WO2022191645A1 - 전극 및 이의 제조방법 - Google Patents
전극 및 이의 제조방법 Download PDFInfo
- Publication number
- WO2022191645A1 WO2022191645A1 PCT/KR2022/003385 KR2022003385W WO2022191645A1 WO 2022191645 A1 WO2022191645 A1 WO 2022191645A1 KR 2022003385 W KR2022003385 W KR 2022003385W WO 2022191645 A1 WO2022191645 A1 WO 2022191645A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rubber
- based binder
- active material
- electrode
- slurry
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 204
- 229920001971 elastomer Polymers 0.000 claims abstract description 187
- 239000005060 rubber Substances 0.000 claims abstract description 187
- 239000011149 active material Substances 0.000 claims abstract description 108
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 64
- 239000002033 PVDF binder Substances 0.000 claims abstract description 58
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 54
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000007772 electrode material Substances 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims description 122
- 238000001035 drying Methods 0.000 claims description 47
- -1 lithium iron phosphate compound Chemical class 0.000 claims description 46
- 239000002612 dispersion medium Substances 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 229920000131 polyvinylidene Polymers 0.000 claims description 9
- 229920001166 Poly(vinylidene fluoride-co-trifluoroethylene) Polymers 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 27
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 23
- 239000004020 conductor Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 239000006229 carbon black Substances 0.000 description 15
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 150000001993 dienes Chemical class 0.000 description 8
- 150000002825 nitriles Chemical class 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
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- 239000004745 nonwoven fabric Substances 0.000 description 2
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- FPFVPEGEWVRCGK-UHFFFAOYSA-N 1-ethenoxy-2-fluoroethane Chemical compound FCCOC=C FPFVPEGEWVRCGK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
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- 229910000733 Li alloy Inorganic materials 0.000 description 1
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- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910006555 Li—Co—Ni Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 239000006231 channel black Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 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
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
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- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
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- 239000006233 lamp black Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 239000002905 metal composite material Substances 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
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- 239000004332 silver Substances 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
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- H—ELECTRICITY
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Definitions
- the present invention relates to an electrode having enhanced flexibility and a method for manufacturing the same.
- a lithium secondary battery has a structure in which an electrolyte containing lithium salt is impregnated in a negative electrode assembly with a porous separator interposed between a positive electrode and a negative electrode, each of which is coated with an active material on an anode current collector.
- the negative electrode is prepared by applying a slurry in which an active material, a binder, and a conductive material are dispersed in a solvent to a current collector, drying and pressing.
- a secondary battery is composed of a positive electrode, a negative electrode, an electrolyte, and a separator. Electrodes such as a positive electrode and a negative electrode are manufactured by forming an electrode active material layer including an electrode active material on at least one surface of a current collector. At this time, in order to secure the performance of the electrode active material, there has been an attempt to apply an active material having a small particle size, for example, a particle size of several hundred nanometers to several micrometers during the manufacture of the active material.
- a battery to be applied to such a wearable device requires flexibility that does not deform even in repeated bending, and in particular, an electrode applied to such a battery requires excellent flexibility.
- a soft material as a binder constituting the electrode active material layer, but the solid content of the slurry for forming the electrode active material layer is lowered, so that the coating productivity is lowered or a large amount is added unnecessarily to reduce the electrode thickness.
- There were limitations such as decreasing the energy density by increasing it.
- An object of the present invention is to solve the above problems, and to provide an electrode with improved flexibility and improved adhesion between a current collector and an electrode active material layer, and a method for manufacturing the same.
- Another object of the present invention is to provide a lithium secondary battery including the electrode.
- the present invention is to solve the above problems, and according to one aspect of the present invention, there is provided a method of manufacturing a negative electrode of the following embodiment.
- the electrode active material layer consists of a lower layer region that interfaces with the current collector and an upper layer region that extends to the surface of the electrode active material layer while interfacing with the lower layer region,
- the lower layer region includes a first active material and a first non-rubber-based binder, but does not include a rubber-based binder,
- the upper layer region includes a second active material, a second non-rubber-based binder, and a rubber-based binder,
- the rubber-based binder is hydrogenated nitrile rubber (H-NBR, Hydrogenated Nitrile Butadiene Rubber),
- the first non-rubber-based binder and the second non-rubber-based binder include a polyvinylidene fluoride (PVDF)-based polymer,
- the weight ratio of the second non-rubber-based binder and the rubber-based binder is 1:0.03 to 1:0.07.
- a weight ratio of the lower layer region and the upper layer region may be 1:1 to 1:5.
- the electrode is an anode
- the first active material and the second active material may include a lithium iron phosphate compound (LFP).
- LFP lithium iron phosphate compound
- An average particle diameter (D50) of the lithium iron phosphate compound (LFP) may be 0.8 ⁇ m to 2.5 ⁇ m.
- the polyvinylidene fluoride (PVDF)-based polymer is poly(vinylidene fluoride) (poly(vinylidene fluoride)), poly(vinylidene fluoride-hexafluoropropylene) (poly(vinylidene fluoride-co-hexafluoropropylene)) , poly(vinylidene fluoride-chlorotrifluoroethylene) (poly(vinylidene fluoride-co-chlorotrifluoroethylene)), poly(vinylidene fluoride-tetrafluoroethylene) (poly(vinylidene fluoride-co-tetrafluoroethylene)), poly(vinylidene fluoride-co-trichloroethylene)), poly(vinylidene fluoride-trifluoroethylene) (poly(vinylidene fluoride-co-trifluoroethylene)), or any of these It may include two or more.
- a weight ratio of the second non-rubber-based binder and the rubber-based binder may be 1:0.04 to 1:0.06.
- a slurry for a lower layer comprising a first active material, a first non-rubber-based binder, and a first dispersion medium, but not including a rubber-based binder; and a second active material, a second non-rubber-based binder, a rubber-based binder, and a second dispersion medium preparing a slurry for the upper layer;
- the rubber-based binder is hydrogenated nitrile butadiene rubber (H-NBR), the first non-rubber-based binder and the second non-rubber-based binder include a polyvinylidene fluoride (PVDF)-based polymer, and the upper layer slurry
- H-NBR hydrogenated nitrile butadiene rubber
- PVDF polyvinylidene fluoride
- forming a lower active material layer by coating the lower layer slurry including the first active material, the first non-rubber-based binder, and the first dispersion medium, but not including the rubber binder, on at least one surface of the electrode current collector and drying;
- an upper active material layer by coating and drying an upper layer slurry comprising a second active material, a second non-rubber-based binder, a rubber-based binder, and a second dispersion medium on the upper surface of the lower active material layer;
- the rubber-based binder is hydrogenated nitrile butadiene rubber (H-NBR), the first non-rubber-based binder and the second non-rubber-based binder include a polyvinylidene fluoride (PVDF)-based polymer, and the upper layer slurry
- H-NBR hydrogenated nitrile butadiene rubber
- PVDF polyvinylidene fluoride
- the electrode is an anode
- the first active material and the second active material may include a lithium iron phosphate compound (LFP).
- LFP lithium iron phosphate compound
- An average particle diameter (D50) of the lithium iron phosphate compound (LFP) may be 0.8 ⁇ m to 2.5 ⁇ m.
- a lithium secondary battery comprising the electrode of one embodiment of the first to sixth embodiments as at least one of a positive electrode and a negative electrode.
- the flexibility of the electrode is strengthened by using a hydrogenated nitrile rubber having excellent impregnation property to an electrolyte solution, which causes swelling and flexible properties, as a binder for the electrode active material layer, and at the same time, hydrogenated nitrile rubber.
- a hydrogenated nitrile rubber having excellent impregnation property to an electrolyte solution, which causes swelling and flexible properties as a binder for the electrode active material layer, and at the same time, hydrogenated nitrile rubber.
- the electrode is configured as a double layer, but the hydrogenated nitrile rubber is added as an additional binder only to the upper layer region of the double layer to reduce the amount of hydrogenated nitrile rubber used, thereby maintaining the adhesive force between the electrode layer and the current collector
- the flexibility of the electrode can be improved.
- the electrode active material layer consists of a lower layer region that interfaces with the current collector and an upper layer region that extends to the surface of the electrode active material layer while interfacing with the lower layer region,
- the lower layer region includes a first active material and a first non-rubber-based binder, but does not include a rubber-based binder,
- the upper layer region includes a second active material, a second non-rubber-based binder, and a rubber-based binder,
- the rubber-based binder is hydrogenated nitrile rubber (H-NBR, Hydrogenated Nitrile Butadiene Rubber),
- the first non-rubber-based binder and the second non-rubber-based binder include a polyvinylidene fluoride (PVDF)-based polymer,
- the weight ratio of the second non-rubber-based binder and the rubber-based binder is 1:0.03 to 1:0.07.
- the electrode may be an anode or a cathode.
- the first active material and the second active material include LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiCoPO 4 , LiFePO 4 and LiNi 1-xyz Co x M1 y M2 z O 2
- M1 and M2 is any one independently selected from the group consisting of Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo, and x, y and z are each independently of the oxide composition elements.
- any one active material particle selected from the group consisting of 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.5, 0 ⁇ x+y+z ⁇ 1) or a mixture of two or more thereof may include
- the electrode may be a positive electrode, and the first active material and the second active material may include a lithium iron phosphate compound (LFP).
- LFP lithium iron phosphate compound
- the average particle diameter (D50) of the lithium iron phosphate compound (LFP) may be 0.8 to 2.5, or 0.8 to 1.2, or 1.8 to 2.5, or.
- the average particle diameter D50 is the particle diameter at 50% of the cumulative distribution of the number of particles according to the particle diameter.
- the D50 may be measured using a laser diffraction method. Specifically, after dispersing the powder to be measured in the dispersion medium, it is introduced into a commercially available laser diffraction particle size measuring device (eg Microtrac S3500) to measure the diffraction pattern difference according to the particle size when the particles pass through the laser beam to measure the particle size distribution to calculate The average particle diameter D50 can be measured by calculating the particle diameter at the point used as 50% of the particle number cumulative distribution according to the particle diameter in a measuring apparatus.
- a laser diffraction particle size measuring device eg Microtrac S3500
- the electrode is a negative electrode
- the first active material and the second active material are each independently a carbon-based material or a silicon-based material (eg, silicon oxide of SiOx (0 ⁇ x ⁇ 2)) ), Si, Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1-x Me' y O z (Me: Mn, Fe, Pb, Ge; Me': Al, B, P, Si, elements of Groups 1, 2, and 3 of the periodic table, halogen; 0 ⁇ x ⁇ 1;1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8) metal composite oxide ; lithium metal; lithium alloy; silicon-based alloys; tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3
- Si silicon oxide of SiOx
- the carbon-based material is at least one selected from the group consisting of crystalline natural graphite, artificial graphite, amorphous hard carbon, low crystalline soft carbon, carbon black, acetylene black, Ketjen black, super P, graphene, and fibrous carbon.
- the average particle diameter and shape of the first active material included in the lower layer region and the second active material included in the upper layer region are different from each other in the electrode of the present invention, these different kinds of active materials are added to the portion where the lower layer region and the upper layer region contact each other.
- the first active material in the lower region of the active material layer and the second active material in the upper region of the active material layer may have the same or different physical properties such as average particle diameter and tap density.
- the weight ratio of the first active material in the lower region of the active material layer to the second active material in the upper region of the active material layer may be 1:1 to 1:5, or 1:2 to 1:3.
- H-NBR hydrogenated nitrile rubber
- a ratio of the thickness of the upper layer region and the lower layer region may be 1:1 to 5:1, or 2:1 to 3:1.
- the total thickness of the electrode active material layer is not particularly limited. For example, it may be 40 to 200 ⁇ m.
- the thickness of the lower layer region may be 20 to 98 ⁇ m, or 7 to 35 ⁇ m, and the thickness of the upper layer region may be 102 to 180 ⁇ m, or 33 to 165 ⁇ m.
- H-NBR hydrogenated nitrile rubber
- a weight ratio (or a loading amount per unit area) of the lower layer region and the upper layer region may be 1:1 to 1:5, or 1:2 to 1:3.
- H-NBR hydrogenated nitrile rubber
- a weight ratio of the second non-rubber-based binder and the rubber-based binder is 1:0.03 to 1:0.07. According to one embodiment of the present invention, the weight ratio of the second non-rubber-based binder and the rubber-based binder in the upper layer region may be 1:0.04 to 1:0.06.
- the weight ratio of the second non-rubber-based binder and the rubber-based binder in the upper layer region is less than 1:0.03, that is, when the content ratio of the rubber-based binder is further reduced, there is a problem in that the electrode flexibility improvement effect does not appear at all,
- the weight ratio of the second non-rubber-based binder and the rubber-based binder is greater than 1:0.07, that is, when the content ratio of the rubber-based binder is further increased, uniform application of the slurry on the current collector is impossible due to the high viscosity of the slurry, so that the electrode manufacturing itself There is an impossible problem.
- the weight ratio of the non-rubber-based and rubber-based binders in the finally manufactured electrode can be measured through spectroscopic analysis. For example, it is possible through the comparison of the intensity (intensity) at which each binder is detected by measuring the electrode with IR.
- the rubber binder is hydrogenated nitrile rubber (H-NBR, Hydrogenated Nitrile Butadiene Rubber).
- the hydrogenated nitrile rubber includes a repeating unit having a structure derived from ⁇ , ⁇ -unsaturated nitrile and a repeating unit having a structure derived from a hydrogenated conjugated diene.
- the hydrogenated nitrile rubber may be specifically prepared by copolymerizing ⁇ , ⁇ -unsaturated nitrile, conjugated diene and optionally other copolymerizable comonomers, and then hydrogenating C ⁇ C double bonds in the copolymer.
- the polymerization reaction process and the hydrogenation process may be performed according to a conventional method.
- the ⁇ , ⁇ -unsaturated nitrile may include acrylonitrile or methacrylonitrile, and any one of them or a mixture of two or more thereof may be used.
- the conjugated diene may include a conjugated diene having 4 to 6 carbon atoms, such as 1,3-butadiene, isoprene, and 2,3-methylbutadiene, and any one or a mixture of two or more thereof may be used.
- a conjugated diene having 4 to 6 carbon atoms such as 1,3-butadiene, isoprene, and 2,3-methylbutadiene, and any one or a mixture of two or more thereof may be used.
- Examples of other copolymerizable comonomers that can be optionally used include aromatic vinyl monomers (eg, styrene, ⁇ -methylstyrene, vinylpyridine, fluoroethyl vinyl ether, etc.), ⁇ , ⁇ -unsaturated carboxylic acids (eg, For example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, etc.), esters or amides of ⁇ , ⁇ -unsaturated carboxylic acids (eg, methyl (meth)acrylate, ethyl (meth)acrylate, n- dodecyl (meth)acrylate, methoxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, or polyethylene glycol (meth)acrylate, etc.), anhydrides of ⁇ , ⁇ -unsaturated dicarboxylic acids (e.g. For example, maleic anhydride, itaconic anhydride, citraconic anhydride, etc.
- a repeating unit of an ⁇ , ⁇ -unsaturated nitrile-derived structure, a repeating unit of a conjugated diene-derived structure, a repeating unit of a hydrogenated conjugated diene-derived structure, and optionally other copolymerizable units may vary within a wide range, and in each case, the sum of the repeating units of the structure becomes 100% by weight.
- the content of the repeating unit of the ⁇ , ⁇ -unsaturated nitrile-derived structure may be 20 wt% to 50 wt%, more specifically 20 wt% to 30 wt%, based on the total weight of the hydrogenated nitrile rubber.
- the content of the repeating unit of the structure derived from ⁇ , ⁇ -unsaturated nitrile in the hydrogenated nitrile rubber is the weight ratio of the repeating unit of the structure derived from the ⁇ , ⁇ -unsaturated nitrile to the entire rubber, and the measurement of the content is JIS It is the median value of the value quantified by measuring the amount of nitrogen generated according to the mill-oven method of K6364 and converting its binding amount from the molecular weight of acrylonitrile.
- the hydrogenated nitrile rubber contains the repeating unit of the hydrogenated conjugated diene-derived structure in an amount of 20 wt% to 70 wt%, more specifically 20 wt% to 50 wt%, even more specifically 30 wt%, based on the total weight of the hydrogenated nitrile rubber. % to 50% by weight may be included.
- the hydrogenated nitrile rubber may have a weight average molecular weight of 10,000 g/mol to 700,000 g/mol, more specifically, 10,000 g/mol to 200,000 g/mol.
- the hydrogenated nitrile rubber may have a polydispersity index PDI (Ratio of Mw/Mn, Mw is a weight average molecular weight and Mn is a number average molecular weight) in the range of 2.0 to 6.0, specifically 2.0 to 4.0. .
- the weight average molecular weight and the number average molecular weight are polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).
- the weight% of the first non-rubber-based polymer in the lower layer region may be the same as or greater than the total weight% of the second non-rubber-based polymer and the rubber binder in the upper layer region.
- the weight % of the first binder polymer in the lower layer region may be 1 to 3 times, or 1.5 to 2 times, than the total weight % of the second non-rubber-based polymer and the rubber binder in the upper layer region.
- the adhesive force between the active material layer and the current collector may be improved.
- the ratio (wt%) of the first non-rubber binder in the lower layer of the electrode active material layer is 2 to 4 wt%, or 2.5 to 3.5 wt%, and the second non-rubber-based binder in the upper layer of the anode active material layer
- the weight% of the total of the binder and the rubber binder may be 0.5 to 2% by weight, or 1.2 to 1.8% by weight.
- the total weight% of the first non-rubber-based binder, the second non-rubber-based binder, and the rubber-based binder in the entire electrode active material layer may be 1 to 4% by weight, or 2.5 to 3.5% by weight.
- the current collector for an electrode used as a substrate for forming the active material layer is not particularly limited as long as it has conductivity without causing a chemical change in the battery, for example, copper, stainless steel, Aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, silver, etc., an aluminum-cadmium alloy, etc. may be used.
- the thickness of the current collector is not particularly limited, but may have a commonly applied thickness of 3 to 500 ⁇ m.
- the first non-rubber-based binder and the second non-rubber-based binder include a polyvinylidene fluoride (PVDF)-based polymer.
- PVDF polyvinylidene fluoride
- the polyvinylidene fluoride (PVDF)-based polymer is poly(vinylidene fluoride) (poly(vinylidene fluoride)), poly(vinylidene fluoride-hexafluoropropylene) (poly(vinylidene fluoride-co-hexafluoropropylene)) , poly(vinylidene fluoride-chlorotrifluoroethylene) (poly(vinylidene fluoride-co-chlorotrifluoroethylene)), poly(vinylidene fluoride-tetrafluoroethylene) (poly(vinylidene fluoride-co-tetrafluoroethylene)), poly(vinylidene fluoride-co-trichloroethylene)), poly(vinylidene fluoride-trifluoroethylene) (poly(vinylidene fluoride-co-trifluoroethylene)), or any of these It may include two or more.
- the first non-rubber-based binder and the second non-rubber-based binder included in the upper layer region and the lower layer region may each independently include one or more of the aforementioned polyvinylidene fluoride (PVDF)-based polymer.
- PVDF polyvinylidene fluoride
- first non-rubber-based binder and the second non-rubber-based binder are each independently, in addition to a polyvinylidene fluoride (PVDF)-based polymer, polyacrylonitrile, polymethylmethacrylate, polyvinyl Alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, and the like may further include a polymer.
- PVDF polyvinylidene fluoride
- first non-rubber-based binder and the second non-rubber-based binder may increase the viscosity of the slurry for the active material layer and serve as a thickener to improve the dispersion characteristics of the active material.
- carboxymethyl cellulose (CMC) carboxyethyl cellulose, polyvinylpyrrolidone, and the like may serve as a thickener.
- At least one of the lower layer area and the upper layer area may further include a conductive material.
- the conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery.
- a slurry for a lower layer comprising a first active material, a first non-rubber-based binder, and a first dispersion medium, but not including a rubber-based binder; and a second active material, a second non-rubber-based binder, a rubber-based binder, and a second dispersion medium preparing a slurry for the upper layer;
- the rubber-based binder is hydrogenated nitrile butadiene rubber (H-NBR), the first non-rubber-based binder and the second non-rubber-based binder include a polyvinylidene fluoride (PVDF)-based polymer, and the upper layer slurry
- H-NBR hydrogenated nitrile butadiene rubber
- PVDF polyvinylidene fluoride
- the weight ratio of the second non-rubber-based binder and the rubber-based binder is provided in the range of 1:0.03 to 1:0.07.
- the first active material, the second active material, the first non-rubber binder, the second non-rubber binder, and the rubber binder included in the slurry for the lower layer and the slurry for the upper layer are as described above.
- the first dispersion medium and the second dispersion medium as the dispersion medium may each independently use N-methylpyrrolidone, acetone, water, or the like.
- the lower region of the active material layer of the negative electrode of the present invention is formed from the coated lower layer slurry, and the upper region of the active material layer of the negative electrode of the present invention is formed from the upper layer slurry.
- the thickness of the lower layer region and the upper layer region of the active material layer of the negative electrode of the present invention may not completely match the thickness of the coated slurry for the lower layer and the coated slurry for the upper layer.
- the ratio of the thickness of the lower layer region and the upper layer region of the active material layer of the negative electrode of the negative electrode of the present invention finally obtained is the thickness of the coated lower layer slurry and the coated upper layer slurry. It can match the ratio.
- the method of coating the slurry for the lower layer and coating the slurry for the upper layer on the slurry for the lower layer at the same time or with a predetermined time difference is performed by using an apparatus such as a double slot die. Available.
- the step of simultaneously drying the coated slurry for the lower layer and the slurry for the upper layer to form the active material layer is carried out in a manner that uses a drying apparatus using an oven composed of several zones, and controls the temperature and air volume.
- the coated first slurry and the second slurry are simultaneously dried using a drying device including a hot air blower and an infrared (IR) heater to form an active material layer.
- a drying device including a hot air blower and an infrared (IR) heater to form an active material layer.
- the drying apparatus includes a drying chamber configured to pass through a current collector and an electrode sheet including an electrode active material slurry applied to the current collector; a stage positioned on the lower surface of the electrode sheet to move the electrode sheet up, down, left and right inside the drying chamber; a hot air blower for supplying hot air to the electrode sheet to apply convection heat to the electrode sheet; and an infrared (IR) dryer that applies radiant heat to the electrode sheet.
- a drying chamber configured to pass through a current collector and an electrode sheet including an electrode active material slurry applied to the current collector
- a stage positioned on the lower surface of the electrode sheet to move the electrode sheet up, down, left and right inside the drying chamber
- a hot air blower for supplying hot air to the electrode sheet to apply convection heat to the electrode sheet
- an infrared (IR) dryer that applies radiant heat to the electrode sheet.
- the step of forming the active material layer may further include rolling the active material layer after the drying step.
- the rolling may be performed by a method commonly used in the art, such as roll pressing, for example, may be performed at a pressure of 1 to 20 MPa and a temperature of 15 to 30 °C.
- forming a lower active material layer by coating the lower layer slurry including the first active material, the first non-rubber-based binder, and the first dispersion medium, but not including the rubber-based binder, on at least one surface of the electrode current collector and drying;
- an upper active material layer by coating and drying an upper layer slurry comprising a second active material, a second non-rubber-based binder, a rubber-based binder, and a second dispersion medium on the upper surface of the lower active material layer;
- the rubber-based binder is hydrogenated nitrile butadiene rubber (H-NBR), the first non-rubber-based binder and the second non-rubber-based binder include a polyvinylidene fluoride (PVDF)-based polymer, and the upper layer slurry
- H-NBR hydrogenated nitrile butadiene rubber
- PVDF polyvinylidene fluoride
- the weight ratio of the second non-rubber-based binder and the rubber-based binder may be 1:0.03 to 1:0.07.
- the lower active material layer is formed by coating and drying the slurry for the lower layer, and then the lower layer It proceeds by coating and drying the slurry for the upper layer on the active material layer. Thereafter, a rolling process may be performed.
- the coating, drying and rolling process may be applied to the contents described in the above-described method.
- the thickness ratio of the coated slurry for the lower layer and the coated slurry for the upper layer may be 1:1 to 1:5, or 1:2 to 1:3.
- the thickness of the coated slurry for the lower layer and the coated slurry for the upper layer may be controlled through a double slot die.
- the thickness of the coated lower layer slurry may be 20 to 98 ⁇ m, or 7 to 35 ⁇ m, and the coated upper layer slurry may have a thickness of 102 to 180 ⁇ m, or 33 to 165 ⁇ m.
- H-NBR hydrogenated nitrile rubber
- the weight ratio of the solid content of the coated slurry for the lower layer and the solid content of the coated slurry for the upper layer may be 1:1 to 1:5, or 1:2 to 1:3.
- the weight % of the first binder polymer in the solid content of the slurry for the lower layer may be the same as or more than the weight % of the second binder polymer in the solid content of the slurry for the upper layer.
- the weight % of the first binder polymer in the solid content of the slurry for the lower layer is 1 to 3 times, or 1.5 to 2.5 times greater than the weight % of the second binder polymer in the solid content of the slurry for the upper layer.
- H-NBR hydrogenated nitrile rubber
- the weight% of the first binder polymer is 2 to 4 wt%, or 1.5 to 3.5 wt%
- the weight% of the second binder polymer is 0.5 to 2 wt%, or 1.2 to 1.8% by weight.
- the total ratio (wt%) of the first binder polymer and the second binder polymer in the total solids of the slurry for the lower layer and the slurry for the upper layer may be 1 to 4 wt%, or 2.5 to 3.5 wt%.
- a lithium secondary battery comprising the above-described electrode as at least one of a positive electrode and a negative electrode.
- the positive electrode or the negative electrode, which is the other electrode is manufactured by including an electrode material such as a conventional active material and a binder.
- the lithium secondary battery may be manufactured by injecting a lithium salt-containing electrolyte into a negative electrode assembly including a positive electrode, a negative electrode, and a separator interposed therebetween.
- the separator is a conventional porous polymer film used as a conventional separator, for example, polyolefin-based films such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer.
- a porous polymer film made of a polymer may be used alone or by laminating them.
- an insulating thin film having high ion permeability and mechanical strength may be used.
- the separator may include a safety reinforced separator (SRS) in which a ceramic material is thinly coated on a surface of the separator.
- a conventional porous nonwoven fabric may be used, for example, a nonwoven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, or the like, but is not limited thereto.
- the electrolyte includes a lithium salt as an electrolyte and an organic solvent for dissolving the same.
- the lithium salt may be used without limitation as long as it is commonly used in electrolytes for secondary batteries.
- the organic solvent included in the electrolyte may be used without limitation as long as it is commonly used, and representatively, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, dipropyl carbonate, dimethyl sulfoxide At least one selected from the group consisting of side, acetonitrile, dimethoxyethane, diethoxyethane, vinylene carbonate, sulfolane, gamma-butyrolactone, propylene sulfite and tetrahydrofuran may be used.
- ethylene carbonate and propylene carbonate which are cyclic carbonates
- a low-viscosity, low-dielectric constant linear carbonate such as carbonate is mixed in an appropriate ratio, an electrolyte having a high electrical conductivity can be prepared, which can be more preferably used.
- the electrolyte stored according to the present invention may further include additives such as an overcharge inhibitor included in a conventional electrolyte.
- a separator is disposed between a positive electrode and a negative electrode to form a negative electrode assembly, and the negative electrode assembly is placed in, for example, a pouch, a cylindrical battery case or a prismatic battery case, and then the electrolyte When injected, the secondary battery can be completed.
- a lithium secondary battery may be completed by stacking the negative electrode assembly, impregnating it with an electrolyte, and sealing the resultant result in a battery case.
- the lithium secondary battery may be a stack type, a winding type, a stack and fold type, or a cable type.
- the lithium secondary battery according to the present invention can be used not only in a battery cell used as a power source for a small device, but can also be preferably used as a unit cell in a medium or large battery module including a plurality of battery cells.
- Preferred examples of the medium and large-sized devices include electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, and power storage systems. In particular, it is useful for hybrid electric vehicles and new and renewable energy storage batteries, which are areas requiring high output. can be used
- Lithium iron phosphate oxide (average particle diameter D50: 2 ⁇ m) having a composition of LiFePO 4 as a first active material, carbon black as a conductive material, and polyvinylidene fluoride (PVdF) as a first non-rubber binder 94: It was added to and dispersed in N-methylpyrrolidone (NMP) as the first dispersion medium in a weight ratio of 3:3 to prepare a lower layer slurry.
- NMP N-methylpyrrolidone
- the slurry for the lower layer was coated on one surface of an aluminum (Al) thin film serving as a positive electrode current collector having a thickness of 10 ⁇ m, and at the same time, the slurry for the upper layer was coated on the slurry for the lower layer.
- the loading amount of the slurry for the lower layer and the slurry for the upper layer was 300 mg/cm 2 and 300 mg/cm 2 , respectively.
- the coated first slurry and the second slurry were simultaneously dried using a drying device including a hot air blower and an IR heater to form an active material layer.
- the drying room of the drying apparatus had 10 drying zones from the first drying zone to the tenth drying zone, where the slurry-coated current collector first entered, and at this time, 8 hot air fans only from the first drying zone to the third drying zone.
- IR heaters were respectively disposed between the and the hot air blowers, so that a total of 8 IR heaters were provided.
- the hot air flow of the hot air machine is controlled only in such a way that it proceeds from the top to the bottom of the dryer, and in the seventh drying zone to the tenth drying zone, the hot air flow proceeds from the top to the bottom of the dryer.
- the hot air blower and the hot air fan that flowed from the bottom to the top were alternately arranged and operated.
- a stage was positioned on the lower surface of the slurry-coated current collector (electrode sheet) in the drying apparatus to move the slurry-coated current collector, and the running speed of the slurry-coated current collector was 50 m/min.
- the speed of the air supply fan forming the supply air flow from the outside of the drying chamber was 1000 rpm
- the speed of the exhaust fan forming the exhaust flow from the inside of the drying chamber was 1000 rpm.
- the temperature of the hot air blower was 140°C in the first drying zone, 130°C in the second drying zone, 120°C in the third to eighth drying zones, 90°C in the ninth drying zone, and 50°C in the tenth drying zone.
- the IR heaters installed in the first to third drying zones emit near-infrared rays with a wavelength of 0.7 ⁇ m, and the irradiation length of the IR heater is 30 cm per heater (the length of the lamp irradiated with near-infrared rays from the IR heater is 30 cm), Twenty-four IR heaters (8 per drying zone, 24 in 3 zones) were evenly spaced throughout the three drying zones. At this time, only three IR heaters were used while maintaining a uniform spacing among all 24 IR heaters. That is, the IR heater was operated with an efficiency of 12.5% based on the efficiency when all the IR heaters were used.
- a positive electrode having an upper/lower double-layered active material layer having a loading amount of 16 mg/cm 2 in weight per unit area after drying is manufactured did.
- the thickness of the lower layer region was 55 ⁇ m
- the thickness of the upper layer region was 55 ⁇ m
- the weight ratio of the lower layer region and the upper layer region was 1:1.
- the weight ratio of the second non-rubber-based binder and the rubber-based binder in the upper layer region was 1:0.03.
- the slurry was coated on one surface of a copper (Cu) thin film having a thickness of 10 ⁇ m, which is a negative electrode current collector, and dried and rolled under the same conditions as the positive electrode to prepare a negative electrode.
- the loading amount based on the dry weight of the anode active material layer was 11 mg/cm 2 , and the thickness was 80 ⁇ m.
- LiPF 6 was dissolved to a concentration of 1.0M to obtain a non-aqueous electrolyte solution.
- EC ethylene carbonate
- PC propylene carbonate
- DEC diethyl carbonate
- the electrolyte was injected to prepare a lithium secondary battery.
- a slurry for the upper layer was prepared by adding hydrogenated nitrile rubber (H-NBR, Hydrogenated Nitrile Butadiene Rubber) as a rubber binder to N-methylpyrrolidone (NMP), a second dispersion medium, in a weight ratio of 94:3:3:0.15.
- a positive electrode was prepared in the same manner as in Example 1, except that. At this time, the weight ratio of the second non-rubber-based binder and the rubber-based binder in the upper layer region of the positive electrode was 1:0.05.
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that the positive electrode thus prepared was used.
- H-NBR Hydrogenated Nitrile Butadiene Rubber
- NMP N-methylpyrrolidone
- a positive electrode was manufactured in the same manner as in Example 1, except that. At this time, the weight ratio of the second non-rubber-based binder and the rubber-based binder in the upper layer region of the positive electrode was 1:0.07.
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that the positive electrode thus prepared was used.
- a positive electrode was prepared in the same manner as in Example 1, except that a slurry for an upper layer was prepared by adding it to N-methylpyrrolidone (NMP) as the second dispersion medium in a weight ratio of 94:3:3. In this case, the weight ratio of the second non-rubber-based binder and the rubber-based binder in the upper layer region of the positive electrode was 1:0.
- NMP N-methylpyrrolidone
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that the positive electrode thus prepared was used.
- a slurry for the upper layer was prepared by adding hydrogenated nitrile rubber (H-NBR, Hydrogenated Nitrile Butadiene Rubber) as a rubber binder to N-methylpyrrolidone (NMP), a second dispersion medium, in a weight ratio of 94:3:3:0.03.
- a positive electrode was prepared in the same manner as in Example 1, except that. In this case, the weight ratio of the second non-rubber-based binder and the rubber-based binder in the upper layer region of the positive electrode was 1:0.01.
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that the positive electrode thus prepared was used.
- a slurry for the upper layer was prepared by adding hydrogenated nitrile rubber (H-NBR, Hydrogenated Nitrile Butadiene Rubber) as a rubber binder to N-methylpyrrolidone (NMP), a second dispersion medium, in a weight ratio of 94:3:3:0.3.
- H-NBR Hydrogenated Nitrile Butadiene Rubber
- NMP N-methylpyrrolidone
- a positive electrode was prepared in the same manner as in Example 1, except that it was difficult to uniformly apply the slurry on the current collector due to the high viscosity of the slurry, so that the positive electrode could not be manufactured.
- the weight ratio of the second non-rubber-based binder and the rubber-based binder in the slurry for the upper layer of the positive electrode was 1:0.1.
- Lithium iron phosphate oxide (average particle diameter D50: 2 ⁇ m) having a composition of LiFePO 4 as the first active material, carbon black as a conductive material, polyvinylidene fluoride (PVdF) as the first non-rubber binder, and a rubber binder Hydrogenated nitrile rubber (H-NBR, Hydrogenated Nitrile Butadiene Rubber) was added to N-methylpyrrolidone (NMP) as a first dispersion medium in a weight ratio of 94:3:3:0.15 and dispersed to prepare a slurry for the lower layer. That is, the weight ratio of the first non-rubber-based binder and the rubber-based binder in the lower layer slurry was 1:0.05.
- NMP N-methylpyrrolidone
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that the slurry for the lower layer and the slurry for the upper layer were used to prepare the positive electrode.
- Lithium iron phosphate oxide (average particle diameter D50: 2 ⁇ m) having a composition of LiFePO 4 as the first active material, carbon black as a conductive material, polyvinylidene fluoride (PVdF) as the first non-rubber binder, and a rubber binder Hydrogenated nitrile rubber (H-NBR, Hydrogenated Nitrile Butadiene Rubber) was added to N-methylpyrrolidone (NMP) as a first dispersion medium in a weight ratio of 94:3:3:0.15 and dispersed to prepare a slurry for the lower layer. That is, the weight ratio of the first non-rubber-based binder and the rubber-based binder in the lower layer slurry was 1:0.05.
- NMP N-methylpyrrolidone
- NMP N-methylpyrrolidone
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that the slurry for the lower layer and the slurry for the upper layer were used to prepare the positive electrode.
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that the positive electrode thus prepared was used.
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that the positive electrode thus prepared was used.
- the current collector After fixing the active material layer of the sample cut and prepared above to the slide glass so that it is in contact, the current collector is peeled off at a speed of 100 mm/min using a UTM (TA company) device, and the peeling force is measured from the slide glass. is shown in Table 2 below. At this time, the measurement angle between the slide glass and the electrode was 90°.
- a rubber-based binder is included so that the weight ratio of the second non-rubber-based binder and the rubber-based binder in the upper layer region satisfies 1:0.03 to 1:0.07, but the rubber-based binder is in the lower layer region. It can be seen that the electrode adhesion strength of Example 2, which does not contain , is significantly improved. In particular, according to Comparative Examples 4 and 5 containing the rubber-based binder in the lower layer region, it was confirmed that there was a problem in that the electrode adhesion strength was weakened.
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Abstract
Description
양극의 벤딩 시험결과 활물질층에 크랙이 발생하는 막대기의 지름 (단위: mm) |
|
실시예 1 | 5 |
실시예 2 | 4 |
실시예 3 | 3 |
실시예 4 | 3 |
실시예 5 | 2 |
비교예 1 | 6 |
비교예 2 | 6 |
비교예 3 | 양극제작불가 |
전극 접착력 (gf/20 mm) | |
실시예 2 | 50 |
비교예 4 | 16 |
비교예 5 | 18 |
Claims (11)
- 집전체; 및상기 집전체의 적어도 일면에 위치하는 전극활물질층을 구비하고,상기 전극활물질층이 상기 집전체와 면접하는 하층 영역과 상기 하층 영역과 면접하면서 전극활물질층의 표면까지 연장되는 상층 영역으로 이루어지고,상기 하층 영역은 제1 활물질, 제1 비고무계 바인더를 포함하되, 고무계 바인더는 포함하지 않고,상기 상층 영역은 제2 활물질, 제2 비고무계 바인더 및 고무계 바인더를 포함하고,상기 고무계 바인더가 수소화 니트릴 고무(H-NBR, Hydrogenated Nitrile Butadiene Rubber)이고,상기 제1 비고무계 바인더 및 제2 비고무계 바인더가 폴리비닐리덴플루오라이드(PVDF)계 고분자를 포함하고,상기 상층 영역에서 상기 제2 비고무계 바인더 및 고무계 바인더의 중량비가 1:0.03 내지 1:0.07인 것을 특징으로 하는 전극.
- 제1항에서,상기 하층 영역 및 상층 영역의 중량비가 1:1 내지 1:5인 것을 특징으로 하는 전극.
- 제1항에서,상기 전극이 양극이고,상기 제1 활물질 및 제2 활물질이 리튬인산철 화합물(LFP)를 포함하는 것을 특징으로 하는 전극.
- 제3항에서,상기 리튬인산철 화합물(LFP)의 평균입경(D50)이 0.8㎛ 내지 2.5㎛인 것을 특징으로 하는 전극.
- 제1항에서,상기 폴리비닐리덴플루오라이드(PVDF)계 고분자가 폴리(비닐리덴 플루오라이드)(poly(vinylidene fluoride)), 폴리(비닐리덴 플루오라이드-헥사플루오로프로필렌)(poly(vinylidene fluoride-co-hexafluoropropylene)), 폴리(비닐리덴 플루오라이드-클로로트리플루오로에틸렌)(poly(vinylidene fluoride-co-chlorotrifluoroethylene)), 폴리(비닐리덴 플루오라이드-테트라플루오로에틸렌)(poly(vinylidene fluoride-co-tetrafluoroethylene)), 폴리(비닐리덴 플루오라이드-트리클로로에틸렌)(poly(vinylidene fluoride-co-trichloroethylene)), 폴리(비닐리덴 플루오라이드-트리플루오로에틸렌)(poly(vinylidene fluoride-co-trifluoroethylene)), 또는 이들 중 2 이상을 포함하는 것을 특징으로 하는 전극.
- 제1항에서,상기 상층 영역에서 상기 제2 비고무계 바인더 및 고무계 바인더의 중량비가 1:0.04 내지 1:0.06인 것을 특징으로 하는 전극.
- 제1 활물질, 제1 비고무계 바인더, 및 제1 분산매를 포함하고, 고무계 바인더는 포함하지 않는 하층용 슬러리;와, 제2 활물질, 제2 비고무계 바인더, 고무계 바인더, 및 제2 분산매를 포함하는 상층용 슬러리;를 준비하는 단계;전극 집전체의 일면에 상기 하층용 슬러리를 코팅하고, 동시에 또는 소정의 시간차를 두고 상기 하층용 슬러리 위에 상기 상층용 슬러리를 코팅하는 단계; 및상기 코팅된 하층용 슬러리 및 상층용 슬러리를 동시에 건조하여 활물질층을 형성하는 단계;를 포함하고,상기 고무계 바인더가 수소화 니트릴 고무(H-NBR, Hydrogenated Nitrile Butadiene Rubber)이고, 상기 제1 비고무계 바인더 및 제2 비고무계 바인더가 폴리비닐리덴플루오라이드(PVDF)계 고분자를 포함하고, 상기 상층용 슬러리에서 상기 제2 비고무계 바인더 및 고무계 바인더의 중량비가 1:0.03 내지 1:0.07인 것을 특징으로 하는 제1항의 전극의 제조방법.
- 제1 활물질, 제1 비고무계 바인더, 및 제1 분산매를 포함하고, 고무계 바인더는 포함하지 않는 하층용 슬러리를 전극 집전체의 적어도 일면 상에 코팅하고 건조하여 하층 활물질층을 형성하는 단계; 및상기 하층 활물질층의 상면에 제2 활물질, 제2 비고무계 바인더, 고무계 바인더, 및 제2 분산매를 포함하는 상층용 슬러리를 코팅하고 건조하여 상층 활물질층을 형성하는 단계;를 포함하고,상기 고무계 바인더가 수소화 니트릴 고무(H-NBR, Hydrogenated Nitrile Butadiene Rubber)이고, 상기 제1 비고무계 바인더 및 제2 비고무계 바인더가 폴리비닐리덴플루오라이드(PVDF)계 고분자를 포함하고, 상기 상층용 슬러리에서 상기 제2 비고무계 바인더 및 고무계 바인더의 중량비가 1:0.03 내지 1:0.07인 것을 특징으로 하는 제1항의 전극의 제조방법.
- 제7항 또는 제8항에서,상기 전극이 양극이고,상기 제1 활물질 및 제2 활물질이 리튬인산철 화합물(LFP)를 포함하는 것을 특징으로 하는 전극의 제조방법.
- 제9항에서,상기 리튬인산철 화합물(LFP)의 평균입경(D50)이 0.8㎛ 내지 2.5㎛인 것을 특징으로 하는 전극의 제조방법.
- 제1항 내지 제6항 중 어느 한 항의 전극을 양극 및 음극 중 1종 이상으로 포함하는 리튬 이차전지.
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