WO2023085691A1 - 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 - Google Patents
음극 조성물, 이를 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 Download PDFInfo
- Publication number
- WO2023085691A1 WO2023085691A1 PCT/KR2022/017126 KR2022017126W WO2023085691A1 WO 2023085691 A1 WO2023085691 A1 WO 2023085691A1 KR 2022017126 W KR2022017126 W KR 2022017126W WO 2023085691 A1 WO2023085691 A1 WO 2023085691A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- active material
- negative electrode
- weight
- parts
- silicon
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims description 22
- 239000002409 silicon-based active material Substances 0.000 claims abstract description 117
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 61
- 239000010410 layer Substances 0.000 claims abstract description 51
- 239000011737 fluorine Substances 0.000 claims abstract description 48
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 48
- 239000011247 coating layer Substances 0.000 claims abstract description 46
- 239000004020 conductor Substances 0.000 claims description 106
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 41
- 239000007773 negative electrode material Substances 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011884 anode binding agent Substances 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- 239000006183 anode active material Substances 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 39
- 238000007599 discharging Methods 0.000 abstract description 20
- 239000002245 particle Substances 0.000 description 109
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- 239000011163 secondary particle Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- -1 LiCoO 2 Chemical class 0.000 description 23
- 239000011149 active material Substances 0.000 description 22
- 239000011164 primary particle Substances 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 239000011267 electrode slurry Substances 0.000 description 18
- 239000007774 positive electrode material Substances 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 14
- 239000006182 cathode active material Substances 0.000 description 14
- 229910002804 graphite Inorganic materials 0.000 description 14
- 239000010439 graphite Substances 0.000 description 14
- 239000002033 PVDF binder Substances 0.000 description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 13
- 239000011856 silicon-based particle Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- 125000000524 functional group Chemical group 0.000 description 11
- 239000002210 silicon-based material Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 150000003623 transition metal compounds Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000011883 electrode binding agent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 230000000116 mitigating effect Effects 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000002388 carbon-based active material Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000002391 graphite-based active material Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 229920000265 Polyparaphenylene Chemical class 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000006231 channel black Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000006233 lamp black Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011356 non-aqueous organic solvent Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920005608 sulfonated EPDM Polymers 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical group 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZHGDJTMNXSOQDT-UHFFFAOYSA-N NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O Chemical compound NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O ZHGDJTMNXSOQDT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QDDVNKWVBSLTMB-UHFFFAOYSA-N [Cu]=O.[Li] Chemical compound [Cu]=O.[Li] QDDVNKWVBSLTMB-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 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
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- CASZBAVUIZZLOB-UHFFFAOYSA-N lithium iron(2+) oxygen(2-) Chemical group [O-2].[Fe+2].[Li+] CASZBAVUIZZLOB-UHFFFAOYSA-N 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 235000015041 whisky Nutrition 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
- H01M4/13—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
-
- 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
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Definitions
- the present application relates to a negative electrode composition, a negative electrode for a lithium secondary battery including the negative electrode, a lithium secondary battery including the negative electrode, and a method for preparing the negative electrode composition.
- a secondary battery is a representative example of an electrochemical device using such electrochemical energy, and its use area is gradually expanding.
- lithium secondary batteries having high energy density and voltage, long cycle life, and low self-discharge rate have been commercialized and widely used.
- an electrode for such a high-capacity lithium secondary battery research is being actively conducted on a method for manufacturing a high-density electrode having a higher energy density per unit volume.
- a secondary battery is composed of an anode, a cathode, an electrolyte, and a separator.
- the negative electrode includes a negative electrode active material for intercalating and deintercalating lithium ions from the positive electrode, and silicon-based particles having a high discharge capacity may be used as the negative electrode active material.
- volume expansion itself is suppressed, such as a method of adjusting the driving potential, a method of additionally coating a thin film on the active material layer, and a method of controlling the particle diameter of the silicon-based compound.
- Various methods for preventing or preventing the conductive path from being disconnected are being discussed, but in the case of the above methods, the performance of the battery may be deteriorated, so there is a limit to the application, and a negative electrode battery with a high silicon-based compound content is still Commercialization of manufacturing has limitations.
- lithium secondary batteries are typically manufactured by using a lithium-intercalated compound such as LiCoO 2 , LiMn 2 O 4 , etc. at the cathode, and using a material in which lithium is not intercalated, such as carbon-based or Si-based, at the anode.
- a lithium-intercalated compound such as LiCoO 2 , LiMn 2 O 4 , etc.
- a material in which lithium is not intercalated such as carbon-based or Si-based
- This SEI can stabilize the structure of the anode by preventing the decomposition reaction of the electrolyte by suppressing the movement of electrons required for the reaction between the anode and the electrolyte, while it is more stable because it consumes lithium ions because it is an irreversible reaction.
- Research on an SEI layer capable of utilizing the above advantages is being conducted.
- the present application relates to a negative electrode composition, a negative electrode for a lithium secondary battery including the negative electrode, a lithium secondary battery including the negative electrode, and a method for preparing the negative electrode composition.
- Preparation of a negative electrode composition provides a way
- a negative electrode current collector layer In another exemplary embodiment, a negative electrode current collector layer; and a negative electrode active material layer including the negative electrode composition according to the present application formed on one side or both sides of the negative electrode current collector layer.
- the anode A negative electrode for a lithium secondary battery according to the present application; a separator provided between the anode and the cathode; And an electrolyte; it provides a lithium secondary battery comprising a.
- the silicon-based active material in using a silicon-based active material, which is a high-capacity material, to manufacture a high-capacity battery, rather than adjusting the characteristics of the conductive material and the binder according to the volume expansion of the silicon-based active material, the silicon-based active material itself
- the surface of the silicon-based active material includes a carbon coating layer, and the carbon coating layer is doped with fluorine (F) to alleviate rapid volume expansion during charging and discharging of the silicon-based active material, Fluorine is doped and reacts with FEC to form a more stable LiF film on the cathode along with the SEI layer.
- F fluorine
- the negative electrode composition according to the present application has a high content of pure Si particles to obtain a high-capacity and high-density negative electrode, and at the same time, in order to solve problems such as volume expansion due to the high content of pure Si particles, As the silicon-based active material itself having high content is coated with a carbon layer containing fluorine and used, the problem of volume expansion can be solved and the advantages of the silicon-based active material can be utilized.
- FIG. 1 is a diagram showing a laminated structure of a negative electrode for a lithium secondary battery according to an exemplary embodiment of the present application.
- FIG. 2 is a diagram showing a laminated structure of a lithium secondary battery according to an exemplary embodiment of the present application.
- 'p to q' means a range of 'p or more and q or less'.
- specific surface area is measured by the BET method, and is specifically calculated from the nitrogen gas adsorption amount under liquid nitrogen temperature (77K) using BELSORP-mino II of BEL Japan. That is, in the present application, the BET specific surface area may mean the specific surface area measured by the above measuring method.
- Dn means the average particle diameter, and means the particle diameter at the n% point of the cumulative distribution of the number of particles according to the particle diameter. That is, D50 is the particle size at the 50% point of the cumulative distribution of the number of particles according to the particle size, D90 is the particle size at the 90% point of the cumulative distribution of the number of particles according to the particle size, and D10 is the 10% of the cumulative distribution of the number of particles according to the particle size. is the particle diameter at the point.
- the average particle diameter can be measured using a laser diffraction method. Specifically, after dispersing the powder to be measured in a dispersion medium, it is introduced into a commercially available laser diffraction particle size measuring device (e.g. Microtrac S3500) to measure the difference in diffraction pattern according to the particle size when the particles pass through the laser beam to distribute the particle size. yields
- a laser diffraction particle size measuring device e.g. Microtrac S3500
- a polymer includes a certain monomer as a monomer unit means that the monomer participates in a polymerization reaction and is included as a repeating unit in the polymer.
- this is interpreted as the same as that the polymer includes a monomer as a monomer unit.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured using a commercially available monodisperse polystyrene polymer (standard sample) of various degrees of polymerization for molecular weight measurement as a standard material, and gel permeation chromatography (Gel Permeation It is the molecular weight in terms of polystyrene measured by chromatography; GPC).
- molecular weight means a weight average molecular weight unless otherwise specified.
- the silicon-based active material in using a silicon-based active material, which is a high-capacity material, to manufacture a high-capacity battery, rather than adjusting the characteristics of the conductive material and the binder according to the volume expansion of the silicon-based active material, the silicon-based active material itself
- the surface of the silicon-based active material includes a carbon coating layer, and using the carbon coating layer doped with fluorine (F), while mitigating rapid volume expansion during charging and discharging of the silicon-based active material, Fluorine is doped and reacts with FEC to form a more stable LiF film on the cathode along with the SEI layer.
- the silicon-based active material may include a metal impurity, wherein the metal impurity is a common metal that may be included in the silicon-based active material, and the content is 1 part by weight or less based on 100 parts by weight of the total silicon-based active material, It may contain 0.1 part by weight or less.
- the silicon-based active material may use pure silicon (Si) as the silicon-based active material.
- SiOx (0 ⁇ x ⁇ 2) series As a main material, the SiOx (0 ⁇ x ⁇ 2) series has a disadvantage that the theoretical capacity is much lower than that of the silicon-based active material of the present application. That is, when using a SiOx (0 ⁇ x ⁇ 2)-based active material, even if the active material itself is treated in any way, it is not possible to implement conditions equal to the charging and discharging capacity compared to the case of having the silicon-based active material of the present invention.
- the surface of the silicon-based active material is coated with a specific material as described above, particularly a carbon coating.
- the feature of the present invention is that the volume expansion of the silicon-based active material is alleviated and the fluorine doped in the carbon coating layer reacts with the FEC to form a more stable LiF inorganic film together with the SEI layer to solve the existing problems.
- the average particle diameter (D50) of the silicon-based active material of the present invention may be 5 ⁇ m to 10 ⁇ m, specifically 5.5 ⁇ m to 8 ⁇ m, and more specifically 6 ⁇ m to 7 ⁇ m.
- the average particle diameter is within the above range, the viscosity of the negative electrode slurry is formed within an appropriate range, including the specific surface area of the particles within a suitable range. Accordingly, the dispersion of the particles constituting the negative electrode slurry becomes smooth.
- the contact area between the silicon particles and the conductive material is excellent due to the composite made of the conductive material and the binder in the negative electrode slurry, so that the possibility of continuing the conductive network increases, thereby increasing the capacity retention rate is increased.
- the average particle diameter satisfies the above range, excessively large silicon particles are excluded to form a smooth surface of the negative electrode, thereby preventing current density non-uniformity during charging and discharging.
- the silicon-based active material generally has a characteristic BET specific surface area.
- the BET specific surface area of the silicon-based active material is preferably 0.01 to 150.0 m 2 /g, more preferably 0.1 to 100.0 m 2 /g, particularly preferably 0.2 to 80.0 m 2 /g, and most preferably 0.2 to 18.0 m 2 /g.
- the BET specific surface area is determined according to DIN 66131 (using nitrogen).
- the silicon-based active material may exist, for example, in a crystalline or amorphous form, and is preferably not porous.
- the silicon particles are preferably spherical or fragment-shaped particles. Alternatively but less preferably, the silicon particles may also have a fibrous structure or be present in the form of a silicon-comprising film or coating.
- the silicon-based active material provides a negative electrode composition that is 60 parts by weight or more based on 100 parts by weight of the negative electrode composition.
- the silicon-based active material may include 60 parts by weight or more, preferably 65 parts by weight or more, more preferably 70 parts by weight or more, based on 100 parts by weight of the negative electrode composition, and 95 parts by weight or less , preferably 90 parts by weight or less, more preferably 80 parts by weight or less.
- the negative electrode composition according to the present application uses a specific surface coating capable of controlling the volume expansion rate during charging and discharging even when a silicon-based active material having a significantly high capacity is used in the above range, and even within the above range, the performance of the negative electrode is deteriorated. and has excellent output characteristics in charging and discharging.
- the silicon-based active material may have a non-spherical shape and its sphericity is, for example, 0.9 or less, for example, 0.7 to 0.9, for example 0.8 to 0.9, for example 0.85 to 0.9 am.
- the circularity (circularity) is determined by the following formula 1, A is the area, P is the boundary line.
- the fluorine (F) doped in the carbon coating layer provides a negative electrode composition formed by a single bond between carbon and fluorine (F).
- the carbon coating layer may have a thickness of 1 nm or more and 20 nm or less, preferably 5 nm or more and 15 nm or less, and 10 nm or more and 15 nm or less.
- the amount of carbon included in the carbon coating layer may include 5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the silicon-based active material.
- the content of carbon included in the carbon coating layer may satisfy the range of 5 parts by weight or more and 20 parts by weight or less, preferably 7 parts by weight or more and 15 parts by weight or less based on 100 parts by weight of the silicon-based active material. there is.
- a negative electrode composition comprising 0.1 part by weight or more and 20 parts by weight or less of the fluorine (F) based on 100 parts by weight of the silicon-based active material is provided.
- the fluorine (F) is 0.1 parts by weight or more and 20 parts by weight or less, preferably 0.1 parts by weight or more and 10 parts by weight or less, more preferably 0.2 parts by weight or more 5 It may be parts by weight or less, and may satisfy the range of 3 parts by weight or less and 1 part by weight or less.
- the thickness of the coating layer is appropriate and the capacity per weight can be maintained, rapid volume expansion during charging and discharging of the silicon-based active material is alleviated, and fluorine is doped in the content portion. It reacts with FEC to form a more stable LiF film on the cathode along with the SEI layer.
- the negative electrode conductive material may include at least one selected from the group consisting of a point-shaped conductive material, a planar conductive material, and a linear conductive material.
- the dotted conductive material may be used to improve conductivity of the negative electrode, and preferably has conductivity without causing chemical change.
- the conductive material is natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, channel black, farnes black, lamp black, thermal black, conductive fiber, fluorocarbon, aluminum powder, nickel powder, zinc oxide, titanic acid It may be at least one selected from the group consisting of potassium, titanium oxide, and polyphenylene derivatives, and preferably may include carbon black in terms of implementing high conductivity and excellent dispersibility.
- the point-shaped conductive material may have a BET specific surface area of 40 m 2 /g or more and 70 m 2 /g or less, preferably 45 m 2 /g or more and 65 m 2 /g or less, more preferably 50 m 2 /g or less . /g or more and 60 m 2 /g or less.
- the point-like conductive material may satisfy a functional group content (Volatile matter) of 0.01% or more and 1% or less, preferably 0.01% or more and 0.3% or less, more preferably 0.01% or more and 0.1% or less. there is.
- a functional group content Volatile matter
- the functional group content of the dotted conductive material satisfies the above range, functional groups present on the surface of the dotted conductive material exist, so that the dotted conductive material can be smoothly dispersed in the solvent when water is used as a solvent.
- the functional group content of the point-like conductive material can be lowered by using silicon particles and a specific binder, thereby having an excellent effect in improving dispersibility.
- the present application is characterized in that it includes a silicon-based active material and a dotted conductive material having a functional group content within the above range, the control of the functional group content can be adjusted according to the degree of heat treatment of the dotted conductive material there is.
- a high functional group content means a lot of foreign substances
- a low functional group content means more heat treatment processing
- the point-like conductive material according to the present application has a functional group content within the above range.
- the point-shaped conductive material is subjected to a certain portion of heat treatment to satisfy the functional group content range.
- the dispersibility of the point-like conductive material is improved, even if the content of the point-like conductive material is increased in the negative electrode slurry having the same solid content, the viscosity of the negative electrode slurry can be maintained at an appropriate level, maintaining a stable state of fairness The uniformity of the formed cathode can be improved.
- the particle diameter of the dotted conductive material may be 10 nm to 100 nm, preferably 20 nm to 90 nm, and more preferably 20 nm to 60 nm.
- the conductive material may include a planar conductive material.
- the planar conductive material can improve conductivity by increasing the surface contact between silicon particles in the negative electrode and at the same time suppress the disconnection of the conductive path due to volume expansion, and can be expressed as a plate-shaped conductive material or a bulk-type conductive material.
- the planar conductive material may include at least one selected from the group consisting of plate-like graphite, graphene, graphene oxide, and graphite flakes, and preferably may be plate-like graphite.
- the average particle diameter (D50) of the planar conductive material may be 2 ⁇ m to 7 ⁇ m, specifically 3 ⁇ m to 6 ⁇ m, and more specifically 4 ⁇ m to 5 ⁇ m. .
- D50 average particle diameter
- the planar conductive material provides a negative electrode composition in which D10 is 0.5 ⁇ m or more and 1.5 ⁇ m or less, D50 is 2.5 ⁇ m or more and 3.5 ⁇ m or less, and D90 is 7.0 ⁇ m or more and 15.0 ⁇ m or less.
- the planar conductive material is a high specific surface area planar conductive material having a high BET specific surface area; Alternatively, a planar conductive material having a low specific surface area may be used.
- the planar conductive material includes a high specific surface area planar conductive material;
- a planar conductive material with a low specific surface area can be used without limitation, but in particular, the planar conductive material according to the present application can be affected to some extent in the electrode performance by the dispersion effect, so that a planar conductive material with a low specific surface area that does not cause a problem in dispersion is used. may be particularly desirable.
- the planar conductive material may have a BET specific surface area of 1 m 2 /g or more.
- the planar conductive material may have a BET specific surface area of 1 m 2 /g or more and 500 m 2 /g or less, preferably 5 m 2 /g or more and 300 m 2 /g or less, more preferably 5 m 2 /g or more. g or more and 300 m 2 /g or less.
- the planar conductive material is a high specific surface area planar conductive material, and the BET specific surface area is 50 m 2 /g or more and 500 m 2 /g or less, preferably 80 m 2 /g or more and 300 m 2 /g or less, more preferably Preferably, a range of 100 m 2 /g or more and 300 m 2 /g or less may be satisfied.
- the planar conductive material is a planar conductive material with a low specific surface area
- the BET specific surface area is 1 m 2 /g or more and 40 m 2 /g or less, preferably 5 m 2 /g or more and 30 m 2 /g or less, more preferably Preferably, a range of 5 m 2 /g or more and 25 m 2 /g or less may be satisfied.
- Carbon nanotubes may be bundled carbon nanotubes.
- the bundled carbon nanotubes may include a plurality of carbon nanotube units.
- the term 'bundle type' herein means, unless otherwise specified, a bundle in which a plurality of carbon nanotube units are arranged side by side or entangled in substantially the same orientation with axes in the longitudinal direction of the carbon nanotube units. It refers to a secondary shape in the form of a bundle or rope.
- the carbon nanotube unit has a graphite sheet having a cylindrical shape with a nano-sized diameter and an sp2 bonding structure.
- the characteristics of a conductor or a semiconductor may be exhibited according to the angle and structure of the graphite surface being rolled.
- the bundled carbon nanotubes can be uniformly dispersed during manufacturing of the negative electrode, and the conductivity of the negative electrode can be improved by smoothly forming a conductive network in the negative electrode.
- the negative electrode conductive material is provided in an amount of 10 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the negative electrode composition.
- the negative electrode conductive material is 10 parts by weight or more and 40 parts by weight or less, preferably 10 parts by weight or more and 30 parts by weight or less, more preferably 10 parts by weight or more and 25 parts by weight based on 100 parts by weight of the negative electrode composition. May include the following.
- the negative electrode conductive material is a planar conductive material; and a linear conductive material; including, based on 100 parts by weight of the negative electrode conductive material, 80 parts by weight or more and 99.5 parts by weight or less of the planar conductive material; and 0.5 parts by weight or more and 20 parts by weight or less of the linear conductive material.
- the planar conductive material is 80 parts by weight or more and 99.5 parts by weight or less, preferably 85 parts by weight or more and 99 parts by weight or less, more preferably 90 parts by weight or more 98 parts by weight. May include the following.
- the linear conductive material is 0.5 parts by weight or more and 20 parts by weight or less, preferably 1 part by weight or more and 15 parts by weight or less, more preferably 2 parts by weight or more 10 parts by weight. May include the following.
- the negative electrode conductive material includes a point-shaped conductive material, a planar conductive material, and a linear conductive material, and satisfies the composition and ratio, respectively, it does not significantly affect the lifespan characteristics of an existing lithium secondary battery, ,
- a planar conductive material and a linear conductive material there are many points capable of charging and discharging, so that the output characteristics are excellent at a high C-rate and the amount of high-temperature gas is reduced.
- the negative electrode conductive material according to the present application has a completely different configuration from the conductive material applied to the positive electrode. That is, in the case of the anode conductive material according to the present application, it serves to hold the contact between silicon-based active materials whose volume expansion of the electrode is very large due to charging and discharging. As a role of imparting, its composition and role are completely different from those of the negative electrode conductive material of the present invention.
- the negative electrode conductive material according to the present application is applied to a silicon-based active material, and has a completely different configuration from that of a conductive material applied to a graphite-based active material. That is, since the conductive material used in the electrode having the graphite-based active material simply has smaller particles than the active material, it has characteristics of improving output characteristics and imparting some conductivity, unlike the negative electrode conductive material applied together with the silicon-based active material as in the present invention. Their composition and role are completely different.
- the plate-shaped conductive material used as the negative electrode conductive material described above has a different structure and role from the carbon-based active material generally used as the negative electrode active material.
- the carbon-based active material used as the negative electrode active material may be artificial graphite or natural graphite, and refers to a material processed into a spherical or dotted shape to facilitate storage and release of lithium ions.
- the plate-shaped conductive material used as the negative electrode conductive material is a material having a plane or plate shape, and may be expressed as plate-shaped graphite. That is, as a material included to maintain a conductive path in the negative active material layer, it means a material used to secure a conductive path in a planar shape inside the negative active material layer, rather than playing a role in storing and releasing lithium.
- plate-like graphite is used as a conductive material means that it is processed into a planar or plate-like shape and used as a material that secures a conductive path rather than a role of storing or releasing lithium.
- the negative active material included together has high capacity characteristics for storing and releasing lithium, and serves to store and release all lithium ions transferred from the positive electrode.
- a carbon-based active material as an active material means that it is processed into a point shape or sphere and used as a material that stores or releases lithium.
- the negative electrode binder is polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride, polyacrylonitrile, Polymethylmethacrylate, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene -Selected from the group consisting of propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluororubber, polyacrylic acid, and materials in which hydrogen is substituted with Li, Na or Ca, etc. It may include at least one that is, and may also include various copolymers thereof.
- PVDF-co-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
- the negative electrode binder serves to hold the active material and the conductive material in order to prevent distortion and structural deformation of the negative electrode structure in volume expansion and relaxation of the silicon-based active material.
- All of the binders can be applied, specifically, a water-based binder can be used, and more specifically, a PAM-based binder can be used.
- the negative electrode binder may include 30 parts by weight or less, preferably 25 parts by weight or less, more preferably 20 parts by weight or less, and 5 parts by weight or more based on 100 parts by weight of the negative electrode composition. , 10 parts by weight or more.
- a water-based binder is applied in the above weight part to use a point-type conductive material having a low functional group content. It has a characteristic that the bonding strength is excellent.
- Preparation of a negative electrode composition provides a way
- each composition included in the negative electrode composition may be the same as described above.
- the step of preparing a silicon-based active material including a carbon coating layer doped with fluorine (F) on the surface is adding a silicon-based active material to a polymer solution containing fluorine (F); bonding a polymer containing fluorine (F) to a surface of a silicon-based active material by adding ethanol to the polymer solution; It provides a method for producing a negative electrode composition comprising; and carbonizing the combined polymer.
- the step of carbonizing the bonded polymer may be a step of carbonizing a polymer containing fluorine (F) on the surface of the silicon-based active material.
- the polymer containing fluorine (F) may be used without limitation as long as it is a material providing fluorine (F) and carbon (C) atoms, specifically polyvinylidene fluoride (PVdF) or Teflon or the like may be used, but is not limited thereto.
- PVdF polyvinylidene fluoride
- Teflon Teflon
- the polymer solution containing fluorine (F) may be used without limitation as long as it can dissolve the polymer containing fluorine (F), but specifically dimethylformamide (DMF) ) can be used.
- the step of adding the silicon-based active material to the polymer solution containing fluorine (F) may include adding the silicon-based active material according to the present application to the polymer solution containing fluorine (F). It may further include a step of steering within the range of 1 hour to 12 hours after inclusion.
- a carbon coating layer doped with fluorine may be formed on the surface of the silicon-based active material of the present application through the step of carbonizing the polymer.
- the carbonizing step may include heat treatment at 500° C. to 1000° C. for 30 minutes to 3 hours in an inert gas atmosphere in a high-temperature furnace.
- the surface of the silicon-based active material according to the present application may be surface-modified into a silicon-based active material including a carbon coating layer doped with fluorine (F) on the surface.
- the first mixing and the second mixing step is mixing at 2,000 rpm to 3,000 rpm for 10 minutes to 60 minutes.
- a negative electrode slurry containing the negative electrode composition may be coated on one side or both sides of a current collector to form a negative electrode for a lithium secondary battery.
- the negative electrode slurry includes a negative electrode composition; And a slurry solvent; may include.
- the solid content of the negative electrode slurry may satisfy 5% or more and 40% or less.
- the solid content of the negative electrode slurry may satisfy a range of 5% or more and 40% or less, preferably 7% or more and 35% or less, and more preferably 10% or more and 30% or less.
- the solids content of the negative electrode slurry may refer to the content of the negative electrode composition included in the negative electrode slurry, and may refer to the content of the negative electrode composition based on 100 parts by weight of the negative electrode slurry.
- the negative electrode active material layer can be efficiently formed by minimizing particle aggregation of the negative electrode composition due to appropriate viscosity when forming the negative electrode active material layer.
- the negative current collector layer In one embodiment of the present application, the negative current collector layer; and a negative electrode active material layer including the negative electrode composition according to the present application formed on one side or both sides of the current collector layer.
- FIG. 1 is a diagram showing a laminated structure of a negative electrode for a lithium secondary battery according to an exemplary embodiment of the present application. Specifically, the negative electrode 100 for a lithium secondary battery including the negative electrode active material layer 20 on one surface of the negative electrode current collector layer 10 can be confirmed, and FIG. 1 shows that the negative electrode active material layer is formed on one surface, but the negative electrode collector It can be included on both sides of the entire layer.
- the negative current collector generally has a thickness of 1 ⁇ m to 100 ⁇ m.
- the negative electrode current collector is not particularly limited as long as it does not cause chemical change in the battery and has high conductivity.
- it is made of copper, stainless steel, aluminum, nickel, titanium, fired carbon, copper or stainless steel.
- a surface treated with carbon, nickel, titanium, silver, or the like, an aluminum-cadmium alloy, or the like may be used.
- fine irregularities may be formed on the surface to enhance the bonding strength of the negative active material, and may be used in various forms such as films, sheets, foils, nets, porous materials, foams, and nonwoven fabrics.
- the negative electrode current collector layer has a thickness of 1 ⁇ m or more and 100 ⁇ m or less, and the negative electrode active material layer has a thickness of 20 ⁇ m or more and 500 ⁇ m or less.
- the thickness may be variously modified depending on the type and purpose of the negative electrode used, but is not limited thereto.
- the porosity of the negative electrode active material layer may satisfy a range of 10% or more and 60% or less.
- the porosity of the negative electrode active material layer may satisfy a range of 10% or more and 60% or less, preferably 20% or more and 50% or less, and more preferably 30% or more and 45% or less.
- the porosity is a silicon-based active material included in the negative electrode active material layer; conductive material; And as changed according to the composition and content of the binder, in particular, the silicon-based active material according to the present application; And it is characterized in that it satisfies the above range by including a specific composition and content of the conductive material, so that the electrode has an appropriate range of electrical conductivity and resistance.
- FIG. 2 is a diagram showing a laminated structure of a lithium secondary battery according to an exemplary embodiment of the present application.
- the negative electrode 100 for a lithium secondary battery including the negative electrode active material layer 20 on one surface of the negative electrode current collector layer 10 can be confirmed, and the positive electrode active material layer 40 on one surface of the positive electrode current collector layer 50
- the positive electrode 200 for a lithium secondary battery including a and the negative electrode 100 for a lithium secondary battery and the positive electrode 200 for a lithium secondary battery are formed in a laminated structure with a separator 30 interposed therebetween.
- a secondary battery may include the anode for a lithium secondary battery described above.
- the secondary battery may include a negative electrode, a positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, and the negative electrode is the same as the negative electrode described above. Since the cathode has been described above, a detailed description thereof will be omitted.
- the positive electrode may include a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector and including the positive electrode active material.
- the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- stainless steel, aluminum, nickel, titanium, fired carbon, or carbon on the surface of aluminum or stainless steel. , those surface-treated with nickel, titanium, silver, etc. may be used.
- the cathode current collector may have a thickness of typically 3 ⁇ m to 500 ⁇ m, and adhesion of the cathode active material may be increased by forming fine irregularities on the surface of the current collector.
- it may be used in various forms such as films, sheets, foils, nets, porous materials, foams, and non-woven fabrics.
- the cathode active material may be a commonly used cathode active material.
- the cathode active material may include layered compounds such as lithium cobalt oxide (LiCoO 2 ) and lithium nickel oxide (LiNiO 2 ), or compounds substituted with one or more transition metals; lithium iron oxides such as LiFe 3 O 4 ; lithium manganese oxides such as Li 1+c1 Mn 2-c1 O 4 (0 ⁇ c1 ⁇ 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 ; lithium copper oxide (Li 2 CuO 2 ); vanadium oxides such as LiV 3 O 8 , V 2 O 5 , Cu 2 V 2 O 7 ; Represented by the formula LiNi 1-c2 M c2 O 2 (where M is at least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B, and Ga, and satisfies 0.01 ⁇ c2 ⁇ 0.6) Ni site-type lithium nickel oxide; Formula Li
- the positive electrode active material includes a lithium composite transition metal compound including nickel (Ni), cobalt (Co), and manganese (Mn), and the lithium composite transition metal compound is a single particle or a secondary particle.
- the average particle diameter (D50) of the single particles may be 1 ⁇ m or more.
- the average particle diameter (D50) of the single particles is 1 ⁇ m or more and 12 ⁇ m or less, 1 ⁇ m or more and 8 ⁇ m or less, 1 ⁇ m or more and 6 ⁇ m or less, 1 ⁇ m or more and 12 ⁇ m or less, 1 ⁇ m or more and 8 ⁇ m or less, or 1 ⁇ m. It may be more than 6 ⁇ m or less.
- the particle strength may be excellent.
- the single particle may have a particle strength of 100 to 300 MPa when rolling with a force of 650 kgf/cm 2 . Accordingly, even if the single particle is rolled with a strong force of 650 kgf/cm 2 , the phenomenon of increasing fine particles in the electrode due to particle breakage is alleviated, thereby improving the lifespan characteristics of the battery.
- the single particle may be prepared by mixing and calcining a transition metal precursor and a lithium source material.
- the secondary particles may be prepared in a different way from the single particles, and their composition may be the same as or different from that of the single particles.
- the method of forming the single particles is not particularly limited, but generally can be formed by underfiring by raising the firing temperature, using additives such as grain growth promoters that help underfiring, or by changing the starting material. can be manufactured
- the firing is performed at a temperature capable of forming single particles.
- firing should be performed at a temperature higher than that of the secondary particles, for example, if the composition of the precursor is the same, firing should be performed at a temperature about 30° C. to 100° C. higher than that of the secondary particles.
- the firing temperature for forming the single particle may vary depending on the metal composition in the precursor. For example, a high-Ni NCM-based lithium composite transition metal oxide having a nickel (Ni) content of 80 mol% or more is used. In the case of forming single particles, the firing temperature may be about 700°C to 1000°C, preferably about 800°C to 950°C.
- a cathode active material including single particles having excellent electrochemical properties may be prepared. If the firing temperature is less than 790 ° C, a cathode active material containing a lithium complex transition metal compound in the form of secondary particles can be prepared, and if it exceeds 950 ° C, excessive firing occurs and the layered crystal structure is not properly formed, resulting in electrochemical characteristics may deteriorate.
- the single particle is a term used to distinguish from conventional secondary particles formed by aggregation of tens to hundreds of primary particles, and includes a single particle composed of one primary particle and 30 or less primary particles. It is a concept that includes pseudo-single-particle forms that are aggregates.
- the single particle may be in the form of a single particle composed of one primary particle or a quasi-single particle, which is an aggregate of 30 or less primary particles, and the secondary particle may be in the form of an aggregate of hundreds of primary particles. .
- the lithium composite transition metal compound which is the cathode active material, further includes secondary particles, and the average particle diameter (D50) of the single particles is smaller than the average particle diameter (D50) of the secondary particles.
- the single particle may be in the form of a single particle composed of one primary particle or a quasi-single particle, which is an aggregate of 30 or less primary particles, and the secondary particle may be in the form of an aggregate of hundreds of primary particles.
- the above-described lithium composite transition metal compound may further include secondary particles.
- a secondary particle means a form formed by aggregation of primary particles, and can be distinguished from the concept of a single particle including one primary particle, one single particle, or a quasi-single particle form, which is an aggregate of 30 or less primary particles. .
- the secondary particle may have a particle diameter (D50) of 1 ⁇ m to 20 ⁇ m, 2 ⁇ m to 17 ⁇ m, and preferably 3 ⁇ m to 15 ⁇ m.
- the specific surface area (BET) of the secondary particles may be 0.05 m 2 /g to 10 m 2 /g, preferably 0.1 m 2 /g to 1 m 2 /g, and more preferably 0.3 m 2 /g to 0.8 m 2 /g.
- the secondary particles are aggregates of primary particles, and the average particle diameter (D50) of the primary particles is 0.5 ⁇ m to 3 ⁇ m.
- the secondary particles may be in the form of an aggregate of hundreds of primary particles, and the average particle diameter (D50) of the primary particles may be 0.6 ⁇ m to 2.8 ⁇ m, 0.8 ⁇ m to 2.5 ⁇ m, or 0.8 ⁇ m to 1.5 ⁇ m. .
- the average particle diameter (D50) of the primary particles satisfies the above range, a single-particle cathode active material having excellent electrochemical properties may be formed. If the average particle diameter (D50) of the primary particles is too small, the number of agglomerations of the primary particles forming lithium nickel-based oxide particles increases, reducing the effect of suppressing particle breakage during rolling, and the average particle diameter (D50) of the primary particles is too small. If it is large, the lithium diffusion path inside the primary particle becomes long, and resistance may increase and output characteristics may deteriorate.
- the average particle diameter (D50) of the single particles is smaller than the average particle diameter (D50) of the secondary particles.
- the average particle diameter (D50) of the single particles is smaller than the average particle diameter (D50) of the secondary particles by 1 ⁇ m to 18 ⁇ m.
- the average particle diameter (D50) of the single particles may be 1 ⁇ m to 16 ⁇ m smaller, 1.5 ⁇ m to 15 ⁇ m smaller, or 2 ⁇ m to 14 ⁇ m smaller than the average particle diameter (D50) of the secondary particles.
- the single particles When the average particle diameter (D50) of the single particles is smaller than the average particle diameter (D50) of the secondary particles, for example, when the above range is satisfied, the single particles may have excellent particle strength even if they are formed with a small particle diameter, and thereby The phenomenon of increasing fine particles in the electrode due to cracking is alleviated, and there is an effect of improving the lifespan characteristics and energy density of the battery.
- the single particle is included in 15 parts by weight to 100 parts by weight based on 100 parts by weight of the positive electrode active material.
- the single particle may be included in an amount of 20 parts by weight to 100 parts by weight, or 30 parts by weight to 100 parts by weight based on 100 parts by weight of the cathode active material.
- the single particle may be included in an amount of 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, or 45 parts by weight or more based on 100 parts by weight of the positive electrode active material.
- the single particle may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the positive electrode active material.
- the single particle within the above range When the single particle within the above range is included, excellent battery characteristics may be exhibited in combination with the anode material described above.
- the single particle when the single particle is 15 parts by weight or more, the increase in fine particles in the electrode due to particle breakage during the rolling process after fabrication of the electrode can be alleviated, and thus the lifespan characteristics of the battery can be improved.
- the lithium composite transition metal compound may further include secondary particles, and the secondary particles may be 85 parts by weight or less based on 100 parts by weight of the positive electrode active material.
- the amount of the secondary particles may be 80 parts by weight or less, 75 parts by weight or less, or 70 parts by weight or less based on 100 parts by weight of the cathode active material.
- the secondary particles may be 0 parts by weight or more based on 100 parts by weight of the positive electrode active material.
- the component may be the same as those exemplified in the single-particle cathode active material described above, or may be other components, and may mean a form in which a single particle form is aggregated.
- the positive electrode active material in 100 parts by weight of the positive electrode active material layer is 80 parts by weight or more and 99.9 parts by weight or less, preferably 90 parts by weight or more and 99.9 parts by weight or less, more preferably 95 parts by weight or more and 99.9 parts by weight or less. parts or less, more preferably 98 parts by weight or more and 99.9 parts by weight or less.
- the positive electrode active material layer may include a positive electrode conductive material and a positive electrode binder together with the positive electrode active material described above.
- the positive electrode conductive material is used to impart conductivity to the electrode, and in the configured battery, any material that does not cause chemical change and has electronic conductivity can be used without particular limitation.
- any material that does not cause chemical change and has electronic conductivity can be used without particular limitation.
- Specific examples include graphite such as natural graphite or artificial graphite; carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black, and carbon fiber; metal powders or metal fibers such as copper, nickel, aluminum, and silver; conductive whiskeys such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; or conductive polymers such as polyphenylene derivatives, and the like, and one of them alone or a mixture of two or more may be used.
- the positive electrode binder serves to improve adhesion between particles of the positive electrode active material and adhesion between the positive electrode active material and the positive electrode current collector.
- specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose (CMC) ), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, or various copolymers thereof, and the like may be used alone or in a mixture of two or more of them.
- PVDF polyvinylidene fluoride
- PVDF-co-HFP vinylidene fluoride-
- the separator separates the negative electrode and the positive electrode and provides a passage for lithium ion movement. If it is normally used as a separator in a secondary battery, it can be used without particular limitation. It is desirable Specifically, a porous polymer film, for example, a porous polymer film made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, or these A laminated structure of two or more layers of may be used.
- a porous polymer film for example, a porous polymer film made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, or these A laminated structure of two or more layers of may be used.
- porous non-woven fabrics for example, non-woven fabrics made of high-melting glass fibers, polyethylene terephthalate fibers, and the like may be used.
- a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be selectively used in a single-layer or multi-layer structure.
- electrolyte examples include, but are not limited to, organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel polymer electrolytes, solid inorganic electrolytes, and molten inorganic electrolytes that can be used in manufacturing a lithium secondary battery.
- the electrolyte may include a non-aqueous organic solvent and a metal salt.
- non-aqueous organic solvent for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyllolactone, 1,2-dimethine Toxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxorane, formamide, dimethylformamide, dioxorane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid Triester, trimethoxy methane, dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ether, methyl propionate, propionic acid
- An aprotic organic solvent such as ethyl may be used.
- ethylene carbonate and propylene carbonate which are cyclic carbonates
- an electrolyte having high electrical conductivity can be made and can be used more preferably.
- the metal salt may be a lithium salt, and the lithium salt is a material that is easily soluble in the non-aqueous electrolyte.
- the anion of the lithium salt is F - , Cl - , I - , NO 3 - , N (CN ) 2 - , BF 4 - , ClO 4 - , PF 6 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3 SO 2 ) 3
- the electrolyte may include, for example, haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and triglycerides for the purpose of improving battery life characteristics, suppressing battery capacity decrease, and improving battery discharge capacity.
- haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and triglycerides
- Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphoric acid triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N,N-substituted imida
- One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be further included.
- One embodiment of the present invention provides a battery module including the secondary battery as a unit cell and a battery pack including the same. Since the battery module and the battery pack include the secondary battery having high capacity, high rate and cycle characteristics, a medium or large-sized device selected from the group consisting of an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system can be used as a power source for
- Polyvinylidene fluoride (PvdF) was added at 0.5 wt% in dimethylformamide (DMF), and after 1 hour of sonication, overnight stirring was performed. After that, 2 wt% of Si was added to the solution and stirred for 3 hours, followed by stirring for an additional 1 hour while dropping ethanol. After centrifugation with ethanol three times, vacuum drying at 70 ° C. for 12 hours, heat treatment at 700 ° C. for 1 hour in an Ar atmosphere in a high-temperature furnace to obtain carbon-coated Si. At this time, the amount of carbon coated is 7% compared to Si, the coating thickness is 10 nm, and the amount of F is 0.2 wt% compared to Si.
- DMF dimethylformamide
- Si prepared above as an active material including a carbon coating layer containing F in 100% Si
- a plate-shaped graphite conductive material (average particle diameter of 3.5 ⁇ m)
- SWCNT as a second conductive material
- acrylamide as a binder
- a negative electrode active material layer was coated on a 15 ⁇ m thick Cu foil to a thickness of 30 ⁇ m, dried at 130 ° C. for 12 hours, and rolled to a porosity of 40% to prepare a negative electrode.
- Example 1 it was prepared in the same manner as in Example 1, except that 2 wt% of polyvinylidene fluoride (PvdF) was added in dimethylformamide (DMF). At this time, the amount of coated carbon was compared to Si 12%, the coating thickness is 13nm, and the amount of F is 0.4wt% compared to Si.
- PvdF polyvinylidene fluoride
- DMF dimethylformamide
- Example 1 it was prepared in the same manner as in Example 1, except that 0.25 wt% of polyvinylidene fluoride (PvdF) was added in dimethylformamide (DMF). At this time, the amount of coated carbon was Si Compared to 4%, the coating thickness is 5 nm, and the amount of F is 0.003 wt% compared to Si.
- PvdF polyvinylidene fluoride
- DMF dimethylformamide
- Example 1 the prepared Si was used as an active material (including a carbon coating layer containing F in 100% Si), SWCNT as a conductive material, and acrylamide as a binder in a weight ratio of 89.5:0.5:10 as a solvent.
- An anode was prepared in the same manner as in Example 1, except that distilled water was added to prepare a cathode slurry.
- Example 1 the Si prepared above was used as an active material (including a carbon coating layer containing F in 100% Si), and point-like carbon black (Super-P) and plate-shaped graphite conductive material (average A negative electrode was prepared in the same manner as in Example 1, except that a negative electrode slurry was prepared by adding distilled water as a solvent in a weight ratio of 79.5:5:5:0.5:10, SWCNT, and acrylamide as a binder.
- Example 1 an anode was manufactured in the same manner as in Example 1, except that a Si active material (Si 100%) not containing an F-doped carbon coating layer was used.
- Example 1 a negative electrode was prepared in the same manner as in Example 1, except that the SiO active material was used.
- Example 1 a negative electrode was prepared in the same manner as in Example 1, except that SiO containing 5 wt% of a carbon coating layer without F was used (SiO 100% including a carbon coating layer).
- Example 1 an anode was manufactured in the same manner as in Example 1, except that a Si active material (Si 100%) including a carbon coating layer not doped with F was used.
- LiNi 0.6 Co 0.2 Mn 0.2 O 2 (average particle diameter (D50): 15 ⁇ m) as a cathode active material, carbon black (product name: Super C65, manufacturer: Timcal) as a conductive material, and polyvinylidene fluoride (PVdF) as a binder.
- a positive electrode slurry was prepared by adding N-methyl-2-pyrrolidone (NMP) as a solvent for forming a positive electrode slurry at a weight ratio of 1.5:1.5 (solid content concentration: 78% by weight).
- NMP N-methyl-2-pyrrolidone
- both sides of an aluminum current collector were coated with the positive electrode slurry at a loading amount of 537 mg/25 cm 2 , rolled, and dried in a vacuum oven at 130° C. for 10 hours to obtain a positive electrode
- An active material layer was formed to prepare a positive electrode (anode thickness: 77 ⁇ m, porosity: 26%).
- a lithium secondary battery was manufactured by injecting an electrolyte with a polyethylene separator interposed between the positive electrode and the negative electrode of the Examples and Comparative Examples.
- the electrolyte is an organic solvent in which fluoroethylene carbonate (FEC) and diethyl carbonate (DMC) are mixed in a volume ratio of 30:70, vinylene carbonate is added in an amount of 3% by weight based on the total weight of the electrolyte, and LiPF as a lithium salt 6 was added at a concentration of 1M.
- FEC fluoroethylene carbonate
- DMC diethyl carbonate
- the first charge/discharge capacity and initial efficiency of the lithium secondary batteries prepared in Examples and Comparative Examples were evaluated using an electrochemical charger/discharger.
- Capacity retention rates of the lithium secondary batteries prepared in Examples and Comparative Examples were evaluated using an electrochemical charger/discharger.
- the number of cycles until the capacity reached 80% was confirmed under the conditions of charging (0.5C CC/CV charging, 0.005V, 0.005C cut) and discharging (0.5C CC discharging, 1.0V cut) of the coin half-cell battery.
- the N-th capacity retention rate was evaluated by the following formula. The results are shown in Table 2 below.
- Capacity retention rate (%) ⁇ (discharge capacity at Nth cycle) / (discharge capacity at first cycle) ⁇ x 100
- Comparative Example 1 of Tables 1 and 2 Pure Si is used as an active material but does not include an F-doped carbon coating layer, and Comparative Example 4 uses Pure Si as an active material but includes only a simple carbon coating layer . That is, Comparative Example 1 and Comparative Example 4 used the same type of active material, and the initial efficiency was in a similar range to that of Example, but it was confirmed that the capacity retention rate and discharge capacity in Table 2 were lower. This is a result of not mitigating the volume expansion of the active material and not forming a stable LiF film.
- Comparative Example 2 a carbon layer doped with F was used in SiO, and in Comparative Example 3, only a carbon coating layer was used in SiO. Although it can be raised, it was confirmed that the initial efficiency is lower than that of the examples, and the charge / discharge capacity is very low compared to the case of having pure Si as an active material.
- Comparative Example 2 and Comparative Example 3 using the SiO active material are 1:1 composites of Si and SiO 2 and show low initial efficiency by causing an irreversible reaction between oxide and Li, but after that, the reversible reaction has a capacity retention rate compared to the Si active material can be rated as good (see Table 2).
- Table 2 the theoretical capacity is much lower than that of Si, and when the SiO active material is used, conditions equivalent to the charging and discharging capacity of Example 1 of the present invention cannot be implemented. Accordingly, it was confirmed that the high-capacity lithium secondary battery intended in the present application could not be manufactured.
- the negative electrode composition according to an exemplary embodiment of the present invention in using a silicon-based active material, which is a high-capacity material, to manufacture a high-capacity lithium secondary battery, according to the volume expansion of the silicon-based active material Rather than adjusting the properties of the conductive material and the binder, the properties of the silicon-based active material itself are adjusted, the surface of the silicon-based active material includes a carbon coating layer, and the carbon coating layer is doped with fluorine (F), so that the silicon-based active material It was confirmed that while mitigating rapid volume expansion during charging and discharging of , fluorine was doped and reacted with FEC to form a more stable LiF film on the negative electrode along with the SEI layer.
- fluorine fluorine
- Examples 1 and 2 are cases where the amount of F doped is larger than that of Example 3, and as the fluorine content is included, the thickness of the coating layer is appropriate, and the capacity per weight is more excellent than Example 3. was able to confirm
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)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
충전(mAh/g) | 방전(mAh/g) | 초기효율(%) | |
실시예 1 | 3003 | 2762 | 92 |
실시예 2 | 2990 | 2751 | 92 |
실시예 3 | 3030 | 2727 | 90 |
실시예 4 | 3005 | 2674 | 89 |
실시예 5 | 2997 | 2727 | 91 |
비교예 1 | 3059 | 2753 | 90 |
비교예 2 | 1640 | 1230 | 75 |
비교예 3 | 1642 | 1199 | 73 |
비교예 4 | 2987 | 2629 | 88 |
CHC 용량유지율@SOH80% | 2C 방전시 용량(% 0.5C 방전용량) | |
실시예 1 | 25cycle | 90% |
실시예 2 | 24cycle | 90% |
실시예 3 | 20cycle | 83% |
실시예 4 | 20cycle | 87% |
실시예 5 | 24cycle | 85% |
비교예 1 | 19cycle | 82% |
비교예 2 | 28cycle | 90% |
비교예 3 | 27cycle | 88% |
비교예 4 | 23cycle | 85% |
Claims (12)
- 실리콘계 활물질; 음극 도전재; 및 음극 바인더;를 포함하는 음극 조성물로,상기 실리콘계 활물질의 표면은 탄소 코팅층을 포함하며,상기 탄소 코팅층은 불소(F)가 도핑된 것으로,상기 실리콘계 활물질은 SiOx (x=0) 및 SiOx (0<x<2)로 이루어진 군에서 선택되는 1 이상을 포함하며, 상기 실리콘계 활물질 100 중량부 기준 상기 SiOx (x=0)를 70 중량부 이상 포함하는 것인 음극 조성물.
- 청구항 1에 있어서, 상기 음극 도전재는 면형 도전재; 및 선형 도전재;를 포함하고,상기 음극 도전재 100 중량부 기준 상기 면형 도전재 80 중량부 이상 99.5 중량부 이하; 및 상기 선형 도전재 0.5 중량부 이상 20 중량부 이하를 포함하는 것인 음극 조성물.
- 청구항 1에 있어서,상기 음극 조성물 100 중량부 기준 상기 실리콘계 활물질 60 중량부 이상 포함하는 것인 음극 조성물.
- 청구항 1에 있어서,상기 음극 도전재는 상기 음극 조성물 100 중량부 기준 10 중량부 이상 40 중량부 이하인 것인 음극 조성물.
- 청구항 1에 있어서,상기 탄소 코팅층 내 도핑된 불소(F)는 탄소와 불소(F)의 단일결합으로 형성된 것인 음극 조성물.
- 청구항 1에 있어서,상기 실리콘계 활물질 100 중량부 기준 상기 불소(F) 0.1 중량부 이상 20 중량부 이하를 포함하는 것인 음극 조성물.
- 표면에 불소(F)가 도핑된 탄소 코팅층을 포함하는 실리콘계 활물질을 준비하는 단계;음극 도전재, 및 음극 바인더를 혼합하여 혼합물을 형성하는 단계;상기 혼합물에 물을 추가하여 제1 믹싱(mixing)하는 단계; 및상기 믹싱된 혼합물에 불소(F)가 도핑된 탄소 코팅층을 포함하는 실리콘계 활물질을 첨가하여 제2 믹싱(mixing)하는 단계;를 포함하는 음극 조성물의 제조 방법으로,상기 실리콘계 활물질은 SiOx (x=0) 및 SiOx (0<x<2)로 이루어진 군에서 선택되는 1 이상을 포함하며, 상기 실리콘계 활물질 100 중량부 기준 상기 SiOx (x=0)를 70 중량부 이상 포함하는 것인 음극 조성물의 제조 방법.
- 청구항 7에 있어서,상기 표면에 불소(F)가 도핑된 탄소 코팅층을 포함하는 실리콘계 활물질을 준비하는 단계는실리콘계 활물질을 불소(F)를 포함하는 고분자 용액에 첨가하는 단계;상기 고분자 용액에 에탄올을 첨가하여 실리콘계 활물질 표면에 불소(F)를 포함하는 고분자를 결합하는 단계; 및상기 결합된 고분자를 탄화하는 단계;를 포함하는 것인 음극 조성물의 제조 방법.
- 청구항 7에 있어서, 상기 제1 믹싱 및 제2 믹싱하는 단계는 2,000rpm 내지 3,000rpm으로 10분 내지 60 분간 믹싱하는 단계인 것인 음극 조성물의 제조 방법.
- 음극 집전체층; 및상기 음극 집전체층의 일면 또는 양면에 형성된 청구항 1 내지 청구항 6 중 어느 한 항에 따른 음극 조성물을 포함하는 음극 활물질층;을 포함하는 리튬 이차 전지용 음극.
- 청구항 10에 있어서,상기 음극 집전체층의 두께는 1μm 이상 100μm 이하이며,상기 음극 활물질층의 두께는 20μm 이상 500μm 이하인 것인 리튬 이차 전지용 음극.
- 양극;청구항 10에 따른 리튬 이차 전지용 음극;상기 양극과 상기 음극 사이에 구비된 분리막; 및전해질;을 포함하는 리튬 이차 전지.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202280044193.3A CN117546314A (zh) | 2021-11-11 | 2022-11-03 | 负极组合物、包含其的锂二次电池用负极、包含负极的锂二次电池以及制备负极组合物的方法 |
EP22893113.5A EP4345946A1 (en) | 2021-11-11 | 2022-11-03 | Anode composition, anode for lithium secondary battery comprising same, lithium secondary battery comprising anode, and method for preparing anode composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20210154386 | 2021-11-11 | ||
KR10-2021-0154386 | 2021-11-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023085691A1 true WO2023085691A1 (ko) | 2023-05-19 |
Family
ID=86335999
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2022/017126 WO2023085691A1 (ko) | 2021-11-11 | 2022-11-03 | 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP4345946A1 (ko) |
KR (1) | KR20230069008A (ko) |
CN (1) | CN117546314A (ko) |
WO (1) | WO2023085691A1 (ko) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009080971A (ja) | 2007-09-25 | 2009-04-16 | Tokyo Univ Of Science | リチウムイオン電池用負極 |
KR20170078203A (ko) * | 2015-12-29 | 2017-07-07 | 한국과학기술연구원 | 리튬 이차전지용 실리콘계 활물질 및 이의 제조방법 |
KR20180124769A (ko) * | 2017-05-12 | 2018-11-21 | 주식회사 엘지화학 | 음극 활물질, 상기 음극 활물질을 포함하는 음극, 및 상기 음극을 포함하는 이차 전지 |
JP2019021451A (ja) * | 2017-07-13 | 2019-02-07 | 株式会社豊田自動織機 | フッ素層被覆−炭素層被覆−負極活物質 |
KR20200089568A (ko) * | 2019-01-17 | 2020-07-27 | 주식회사 엘지화학 | 음극 및 이를 포함하는 리튬 이차 전지 |
KR20210097303A (ko) * | 2020-01-30 | 2021-08-09 | 주식회사 엘지에너지솔루션 | 음극 활물질, 이를 포함하는 음극 및 이차전지 |
KR20210154386A (ko) | 2020-06-12 | 2021-12-21 | 미리방재 주식회사 | 비화재보율 감소 p형 수신기 |
-
2022
- 2022-11-03 CN CN202280044193.3A patent/CN117546314A/zh active Pending
- 2022-11-03 EP EP22893113.5A patent/EP4345946A1/en active Pending
- 2022-11-03 WO PCT/KR2022/017126 patent/WO2023085691A1/ko active Application Filing
- 2022-11-03 KR KR1020220145211A patent/KR20230069008A/ko unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009080971A (ja) | 2007-09-25 | 2009-04-16 | Tokyo Univ Of Science | リチウムイオン電池用負極 |
KR20170078203A (ko) * | 2015-12-29 | 2017-07-07 | 한국과학기술연구원 | 리튬 이차전지용 실리콘계 활물질 및 이의 제조방법 |
KR20180124769A (ko) * | 2017-05-12 | 2018-11-21 | 주식회사 엘지화학 | 음극 활물질, 상기 음극 활물질을 포함하는 음극, 및 상기 음극을 포함하는 이차 전지 |
JP2019021451A (ja) * | 2017-07-13 | 2019-02-07 | 株式会社豊田自動織機 | フッ素層被覆−炭素層被覆−負極活物質 |
KR20200089568A (ko) * | 2019-01-17 | 2020-07-27 | 주식회사 엘지화학 | 음극 및 이를 포함하는 리튬 이차 전지 |
KR20210097303A (ko) * | 2020-01-30 | 2021-08-09 | 주식회사 엘지에너지솔루션 | 음극 활물질, 이를 포함하는 음극 및 이차전지 |
KR20210154386A (ko) | 2020-06-12 | 2021-12-21 | 미리방재 주식회사 | 비화재보율 감소 p형 수신기 |
Also Published As
Publication number | Publication date |
---|---|
CN117546314A (zh) | 2024-02-09 |
EP4345946A1 (en) | 2024-04-03 |
KR20230069008A (ko) | 2023-05-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2021154026A1 (ko) | 이차전지용 양극 활물질 전구체, 양극 활물질 및 이를 포함하는 리튬 이차전지 | |
WO2018221827A1 (ko) | 음극 활물질, 상기 음극 활물질을 포함하는 음극, 및 상기 음극을 포함하는 이차 전지 | |
WO2023282684A1 (ko) | 리튬 이차 전지용 음극, 리튬 이차 전지용 음극의 제조 방법 및 음극을 포함하는 리튬 이차 전지 | |
WO2023059015A1 (ko) | 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 | |
WO2023113464A1 (ko) | 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극 및 음극을 포함하는 리튬 이차 전지 | |
WO2020180160A1 (ko) | 리튬 이차전지 | |
WO2022182162A1 (ko) | 양극 활물질, 이를 포함하는 양극 및 이차 전지 | |
WO2020180125A1 (ko) | 리튬 이차전지 | |
WO2023085691A1 (ko) | 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 | |
WO2023121257A1 (ko) | 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 | |
WO2023055215A1 (ko) | 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 | |
WO2023059149A1 (ko) | 음극 선분산액, 이를 포함하는 음극 조성물, 음극 조성물을 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 | |
WO2023059151A1 (ko) | 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 | |
WO2023068880A1 (ko) | 음극 선분산액, 이를 포함하는 음극 조성물, 음극 조성물을 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 | |
WO2024054019A1 (ko) | 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극 및 음극을 포함하는 리튬 이차 전지 | |
WO2023068838A1 (ko) | 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 | |
WO2023055216A1 (ko) | 음극 선분산액, 이를 포함하는 음극 조성물, 음극 조성물을 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법 | |
WO2023167449A1 (ko) | 리튬 이차 전지의 제조 방법 및 리튬 이차 전지 | |
WO2024085708A1 (ko) | 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극 및 음극을 포함하는 리튬 이차 전지 | |
WO2023068601A1 (ko) | 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 리튬 이차 전지용 음극의 제조 방법 | |
WO2024014897A1 (ko) | 음극 활물질, 음극 활물질의 제조 방법, 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극 및 음극을 포함하는 리튬 이차 전지 | |
WO2024063554A1 (ko) | 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 | |
WO2023113462A1 (ko) | 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극 및 음극을 포함하는 리튬 이차 전지 | |
WO2023059016A1 (ko) | 리튬 이차 전지용 음극, 리튬 이차 전지용 음극의 제조 방법 및 음극을 포함하는 리튬 이차 전지 | |
WO2024049235A1 (ko) | 음극 활물질, 음극 활물질의 제조 방법, 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극 및 음극을 포함하는 리튬 이차 전지 |
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: 22893113 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2023578820 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280044193.3 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022893113 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2022893113 Country of ref document: EP Effective date: 20231229 |