を含む複数の金属原料が溶融されて特定金属溶湯が調製される。かかる場合、ケイ素(Si)は、ケイ素相が析出するように金属原料に添加される。ケイ素(Si)の添加量は、平衡状態図を利用すれば、容易に決定することができる。なお、金属原料は、必ずしも同時に溶融される必要はなく、段階的に溶融されてもかまわない。
急冷凝固工程では、特定合金溶湯が急冷凝固されて特定合金固化物が生成される。なお、この急冷凝固工程では、100K/秒以上の冷却速度で特定合金溶湯が急冷凝固されるのが好ましく、1,000K/秒以上の冷却速度で特定合金溶湯が急冷凝固されるのがより好ましい。
粉砕工程では、特定合金固化物が粉砕されて特定合金粉末が形成される。この粉砕工程は、非酸化性雰囲気下で実施されるのが好ましい。粉砕工程では、特定合金固化物が粉砕されると、新生面が形成されると共に比表面積も増大するからである。なお、非酸化性雰囲気としては、不活性ガス雰囲気が好ましいが、2から5体積%程度の酸素が含まれていても特段の問題はない。
メカニカルグラインディング工程では、特定合金粉末がメカニカルグラインディング処理(以下「MG処理」と称する)されて上述の合金粒子が製造される。なお、MG処理に供する特定合金粉末は、5mm以下の平均粒子径を有するのが好ましく、1mm以下の平均粒子径を有するのがより好ましく、500μm以下の平均粒子径を有するのがさらに好ましく、100μm以下の平均粒子径を有するのがさらに好ましい。
結着部は、非黒鉛質炭素及び炭素前駆体の少なくとも一方を主成分とし、ケイ素相含有粒子部を結着している。なお、結着部は、非黒鉛質炭素及び炭素前駆体の少なくとも炭素前駆体を主成分とすることが好ましい。炭素前駆体を主成分とすることにより、電解液溶媒の分解を安定して抑制することができるからである。
本発明の実施の形態に係る複合粒子は、混合工程および熱処理工程を経て製造される。
本発明の実施の形態に係る複合粒子は、非水電解質二次電池の電極活物質として使用されると、その充放電サイクル特性をさらに向上させることができる。
本発明の実施の形態に係る電極は、上述の複合粒子から形成することができる。例えば、複合粒子に適当な結着剤を混合し、必要に応じて導電性向上のために適当な導電粉を混合して、電極合剤を調製する。次いで、結着剤を溶解する溶媒を電極合剤に加え、必要であればホモジナイザーとガラスビーズを用いて充分に攪拌して電極合剤をスラリー状にする。なお、このとき、自転運動と公転運動とを組み合わせたスラリー混練機を用いてもよい。このスラリー状の電極合剤を圧延銅箔、銅電析銅箔などの電極基板(集電体)にドクターブレード等を用いて塗布し、乾燥した後、ロール圧延等で圧密化させると、非水電解質二次電池用電極が得られる。なお、この電極は、通常、負極として利用される。
本発明の実施の形態に係る非水電解質二次電池は、上述の負極を利用して作製される。なお、非水電解質二次電池は、例えば、リチウムイオン二次電池である。そして、上述の複合粒子および電極は、リチウムイオン二次電池の負極活物質および負極として好適である。ただし、本実施の形態に係る複合粒子および電極は、理論的には、他の非水電解質二次電池にも適用することができる。
以下、実施例および比較例を示して、本発明について詳述する。なお、本発明は、これらの実施例に限定されることはない。
(1)合金粒子の調製
先ず、銅(Cu)、ニッケル(Ni)、チタン(Ti)及びケイ素(Si)の質量比が8.4:16.5:13.0:62.1となるように銅、ニッケル、チタン及びケイ素の純原料をチタン酸アルミ製溶解るつぼに投入した。次いで、その溶解るつぼ内をアルゴン(Ar)雰囲気とした後、溶解るつぼ内の純原料(金属混合物)を高周波誘導加熱により1500℃まで加熱して完全に溶解させた。続いて、その溶解物を、周速90m/分で回転する銅製の水冷ロール上に接触させることにより急冷凝固させて、薄片状の鋳片を得た(ストリップキャスティング(SC)法)。なお、このときの冷却速度はおよそ500~2,000℃/秒程度であると推察される。そして、このようにして得られた鋳片を粉砕した後、63μmの篩で分級して平均粒径25~30μmの一次粉末を作製した。さらに、その一次粉末をステアリン酸(一次粉末に対して1質量%の量)と共に高速ボールミル(容積5リットル)に投入して、その一次粉末を回転数300rpmで15時間、メカニカルグラインディング処理(以下「MG処理」と略する)して合金粉末(以下、合金粉末の一粒を「合金粒子」という場合がある)を調製した。このとき、一次粉末10gに対して約8mmφのSUJ2製ボール450gを投入した。
次いで、上述の合金粉末の質量と石炭系ピッチ粉末(軟化点86℃、平均粒径20μm、1000℃加熱後の残炭率50%)の質量との和に対する合金粉末の質量の割合が96.0%となるように、合金粉末と石炭系ピッチ粉末とをロッキングミキサー(愛知電気株式会社製)に投入して混合粉末を調製した。
続いて、上述の混合粉末を黒鉛るつぼに投入し、その混合粉末を窒素気流中、200℃の温度で1時間加熱した後に400℃の温度でさらに1時間加熱して、目的の複合粒子を得た。なお、この複合粒子において合金粉末の質量と石炭系ピッチ粉末由来の物質(主に炭素前駆体と思われる)の質量の和に対する合金粉末の質量の割合は98.0%であった(表1参照)。
(1)ケイ素相の結晶サイズ測定
透過型電子顕微鏡写真(明視野像)(図2参照)を利用してnmオーダー(1μm未満)のケイ素相の直径を直接的に計測した。また、合金粒子の断面が露出するように複合粒子を切断した試料片の断面の走査型電子顕微鏡写真を利用してμmオーダー(1μm以上)のケイ素相の長径を直接的に計測した。本実施例に係る合金粒子中のケイ素相の最大粒径(長径)は190nmであった(表1参照)。
ユアサアイオニクス株式会社製カンタソープを用いて、上述の複合粒子の比表面積をBET1点法により求めた。その結果、上述の複合粒子のBET比表面積は、2.5m2/gであった(表1参照)。
(3-1)電極作製
上述の複合粒子にCMC(カルボキシメチルセルロースナトリウム)粉末およびアセチレンブラック(電気化学工業株式会社製デンカブラック,粉状品)を混合し、その混合粉末にSBR(スチレン-ブタジエンゴム)の水性分散液を加えた後、その混合物を攪拌して電極合剤スラリーを得た。ここで、CMC及びSBRは結着剤である。複合粒子、CMC、アセチレンブラックおよびSBRの配合比は、質量比で75.0:5.0:15.0:5.0であった。そして、この電極合剤スラリーを、厚み17μmの銅箔(集電体)上にドクターブレード法により塗布した(塗布量は2.5~3.5mg/cm2であった)。塗布液を乾燥させて塗膜を得た後、その塗膜を直径13mmのディスク状に打ち抜いた。
ポリオレフィン製セパレーターの両側に上述の電極と対極のLi金属箔とを配置して電極組立体を作製した。そして、その電極組立体の内部に電解液を注入してセルサイズ2016のコイン型非水試験セルを作製した。なお、電解液の組成は、LiPF6:ジメチルカーボネート(DMC):エチレンカーボネート(EC):エチルメチルカーボネート(EMC):ビニレンカーボネート(VC):フルオロエチレンカーボネート(FEC)=16:48:23:4:1:8(質量比)とした。
先ず、対極に対して電位差5mVになるまで0.56mA/cm2の電流値でコイン型非水試験セルに対して定電流ドープ(電極へのリチウムイオンの挿入、リチウムイオン二次電池の充電に相当)を行った後、さらに5mVを保持したまま、7.5μA/cm2になるまで定電圧で対極に対してドープを続け、ドープ容量を測定した。次に、0.56mA/cm2の定電流で、電位差1.2Vになるまで脱ドープ(電極からのリチウムイオンの離脱、リチウムイオン二次電池の放電に相当)を行い、脱ドープ容量を測定した。このときのドープ容量、脱ドープ容量は、この電極をリチウムイオン二次電池の負極として用いた時の充電容量(mAh/g)、放電容量(mAh/g)に相当するので、これらを充電容量、放電容量とした。そして、「1サイクル目の脱ドープ時の放電容量」を「1サイクル目のドープ時の充電容量」で除して100を乗じたものを初回充放電効率(%)とした。
先ず、コイン型非水試験セルにおいて対極に対する電位差を2.00V、1.80V、1.60V、1.55V、1.50V、1.45V、1.4V、1.35V、1.30V、1.25V、1.20V、1.18V、1.15V、1.10V、1.05V、1.00Vと段階的に低下させるようにして電解液の定電位電気分解を行いながら、各電位差において流れる電流を計測し、その電流値から各電位差における反応電気量を算出した。本実施例では、これらの複数の電位差における反応電気量のうち最大の反応電気量(mAh/g)を電解液分解性の指標とした。なお、本実施例に係る電解液分解性は2.1mAh/gであった。
実施例1における「(1)合金粒子の調製」で得られた合金粉末について、実施例1の<複合粒子の特性評価>に記載される各種方法により合金粒子の特性評価を行った。
Claims (11)
- ケイ素相を含有する粒子(以下「ケイ素相含有粒子」という)と熱可塑性有機物粉末とを混合して混合粉末を調製する混合工程と、
前記混合粉末を熱処理する熱処理工程と
を備える、複合粒子の製造方法。 - 前記混合工程では、前記ケイ素相含有粒子の質量と前記熱可塑性有機物粉末の質量との和に対する前記ケイ素相含有粒子の質量の割合が85%以上99%以下の範囲内となるように前記ケイ素相含有粒子と前記熱可塑性有機物粉末とが混合されて前記混合粉末が調製される
請求項1に記載の複合粒子の製造方法。 - 前記熱処理工程では、前記混合粉末が300℃以上900℃以下の範囲内の温度で熱処理される
請求項1または2に記載の複合粒子の製造方法。 - 請求項1から3のいずれかに記載の複合粒子の製造方法により製造される
複合粒子。 - ケイ素相を含有する粒子部(以下「ケイ素相含有粒子部」という)と、
非黒鉛質炭素および炭素前駆体の少なくとも一方を主成分とし、前記ケイ素相含有粒子部を結着する結着部と
を備える複合粒子。 - 前記ケイ素相含有粒子部の質量と前記結着部の質量との和に対する前記ケイ素相含有粒子部の質量の割合は、92%以上99.5%以下の範囲内である
請求項5に記載の複合粒子。 - 前記ケイ素相含有粒子部は、少なくとも一部が外部に露出している
請求項5または6に記載の複合粒子。 - 前記ケイ素相の最大粒径が1000nm以下の範囲内である
請求項5から7のいずれかに記載の複合粒子。 - 比表面積値が0.5m2/g以上16m2/g以下の範囲内である
請求項5から8のいずれかに記載の複合粒子。 - 請求項4から9のいずれかに記載の複合粒子を活物質とする電極。
- 請求項10に記載の電極を備える非水電解質二次電池。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201480041058.9A CN105393386A (zh) | 2013-07-23 | 2014-07-04 | 复合颗粒及其制造方法以及电极和非水电解质二次电池 |
US14/906,587 US20160181601A1 (en) | 2013-07-23 | 2014-07-04 | Composite particles, method for manufacturing same, electrode, and non-aqueous electrolyte secondary cell |
KR1020167000383A KR20160018717A (ko) | 2013-07-23 | 2014-07-04 | 복합 입자 및 그 제조 방법과 전극 및 비수 전해질 이차 전지 |
JP2015528209A JPWO2015012086A1 (ja) | 2013-07-23 | 2014-07-04 | 複合粒子及びその製造方法並びに電極及び非水電解質二次電池 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-152409 | 2013-07-23 | ||
JP2013152409 | 2013-07-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015012086A1 true WO2015012086A1 (ja) | 2015-01-29 |
Family
ID=52393136
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/067918 WO2015012086A1 (ja) | 2013-07-23 | 2014-07-04 | 複合粒子及びその製造方法並びに電極及び非水電解質二次電池 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20160181601A1 (ja) |
JP (1) | JPWO2015012086A1 (ja) |
KR (1) | KR20160018717A (ja) |
CN (1) | CN105393386A (ja) |
WO (1) | WO2015012086A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017091724A (ja) * | 2015-11-06 | 2017-05-25 | 新日鐵住金株式会社 | 負極活物質材料、負極活物質材料の製造方法、負極及び電池 |
WO2021065173A1 (ja) * | 2019-09-30 | 2021-04-08 | パナソニックIpマネジメント株式会社 | 非水電解質二次電池 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102016203352A1 (de) * | 2016-03-01 | 2017-09-07 | Wacker Chemie Ag | Verfahren zur Verarbeitung von Elektrodenmaterialien für Batterien |
JP6229245B1 (ja) * | 2017-04-27 | 2017-11-15 | テックワン株式会社 | 炭素−珪素複合材、負極、二次電池 |
JP7060699B2 (ja) * | 2018-02-16 | 2022-04-26 | ナイキ イノベイト シーブイ | 付加製造用の焼鈍熱可塑性エラストマー粉末、その方法、および粉末を含む物品 |
US11167375B2 (en) | 2018-08-10 | 2021-11-09 | The Research Foundation For The State University Of New York | Additive manufacturing processes and additively manufactured products |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006049266A (ja) * | 2004-07-09 | 2006-02-16 | Samsung Sdi Co Ltd | リチウム二次電池 |
JP2006210348A (ja) * | 2005-01-28 | 2006-08-10 | Samsung Sdi Co Ltd | 負極活物質、その製造方法及びそれを採用した負極とリチウム電池 |
JP2006339093A (ja) * | 2005-06-06 | 2006-12-14 | Matsushita Electric Ind Co Ltd | 巻回型非水電解液二次電池およびその負極 |
JP2007087956A (ja) * | 2005-09-23 | 2007-04-05 | Samsung Sdi Co Ltd | 陰極活物質、その製造方法及びそれを採用したリチウム電池 |
JP2010033830A (ja) * | 2008-07-28 | 2010-02-12 | Nec Tokin Corp | 非水電解質二次電池用負極およびそれを用いた非水電解質二次電池 |
JP2011057541A (ja) * | 2009-08-11 | 2011-03-24 | Sekisui Chem Co Ltd | 炭素材料、電極材料及びリチウムイオン二次電池負極材料 |
JP2012043546A (ja) * | 2010-08-12 | 2012-03-01 | Hitachi Chem Co Ltd | リチウム二次電池用負極材、リチウムイオン二次電池用負極、およびリチウムイオン二次電池 |
JP2013506264A (ja) * | 2009-09-29 | 2013-02-21 | ジョージア テック リサーチ コーポレイション | 電極、リチウムイオン電池ならびにこれらを作製する方法および使用する方法 |
JP2013222534A (ja) * | 2012-04-13 | 2013-10-28 | Toyota Industries Corp | 非水電解質二次電池用負極活物質、その製造方法、非水電解質二次電池用負極、非水電解質二次電池、及び車両 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3856525B2 (ja) | 1997-05-21 | 2006-12-13 | 旭化成エレクトロニクス株式会社 | 二次電池 |
JP3952180B2 (ja) | 2002-05-17 | 2007-08-01 | 信越化学工業株式会社 | 導電性珪素複合体及びその製造方法並びに非水電解質二次電池用負極材 |
JP5011629B2 (ja) | 2004-02-19 | 2012-08-29 | 株式会社Gsユアサ | 非水電解質二次電池 |
KR100814329B1 (ko) * | 2006-10-09 | 2008-03-18 | 한국전기연구원 | 음극 활물질. 그 제조방법 및 이를 구비한 리튬이차전지 |
CN101210119B (zh) * | 2006-12-29 | 2012-01-25 | 比亚迪股份有限公司 | 一种含硅复合材料及其制备方法和用途 |
-
2014
- 2014-07-04 JP JP2015528209A patent/JPWO2015012086A1/ja active Pending
- 2014-07-04 KR KR1020167000383A patent/KR20160018717A/ko not_active Application Discontinuation
- 2014-07-04 US US14/906,587 patent/US20160181601A1/en not_active Abandoned
- 2014-07-04 WO PCT/JP2014/067918 patent/WO2015012086A1/ja active Application Filing
- 2014-07-04 CN CN201480041058.9A patent/CN105393386A/zh active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006049266A (ja) * | 2004-07-09 | 2006-02-16 | Samsung Sdi Co Ltd | リチウム二次電池 |
JP2006210348A (ja) * | 2005-01-28 | 2006-08-10 | Samsung Sdi Co Ltd | 負極活物質、その製造方法及びそれを採用した負極とリチウム電池 |
JP2006339093A (ja) * | 2005-06-06 | 2006-12-14 | Matsushita Electric Ind Co Ltd | 巻回型非水電解液二次電池およびその負極 |
JP2007087956A (ja) * | 2005-09-23 | 2007-04-05 | Samsung Sdi Co Ltd | 陰極活物質、その製造方法及びそれを採用したリチウム電池 |
JP2010033830A (ja) * | 2008-07-28 | 2010-02-12 | Nec Tokin Corp | 非水電解質二次電池用負極およびそれを用いた非水電解質二次電池 |
JP2011057541A (ja) * | 2009-08-11 | 2011-03-24 | Sekisui Chem Co Ltd | 炭素材料、電極材料及びリチウムイオン二次電池負極材料 |
JP2013506264A (ja) * | 2009-09-29 | 2013-02-21 | ジョージア テック リサーチ コーポレイション | 電極、リチウムイオン電池ならびにこれらを作製する方法および使用する方法 |
JP2012043546A (ja) * | 2010-08-12 | 2012-03-01 | Hitachi Chem Co Ltd | リチウム二次電池用負極材、リチウムイオン二次電池用負極、およびリチウムイオン二次電池 |
JP2013222534A (ja) * | 2012-04-13 | 2013-10-28 | Toyota Industries Corp | 非水電解質二次電池用負極活物質、その製造方法、非水電解質二次電池用負極、非水電解質二次電池、及び車両 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017091724A (ja) * | 2015-11-06 | 2017-05-25 | 新日鐵住金株式会社 | 負極活物質材料、負極活物質材料の製造方法、負極及び電池 |
WO2021065173A1 (ja) * | 2019-09-30 | 2021-04-08 | パナソニックIpマネジメント株式会社 | 非水電解質二次電池 |
CN114503308A (zh) * | 2019-09-30 | 2022-05-13 | 松下知识产权经营株式会社 | 非水电解质二次电池 |
EP4040527A4 (en) * | 2019-09-30 | 2022-11-09 | Panasonic Intellectual Property Management Co., Ltd. | SECONDARY NON-AQUEOUS ELECTROLYTE BATTERY |
CN114503308B (zh) * | 2019-09-30 | 2024-05-07 | 松下知识产权经营株式会社 | 非水电解质二次电池 |
Also Published As
Publication number | Publication date |
---|---|
US20160181601A1 (en) | 2016-06-23 |
JPWO2015012086A1 (ja) | 2017-03-02 |
KR20160018717A (ko) | 2016-02-17 |
CN105393386A (zh) | 2016-03-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Li et al. | Lithium polyacrylate as a binder for tin–cobalt–carbon negative electrodes in lithium-ion batteries | |
JP5476411B2 (ja) | 非水系二次電池用黒鉛質複合粒子、それを含有する負極活物質材料、負極及び非水系二次電池 | |
JP5458689B2 (ja) | 非水系二次電池用複合黒鉛粒子、それを含有する負極材料、負極及び非水系二次電池 | |
CN102576874B (zh) | 锂离子二次电池负极用碳粒子、锂离子二次电池用负极以及锂离子二次电池 | |
JP5064728B2 (ja) | 非水系二次電池用黒鉛質複合粒子、それを含有する負極活物質材料、負極及び非水系二次電池 | |
WO2015012086A1 (ja) | 複合粒子及びその製造方法並びに電極及び非水電解質二次電池 | |
TW201603368A (zh) | 鋰離子二次電池用負極活性物質及其製造方法 | |
JP2008181870A (ja) | 非水系二次電池用複合黒鉛粒子、それを含有する負極材料、負極及び非水系二次電池 | |
EP2497144A2 (en) | High capacity anode materials for lithium ion batteries | |
TW201417380A (zh) | 鋰離子二次電池用電極材料、此電極材料的製造方法及鋰離子二次電池 | |
JP2009016265A (ja) | リチウム系電池用電極、リチウム系電池用電極の製造方法、リチウム系電池、及びリチウム系電池の製造方法 | |
JP6365658B2 (ja) | 複合粒子、負極及び電池 | |
WO2015041063A1 (ja) | ケイ素相含有物黒鉛複合粒子およびその製造方法 | |
KR101572364B1 (ko) | 탄소-실리콘 복합체, 이를 이용한 리튬 이차전지용 음극 및 리튬 이차전지 | |
JP2013225471A (ja) | 二次電池用正極活物質及びその製造方法 | |
JP2015141897A (ja) | 負極活物質、それを採用した負極及び該リチウム電池、並びに該負極活物質の製造方法 | |
JP2012014866A (ja) | リチウム二次電池用負極活物質およびその製造方法 | |
JP6739142B2 (ja) | リチウムイオン2次電池用負極活物質およびその製造方法 | |
Guo et al. | A novel SnxSbNi composite as anode materials for Li rechargeable batteries | |
JP2017050204A (ja) | 非水電解質二次電池用正極材料、その製造方法および非水電解質二次電池 | |
JP2008147024A (ja) | 電極材料の複合化方法及び電極並びにリチウムイオン電池 | |
JP6187706B2 (ja) | 負極活物質材料、負極及び電池 | |
JP2021150111A (ja) | 非水電解質二次電池用の電極活物質層、非水電解質二次電池用の電極、及び、非水電解質二次電池 | |
JP2020009754A (ja) | 電池の負極における使用のための活物質粉末及びそのような活物質粉末を含む電池 | |
JP2015060640A (ja) | 合金黒鉛複合粒子およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480041058.9 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14828707 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015528209 Country of ref document: JP Kind code of ref document: A Ref document number: 20167000383 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14906587 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14828707 Country of ref document: EP Kind code of ref document: A1 |