JPWO2013114946A1 - リチウム二次電池 - Google Patents
リチウム二次電池 Download PDFInfo
- Publication number
- JPWO2013114946A1 JPWO2013114946A1 JP2013556299A JP2013556299A JPWO2013114946A1 JP WO2013114946 A1 JPWO2013114946 A1 JP WO2013114946A1 JP 2013556299 A JP2013556299 A JP 2013556299A JP 2013556299 A JP2013556299 A JP 2013556299A JP WO2013114946 A1 JPWO2013114946 A1 JP WO2013114946A1
- Authority
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- Japan
- Prior art keywords
- fluorine
- secondary battery
- lithium secondary
- compound
- volume
- 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.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 73
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 65
- -1 ether compound Chemical class 0.000 claims abstract description 157
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 90
- 239000011737 fluorine Substances 0.000 claims abstract description 84
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 82
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 40
- 239000007774 positive electrode material Substances 0.000 claims abstract description 38
- 239000007773 negative electrode material Substances 0.000 claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 20
- 239000011149 active material Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims description 36
- 239000008151 electrolyte solution Substances 0.000 claims description 35
- 229910019142 PO4 Inorganic materials 0.000 claims description 22
- 239000010452 phosphate Substances 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000005001 laminate film Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910013275 LiMPO Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 38
- 150000004706 metal oxides Chemical class 0.000 description 38
- 229910052751 metal Inorganic materials 0.000 description 37
- 239000002184 metal Substances 0.000 description 37
- 239000002245 particle Substances 0.000 description 36
- 239000012046 mixed solvent Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 30
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 29
- 239000007789 gas Substances 0.000 description 19
- 238000005259 measurement Methods 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 239000003575 carbonaceous material Substances 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 125000001153 fluoro group Chemical group F* 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000007599 discharging Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 150000002170 ethers Chemical class 0.000 description 7
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- 229910052596 spinel Inorganic materials 0.000 description 7
- 239000011029 spinel Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- JLEXUIVKURIPFI-UHFFFAOYSA-N tris phosphate Chemical compound OP(O)(O)=O.OCC(N)(CO)CO JLEXUIVKURIPFI-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011883 electrode binding agent Substances 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
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- 150000003839 salts Chemical class 0.000 description 5
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 229940021013 electrolyte solution Drugs 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
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- 229910052709 silver Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- RPSFZSRVLPIAMN-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane Chemical compound FC(F)C(F)(F)OCC(F)(F)C(F)(F)F RPSFZSRVLPIAMN-UHFFFAOYSA-N 0.000 description 2
- PYSYKOPZHYNYSZ-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-3-(1,2,2,2-tetrafluoroethoxy)propane Chemical compound FC(F)(F)C(F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F PYSYKOPZHYNYSZ-UHFFFAOYSA-N 0.000 description 2
- ZNBGTBKGFZMWKR-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-5-(1,1,2,2-tetrafluoroethoxy)pentane Chemical compound FC(F)C(F)(F)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNBGTBKGFZMWKR-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- TXJIDOLTOGSNPD-UHFFFAOYSA-N 2-nitro-n-(4-nitrophenyl)aniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC1=CC=CC=C1[N+]([O-])=O TXJIDOLTOGSNPD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-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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- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
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- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
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- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 229940052303 ethers for general anesthesia Drugs 0.000 description 2
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 2
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- 239000010416 ion conductor Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WTZYOEZOPLDMKT-UHFFFAOYSA-N methyl 2,2,3,3-tetrafluoropropanoate Chemical compound COC(=O)C(F)(F)C(F)F WTZYOEZOPLDMKT-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
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- CUTPKDUMZWIJKT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2,2-tetrafluoroethoxy)propane Chemical compound FC(F)(F)C(F)OC(F)(F)C(F)(F)C(F)(F)F CUTPKDUMZWIJKT-UHFFFAOYSA-N 0.000 description 1
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- JFTQGIOLLLWQSI-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-3-(1,1,2,2,2-pentafluoroethoxy)propane Chemical compound FC(F)(F)C(F)(F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F JFTQGIOLLLWQSI-UHFFFAOYSA-N 0.000 description 1
- QRLOKTBZZPZAMX-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]-3-(1,2,2,2-tetrafluoroethoxy)propane Chemical compound FC(F)(F)C(F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F QRLOKTBZZPZAMX-UHFFFAOYSA-N 0.000 description 1
- LMRGTZDDPWGCGL-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoro-3-(2,2,2-trifluoroethoxy)propane Chemical compound FC(F)(F)C(F)C(F)(F)OCC(F)(F)F LMRGTZDDPWGCGL-UHFFFAOYSA-N 0.000 description 1
- JOROOXPAFHWVRW-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoro-3-(2,2,3,3,3-pentafluoropropoxy)propane Chemical compound FC(F)(F)C(F)C(F)(F)OCC(F)(F)C(F)(F)F JOROOXPAFHWVRW-UHFFFAOYSA-N 0.000 description 1
- DOESGSGKEZIPFW-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoro-3-(2,2,3,3-tetrafluoropropoxy)propane Chemical compound FC(F)C(F)(F)COC(F)(F)C(F)C(F)(F)F DOESGSGKEZIPFW-UHFFFAOYSA-N 0.000 description 1
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- JVHJRIQPDBCRRE-UHFFFAOYSA-N ethyl 2,2,3,3,4,4,4-heptafluorobutanoate Chemical compound CCOC(=O)C(F)(F)C(F)(F)C(F)(F)F JVHJRIQPDBCRRE-UHFFFAOYSA-N 0.000 description 1
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- JDVCDTVFGALNDG-UHFFFAOYSA-N ethyl bis(2,2,2-trifluoroethyl) phosphate Chemical compound FC(F)(F)COP(=O)(OCC)OCC(F)(F)F JDVCDTVFGALNDG-UHFFFAOYSA-N 0.000 description 1
- AWIZDAABIHLIDY-UHFFFAOYSA-N ethyl methyl 2,2,2-trifluoroethyl phosphate Chemical compound CCOP(=O)(OC)OCC(F)(F)F AWIZDAABIHLIDY-UHFFFAOYSA-N 0.000 description 1
- FZRDCNKIFCPZSZ-UHFFFAOYSA-N ethyl propyl 2,2,2-trifluoroethyl phosphate Chemical compound CCCOP(=O)(OCC)OCC(F)(F)F FZRDCNKIFCPZSZ-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
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- 159000000002 lithium salts Chemical class 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
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- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- JMKJCPUVEMZGEC-UHFFFAOYSA-N methyl 2,2,3,3,3-pentafluoropropanoate Chemical compound COC(=O)C(F)(F)C(F)(F)F JMKJCPUVEMZGEC-UHFFFAOYSA-N 0.000 description 1
- MRPUVAKBXDBGJQ-UHFFFAOYSA-N methyl 2,2,3,3,4,4,4-heptafluorobutanoate Chemical compound COC(=O)C(F)(F)C(F)(F)C(F)(F)F MRPUVAKBXDBGJQ-UHFFFAOYSA-N 0.000 description 1
- CSSYKHYGURSRAZ-UHFFFAOYSA-N methyl 2,2-difluoroacetate Chemical compound COC(=O)C(F)F CSSYKHYGURSRAZ-UHFFFAOYSA-N 0.000 description 1
- CGMUKBZUGMXXEF-UHFFFAOYSA-N methyl 2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanoate Chemical compound COC(=O)C(F)(C(F)(F)F)C(F)(F)F CGMUKBZUGMXXEF-UHFFFAOYSA-N 0.000 description 1
- CAWRUEZRLRNISR-UHFFFAOYSA-N methyl 2,3,3,3-tetrafluoro-2-methoxypropanoate Chemical compound COC(=O)C(F)(OC)C(F)(F)F CAWRUEZRLRNISR-UHFFFAOYSA-N 0.000 description 1
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- BFOZREDKUJLFOI-UHFFFAOYSA-N methyl 3,3,3-trifluoropropyl carbonate Chemical compound COC(=O)OCCC(F)(F)F BFOZREDKUJLFOI-UHFFFAOYSA-N 0.000 description 1
- RVNWLMWNUJPCQD-UHFFFAOYSA-N methyl 4,4,4-trifluorobutanoate Chemical compound COC(=O)CCC(F)(F)F RVNWLMWNUJPCQD-UHFFFAOYSA-N 0.000 description 1
- QPXDTULTYTZDQM-UHFFFAOYSA-N methyl bis(2,2,2-trifluoroethyl) phosphate Chemical compound FC(F)(F)COP(=O)(OC)OCC(F)(F)F QPXDTULTYTZDQM-UHFFFAOYSA-N 0.000 description 1
- XZIOCKSAUMRABB-UHFFFAOYSA-N methyl propyl 2,2,2-trifluoroethyl phosphate Chemical compound CCCOP(=O)(OC)OCC(F)(F)F XZIOCKSAUMRABB-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- ASAXRKSDVDALDT-UHFFFAOYSA-N propan-2-yl 2,2,2-trifluoroacetate Chemical compound CC(C)OC(=O)C(F)(F)F ASAXRKSDVDALDT-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- UQJLSMYQBOJUGG-UHFFFAOYSA-N tert-butyl 2,2,2-trifluoroacetate Chemical compound CC(C)(C)OC(=O)C(F)(F)F UQJLSMYQBOJUGG-UHFFFAOYSA-N 0.000 description 1
- ZDCRNXMZSKCKRF-UHFFFAOYSA-N tert-butyl 4-(4-bromoanilino)piperidine-1-carboxylate Chemical compound C1CN(C(=O)OC(C)(C)C)CCC1NC1=CC=C(Br)C=C1 ZDCRNXMZSKCKRF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- ZMQDTYVODWKHNT-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) phosphate Chemical compound FC(F)(F)COP(=O)(OCC(F)(F)F)OCC(F)(F)F ZMQDTYVODWKHNT-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
Description
前記正極活物質は、4.5V以上の電位でリチウムイオンを吸蔵又は放出可能な活物質を含み、
前記非水電解液は、下記一般式(1):
2H−パーフルオロ−5−メチル−3,6−ジオキサノナン:
CF3CHF−O−(CF2CF(CF3)O)−C3F7;
2H−パーフルオロ−5,8−ジメチル−3,6,9−トリオキサドデカン:
CF3CHF−O−(CF2CF(CF3)O)2−C3F7;
パーフルオロジグライム:
CF3−O−(CF2CF2O)2−C3F7;
パーフルオロトリグライム:
CF3−O−(CF2CF2O)3−C3F7;
が挙げられる。
で表される化合物が好ましい。式(2)において、n1及びn2は2以上が好ましく、m1、m2及びm3は4以下が好ましく、特にm2は3又は4であることが好ましい。式(1)さらに式(2)で表される化合物として、特に2H−パーフルオロ−5−メチル−3,6−ジオキサノナン(CF3CHF−O−(CF2CF(CF3)O)−C3F7)、2H−パーフルオロ−5,8−ジメチル−3,6,9−トリオキサドデカン(CF3CHF−O−(CF2CF(CF3)O)2−C3F7)が好ましい。
O=P(OR)3
(式中、Rはそれぞれ独立に炭素数1〜5のアルキル基又はフルオロアルキル基を示し、少なくとも一つのRがフルオロアルキル基である。)
で示されるフッ素化リン酸エステルがより好ましく、さらに下記式:
O=P(OCH2Ra)3
(式中、Raは炭素数1〜4のフルオロアルキル基を示す。)
で示されるフッ素化リン酸エステルが特に好ましい。式中の三つのRaは同じフルオロアルキル基であることが好ましい。式中のRaは炭素数が1〜3であることが好ましい。またRaは、各炭素原子にフッ素原子が少なくとも一つ結合していることが好ましい。これらのフッ素含有リン酸エステル化合物の中でもリン酸トリス(2,2,2−トリフルオロエチル)が特に好ましい。
本実施形態によるリチウム二次電池の正極は、高エネルギー密度を得る観点から、リチウム金属に対して4.5V以上の電位でリチウムイオンを吸蔵又は放出可能な正極活物質を含む。
(式中、0≦x≦1.2、0≦y、x+y<2、0≦a≦1.2、0≦w≦1であり、MはCo、Ni、Fe、Cr、Cuから選ばれる少なくとも一種であり、YはLi、B、Na、Al、Mg、Ti、Si、K、Caから選ばれる少なくとも一種であり、ZはF及びClの少なくとも一方である。)
負極は、負極活物質として、リチウムを吸蔵及び放出し得る材料を含むものであれば特に限定されない。
正極と負極との間に設けられるセパレータとしては、例えば、ポリエチレンやポリプロピレンなどのポリオレフィン、ポリイミド、ポリフッ化ビニリデン等のフッ素樹脂等からなる多孔質ポリマー膜や織布、不織布、あるいはイオン伝導性ポリマー電解質膜が挙げられる。これらは単独または組み合わせで使用することができる。
電池の形状としては、例えば、円筒形、角形、コイン型、ボタン型、ラミネート型が挙げられる。
本実施形態によるラミネート型のリチウム二次電池の断面図を図1に示す。図1に示すように、本実施形態によるリチウム二次電池は、アルミニウム箔等の金属からなる正極集電体3と、その上に設けられた正極活物質を含有する正極活物質層1とからなる正極、及び銅箔等の金属からなる負極集電体4と、その上に設けられた負極活物質を含有する負極活物質層2とからなる負極を有する。正極および負極は、正極活物質層1と負極活物質層2とが対向するように、不織布やポリプロピレン微多孔膜などからなるセパレータ5を介して積層されている。この電極対は、アルミニウムラミネートフィルム等の外装体6、7で形成された容器内に収容されている。正極集電体3には正極タブ9が接続けられ、負極集電体4には負極タブ8が接続され、これらのタブは容器の外に引き出されている。容器内には電解液が注入され封止される。複数の電極対が積層された電極群が容器内に収容された構造とすることもできる。
正極活物質としてのLiNi0.5Mn1.5O4(90質量部)と、結着剤としてのポリフッ化ビニリデン(5質量部)と、導電剤としてカーボンブラック(5質量部)と、を混合して正極合剤を調製した。この正極合剤をN−メチル−2−ピロリドンに分散させることにより、正極用スラリーを調製した。この正極用スラリーを厚さ20μmのアルミニウム製集電体の片面に、均一に塗布した。単位面積当たりの初回充電容量が2.5mAh/cm2となるように塗布膜の厚さを調整した。乾燥させた後、ロールプレスで圧縮成形して正極を得た。
フッ素含有エーテル化合物として、ET7に代えて、2H−パーフルオロ−5,8−ジメチル−3,6,9−トリオキサドデカン(CF3CHF−O−(CF2CF(CF3)O)2−C3F7、以下「ET8」という)を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物およびTTFEPを含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとジエチルカーボネート(DEC)を3/7の体積比(EC/DEC)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPを3/7の体積比(EC/TTFEP)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPとジプロピルエーテル(以下「ET1」という)を3/6/1の体積比(EC/TTFEP/ET1)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPとジエチレングリコールジメチルエーテル(以下「ET2」という)を3/6/1の体積比(EC/TTFEP/ET2)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPとトリエチレングリコールジメチルエーテル(以下「ET3」という)を3/6/1の体積比(EC/TTFEP/ET3)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPとn−ブチル−1,1,2,2−テトラフルオロエチルエーテル(以下「ET4」という)を3/6/1の体積比(EC/TTFEP/ET4)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPとメチル−1H,1H−ヘプタフルオロブチルエーテル(以下「ET5」という)を3/6/1の体積比(EC/TTFEP/ET5)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPとフルオロメチル−2,2,3,3−テトラフルオロプロピルエーテル(以下「ET6」という)を3/6/1の体積比(EC/TTFEP/ET6)で混合。
正極活物質として、Li(Li0.15Ni0.2Co0.1Mn0.55)O2を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表2に示す。
正極活物質として、LiCoPO4を用い、充電電圧(上限電圧)を5.0Vにした以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表2に示す。
実施例3で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例3と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表2に示す。
混合溶媒の組成:ECとTTFEPを3/7の体積比(EC/TTFEP)で混合。
実施例4で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例4と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表2に示す。
混合溶媒の組成:ECとTTFEPを3/7の体積比(EC/TTFEP)で混合。
2 負極活物質層
3 正極集電体
4 負極集電体
5 セパレータ
6 ラミネート外装体
7 ラミネート外装体
8 負極タブ
9 正極タブ
Claims (16)
- 一般式(1)において、n1〜n5は2以上である、請求項1に記載のリチウム二次電池。
- 一般式(1)において、n2=2m2、n3=2m3、n4=2m4である、請求項1に記載のリチウム二次電池。
- 一般式(1)において、m2、m3、m4は3以上である、請求項3に記載のリチウム二次電池。
- 一般式(1)において、1≦p+q+r≦2を満たす、請求項1から4のいずれか一項に記載のリチウム二次電池。
- 前記フッ素含有エーテル化合物は、
CF3CHF−O−(CF2CF(CF3)O)−C3F7及び
CF3CHF−O−(CF2CF(CF3)O)2−C3F7
の少なくとも一方である、請求項1に記載のリチウム二次電池。 - 前記非水電解液の溶媒(前記フッ素含有エーテル化合物を含む)中の前記フッ素含有エーテル化合物の含有量は、1体積%以上40体積%以下の範囲にある、請求項1から6のいずれか一項に記載のリチウム二次電池。
- 前記非水電解液は、溶媒成分としてフッ素含有リン酸エステル化合物を含有する、請求項1から7のいずれか一項に記載のリチウム二次電池。
- 前記非水電解液の溶媒(前記フッ素含有エーテル化合物を含む)中の前記フッ素含有リン酸エステル化合物の含有量は、5体積%以上80体積%以下の範囲にある、請求項8に記載のリチウム二次電池。
- 前記フッ素含有リン酸エステル化合物は、下記式:
O=P(OR)3
(式中、Rはそれぞれ独立に炭素数1〜5のアルキル基又はフルオロアルキル基を示し、少なくとも一つのRがフルオロアルキル基である。)
で示される化合物である、請求項8又は9に記載のリチウム二次電池。 - 前記非水電解液は、溶媒成分として環状カーボネート化合物を含有する、請求項1から10のいずれか一項に記載のリチウム二次電池。
- 前記非水電解液の溶媒(前記フッ素含有エーテル化合物を含む)中の前記環状カーボネート化合物の含有量は、5体積%以上60体積%以下の範囲にある、請求項11に記載のリチウム二次電池。
- 前記非水電解液は、さらにフッ素含有有機溶媒及び環状カーボネート化合物を含有する、請求項1から7のいずれか一項に記載のリチウム二次電池。
- 前記フッ素含有有機溶媒は、フッ素含有リン酸エステル化合物、フッ素含有鎖状カーボネート化合物、フッ素含有エーテル化合物、フッ素含有カルボン酸エステル化合物から選ばれる、請求項13に記載のリチウム二次電池。
- セパレータを含み、該セパレータを介して前記正極と前記負極が対向配置され、これらを内包するラミネートフィルム外装体を含む、請求項1から14のいずれか一項に記載のリチウム二次電池。
- 前記正極活物質は、4.5V以上の電位でリチウムイオンを吸蔵又は放出可能な前記活物質として、下記式(3)、(4)及び(5)のいずれかで表される活物質を含む、請求項1から15のいずれか一項に記載のリチウム二次電池。
Lia(MxMn2-x-yYy)(O4-wZw) (3)
(式中、0≦x≦1.2、0≦y、x+y<2、0≦a≦1.2、0≦w≦1であり、MはCo、Ni、Fe、Cr、Cuから選ばれる少なくとも一種であり、YはLi、B、Na、Al、Mg、Ti、Si、K、Caから選ばれる少なくとも一種であり、ZはF及びClの少なくとも一方である。)
LiMPO4 (4)
(式中、MはCo及びNiの少なくとも一方である。)
Li(LixM1-x-zMnz)O2 (5)
(式中、0≦x<0.3、0.3≦z≦0.7であり、MはCo及びNiの少なくとも一方である。)
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WO2015025915A1 (ja) * | 2013-08-23 | 2015-02-26 | 日本電気株式会社 | 二次電池 |
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