KR102660453B1 - Anode free lithium secondary battery comprising porous carbon layer and method of preparing same - Google Patents
Anode free lithium secondary battery comprising porous carbon layer and method of preparing same Download PDFInfo
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- KR102660453B1 KR102660453B1 KR1020210159446A KR20210159446A KR102660453B1 KR 102660453 B1 KR102660453 B1 KR 102660453B1 KR 1020210159446 A KR1020210159446 A KR 1020210159446A KR 20210159446 A KR20210159446 A KR 20210159446A KR 102660453 B1 KR102660453 B1 KR 102660453B1
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- Prior art keywords
- secondary battery
- lithium
- lithium secondary
- positive electrode
- current collector
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 80
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 11
- 239000004917 carbon fiber Substances 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000003273 ketjen black Substances 0.000 claims description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910013553 LiNO Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- OIXUJRCCNNHWFI-UHFFFAOYSA-N 1,2-dioxane Chemical compound C1CCOOC1 OIXUJRCCNNHWFI-UHFFFAOYSA-N 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004962 Polyamide-imide Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- MYRUXGCOHIYOBX-UHFFFAOYSA-K [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O.FOC(=O)C(=O)OF Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O.FOC(=O)C(=O)OF MYRUXGCOHIYOBX-UHFFFAOYSA-K 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 3
- 229930188620 butyrolactone Natural products 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920002312 polyamide-imide Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 210000001787 dendrite Anatomy 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 229910003472 fullerene Inorganic materials 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 206010014415 Electrolyte depletion Diseases 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- GBSMZJHLDLLJAO-UHFFFAOYSA-N [Li].COCCOC Chemical compound [Li].COCCOC GBSMZJHLDLLJAO-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/36—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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- 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
Abstract
본 발명은 양극집전체; 상기 양극집전체 상에 형성되는 양극; 상기 양극 상에 형성되는 분리막; 상기 분리막 상에 형성되고, 카본소재를 포함하는 카본층; 및 상기 다공성 카본층 상에 형성되는 음극집전체;를 포함하는 무음극 리튬이차전지에 관한 것이다. 본 발명의 무음극 리튬이차전지 및 그의 제조방법은 음극집전체와 분리막 사이에 다공성 카본층을 포함으로써, 양극내 리튬이온이 음극집전체에 균일하게 증착되고, 리튬 덴드라이트 생성이 억제되어 사이클 특성이 우수한 효과가 있다.The present invention relates to a positive electrode current collector; A positive electrode formed on the positive electrode current collector; A separator formed on the anode; A carbon layer formed on the separator and containing a carbon material; and a negative electrode current collector formed on the porous carbon layer. It relates to a non-negative electrode lithium secondary battery including a. The non-negative electrode lithium secondary battery of the present invention and its manufacturing method include a porous carbon layer between the negative electrode current collector and the separator, so that lithium ions in the positive electrode are uniformly deposited on the negative electrode current collector and the formation of lithium dendrites is suppressed, thereby improving cycle characteristics. This has excellent effects.
Description
본 발명은 다공성 카본층을 포함하는 무음극 리튬이차전지 및 그의 제조방법 에 관한 것으로서, 보다 상세하게는 음극 집전체와 분리막 사이에 다공성 카본층을 포함함으로써, 리튬덴드라이트 생성이 억제되어 사이클 특성이 우수한 무음극 리튬이차전지 및 그의 제조방법에 관한 것이다.The present invention relates to a non-negative electrode lithium secondary battery including a porous carbon layer and a method of manufacturing the same. More specifically, by including a porous carbon layer between the negative electrode current collector and the separator, lithium dendrite formation is suppressed and cycle characteristics are improved. It relates to an excellent non-cathode lithium secondary battery and its manufacturing method.
최근, 리튬전지의 활용은 휴대폰, 노트북과 같은 소형 전자기기의 주요 전력원을 넘어서 전기 자동차 및 전력저장 장치로 그 영역이 확대되고 있다. 이와 같이 전기화학 에너지 저장체로써 리튬이차전지는 그 사용 범위가 다양해지고 있으며, 고에너지밀도 배터리에 대한 요구가 증가하고 있다. Recently, the use of lithium batteries has expanded beyond the main power source for small electronic devices such as mobile phones and laptops to electric vehicles and power storage devices. As such, the scope of use of lithium secondary batteries as electrochemical energy storage is becoming more diverse, and the demand for high energy density batteries is increasing.
리튬이차전지의 음극은 일반적으로 탄소, 탄소-Si 합금, 리튬금속 등을 활물질로 사용하는데 리튬 금속은 전위가 낮고 용량이 커서 높은 에너지밀도를 구현할 수 있다. 그러나, 리튬이차전지의 음극으로 리튬 금속을 사용하는 경우, 높은 반응성으로 인해 전해액과의 반응성을 나타내고, 음극집전체에 불균일한 리튬전착특성이 나타나거나, 리튬덴드라이트 성장에 의해 전지의 내부단락을 일으키는 문제가 있다. 또한 리튬금속을 음극으로 사용한 리튬이차전지는 조립상에 어려움도 지니고 있다. 따라서 리튬 음극 없이 집전체만 사용할 수 있다면, 리튬이차전지의 에너지밀도도를 향상시킬 수 있고, 전지의 조립도 간편하게 할 수 있어 이에 대한 연구가 활발하게 진행되고 있다. The negative electrode of a lithium secondary battery generally uses carbon, carbon-Si alloy, and lithium metal as active materials, and lithium metal has a low potential and large capacity, enabling high energy density. However, when lithium metal is used as the negative electrode of a lithium secondary battery, it shows reactivity with the electrolyte solution due to its high reactivity, and non-uniform lithium electrodeposition characteristics appear on the negative electrode current collector, or internal short circuit of the battery occurs due to lithium dendrite growth. There is a problem causing it. In addition, lithium secondary batteries using lithium metal as a negative electrode have difficulties in assembly. Therefore, if only a current collector can be used without a lithium negative electrode, the energy density of a lithium secondary battery can be improved and battery assembly can be simplified, so research on this is actively underway.
그러나 무음극 리튬이차전지는 충전시 양극내 포함된 리튬이 이동하여 음극집전체에 불균일한 증착으로 리튬 덴드라이트의 생성이 용이하고, 또한 충전시 리튬이 음극집전체에 증착함으로써 부피가 팽창되게 된다. 따라서 충방전을 반복함에 따른 셀의 부피팽창과 리튬금속의 덴드라이트 성장은 전해질 고갈, 낮은 쿨롱효율 및 안전성 등 리튬이차전지의 성능 및 수명특성에 문제점을 지니고 있다.However, when charging a non-cathode lithium secondary battery, the lithium contained in the anode moves and is unevenly deposited on the anode current collector, making it easy to create lithium dendrites. Additionally, during charging, lithium is deposited on the anode current collector, causing the volume to expand. . Therefore, volume expansion of the cell and dendrite growth of lithium metal due to repeated charging and discharging have problems with the performance and lifespan characteristics of lithium secondary batteries, such as electrolyte depletion, low coulombic efficiency, and safety.
본 발명의 목적은 음극집전체와 분리막 사이에 다공성 카본층을 포함함으로써, 양극내 리튬이 음극집전체에 균일하게 증착되고, 리튬 덴드라이트 생성이 억제되어 사이클 특성이 우수한 무음극 리튬이차전지 및 그의 제조방법을 제공하는 데 있다.The object of the present invention is to provide a non-cathode lithium secondary battery with excellent cycle characteristics by including a porous carbon layer between the anode current collector and the separator, so that lithium in the anode is uniformly deposited on the anode current collector, and lithium dendrite formation is suppressed, and the same. The goal is to provide a manufacturing method.
본 발명의 일 측면에 따르면, 양극집전체; 상기 양극집전체 상에 형성되는 양극; 상기 양극 상에 형성되는 분리막; 상기 분리막 상에 형성되고, 카본소재를 포함하는 카본층; 및 상기 카본층 상에 형성되는 음극집전체;를 포함하는 무음극 리튬이차전지가 제공된다.According to one aspect of the present invention, a positive electrode current collector; A positive electrode formed on the positive electrode current collector; A separator formed on the anode; A carbon layer formed on the separator and containing a carbon material; and a negative electrode current collector formed on the carbon layer. A non-negative electrode lithium secondary battery including a is provided.
상기 카본소재가 카본 펠트(carbon felt), 카본 종이 (carbon paper), 카본 천(carbon cloth), 카본 화이버 (carbon fiber), 할로우카본화이버 (hollow carbon fiber), 카본나노튜브, 그래핀, 그래핀옥사이드, 그래파이트, 카본블랙, 활성탄소, 플러렌, 케첸블랙(Ketjenblack) 및 아세틸렌 블랙(Acetylene black)으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The carbon material includes carbon felt, carbon paper, carbon cloth, carbon fiber, hollow carbon fiber, carbon nanotube, graphene, and graphene. It may include one or more selected from the group consisting of oxide, graphite, carbon black, activated carbon, fullerene, Ketjenblack, and acetylene black.
상기 카본층의 두께가 5 내지 250 μm일 수 있다.The thickness of the carbon layer may be 5 to 250 μm.
상기 양극이 양극활물질, 도전재 및 바인더를 포함할 수 있다.The positive electrode may include a positive electrode active material, a conductive material, and a binder.
상기 양극활물질이 화학식 1로 표시되는 리튬-니켈-코발트-망간계 산화물(NCM)을 포함할 수 있다.The positive electrode active material may include lithium-nickel-cobalt-manganese oxide (NCM) represented by Chemical Formula 1.
[화학식 1][Formula 1]
Li1+aNixCoyMnzO2 (0≤a≤0.2, 0<x<1, 0<y<1, 0<z<1, x+y+z=1)Li 1+a Ni x Co y Mn z O 2 (0≤a≤0.2, 0<x<1, 0<y<1, 0<z<1, x+y+z=1)
상기 도전재가 카본 블랙, 아세틸렌 블랙, 케첸 블랙, 탄소 섬유, 탄소 나노튜브, 및 그래핀으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The conductive material may include one or more selected from the group consisting of carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanotube, and graphene.
상기 바인더가 폴리비닐리덴플로라이드(polyvinylidenefloride; PVDF), 폴리테트라플루오르에틸렌(polytetrafluoroethylene; PTFE), 카르복시메틸셀룰로오스(carboxymethylcellulose; CMC), 폴리비닐알코올(poly vinyl alcohol; PVA), 폴리비닐부티랄(poly vinyl butyral; PVB), 폴리비닐피롤리돈(poly-Nvinylpyrrolidone; PVP), 스티렌부타디엔고무(styrene butadiene rubber; SBR), 폴리아마이드-이미드(Polyamide-imide), 에틸렌비닐아세테이트 (Ethylene Vinyl Acetate) 및 폴리이미드(polyimide)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The binder is polyvinylidenefloride (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (polyvinyl alcohol). vinyl butyral (PVB), poly-Nvinylpyrrolidone (PVP), styrene butadiene rubber (SBR), polyamide-imide, ethylene vinyl acetate and It may include one or more types selected from the group consisting of polyimide.
상기 분리막이 폴리올레핀, 폴리이미드, 폴리프로필렌, 폴리에틸렌 테레프탈레이트(PET; Polyethylene terephthalate) 및 부직포로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The separator may include one or more selected from the group consisting of polyolefin, polyimide, polypropylene, polyethylene terephthalate (PET), and nonwoven fabric.
상기 양극집전체 및 상기 음극집전체가 각각 알루미늄(Al), 인듐(In), 구리(Cu), 마그네슘(Mg), 스테인레스 스틸(SUS, stainless steel), 티타늄(Ti), 철(Fe), 코발트(Co), 니켈(Ni), 아연(Zn), 게르마늄(Ge), 리튬(Li) 또는 이들의 합금The positive electrode current collector and the negative electrode current collector are each made of aluminum (Al), indium (In), copper (Cu), magnesium (Mg), stainless steel (SUS), titanium (Ti), iron (Fe), Cobalt (Co), nickel (Ni), zinc (Zn), germanium (Ge), lithium (Li) or alloys thereof
상기 무음극 리튬이차전지가 전해질을 추가로 포함할 수 있다.The non-cathode lithium secondary battery may additionally include an electrolyte.
상기 전해질이 유기용매 및 리튬염을 포함할 수 있다.The electrolyte may include an organic solvent and a lithium salt.
상기 유기용매가 에틸렌 카보네이트(elthylene carbonate, EC), 에틸메틸 카보네이트(ethylmethyl carbonate), 디메틸 카보네이트(dimethyl carbonate, DMC), 디에틸 카보네이트(diethyl carbonate, DEC), 아세토니트릴(acetonitrile, AC), 프로필렌 카보네이트(propylene carbonate, PC), 폴리에틸렌글리콜(polyehthylen glycol), 부틸렌 카보네이트, 비닐렌 카보네이트(Vinylene carbonate, VC), 1,3-프로판설톤(1,3-propane sultone, PS), 플루오로에틸렌 카보네이트(fluoroelthylene carbonate, FEC), 테트라히드로푸란, 1,2-디옥산, 2-메틸테트라히드로푸란, 부티로락톤, 디메틸포름아미드, 디메톡시에탄 (DME) 및 석시노니트릴(Succinonitrile, SC)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The organic solvent is ethylene carbonate (EC), ethylmethyl carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), acetonitrile (AC), and propylene carbonate. (propylene carbonate, PC), polyethylene glycol, butylene carbonate, vinylene carbonate (VC), 1,3-propane sultone (PS), fluoroethylene carbonate ( A group consisting of fluoroelthylene carbonate (FEC), tetrahydrofuran, 1,2-dioxane, 2-methyltetrahydrofuran, butyrolactone, dimethylformamide, dimethoxyethane (DME) and succinonitrile (SC) It may include one or more types selected from.
상기 리튬염이 리튬나이트레이트(LiNO3), 리튬퍼클로레이트(LiClO4), 리튬비스플루오로설포닐이미드(Lithium bis(fluorosulfonyl)imide, LiFSI), 리튬트리플레이트(LiCF3SO3), 리튬헥사플루오로포스페이트(LiPF6), 리튬테트라플루오로보레이트(LiBF4), 리튬트리플루오로메탄설포닐이미드(LiN(CF3SO2)2), 리튬 다이플루오로 비스옥살레이토포스페이트(Lithium difluoro bis(oxalato)phosphate, LiDFBP) 및 리튬 디플루오로 옥살레이트 포스페이트(LiDFOP)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The lithium salt is lithium nitrate (LiNO 3 ), lithium perchlorate (LiClO 4 ), lithium bis(fluorosulfonyl)imide (LiFSI), lithium triflate (LiCF 3 SO 3 ), and lithium hexamethylene. Fluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonylimide (LiN(CF 3 SO 2 ) 2 ), lithium difluoro bisoxalatophosphate (Lithium difluoro bis) (oxalato)phosphate, LiDFBP) and lithium difluoro oxalate phosphate (LiDFOP).
본 발명의 다른 일 측면에 따르면, 양극집전체, 양극, 분리막, 카본소재를 포함하는 카본층 및 음극집전체를 순서대로 적층하여 무음극 리튬이차전지를 제조하는 단계를 포함하는 무음극 리튬이차전지의 제조방법이 제공된다.According to another aspect of the present invention, a non-negative electrode lithium secondary battery comprising the step of manufacturing a non-negative electrode lithium secondary battery by sequentially stacking a positive electrode current collector, a positive electrode, a separator, a carbon layer containing a carbon material, and a negative electrode current collector. A manufacturing method is provided.
상기 카본소재가 카본 펠트(carbon felt), 카본 종이 (carbon paper), 카본 천(carbon cloth), 카본 화이버 (carbon fiber), 할로우카본화이버 (hollow carbon fiber), 카본나노튜브, 그래핀, 그래핀옥사이드, 그래파이트, 카본블랙, 활성탄소, 플러렌, 케첸블랙(Ketjenblack) 및 아세틸렌 블랙(Acetylene black)으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The carbon material includes carbon felt, carbon paper, carbon cloth, carbon fiber, hollow carbon fiber, carbon nanotube, graphene, and graphene. It may include one or more selected from the group consisting of oxide, graphite, carbon black, activated carbon, fullerene, Ketjenblack, and acetylene black.
본 발명의 무음극 리튬이차전지 및 그의 제조방법은 음극집전체와 분리막 사이에 다공성 카본층을 포함으로써, 양극내 리튬이온이 음극집전체에 균일하게 증착되고, 리튬 덴드라이트 생성이 억제되어 사이클 특성이 우수한 효과가 있다. The non-negative electrode lithium secondary battery of the present invention and its manufacturing method include a porous carbon layer between the negative electrode current collector and the separator, so that lithium ions in the positive electrode are uniformly deposited on the negative electrode current collector and the formation of lithium dendrites is suppressed, thereby improving cycle characteristics. This has excellent effects.
도 1은 본 발명에 따른 무음극 리튬이차전지의 구성도이다.
도 2는 실시예 1 및 비교예 1에 따른 전지의 0.1C, 30℃ 조건에서의 충방전 곡선이다.
도 3은 실시예 1 및 비교예 1에 따른 전지의 0.5C, 30℃ 조건에서의 충방전 곡선이다.
도 4a 및 4b는 실시예 1 및 비교예 1에 따른 전지의 0.5C, 30℃ 조건에서의 수명특성 및 쿨롱효율 그래프이다.1 is a configuration diagram of a non-cathode lithium secondary battery according to the present invention.
Figure 2 is a charge/discharge curve of the battery according to Example 1 and Comparative Example 1 at 0.1C and 30°C.
Figure 3 is a charge/discharge curve of the battery according to Example 1 and Comparative Example 1 at 0.5C and 30°C.
Figures 4a and 4b are graphs of life characteristics and coulombic efficiency of the batteries according to Example 1 and Comparative Example 1 at 0.5C and 30°C.
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 예시하고 상세한 설명에 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.Since the present invention can be modified in various ways and can have various embodiments, specific embodiments will be illustrated and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all transformations, equivalents, and substitutes included in the spirit and technical scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.
또한, 이하에서 사용될 제1, 제2 등과 같이 서수를 포함하는 용어는 다양한 구성요소들을 설명하는데 사용될 수 있지만, 상기 구성요소들은 상기 용어들에 의해 한정되지는 않는다. 상기 용어들은 하나의 구성요소를 다른 구성요소로부터 구별하는 목적으로만 사용된다. 예를 들어, 본 발명의 권리 범위를 벗어나지 않으면서 제1 구성요소는 제2 구성요소로 명명될 수 있고, 유사하게 제2 구성요소도 제1 구성요소로 명명될 수 있다. Additionally, terms including ordinal numbers, such as first, second, etc., which will be used below, may be used to describe various components, but the components are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, a first component may be named a second component, and similarly, the second component may also be named a first component without departing from the scope of the present invention.
또한, 어떤 구성요소가 “다른 구성요소 상에,” "다른 구성요소 상에 형성되어," "다른 구성요소 상에 위치하여," 또는 " 다른 구성요소 상에 적층되어" 있다고 언급된 때에는, 그 다른 구성요소의 표면 상의 전면 또는 일면에 직접 부착되어 형성되어, 위치하여 있거나 또는 적층되어 있을 수도 있지만, 중간에 다른 구성요소가 더 존재할 수도 있다고 이해되어야 할 것이다.Additionally, when a component is referred to as being “on another component,” “formed on another component,” “located on another component,” or “stacked on another component,” It may be formed by being directly attached to the front or one side of the surface of another component, positioned, or stacked, but it should be understood that other components may further exist in the middle.
단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, terms such as “comprise” or “have” are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.
도 1은 본 발명에 따른 무음극 리튬이차전지의 구성도이다. 이하, 도 1을 참조하여 본 발명의 무음극 리튬이차전지 및 그의 제조방법에 대해 설명하도록 한다.1 is a configuration diagram of a non-cathode lithium secondary battery according to the present invention. Hereinafter, the non-cathode lithium secondary battery of the present invention and its manufacturing method will be described with reference to FIG. 1.
본 발명은 양극집전체; 상기 양극집전체 상에 형성되는 양극; 상기 양극 상에 형성되는 분리막; 상기 분리막 상에 형성되고, 카본소재를 포함하는 카본층; 상기 다공성 카본층 상에 형성되는 음극집전체;를 포함하는 무음극 리튬이차전지를 제공한다.The present invention relates to a positive electrode current collector; A positive electrode formed on the positive electrode current collector; A separator formed on the anode; A carbon layer formed on the separator and containing a carbon material; It provides a non-negative electrode lithium secondary battery including; a negative electrode current collector formed on the porous carbon layer.
상기 카본소재가 카본 펠트(carbon felt), 카본 종이 (carbon paper), 카본 천(carbon cloth), 카본 화이버 (carbon fiber), 할로우카본화이버 (hollow carbon fiber), 카본나노튜브, 그래핀, 그래핀옥사이드, 그래파이트, 카본블랙, 활성탄소, 플러렌, 케첸블랙(Ketjenblack) 및 아세틸렌 블랙(Acetylene black)으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있고, 바람직하게는 카본펠트를 포함할 수 있다.The carbon material includes carbon felt, carbon paper, carbon cloth, carbon fiber, hollow carbon fiber, carbon nanotube, graphene, and graphene. It may include one or more types selected from the group consisting of oxide, graphite, carbon black, activated carbon, fullerene, Ketjenblack, and acetylene black, and may preferably include carbon felt.
상기 카본층이 다공성 카본층일 수 있다.The carbon layer may be a porous carbon layer.
상기 카본층의 두께가 5 내지 250 μm일 수 있고, 바람직하게는 150 내지 220 μm일 수 있다.The thickness of the carbon layer may be 5 to 250 μm, preferably 150 to 220 μm.
상기 양극이 양극활물질, 도전재 및 바인더를 포함할 수 있다.The positive electrode may include a positive electrode active material, a conductive material, and a binder.
상기 양극활물질이 화학식 1로 표시되는 리튬-니켈-코발트-망간계 산화물(NCM)을 포함할 수 있다. The positive electrode active material may include lithium-nickel-cobalt-manganese oxide (NCM) represented by Chemical Formula 1.
[화학식 1][Formula 1]
Li1+aNixCoyMnzO2 (0≤a≤0.2, 0<x<1, 0<y<1, 0<z<1, x+y+z=1)Li 1+a Ni x Co y Mn z O 2 (0≤a≤0.2, 0<x<1, 0<y<1, 0<z<1, x+y+z=1)
상기 도전재가 카본 블랙, 아세틸렌 블랙, 케첸 블랙, 탄소 섬유, 탄소 나노튜브, 및 그래핀으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The conductive material may include one or more selected from the group consisting of carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanotube, and graphene.
상기 바인더가 폴리비닐리덴플로라이드(polyvinylidenefloride; PVDF), 폴리테트라플루오르에틸렌(polytetrafluoroethylene; PTFE), 카르복시메틸셀룰로오스(carboxymethylcellulose; CMC), 폴리비닐알코올(poly vinyl alcohol; PVA), 폴리비닐부티랄(poly vinyl butyral; PVB), 폴리비닐피롤리돈(poly-Nvinylpyrrolidone; PVP), 스티렌부타디엔고무(styrene butadiene rubber; SBR), 폴리아마이드-이미드(Polyamide-imide), 에틸렌비닐아세테이트 (Ethylene Vinyl Acetate) 및 폴리이미드(polyimide)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The binder is polyvinylidenefloride (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (polyvinyl alcohol). vinyl butyral (PVB), poly-Nvinylpyrrolidone (PVP), styrene butadiene rubber (SBR), polyamide-imide, ethylene vinyl acetate and It may include one or more types selected from the group consisting of polyimide.
상기 분리막이 폴리올레핀, 폴리이미드, 폴리프로필렌, 폴리에틸렌 테레프탈레이트(PET; Polyethylene terephthalate) 및 부직포로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. The separator may include one or more selected from the group consisting of polyolefin, polyimide, polypropylene, polyethylene terephthalate (PET), and nonwoven fabric.
상기 양극집전체 및 상기 음극집전체가 각각 알루미늄(Al), 인듐(In), 구리(Cu), 마그네슘(Mg), 스테인레스 스틸, 티타늄(Ti), 철(Fe), 코발트(Co), 니켈(Ni), 아연(Zn), 게르마늄(Ge), 리튬(Li) 또는 이들의 합금으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The positive electrode current collector and the negative electrode current collector are each made of aluminum (Al), indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), and nickel. It may include one or more selected from the group consisting of (Ni), zinc (Zn), germanium (Ge), lithium (Li), or alloys thereof.
상기 무음극 리튬이차전지가 전해질을 추가로 포함할 수 있다. The non-cathode lithium secondary battery may additionally include an electrolyte.
상기 전해질이 유기용매 및 리튬염을 포함할 수 있다. The electrolyte may include an organic solvent and a lithium salt.
상기 유기용매가 에틸렌 카보네이트(elthylene carbonate, EC), 에틸메틸 카보네이트(ethylmethyl carbonate), 디메틸 카보네이트(dimethyl carbonate, DMC), 디에틸 카보네이트(diethyl carbonate, DEC), 아세토니트릴(acetonitrile, AC), 프로필렌 카보네이트(propylene carbonate, PC), 폴리에틸렌글리콜(polyehthylen glycol), 부틸렌 카보네이트, 비닐렌 카보네이트(Vinylene carbonate, VC), 1,3-프로판설톤(1,3-propane sultone, PS), 플루오로에틸렌 카보네이트(fluoroelthylene carbonate, FEC), 테트라히드로푸란, 1,2-디옥산, 2-메틸테트라히드로푸란, 부티로락톤, 디메틸포름아미드, 디메톡에탄 (DME) 및 석시노니트릴(Succinonitrile, SC)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The organic solvent is ethylene carbonate (EC), ethylmethyl carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), acetonitrile (AC), and propylene carbonate. (propylene carbonate, PC), polyethylene glycol, butylene carbonate, vinylene carbonate (VC), 1,3-propane sultone (PS), fluoroethylene carbonate ( A group consisting of fluoroelthylene carbonate (FEC), tetrahydrofuran, 1,2-dioxane, 2-methyltetrahydrofuran, butyrolactone, dimethylformamide, dimethoxyethane (DME) and succinonitrile (SC) It may include one or more types selected from.
상기 리튬염이 리튬나이트레이트(LiNO3), 리튬퍼클로레이트(LiClO4), 리튬비스플루오로설포닐이미드(Lithium bis(fluorosulfonyl)imide, LiFSI), 리튬트리플레이트(LiCF3SO3), 리튬헥사플루오로포스페이트(LiPF6), 리튬테트라플루오로보레이트(LiBF4), 리튬트리플루오로메탄설포닐이미드(LiN(CF3SO2)2), 리튬 다이플루오로 비스옥살레이토포스페이트(Lithium difluoro bis(oxalato)phosphate, LiDFBP) 및 리튬 디플루오로 옥살레이트 포스페이트(LiDFOP)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The lithium salt is lithium nitrate (LiNO 3 ), lithium perchlorate (LiClO 4 ), lithium bis(fluorosulfonyl)imide (LiFSI), lithium triflate (LiCF 3 SO 3 ), and lithium hexamethylene. Fluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonylimide (LiN(CF 3 SO 2 ) 2 ), lithium difluoro bisoxalatophosphate (Lithium difluoro bis) (oxalato)phosphate, LiDFBP) and lithium difluoro oxalate phosphate (LiDFOP).
본 발명의 다른 일 측면에 따르면, 양극집전체, 양극, 분리막, 카본소재를 포함하는 카본층 및 음극집전체를 순서대로 적층하여 무음극 리튬이차전지를 제조하는 단계를 포함하는 무음극 리튬이차전지의 제조방법이 제공된다.According to another aspect of the present invention, a non-negative electrode lithium secondary battery comprising the step of manufacturing a non-negative electrode lithium secondary battery by sequentially stacking a positive electrode current collector, a positive electrode, a separator, a carbon layer containing a carbon material, and a negative electrode current collector. A manufacturing method is provided.
상기 카본소재가 카본 펠트(carbon felt), 카본 종이 (carbon paper), 카본 천(carbon cloth), 카본 화이버 (carbon fiber), 할로우카본화이버 (hollow carbon fiber), 카본나노튜브, 그래핀, 그래핀옥사이드, 그래파이트, 카본블랙, 활성탄소, 플러렌, 케첸블랙(Ketjenblack) 및 아세틸렌 블랙(Acetylene black)으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. The carbon material includes carbon felt, carbon paper, carbon cloth, carbon fiber, hollow carbon fiber, carbon nanotube, graphene, and graphene. It may include one or more selected from the group consisting of oxide, graphite, carbon black, activated carbon, fullerene, Ketjenblack, and acetylene black.
[실시예] [Example]
이하, 본 발명을 실시예를 들어 더욱 상세하게 설명하도록 한다. 그러나 이는 예시를 위한 것으로서 이에 의하여 본 발명의 범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. However, this is for illustrative purposes only and does not limit the scope of the present invention.
제조예 1: 양극의 제조Preparation Example 1: Preparation of anode
양극활물질, 도전재, 바인더의 중량비가 80:10:10이 되도록 혼합물을 제조하였다. 즉 양극활물질 NCM 100 중량부를 기준으로, 도전재 Super-P 12.5 중량부, PVDF 바인더 12.5 중량부를 혼합하여 혼합물을 제조하였다. 이때, 상기 PVDF 바인더 용액은 KUREHA CORPORATION 사의 불화 폴리비닐리덴 (Polyvinylidene fluoride, PvdF)과 1-메틸-2-피롤리디논 (1-Methyl-2-pyrrolidone, NMP)을 포함하고, 상기 PVDF 가 NMP에 3 wt% 녹아있는 바인더 용액을 사용하였다.A mixture was prepared so that the weight ratio of the positive electrode active material, conductive material, and binder was 80:10:10. That is, based on 100 parts by weight of the positive electrode active material NCM, 12.5 parts by weight of the conductive material Super-P and 12.5 parts by weight of the PVDF binder were mixed to prepare a mixture. At this time, the PVDF binder solution contains polyvinylidene fluoride (PvdF) and 1-Methyl-2-pyrrolidone (NMP) from KUREHA CORPORATION, and the PVDF is added to NMP. A 3 wt% dissolved binder solution was used.
구체적으로, 먼저 Super-p를 상기 중량비로 칭량한 후, 막자 사발을 이용하여 20분 동안 분쇄한 후 양극활물질 NCM과 혼합하여 혼합 분말을 제조하였다. 상기 혼합 분말은 고속 혼합기(Thinky mixer) 전용 용기에 옮겨 담은 후 지르코니아 볼을 넣은 후 고속혼합기로 혼합하였다. 여기에 3wt% PVDF 바인더 용액과 NMP 용액을 추가로 넣어 1,800rpm으로 5분 동안 1회 혼합하여 슬러리 용액을 제조하였다. 다음으로, 상기 혼합물에 1-메틸-2-피롤리디논 (1-Methyl-2-pyrrolidone, NMP)를 혼합하여 적절한 점도로 조절하고, 5mm 지르콘 볼을 넣은 후 1,500rpm으로 5분씩 3회 동안 혼합하여 슬러리를 제조하였다. 상기 슬러리를 알루미늄 포일 상에 캐스팅 하고, 110℃ 조건에서 건조한 후, 압연하여 양극을 제조하였다.Specifically, Super-p was first weighed at the above weight ratio, then ground for 20 minutes using a mortar and pestle, and then mixed with the positive electrode active material NCM to prepare a mixed powder. The mixed powder was transferred to a container dedicated to a high-speed mixer, a zirconia ball was added, and then mixed with a high-speed mixer. A slurry solution was prepared by adding 3 wt% PVDF binder solution and NMP solution and mixing once for 5 minutes at 1,800 rpm. Next, 1-Methyl-2-pyrrolidone (NMP) was mixed with the mixture to adjust the viscosity to an appropriate level, and a 5mm zircon ball was added and mixed three times at 1,500 rpm for 5 minutes each. A slurry was prepared. The slurry was cast on aluminum foil, dried at 110°C, and rolled to produce a positive electrode.
실시예 1: 무음극 리튬이차전지의 제조Example 1: Production of non-cathode lithium secondary battery
알루미늄 포일(양극 집전체), 제조예 1에 따라 제조된 양극, 셀가드 2400 PP 분리막, 카본펠트를 포함하는 다공성 카본층 및 구리 포일(음극 집전체)를 사용하여 무음극 리튬이차전지를 제조하였다. 이때 상기 다공성 카본층은 카본펠트(두께 200um)를 사용하였다. A non-cathode lithium secondary battery was manufactured using aluminum foil (positive electrode current collector), the positive electrode prepared according to Preparation Example 1, Celgard 2400 PP separator, a porous carbon layer containing carbon felt, and copper foil (negative electrode current collector). . At this time, carbon felt (thickness 200um) was used as the porous carbon layer.
구체적으로 제조예 1에 따라 제조된 양극과 PP 분리막을 각각 Ø14, Ø19 사이즈로 펀칭하였다. 상기 양극집전체/양극/PP 분리막/다공성 카본층/음극 집전체를 순서대로 적층하여, 2032 규격의 코인셀로 리튬이차전지를 제조하였다. 그리고 2M LIFSI 리튬염에 디메톡시에탄/ 플루오로에틸렌 카보네이트 (DME/FEC, 8/2) + 5% 리튬나이트레이트(LiNO3) + 1% 리튬 다이플루오로 비스옥살레이토포스페이트(Lithium difluoro bis(oxalato)phosphate, LiDFBP)가 혼합된 용매가 녹아있는 전해액을 주입하여 사용하였다. Specifically, the positive electrode and PP separator manufactured according to Preparation Example 1 were punched into sizes of Ø14 and Ø19, respectively. The positive electrode current collector/positive electrode/PP separator/porous carbon layer/negative electrode current collector were stacked in that order to manufacture a lithium secondary battery using a 2032 standard coin cell. And 2M LIFSI lithium salt dimethoxyethane/fluoroethylene carbonate (DME/FEC, 8/2) + 5% lithium nitrate (LiNO 3 ) + 1% lithium difluoro bis(oxalato) )phosphate, LiDFBP) was used by injecting an electrolyte solution containing a mixed solvent.
비교예 1: 리튬이차전지의 제조Comparative Example 1: Manufacturing of lithium secondary battery
실시예 1에서 카본펠트를 포함하는 다공성 카본층을 사용하는 대신에 카본펠트를 포함하는 다공성 카본층을 사용하지 않는 것을 제외하고는 소자실시예 1과 동일한 방법으로 코인형 반쪽 전지를 제조하였다. A coin-type half cell was manufactured in the same manner as Device Example 1, except that the porous carbon layer containing carbon felt was not used instead of the porous carbon layer containing carbon felt in Example 1.
[시험예] [Test example]
시험예 1: 리튬이차전지의 특성 분석Test Example 1: Characteristic analysis of lithium secondary battery
도 2는 실시예 1 및 비교예 1에 따른 전지의 0.1C, 30℃ 조건에서의 충방전 곡선이고, 도 3은 실시예 1 및 비교예 1에 따른 전지의 0.5C, 30℃ 조건에서의 충방전 곡선이다. 또한 도 4a 및 4b는 실시예 1 및 비교예 1에 따른 전지의 0.5C, 30℃ 조건에서의 수명특성 및 쿨롱효율 그래프이다.Figure 2 is a charge/discharge curve of the battery according to Example 1 and Comparative Example 1 at 0.1C and 30°C, and Figure 3 is a charge/discharge curve of the battery according to Example 1 and Comparative Example 1 at 0.5C and 30°C. This is the discharge curve. Additionally, Figures 4a and 4b are graphs of life characteristics and coulombic efficiency of the batteries according to Example 1 and Comparative Example 1 at 0.5C and 30°C.
도 2를 참조하면, 실시예 1과 비교예1에 의해 제조된 전지의 0.1C 전류에서 충방전 특성을 나타내었다. 0.1C 전류밀도에서 초기 충방전 특성은 분리막과 음극집전체 사이에 다공성 카본층의 유무와 관계없이 설계되었던 용량이 구현됨을 확인할 수 있었다.Referring to Figure 2, the charge/discharge characteristics of the batteries manufactured in Example 1 and Comparative Example 1 were shown at a current of 0.1C. It was confirmed that the initial charge and discharge characteristics at a current density of 0.1C were implemented at the designed capacity regardless of the presence or absence of a porous carbon layer between the separator and the negative electrode current collector.
또한 도 3을 참조하면, 실시예 1과 비교예 1에 의해 제조된 전지의 0.5C 전류에서 충방전 특성을 나타내었다. 0.1C 전류밀도에서 초기 충방전 특성은 분리막과 음극집전체 사이에 다공성 카본층의 유무와 관계없이 설계되었던 용량이 구현됨을 확인할 수 있었다.Also, referring to Figure 3, the charge/discharge characteristics of the batteries manufactured in Example 1 and Comparative Example 1 were shown at a current of 0.5C. It was confirmed that the initial charge and discharge characteristics at a current density of 0.1C were implemented at the designed capacity regardless of the presence or absence of a porous carbon layer between the separator and the negative electrode current collector.
또한 도 4a 및 4b를 참조하면, 실시예 1과 비교예 1에 의해 제조된 전지의 0.5C 전류에서 충전과 방전을 반복적으로 수행한 수명특성에 대한 그래프를 나타내었다. 비교예1의 경우 충방전이 수회 반복됨에 따라 전지의 성능이 급격히 저하되는 것을 확인하였고, 반면 실시예 1의 경우 100사이클 이후에도 전지의 용량이 유지됨을 확인할 수 있었다.Also, referring to FIGS. 4A and 4B, a graph is shown for the lifespan characteristics of the batteries manufactured in Example 1 and Comparative Example 1 after repeated charging and discharging at a current of 0.5C. In Comparative Example 1, it was confirmed that the battery performance deteriorated rapidly as charging and discharging were repeated several times, whereas in Example 1, it was confirmed that the battery capacity was maintained even after 100 cycles.
따라서 본 발명에 따른 무음극 리튬이차전지는 음극집전체와 분리막 사이에 다공성 카본층을 포함함으로써, 양극내 리튬이온이 음극집전체에 균일하게 증착되고, 다공성 카본층에 리튬이온이 삽입되어 충방전에 따른 셀의 부피변화가 적고, 리튬 덴드라이트 생성이 억제되어 높은 셀 용량에서도 사이클 특성이 우수한 것을 알 수 있다.Therefore, the non-negative electrode lithium secondary battery according to the present invention includes a porous carbon layer between the negative electrode current collector and the separator, so that lithium ions in the positive electrode are uniformly deposited on the negative electrode current collector, and lithium ions are inserted into the porous carbon layer to enable charging and discharging. It can be seen that the volume change of the cell is small and the formation of lithium dendrite is suppressed, so the cycle characteristics are excellent even at high cell capacity.
이상, 본 발명의 바람직한 실시예들에 대하여 설명하였으나, 해당 기술 분야에서 통상의 지식을 가진 자라면 특허청구범위에 기재된 본 발명의 사상으로부터 벗어나지 않는 범위 내에서, 구성 요소의 부가, 변경, 삭제 또는 추가 등에 의해 본 발명을 다양하게 수정 및 변경시킬 수 있을 것이며, 이 또한 본 발명의 권리범위 내에 포함된다고 할 것이다. 예를 들어, 단일형으로 설명되어 있는 각 구성 요소는 분산되어 실시될 수도 있으며, 마찬가지로 분산된 것으로 설명되어 있는 구성 요소들도 결합된 형태로 실시될 수 있다. 본 발명의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.Although the preferred embodiments of the present invention have been described above, those skilled in the art will be able to add, change, delete or modify components without departing from the spirit of the present invention as set forth in the patent claims. The present invention may be modified and changed in various ways by addition, etc., and this will also be included within the scope of rights of the present invention. For example, each component described as single may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form. The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present invention. do.
Claims (15)
상기 양극집전체 상에 형성되는 양극;
상기 양극 상에 형성되는 분리막;
상기 분리막 상에 형성되고, 다공성이고, 카본소재를 포함하는 다공성 카본층; 및
상기 다공성 카본층 상에 형성되는 음극집전체;를 포함하고,
상기 카본소재가 카본 펠트(carbon felt)를 포함하는 것인, 무음극 리튬이차전지.positive electrode current collector;
A positive electrode formed on the positive electrode current collector;
A separator formed on the anode;
A porous carbon layer formed on the separator, is porous, and includes a carbon material; and
It includes a negative electrode current collector formed on the porous carbon layer,
A non-cathode lithium secondary battery in which the carbon material includes carbon felt.
상기 다공성 카본층의 두께가 5 내지 250 μm인 것을 특징으로 하는 무음극 리튬이차전지.According to paragraph 1,
A non-cathode lithium secondary battery, characterized in that the thickness of the porous carbon layer is 5 to 250 μm.
상기 양극이 양극활물질, 도전재 및 바인더를 포함하는 것을 특징으로 하는 무음극 리튬이차전지.According to paragraph 1,
A non-cathode lithium secondary battery, characterized in that the positive electrode includes a positive electrode active material, a conductive material, and a binder.
상기 양극활물질이 화학식 1로 표시되는 리튬-니켈-코발트-망간계 산화물(NCM)을 포함하는 것을 특징으로 하는 무음극 리튬이차전지.
[화학식 1]
Li1+aNixCoyMnzO2 (0≤a≤0.2, 0<x<1, 0<y<1, 0<z<1, x+y+z=1)According to clause 4,
A non-cathode lithium secondary battery, characterized in that the positive electrode active material includes lithium-nickel-cobalt-manganese oxide (NCM) represented by Chemical Formula 1.
[Formula 1]
Li 1+a Ni x Co y Mn z O 2 (0≤a≤0.2, 0<x<1, 0<y<1, 0<z<1, x+y+z=1)
상기 도전재가 카본 블랙, 아세틸렌 블랙, 케첸 블랙, 탄소 섬유, 탄소 나노튜브, 및 그래핀으로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것을 특징으로 하는 무음극 리튬이차전지. According to clause 4,
A non-cathode lithium secondary battery, wherein the conductive material includes at least one selected from the group consisting of carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanotube, and graphene.
상기 바인더가 폴리비닐리덴플로라이드(polyvinylidenefloride; PVDF), 폴리테트라플루오르에틸렌(polytetrafluoroethylene; PTFE), 카르복시메틸셀룰로오스(carboxymethylcellulose; CMC), 폴리비닐알코올(poly vinyl alcohol; PVA), 폴리비닐부티랄(poly vinyl butyral; PVB), 폴리비닐피롤리돈(poly-Nvinylpyrrolidone; PVP), 스티렌부타디엔고무(styrene butadiene rubber; SBR), 폴리아마이드-이미드(Polyamide-imide), 에틸렌비닐아세테이트 (Ethylene Vinyl Acetate) 및 폴리이미드(polyimide)로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것을 특징으로 하는 무음극 리튬이차전지.According to clause 4,
The binder is polyvinylidenefloride (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (polyvinyl alcohol). vinyl butyral (PVB), poly-Nvinylpyrrolidone (PVP), styrene butadiene rubber (SBR), polyamide-imide, ethylene vinyl acetate and A non-cathode lithium secondary battery comprising at least one selected from the group consisting of polyimide.
상기 분리막이 폴리올레핀, 폴리이미드, 폴리프로필렌, 폴리에틸렌 테레프탈레이트(PET; Polyethylene terephthalate) 및 부직포로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것을 특징으로 하는 무음극 리튬이차전지.According to paragraph 1,
A non-cathode lithium secondary battery, wherein the separator includes at least one selected from the group consisting of polyolefin, polyimide, polypropylene, polyethylene terephthalate (PET), and nonwoven fabric.
상기 양극집전체 및 상기 음극집전체가 각각 알루미늄(Al), 인듐(In), 구리(Cu), 마그네슘(Mg), 스테인레스 스틸, 티타늄(Ti), 철(Fe), 코발트(Co), 니켈(Ni), 아연(Zn), 게르마늄(Ge), 리튬(Li) 또는 이들의 합금으로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것을 특징으로 하는 무음극 리튬이차전지.According to paragraph 1,
The positive electrode current collector and the negative electrode current collector are each made of aluminum (Al), indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), and nickel. A non-cathode lithium secondary battery comprising at least one selected from the group consisting of (Ni), zinc (Zn), germanium (Ge), lithium (Li), or alloys thereof.
상기 무음극 리튬이차전지가 전해질을 추가로 포함하는 것을 특징으로 하는 무음극 리튬이차전지.According to paragraph 1,
A non-cathode lithium secondary battery, characterized in that the non-cathode lithium secondary battery further includes an electrolyte.
상기 전해질이 유기용매 및 리튬염을 포함하는 것을 특징으로 하는 무음극 리튬이차전지.According to clause 10,
A non-cathode lithium secondary battery, characterized in that the electrolyte contains an organic solvent and a lithium salt.
상기 유기용매가 에틸렌 카보네이트(elthylene carbonate, EC), 에틸메틸 카보네이트(ethylmethyl carbonate), 디메틸 카보네이트(dimethyl carbonate, DMC), 디에틸 카보네이트(diethyl carbonate, DEC), 아세토니트릴(acetonitrile, AC), 프로필렌 카보네이트(propylene carbonate, PC), 폴리에틸렌글리콜(polyehthylen glycol), 부틸렌 카보네이트, 비닐렌 카보네이트(Vinylene carbonate, VC), 1,3-프로판설톤(1,3-propane sultone, PS), 플루오로에틸렌 카보네이트(fluoroelthylene carbonate, FEC), 테트라히드로푸란, 1,2-디옥산, 2-메틸테트라히드로푸란, 부티로락톤, 디메틸포름아미드, 디메톡시에탄 (DME) 및 석시노니트릴(Succinonitrile, SC)로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것을 특징으로 하는 무음극 리튬이차전지.According to clause 11,
The organic solvent is ethylene carbonate (EC), ethylmethyl carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), acetonitrile (AC), and propylene carbonate. (propylene carbonate, PC), polyethylene glycol, butylene carbonate, vinylene carbonate (VC), 1,3-propane sultone (PS), fluoroethylene carbonate ( A group consisting of fluoroelthylene carbonate (FEC), tetrahydrofuran, 1,2-dioxane, 2-methyltetrahydrofuran, butyrolactone, dimethylformamide, dimethoxyethane (DME), and succinonitrile (SC) A non-cathode lithium secondary battery comprising one or more types selected from.
상기 리튬염이 리튬나이트레이트(LiNO3), 리튬퍼클로레이트(LiClO4), 리튬비스플루오로설포닐이미드(Lithium bis(fluorosulfonyl)imide, LiFSI), 리튬트리플레이트(LiCF3SO3), 리튬헥사플루오로포스페이트(LiPF6), 리튬테트라플루오로보레이트(LiBF4), 리튬트리플루오로메탄설포닐이미드(LiN(CF3SO2)2), 리튬 다이플루오로 비스옥살레이토포스페이트(Lithium difluoro bis(oxalato)phosphate, LiDFBP) 및 리튬 디플루오로 옥살레이트 포스페이트(LiDFOP)로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것을 특징으로 하는 무음극 리튬이차전지.According to clause 11,
The lithium salt is lithium nitrate (LiNO 3 ), lithium perchlorate (LiClO 4 ), lithium bis(fluorosulfonyl)imide (LiFSI), lithium triflate (LiCF 3 SO 3 ), and lithium hexamethylene. Fluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonylimide (LiN(CF 3 SO 2 ) 2 ), lithium difluoro bisoxalatophosphate (Lithium difluoro bis) A non-cathode lithium secondary battery comprising at least one selected from the group consisting of (oxalato)phosphate, LiDFBP) and lithium difluoro oxalate phosphate (LiDFOP).
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