JP6128403B2 - リチウム二次電池 - Google Patents
リチウム二次電池 Download PDFInfo
- Publication number
- JP6128403B2 JP6128403B2 JP2015545406A JP2015545406A JP6128403B2 JP 6128403 B2 JP6128403 B2 JP 6128403B2 JP 2015545406 A JP2015545406 A JP 2015545406A JP 2015545406 A JP2015545406 A JP 2015545406A JP 6128403 B2 JP6128403 B2 JP 6128403B2
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- Prior art keywords
- secondary battery
- lithium secondary
- chemical formula
- ionomer
- separation membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052744 lithium Inorganic materials 0.000 title claims description 70
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 66
- 229920000554 ionomer Polymers 0.000 claims description 87
- 239000000126 substance Substances 0.000 claims description 64
- 239000012528 membrane Substances 0.000 claims description 55
- 238000000926 separation method Methods 0.000 claims description 51
- 239000003792 electrolyte Substances 0.000 claims description 30
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- -1 cyclic carbonate compound Chemical class 0.000 claims description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 10
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 150000003951 lactams Chemical class 0.000 claims description 4
- 150000002596 lactones Chemical class 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003462 sulfoxides Chemical class 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-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
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- VUAXHMVRKOTJKP-UHFFFAOYSA-M 2,2-dimethylbutanoate Chemical compound CCC(C)(C)C([O-])=O VUAXHMVRKOTJKP-UHFFFAOYSA-M 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910017008 AsF 6 Inorganic materials 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229920005735 poly(methyl vinyl ketone) Polymers 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 208000028659 discharge Diseases 0.000 description 15
- 239000007772 electrode material Substances 0.000 description 15
- 239000002033 PVDF binder Substances 0.000 description 14
- 239000008151 electrolyte solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000010287 polarization Effects 0.000 description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 13
- 239000011267 electrode slurry Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000004020 conductor Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
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- 238000007796 conventional method Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- 229910011573 LiFe Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910007969 Li-Co-Ni Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910006555 Li—Co—Ni Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QDDVNKWVBSLTMB-UHFFFAOYSA-N [Cu]=O.[Li] Chemical compound [Cu]=O.[Li] QDDVNKWVBSLTMB-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- OHOIHSTWKIMQNC-UHFFFAOYSA-N [Li].[P]=O Chemical class [Li].[P]=O OHOIHSTWKIMQNC-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-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
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
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- H01M10/052—Li-accumulators
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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
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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Description
先ず、本発明では、前記化学式(1)で表されるアイオノマーを含む電極を提供する。具体的に本発明の電極は電極活物質のコーティング成分、電極合剤成分または電極の表面コーティング成分として、前記化学式(1)で表されるアイオノマーを含むことができる。このとき、前記電極は負極または正極であり得、適用範囲を特に制限しない。
具体的に、本発明では電極活物質、及び前記電極活物質の表面に形成された前記化学式(1)で表されるアイオノマーを含むコーティング層を含む電極を提供する。
また、本発明では電極集電体、及び前記電極集電体上にコーティングされた電極合剤を含む電極において、前記電極合剤成分として電極活物質と前記化学式(1)で表されるアイオノマーを含む電極を提供する。
また、本発明では既に製造された電極の表面に前記化学式(1)で表されるアイオノマーからなるコーティング層を含む電極を提供する。
また、本発明では前記化学式(1)で表されるアイオノマーを含む分離膜を提供する。このとき、前記分離膜は化学式(1)で表されるアイオノマーのみからなるメンブレンフィルム(membrane film)形態の独立型(freestanding)分離膜、または多孔性基材上に化学式(1)で表されるアイオノマーを含むコーティング層を含む複合多孔性分離膜であり得る。
具体的に、本発明では化学式(1)で表されるアイオノマーのみからなる独立型分離膜を提供する。
また、本発明ではまた他の実施形態で通常の二次電池用分離膜(多孔性分離膜)上に化学式(1)で表されるアイオノマーを含有するコーティング層を含む複合(多孔性)分離膜を提供することができる。
また、本発明では前記化学式(1)で表されるアイオノマーを含む電解液を提供する。具体的に、電解質塩及び非水性有機溶媒を含む非水電解液において、添加剤として前記化学式(1)で表されるアイオノマーをさらに含む非水系電解液を提供することができる。
(実施例1)
負極活物質としてLTO 96重量%、バインダーとしてポリビニリデンフルオライド(PVdF)4重量%、前記化学式(1)のアイオノマー(重量平均分子量 約308)2重量%、導電材としてカーボンブラック(carbon black)1重量%を溶剤であるN−メチル−2ピロリドン(NMP)に添加して負極混合物スラリーを製造した。前記負極混合物スラリーを厚さが10μmの負極集電体であるアルミニウム薄膜に塗布し乾燥して負極を製造した。
負極製造時に前記化学式(1)のアイオノマーを含まない代わりに、前記バインダーとしてポリビニリデンフルオライド(PVdF)6重量%を含み、また電解液の製造時に0.5M LiPF6の非水電解液を注入することを除いては、前記実施例1と同じ方法で5V級の高電圧電池を製造した。
本発明のアイオノマーを含むリチウム二次電池のC−rate特性を評価するために、下記のように行った。すなわち、前記実施例1のリチウム二次電池と、比較例1のリチウム二次電池を45℃で1C/1Cの充・放電速度でサイクリングを行い、これらの充・放電容量を図1に示した。
前記実施例1及び比較例1のリチウム二次電池をそれぞれ45℃で充電rateは0.5Cで固定し、放電rateを0.5Cから5Cに変化させながら容量変化を観察してrate特性を評価し、その結果を図2に示した。
(実施例2)
正極活物質としてLNMOスピネル系化合物92重量%、導電材としてカーボンブラック4重量%、結合剤成分としてPVdF2重量%、前記化学式(1)のアイオノマー(重量平均分子量 約308)2重量%を溶剤であるN−メチル−2ピロリドン(NMP)に添加して正極スラリーを製造した。前記正極スラリーを厚さが20μmの正極集電体であるアルミニウム(Al)薄膜に塗布し乾燥して正極を製造した。負極はLi metalを用いた。
正極製造時に前記化学式(1)のアイオノマーを含まない代わりに、前記バインダーとしてポリビニリデンフルオライド(PVdF)4重量%を含み、また電解液の製造時に0.5M LiPF6の非水電解液を注入することを除いては、前記実施例2と同じ方法で5V級の高電圧電池を製造した。
本発明のアイオノマーを含むリチウム二次電池の分極現象抑制特性を観察するために、下記のように行った。すなわち、前記実施例2のリチウム二次電池と、比較例2のリチウム二次電池を23℃で1Cで放電しており、これらの放電容量と放電曲線を図3、図4に示した。
前記実施例2及び比較例2のリチウム二次電池をそれぞれ45℃で1C/1C充放電性能を観察して図5に示した。
(実施例3)
負極活物質としてGraphite 96重量%、バインダーとしてポリビニリデンフルオライド(PVdF)5重量%、前記化学式(1)のアイオノマー(重量平均分子量 約308)5重量%、導電材としてカーボンブラック(carbon black)1重量%を溶剤であるN−メチル−2ピロリドン(NMP)に添加して負極混合物スラリーを製造した。前記負極混合物スラリーを厚さが10μmの負極集電体である銅(Al)薄膜に塗布し乾燥して負極を製造した。
負極製造時に前記化学式(1)のアイオノマーを含まない代わりに、前記バインダーとしてポリビニリデンフルオライド(PVdF)10重量%を含み、また電解液の製造時に0.5M LiPF6の非水電解液を注入することを除いては、前記実施例3と同じ方法で5V級の高電圧電池を製造した。
本発明のアイオノマーを含むリチウム二次電池の抵抗減少効果を確認するために、下記のように行った。すなわち、前記実施例3のリチウム二次電池と、比較例3のリチウム二次電池を23℃で1Cのrateで充電を進めており、これらの充電曲線を図6に示した。
Claims (16)
- 前記化学式(1)で表されるアイオノマーは、リチウムイオンソースの役割を担う請求項1に記載のリチウム二次電池。
- 前記正極は、正極活物質のコーティング成分、正極合剤成分または正極コーティング成分として前記化学式(1)で表されるアイオノマーを含む請求項1に記載のリチウム二次電池。
- 前記化学式(1)で表されるアイオノマーは、正極合剤の全含量を基準に0.01から20重量%で含まれる請求項3に記載のリチウム二次電池。
- 前記負極は、負極活物質のコーティング成分、負極合剤成分または負極コーティング成分として前記化学式(1)で表されるアイオノマーを含む請求項1に記載のリチウム二次電池。
- 前記化学式(1)で表されるアイオノマーは、負極合剤の全含量を基準に0.01から20重量%で含まれる請求項5に記載のリチウム二次電池。
- 前記分離膜は、分離膜の構成成分または分離膜のコーティング成分として前記化学式(1)で表されるアイオノマーを含む請求項1に記載のリチウム二次電池。
- 前記分離膜は、前記化学式(1)で表されるアイオノマーからなるメンブレンフィルム(membrane film)形態の独立型(freestanding)分離膜である請求項1または請求項7に記載のリチウム二次電池。
- 前記分離膜は、多孔性基材上に前記化学式(1)で表されるアイオノマー含有コーティング層を含む複合分離膜である請求項1または請求項7に記載のリチウム二次電池。
- 前記化学式(1)で表されるアイオノマーは、分離膜成分の全体100重量部を基準に0.01から20重量部で含まれる請求項7に記載のリチウム二次電池。
- 前記非水電解液は、電解質塩及び非水性有機溶媒を含む請求項1に記載のリチウム二次電池。
- 前記電解質塩は、(i)Li+、Na+及びK+からなる群より選択される少なくとも一つの陽イオンと、(ii)PF6 −、BF4 −、Cl−、Br−、I−、ClO4 −、AsF6 −、CH3CO2 −、CF3SO3 −、N(CF3SO2)2 −及びC(CF2SO2)3 −からなる群より選択される少なくとも一つの陰イオンとの組合せからなる請求項11に記載のリチウム二次電池。
- 前記非水性有機溶媒は、環状カーボネート化合物、線形カーボネート化合物、ラクトン、エーテル化合物、エステル化合物、スルホキシド、ラクタム及びケトンからなる群より選択される少なくとも一つの有機溶媒を含む請求項11に記載のリチウム二次電池。
- 前記環状カーボネートは、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、ブチレンカーボネート(BC)及びフルオロエチレンカーボネート(FEC)からなる群より選択される少なくとも一つを含み、
前記線形カーボネートは、ジエチルカーボネート(DEC)、ジメチルカーボネート(DMC)、ジプロピルカーボネート(DPC)、エチルメチルカーボネート(EMC)、及びメチルプロピルカーボネート(MPC)からなる群より選択される少なくとも一つを含み、
前記ラクトンは、ガンマブチロラクトンを含み、
前記エーテル化合物は、ジブチルエーテル、テトラヒドロフラン、2−メチルテトラヒドロフラン、1,4−ジオキサン、1,2−ジメトキシエタン、及び1,2−ジエトキシエタンからなる群より選択される少なくとも一つを含み、
前記エステル化合物は、ギ酸メチル、ギ酸エチル、ギ酸プロピル、メチルアセテート、エチルアセテート、プロピルアセテート、メチルプロピオネート、エチルプロピオネート、ブチルプロピオネート及びメチルピバレートからなる群より選択される少なくとも一つを含み、
前記スルホキシドは、ジメチルスルホキシドを含み、
前記ラクタムは、N−メチル−2−ピロリドン(NMP)を含み、
前記ケトンとしては、ポリメチルビニルケトンを含む請求項13に記載のリチウム二次電池。 - 前記非水電解液は、添加剤として前記化学式(1)で表されるアイオノマーを含む請求項1に記載のリチウム二次電池。
- 前記化学式(1)で表されるアイオノマーは、非水電解液の全体100重量部を基準に0.01から20重量部を含む請求項15に記載のリチウム二次電池。
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Application Number | Priority Date | Filing Date | Title |
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KR10-2013-0131473 | 2013-10-31 | ||
KR20130131473 | 2013-10-31 | ||
KR10-2014-0150126 | 2014-10-31 | ||
KR1020140150126A KR101607024B1 (ko) | 2013-10-31 | 2014-10-31 | 리튬 이차전지 |
PCT/KR2014/010361 WO2015065102A1 (ko) | 2013-10-31 | 2014-10-31 | 리튬 이차전지 |
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JP2016502744A JP2016502744A (ja) | 2016-01-28 |
JP6128403B2 true JP6128403B2 (ja) | 2017-05-17 |
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KR102019838B1 (ko) * | 2015-09-30 | 2019-09-10 | 주식회사 엘지화학 | 비수성 전해액을 포함하는 리튬 이차 전지 |
US20180301758A1 (en) * | 2015-10-09 | 2018-10-18 | Ube Industries, Ltd. | Nonaqueous electrolyte solution and electricity storage device using same |
KR102217106B1 (ko) | 2016-05-09 | 2021-02-22 | 주식회사 엘지화학 | 고분자 전해질용 조성물 및 이를 포함하는 리튬 이차전지 |
WO2017196012A1 (ko) | 2016-05-09 | 2017-11-16 | 주식회사 엘지화학 | 고분자 전해질용 조성물 및 이를 포함하는 리튬 이차전지 |
US10892523B2 (en) * | 2016-10-27 | 2021-01-12 | Toyota Motor Engineering & Manufacturing North America, Inc. | Aqueous electrolyte with carbonate and batteries using the same |
WO2018216866A1 (ko) * | 2017-05-26 | 2018-11-29 | 주식회사 엘지화학 | 리튬-황 전지용 전해액 및 이를 포함하는 리튬-황 전지 |
KR102183662B1 (ko) | 2017-05-26 | 2020-11-26 | 주식회사 엘지화학 | 리튬-황 전지용 전해액 및 이를 포함하는 리튬-황 전지 |
US10581050B2 (en) * | 2017-06-07 | 2020-03-03 | Robert Bosch Gmbh | Battery having a low counter-ion permeability layer |
CN109037682A (zh) * | 2017-07-17 | 2018-12-18 | 浙江林奈新能源有限公司 | 用于电化学电池电极的离子交联聚合物 |
KR102255538B1 (ko) | 2017-11-28 | 2021-05-25 | 주식회사 엘지에너지솔루션 | 이차전지용 폴리머 전해질 및 이를 포함하는 이차전지 |
KR102274611B1 (ko) | 2018-04-06 | 2021-07-06 | 주식회사 엘지에너지솔루션 | 수명 성능이 향상된 리튬 금속 이차전지 |
KR102328648B1 (ko) * | 2018-07-04 | 2021-11-18 | 주식회사 엘지에너지솔루션 | 리튬 금속 전지용 음극, 이의 제조 방법, 및 이를 포함하는 리튬 금속 전지 |
EP3742527B1 (en) * | 2018-07-04 | 2022-03-23 | LG Energy Solution Ltd. | Anode for lithium metal battery, manufacturing method of the same, and lithium metal battery including the same |
CA3216042A1 (en) * | 2022-03-17 | 2023-09-21 | Lg Energy Solution, Ltd. | Lithium secondary battery |
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AU5099498A (en) | 1996-11-01 | 1998-05-29 | E.I. Du Pont De Nemours And Company | Highly conductive ion exchange polymer and process |
JPH10284128A (ja) | 1997-04-03 | 1998-10-23 | Asahi Glass Co Ltd | リチウム電池 |
US6025092A (en) | 1998-02-13 | 2000-02-15 | E. I. Du Pont De Nemours And Company | Fluorinated ionomers and their uses |
US6100324A (en) | 1998-04-16 | 2000-08-08 | E. I. Du Pont De Nemours And Company | Ionomers and ionically conductive compositions |
MY135964A (en) * | 1998-10-26 | 2008-07-31 | Du Pont | Ionomers and polymers for electrochemical uses |
US6743549B1 (en) * | 1999-07-02 | 2004-06-01 | E.I. Du Pont De Nemours And Company | Nonaqueous electrolyte lithium secondary batteries |
US7307113B2 (en) * | 2001-05-14 | 2007-12-11 | E.I. Du Pont De Nemours And Company | Fluorosulfonic acid organic polymers |
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US20130250485A1 (en) * | 2011-06-09 | 2013-09-26 | Wildcat Discovery Technologies, Inc. | Materials for electrolytes and methods for use |
WO2013101299A1 (en) | 2011-12-29 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Flow battery comprising a composite polymer separator membrane |
US20130181677A1 (en) * | 2012-01-18 | 2013-07-18 | E I Du Pont De Nemours And Company | Compositions, layerings, electrodes and methods for making |
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KR20150050507A (ko) | 2015-05-08 |
EP2899794A1 (en) | 2015-07-29 |
EP2899794B1 (en) | 2020-10-21 |
PL2899794T3 (pl) | 2021-02-22 |
TW201530848A (zh) | 2015-08-01 |
US9553338B2 (en) | 2017-01-24 |
WO2015065102A1 (ko) | 2015-05-07 |
CN104798244B (zh) | 2017-07-28 |
EP2899794A4 (en) | 2015-09-30 |
TWI552416B (zh) | 2016-10-01 |
CN104798244A (zh) | 2015-07-22 |
KR101607024B1 (ko) | 2016-03-28 |
US20160028127A1 (en) | 2016-01-28 |
JP2016502744A (ja) | 2016-01-28 |
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