JP2004221085A - 有機電解液及びこれを採用したリチウム電池 - Google Patents
有機電解液及びこれを採用したリチウム電池 Download PDFInfo
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- JP2004221085A JP2004221085A JP2004006149A JP2004006149A JP2004221085A JP 2004221085 A JP2004221085 A JP 2004221085A JP 2004006149 A JP2004006149 A JP 2004006149A JP 2004006149 A JP2004006149 A JP 2004006149A JP 2004221085 A JP2004221085 A JP 2004221085A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000008151 electrolyte solution Substances 0.000 title abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 32
- -1 phosphonate compound Chemical class 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 239000005486 organic electrolyte Substances 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 24
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 claims description 19
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 19
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 125000004475 heteroaralkyl group Chemical group 0.000 claims description 5
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 5
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- CQCXMYUCNSJSKG-UHFFFAOYSA-N 1-dimethoxyphosphorylethene Chemical compound COP(=O)(OC)C=C CQCXMYUCNSJSKG-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 229910018091 Li 2 S Inorganic materials 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 10
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 125000001424 substituent group Chemical group 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- 238000002484 cyclic voltammetry Methods 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 9
- 230000008961 swelling Effects 0.000 description 9
- 239000006182 cathode active material Substances 0.000 description 8
- 230000002427 irreversible effect Effects 0.000 description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000006183 anode active material Substances 0.000 description 6
- 229910021383 artificial graphite Inorganic materials 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- NYYLZXREFNYPKB-UHFFFAOYSA-N 1-[ethoxy(methyl)phosphoryl]oxyethane Chemical compound CCOP(C)(=O)OCC NYYLZXREFNYPKB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910017698 Ni 1-x-y Co Inorganic materials 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001334 alicyclic compounds Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 2
- PZNTXFRCVDEQCU-UHFFFAOYSA-M CS([O-])(=O)=O.[Li+].F.F.F Chemical compound CS([O-])(=O)=O.[Li+].F.F.F PZNTXFRCVDEQCU-UHFFFAOYSA-M 0.000 description 1
- 229910013063 LiBF 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
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- DRBBFCLWYRJSJZ-UHFFFAOYSA-N N-phosphocreatine Chemical class OC(=O)CN(C)C(=N)NP(O)(O)=O DRBBFCLWYRJSJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 125000005597 hydrazone group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/547—Terminals characterised by the disposition of the terminals on the cells
- H01M50/55—Terminals characterised by the disposition of the terminals on the cells on the same side of the cell
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/552—Terminals characterised by their shape
- H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
- H01M50/557—Plate-shaped terminals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
【解決手段】 リチウム塩と有機溶媒とを含む有機電解液において、下記化学式1で示されるホスホネート化合物を含むことを特徴とする有機電解液及びこれを採用したリチウム電池である。本発明による下記化学式1で示されるホスホネート化合物を含む有機電解液を利用すれば、還元分解安定性を向上させて第一サイクルでの非可逆容量を減少させるだけでなく、電池の充放電効率及び寿命特性を向上させる。また、常温で組立て及び標準充電後、電池の厚さが一定の範囲を超えないので、電池の信頼性を向上させうる。また、高温放置後の電池の回復容量に優れるため、電池の厚さ膨脹が最も激しい高温でも一定の容量を発揮し、実質的な適用に対してほとんど問題がない。
【化1】
Description
本発明の他の課題は、カソードと、アノードと、前記カソードおよび前記アノードの間に介在されたセパレータと、前述した有機電解液とを含むことを特徴とするリチウム電池を提供することにある。
前記ホスホネート化合物は、特にジエチルビニルホスホネート(DEVP)、ジメチルビニルホスホネートよりなる群から選択された一つであることが望ましい。
エチレンカーボネート50体積%、プロピレンカーボネート50体積%よりなる有機溶媒99wt%と、ジエチルビニルホスホネート(DEVP)1wt%とを混合した後、これにリチウム塩であるLiPF6を添加して1.15モル濃度の有機電解液を製造した。
有機電解液がエチレンカーボネート50体積%、プロピレンカーボネート50体積%よりなる有機溶媒95wt%とDEVP5wt%とを混合したことを除いては、実施例1と同じ方法で2電極電池を製造し、CVを利用して電気的特性を調べた。
有機電解液がエチレンカーボネート50体積%、プロピレンカーボネート50体積%よりなる有機溶媒93wt%とDEVP7wt%とを混合したことを除いては、実施例1と同じ方法で2電極電池を製造し、CVを利用して電気的特性を調べた。
有機電解液がエチレンカーボネート50体積%、プロピレンカーボネート50体積%よりなる有機溶媒90wt%とDEVP10wt%とを混合したことを除いては、実施例1と同じ方法によって2電極電池を製造し、CVを利用して電気的特性を調べた。
有機電解液がエチレンカーボネート50体積%、プロピレンカーボネート50体積%よりなる有機溶媒99wt%と、DEVP1wt%とで混合し、比表面積が小さいグラファイト系電極の代わりに比表面積が大きいグラファイト系電極(人造グラファイトとして、比表面積が約4m2/g)を使用したことを除いては、実施例1と同じ方法で2電極電池を製造し、CVを利用して電気的特性を調べた。
有機電解液がエチレンカーボネート50体積%、プロピレンカーボネート50体積%よりなる有機溶媒95wt%と、DEVP5wt%とを混合し、比表面積が小さいグラファイト系電極の代わりに比表面積が大きいグラファイト系電極(人造グラファイトとして、約4m2/gである)を使用したことを除いては、実施例1と同じ方法で2電極電池を製造し、CVを利用して電気的特性を調べた。
有機電解液がエチレンカーボネート50体積%、プロピレンカーボネート50体積%よりなる有機溶媒93wt%と、DEVP7wt%とを混合し、比表面積が小さいグラファイト系電極の代わりに比表面積が大きいグラファイト系電極(人造グラファイトとして、比表面積が約4m2/g)を使用したことを除いては、実施例1と同じ方法で2電極電池を製造し、CVを利用して電気的特性を調べた。
有機電解液の製造時、DEVPを添加しないことを除いては、実施例1と同じ方法で2電極電池を製造し、CVを利用して電気的特性を調べた。
2電極電池の製造時、比表面積が小さいグラファイト系電極の代わりに比表面積が大きいグラファイト系電極(人造グラファイトとして、比表面積が約4m2/g)を使用したことを除いては、比較例1と同じ方法で2電極電池を製造し、CVを利用して電気的特性を調べた。
エチレンカーボネート50体積%、プロピレンカーボネート50体積%よりなる有機溶媒99wt%とDEVP1wt%とからなる有機電解液の代わりに、エチレンカーボネート50体積%、プロピレンカーボネート50体積%よりなる有機溶媒98wt%と、ビニレンカーボネート2wt%とからなる有機電解液を利用したことを除いては、実施例1と同じ方法によって実施して2電極電池を製造し、CVを利用して電気的特性を調べた。
2電極電池の製造時、比表面積が小さいグラファイト系電極の代わりに比表面積が大きいグラファイト系電極を使用したことを除いては、比較例3と同じ方法によって実施して2電極電池を製造し、CVを利用して電気的特性を調べた。
前記実施例1で製造された有機電解液を利用してリチウム電池を次のような過程によって製造した。
エチレンカーボネート30体積%、ジメチルカーボネート10体積%、エチルメチルカーボネート50体積%、及びフルオロベンゼン10体積%よりなる有機溶媒を99wt%とし、ここに添加剤であるジメチルメチルホスホネートを1wt%添加して調製した有機電解液を使用したことを除いては、実施例8と同じ方法でリチウム2次電池を製造した。
エチレンカーボネート30体積%、ジメチルカーボネート10体積%、エチルメチルカーボネート50体積%、及びフルオロベンゼン10体積%よりなる有機溶媒を99wt%とし、ここに添加剤であるジエチルメチルホスホネートを1wt%添加して調製した有機電解液を使用したことを除いては、実施例8と同じ方法でリチウム2次電池を製造した。
エチレンカーボネート30体積%、ジメチルカーボネート10体積%、エチルメチルカーボネート50体積%、及びフルオロベンゼン10体積%よりなる有機溶媒のみを使用し、これに添加剤を添加しないで調製した有機電解液を使用したことを除いては、実施例8と同じ方法によって実施してリチウム2次電池を製造した。
エチレンカーボネート30体積%、ジメチルカーボネート10体積%、エチルメチルカーボネート50体積%、及びフルオロベンゼン10体積%よりなる有機溶媒を99wt%とし、これに添加剤であるビニレンカーボネートを2wt%添加して調製した有機電解液を使用したことを除いては、実施例8と同じ方法でリチウム2次電池を製造した。
Claims (10)
- リチウム塩と有機溶媒とを含む有機電解液において、
下記化学式1で示されるホスホネート化合物を含むことを特徴とする有機電解液。
R3及びR4は、互いに独立して水素原子、置換または非置換のC1〜20のアルキル基である。) - 前記化学式1のホスホネート化合物の含量は、前記有機溶媒50〜99.9質量%に対して0.1〜50質量%であることを特徴とする請求項1に記載の有機電解液。
- 前記化学式1のホスホネート化合物がジエチルビニルホスホネート及びジメチルビニルホスホネートよりなる群から選択されることを特徴とする請求項1に記載の有機電解液。
- 前記有機溶媒が高誘電率溶媒および/または低沸点溶媒を含むことを特徴とする請求項1に記載の有機電解液。
- 前記高誘電率溶媒が、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、γ−ブチロラクトンよりなる群から選択される一つ以上であり、
前記高誘電率溶媒の含量が前記有機溶媒の全量に対して10〜90体積%であることを特徴とする請求項4に記載の有機電解液。 - 前記低沸点溶媒が、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、ジプロピルカーボネート、ジメトキシエタン、炭素数1ないし13の脂肪酸エステル誘導体よりなる群から選択された一つ以上であり、
前記低沸点溶媒の含量が前記有機溶媒の全量に対して10〜90体積%であることを特徴とする請求項4に記載の有機電解液。 - 前記リチウム塩が前記有機電解液中に0.5ないし2.0モル濃度含まれる特徴とする請求項1に記載の有機電解液。
- カソードと、
アノードと、
前記カソードおよび前記アノードの間に介在されたセパレータと、
請求項1〜7の何れか一項に記載の有機電解液を含むことを特徴とするリチウム電池。 - 前記カソードがリチウム複合酸化物、単体硫黄、Li2Sn(n≧1)が溶解されたカソード液、有機硫黄及び(C2Sx)y(xは2.5〜20、y≧2)よりなる群から選択される一つ以上を含む電極であることを特徴とする請求項8に記載のリチウム電池。
- 前記アノードがリチウム金属、リチウム金属合金、リチウム非活性硫黄の複合体、カーボン材、またはグラファイトよりなる群から選択される一つ以上を含む電極であることを特徴とする請求項8に記載のリチウム電池。
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Publication number | Publication date |
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US7217480B2 (en) | 2007-05-15 |
US20040142246A1 (en) | 2004-07-22 |
CN1260849C (zh) | 2006-06-21 |
KR100509604B1 (ko) | 2005-08-22 |
JP4001580B2 (ja) | 2007-10-31 |
KR20040065412A (ko) | 2004-07-22 |
CN1518155A (zh) | 2004-08-04 |
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