WO2022196761A1 - 非水二次電池用電解液及びそれを用いた非水二次電池 - Google Patents
非水二次電池用電解液及びそれを用いた非水二次電池 Download PDFInfo
- Publication number
- WO2022196761A1 WO2022196761A1 PCT/JP2022/012274 JP2022012274W WO2022196761A1 WO 2022196761 A1 WO2022196761 A1 WO 2022196761A1 JP 2022012274 W JP2022012274 W JP 2022012274W WO 2022196761 A1 WO2022196761 A1 WO 2022196761A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- secondary battery
- lithium
- aqueous secondary
- electrolyte
- sulfide
- Prior art date
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 40
- -1 transition metal sulfide Chemical class 0.000 claims abstract description 66
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims abstract description 56
- 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 claims abstract description 56
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 claims description 52
- 239000008151 electrolyte solution Substances 0.000 claims description 44
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 40
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 30
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 15
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 8
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 238000007600 charging Methods 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 37
- 239000002904 solvent Substances 0.000 description 28
- 229910052717 sulfur Inorganic materials 0.000 description 27
- 239000011593 sulfur Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 25
- 238000003701 mechanical milling Methods 0.000 description 22
- 229910003002 lithium salt Inorganic materials 0.000 description 15
- 159000000002 lithium salts Chemical class 0.000 description 15
- 229910052744 lithium Inorganic materials 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229940021013 electrolyte solution Drugs 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 239000005486 organic electrolyte Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910052976 metal sulfide Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000005678 chain carbonates Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 4
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- 229910002804 graphite Inorganic materials 0.000 description 4
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- 238000000227 grinding Methods 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QGMHVMSINPZNBA-UHFFFAOYSA-N [S-2].[Nb+5].[Ti+4] Chemical compound [S-2].[Nb+5].[Ti+4] QGMHVMSINPZNBA-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000002194 amorphous carbon material Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical class [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 2
- NYPFJVOIAWPAAV-UHFFFAOYSA-N sulfanylideneniobium Chemical compound [Nb]=S NYPFJVOIAWPAAV-UHFFFAOYSA-N 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- GKZFQPGIDVGTLZ-UHFFFAOYSA-N 4-(trifluoromethyl)-1,3-dioxolan-2-one Chemical compound FC(F)(F)C1COC(=O)O1 GKZFQPGIDVGTLZ-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- UDKXBPLHYDCWIG-UHFFFAOYSA-M [S-2].[S-2].[SH-].S.[V+5] Chemical compound [S-2].[S-2].[SH-].S.[V+5] UDKXBPLHYDCWIG-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000005314 correlation function Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 150000003949 imides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 239000011135 tin Substances 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- PSDQQCXQSWHCRN-UHFFFAOYSA-N vanadium(4+) Chemical compound [V+4] PSDQQCXQSWHCRN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- H01M10/056—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to an electrolytic solution for non-aqueous secondary batteries and non-aqueous secondary batteries using the same.
- lithium-ion secondary batteries Due to the recent improvements in the performance of portable electronic devices and hybrid vehicles, there is a growing demand for higher capacity lithium-ion secondary batteries used in these devices.
- the capacity of the positive electrode is insufficient compared to that of the negative electrode, and even lithium nickel oxide-based materials, which are said to have relatively high capacity, have a capacity of about 190mAh/g to 220mAh/g. It's nothing more than
- sulfur has a high theoretical capacity of about 1670 mAh/g, and is expected to be used as a positive electrode active material.
- Lithium-free transition metal sulfides have electronic conductivity, and although they are less eluted into organic electrolytes, they are not sufficient.
- vanadium sulfide as an example of a lithium-free transition metal sulfide
- crystalline vanadium sulfide (III) (V 2 S 3 ) sold as a reagent is used as a positive electrode active material, Since the reaction with the organic electrolyte cannot be suppressed, the measured capacity is only about 23 mAh/g for charge capacity and about 52 mAh/g for discharge capacity.
- a low-crystalline vanadium sulfide having a specific composition exhibits a high capacity when used as an electrode active material for a lithium-ion secondary battery, and has excellent charge-discharge cycle characteristics. have also been reported to be excellent (see, for example, Patent Document 1).
- the present inventors have developed a material that exhibits a high capacity when used as an electrode active material for a lithium ion secondary battery and also has excellent charge-discharge cycle characteristics. There is no end to the demand for higher performance of batteries, and further improvements are required for charge-discharge cycle characteristics.
- Causes of cycle deterioration include the deposition of by-products due to the reaction between the lithium-free transition metal sulfide and the electrolyte, and the decrease in the electrode active material components. it is conceivable that.
- an electrolytic solution with low reactivity can be used as a method for suppressing the reaction between the two.
- the present invention has been made in view of the current state of the prior art described above, and the main object thereof is to provide a non-aqueous secondary battery using a lithium-free transition metal sulfide as a positive electrode active material, in which charge-discharge cycle characteristics are improved. is to provide an electrolytic solution capable of improving
- the inventors of the present invention have conducted extensive research in order to achieve the above objectives.
- an organic solvent containing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and a chain carbonate compound LiTFSI
- a lithium-free transition metal sulfide can be used as a positive electrode active material.
- the inventors have found that the charge-discharge cycle characteristics of a water secondary battery can be further improved.
- the present invention was completed as a result of further research based on such knowledge.
- the present invention includes the following configurations.
- the non-aqueous secondary battery is a non-aqueous secondary battery using a lithium-free transition metal sulfide as a positive electrode active material
- the electrolytic solution is an organic solvent containing a chain carbonate compound; lithium bis(trifluoromethanesulfonyl)imide (LiTFSI); containing an additive, Electrolyte for non-aqueous secondary batteries.
- Item 2 The electrolytic solution for a non-aqueous secondary battery according to Item 1, wherein the additive is at least one selected from the group consisting of vinylene carbonate (VC) and fluoroethylene carbonate (FEC).
- VC vinylene carbonate
- FEC fluoroethylene carbonate
- Item 3 The nonaqueous according to item 1 or 2, wherein the content of the chain carbonate compound is 2 to 4 times the content of the lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in terms of molar ratio. Electrolyte for secondary batteries.
- Section 4. The electrolytic solution for a non-aqueous secondary battery according to any one of Items 1 to 3, wherein the content of the additive is 2.5% by weight to 10% by weight based on the total amount of the electrolytic solution being 100% by weight. .
- the chain carbonate compound is at least one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethylmethyl carbonate (EMC), according to any one of items 1 to 4 above. Electrolyte for non-aqueous secondary batteries.
- DMC dimethyl carbonate
- DEC diethyl carbonate
- EMC ethylmethyl carbonate
- Item 6. The electrolysis for a non-aqueous secondary battery according to any one of items 1 to 5, wherein the lithium-free transition metal sulfide is at least one selected from the group consisting of vanadium sulfide and molybdenum sulfide. liquid.
- Item 7 A non-aqueous secondary battery comprising the electrolytic solution for a non-aqueous secondary battery according to any one of Items 1 to 6 above.
- Item 8. The nonaqueous secondary battery according to item 7, which is a lithium ion secondary battery.
- charge-discharge cycle characteristics can be further improved in a non-aqueous secondary battery using a lithium-free transition metal sulfide as a positive electrode active material.
- the concentration (mol/L) of each component means that it contains the desired number of moles per 1 L of the organic solvent.
- Electrolyte solution for non-aqueous secondary battery is an electrolyte solution for non-aqueous secondary battery,
- the non-aqueous secondary battery is a non-aqueous secondary battery using a lithium-free transition metal sulfide as a positive electrode active material,
- the electrolytic solution is an organic solvent containing a chain carbonate compound; lithium bis(trifluoromethanesulfonyl)imide (LiTFSI); and additives.
- Lithium-free transition metal sulfide In the present invention, transition metal sulfides containing lithium must be handled in an inert atmosphere such as an argon gas atmosphere. Containing transition metal sulfides are used. Examples of such lithium-free transition metal sulfides include lithium-free transition metal sulfides used as positive electrode active materials in non-aqueous secondary batteries in which the electrolyte for non-aqueous secondary batteries of the present invention is used. and is not particularly limited as long as it is a lithium-free transition metal sulfide known as a positive electrode active material for lithium ion secondary batteries. Specifically, vanadium sulfide (lithium-free vanadium sulfide: International Publication No.
- niobium sulfide and titanium niobium sulfide lithium-free niobium sulfide and lithium-free titanium niobium sulfide: International Publication No. 2015/049986
- molybdenum sulfides lithium-free molybdenum sulfides
- iron sulfides lithium-free iron sulfides
- lithium-free transition metal sulfides can be used alone or in combination of two or more.
- vanadium sulfide lithium-free vanadium sulfide: International Publication No. 2018/181698
- molybdenum sulfide lithium-free molybdenum sulfide
- Iron sulfide lithium-free iron sulfide
- vanadium sulfide lithium-free vanadium sulfide: International Publication No. 2018/181698
- the non-lithium-containing transition metal sulfide is preferably at least one selected from the group consisting of vanadium sulfide and molybdenum sulfide.
- Both crystalline materials and low-crystalline materials (or amorphous materials) can be used for such lithium-free transition metal sulfides. Among them, particularly excellent charge-discharge capacity, charge-discharge cycle characteristics, etc., and from the viewpoint of easily suppressing the reaction with the organic electrolyte when it comes into contact with the organic electrolyte, low-crystalline materials (or amorphous materials) is preferred.
- the composition ratio (S/M 1 ) of sulfur and transition metal is particularly excellent in charge-discharge capacity, charge-discharge cycle characteristics, etc.
- a molar ratio of 2.1 to 10 is preferable from the viewpoint of easily suppressing the reaction with the organic electrolyte when in contact with the liquid.
- non-lithium containing transition metal sulfides have the general formula (2): M1S x ( 2 ) [In the formula, M 1 represents a transition metal. x indicates 2.1-10. ] It is preferable to have a composition represented by When a plurality of transition metals are contained as M 1 , the composition ratio (S/M 1 ) of sulfur to the total amount of transition metals is preferably 2.1-10 in terms of molar ratio.
- the lithium-free metal sulfide has a high elemental ratio of sulfur to transition metal (M 1 ). Therefore, in the present invention, by using a lithium-free metal sulfide, a high charge-discharge capacity and excellent charge-discharge cycle characteristics can be obtained.
- x is preferably 2.1-10, more preferably 3-8.
- vanadium sulfide lithium-free vanadium sulfide
- lithium-free vanadium sulfide which is a preferred lithium-free transition metal sulfide
- vanadium sulfide preferably has a crystal structure similar to that of crystalline vanadium tetrasulfide (IV) (VS 4 ) (hereinafter sometimes referred to as "VS 4 type crystal structure").
- vanadium sulfide is a sulfide with a high sulfur ratio as an average composition, but sulfur hardly exists as elemental sulfur as described later, and is combined with vanadium to have low crystallinity. preferably forms a sulfide of
- vanadium sulfide has a lower crystallinity, so that there are more sites where lithium ions can be inserted and detached, and gaps that can be three-dimensionally conductive paths for lithium can be made structurally easier to have.
- it has many advantages such as easy three-dimensional volume change during charging and discharging. Therefore, the charge/discharge capacity and charge/discharge cycle characteristics can be further improved.
- vanadium sulfide (V 2 S 3 etc.) used as a raw material is almost absent.
- the average composition of sulfide indicates the element ratio of each element that constitutes the entire sulfide.
- crystalline vanadium sulfide (IV) (VS 4 )
- the number of sites where Li can stably exist tends to increase. And it is easy to improve charge-discharge cycle characteristics.
- the cyclic carbonate compound contained in the electrolyte for non-aqueous secondary batteries of the present invention tends to react with elemental sulfur.
- the vanadium sulfide described above hardly contains elemental sulfur or the like, so when used as a positive electrode active material, cyclic carbonate Even when a compound is used, these problems do not occur, and the charge/discharge capacity and charge/discharge cycle characteristics are likely to be dramatically improved.
- vanadium sulfide can be made a material that hardly contains elemental sulfur, and the concern of causing a reaction with the electrolyte solution as described above is further reduced, and the charge-discharge capacity and charge-discharge cycle characteristics can be further improved.
- PDF analysis X-ray/neutron atom pair correlation function analysis
- vanadium sulfide preferably has not only V-S bonds but also S-S bonds (disulfide bonds).
- the vanadium sulfide described above can be obtained, for example, by using vanadium sulfide and sulfur as raw materials or intermediates and using a production method comprising a step of subjecting them to a mechanical milling method.
- Mechanical milling is a method of grinding and mixing raw materials while applying mechanical energy. According to this method, vanadium sulfide and Sulfur contacts violently and becomes fine, causing reaction of raw materials. In other words, at this time, mixing, grinding and reaction occur simultaneously. Therefore, it is possible to react the raw materials more reliably without heating the raw materials to a high temperature.
- a metastable crystal structure which cannot be obtained by ordinary heat treatment, may be obtained by using mechanical milling treatment.
- mixed grinding can be performed using a mechanical grinding device such as a ball mill, bead mill, rod mill, vibration mill, disk mill, hammer mill, jet mill, or the like.
- All of these raw materials or intermediates can be mixed at the same time and subjected to mechanical milling. Some of the materials or intermediates are first subjected to mechanical milling, and then the remaining materials are added to mechanical milling. can also be provided to
- vanadium sulfide with a high sulfur content composition ratio (S/V) of sulfur and vanadium is 3.3 or more in terms of molar ratio
- crystalline vanadium sulfide may be obtained. Therefore, in order to easily obtain low-crystalline vanadium sulfide having excellent charge-discharge capacity and charge-discharge cycle characteristics, first, vanadium sulfide and a part of sulfur are subjected to mechanical milling to obtain the desired intermediate. After obtaining the low crystalline sulfide, it is preferable to subject the obtained low crystalline sulfide and the remaining sulfur to a mechanical milling treatment.
- vanadium sulfide As a specific raw material, it is preferable to use crystalline vanadium sulfide (III) (V 2 S 3 ) as vanadium sulfide. Vanadium sulfide is not particularly limited, and any commercially available vanadium sulfide can be used. In particular, it is preferable to use a highly pure one. In addition, since the vanadium sulfide is mixed and pulverized by mechanical milling, the particle size of the vanadium sulfide used is not limited, and powdery vanadium sulfide that is commercially available can be used.
- sulfur it is possible to use elemental sulfur (S 8 ) in an amount necessary to form a sulfide having the desired composition.
- the sulfur used as a raw material is also not particularly limited, and any sulfur can be used. In particular, it is preferable to use a highly pure one.
- the particle size of the sulfur used is not limited, and powdered sulfur commercially available can be used.
- a low-crystalline vanadium sulfide (low-crystalline VS 2.5 , etc.) having a desired composition can also be used.
- the ratio of each element in the product is almost the same as the ratio of the raw materials, so it can be the same ratio as the elemental ratio of vanadium and sulfur in the target vanadium sulfide.
- sulfur is preferably 1.2 mol or more (especially 1.2 mol to 17.0 mol, more preferably 3.0 mol to 13.0 mol) per 1 mol of vanadium sulfide.
- the temperature at which the mechanical milling is performed is not particularly limited, and is preferably 300° C. or less, more preferably -10° C. to 200° C., in order to make it difficult for sulfur to volatilize and to make it difficult to generate the previously reported crystal phase. .
- the time of the mechanical milling treatment is not particularly limited, and the mechanical milling treatment can be performed for an arbitrary time until the desired vanadium sulfide precipitates.
- an inert gas atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere can be used.
- mechanical milling can be performed within the processing time range of 0.1 hours to 100 hours (especially 15 hours to 80 hours). It should be noted that this mechanical milling process can also be performed by dividing it into a plurality of times with intervening breaks on the way, if necessary.
- the target vanadium sulfide can be obtained as a fine powder by the mechanical milling treatment described above.
- the electrolytic solution for non-aqueous secondary batteries of the present invention is an organic solvent containing a chain carbonate compound; lithium bis(trifluoromethanesulfonyl)imide (LiTFSI); and additives.
- LiTFSI lithium bis(trifluoromethanesulfonyl)imide
- the electrolyte solution for non-aqueous secondary batteries of the present invention is an electrolyte solution for non-aqueous secondary batteries that uses a lithium-free transition metal sulfide as a positive electrode active material.
- a lithium-free transition metal sulfide as a positive electrode active material.
- the lithium-free transition metal sulfide is used in a non-aqueous secondary battery using the lithium-free transition metal sulfide, by adding the additive described below, the chain carbonate compound and the lithium-free transition metal sulfide It is possible to suppress the reaction with metal sulfides and dramatically improve charge-discharge cycle characteristics.
- Chain carbonate compound The chain carbonate compound is not particularly limited as long as it can be used as an organic solvent in the electrolyte of a lithium ion secondary battery. Carbonate (DEC), ethyl methyl carbonate (EMC) and the like. These chain carbonate compounds can be used alone or in combination of two or more.
- Electrolytes containing cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC) and chain carbonates such as ethylmethyl carbonate (EMC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) generally have -40
- EMC ethylmethyl carbonate
- DEC diethyl carbonate
- DMC dimethyl carbonate
- the electrolytic solution for non-aqueous secondary batteries of the present invention contains a chain carbonate, so it is superior at low temperatures.
- the chain carbonate compound is preferably at least one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), and methylpropyl carbonate.
- the organic solvent constituting the electrolytic solution for non-aqueous secondary batteries may be composed only of the chain carbonate compound described above. It is also possible to include compounds known as organic solvents.
- organic solvent as the third component examples include cyclic carboxylic acid ester compounds such as ⁇ -butyrolactone; chain carboxylic acid ester compounds such as methyl acetate, methyl propionate and ethyl acetate; sulfone compounds; ether compounds such as tetrahydrofuran, 2-methyltetrahydrofuran, and 1,2-dimethoxyethane; These organic solvents as the third component can be used alone or in combination of two or more.
- the content of the organic solvent as the third component is 0.1% by volume to 10% by volume, with the total amount of the organic solvent being 100% by volume, from the viewpoint of charge-discharge cycle characteristics. %, more preferably 0.2% to 5% by volume.
- the electrolytic solution for non-aqueous secondary batteries of the present invention contains: an organic solvent containing a chain carbonate compound; lithium bis(trifluoromethanesulfonyl)imide (LiTFSI); and additives.
- LiTFSI lithium bis(trifluoromethanesulfonyl)imide
- the electrolytic solution for a non-aqueous secondary battery of the present invention contains an additive to suppress the reaction between the carbonate compound and the lithium-free transition metal sulfide, thereby dramatically improving the charge-discharge cycle characteristics. can be improved to
- Such additives are vinylene carbonate (VC), or fluoro Ethylene carbonate (FEC) is preferred.
- VC vinylene carbonate
- FEC fluoro Ethylene carbonate
- additives can be used alone or in combination of two or more. By using a combination of two or more additives, it is possible to improve charge-discharge cycle characteristics even when the additive content is increased.
- the additive is preferably at least one selected from the group consisting of vinylene carbonate (VC) and fluoroethylene carbonate (FEC).
- VC vinylene carbonate
- FEC fluoroethylene carbonate
- the content of the above additives is preferably 2.5 parts by mass to 20.0 parts by mass, and 2.5 parts by mass to 15.0 parts by mass with respect to 100 parts by mass of the organic solvent. parts is more preferred, and 2.5 to 10.0 parts by mass is even more preferred. Even if only one type of additive is used, if only one type such as fluoroethylene carbonate (FEC), trifluoromethylethylene carbonate, vinylethylene carbonate, etc. is used, it is better to charge and discharge with more additives.
- the amount is preferably 2.5 parts by mass to 10.0 parts by mass with respect to 100 parts by mass of the organic solvent, since it is easy to improve cycle characteristics.
- the total content of the additives is 100 parts by mass of the organic solvent. 2.5 parts by mass to 20.0 parts by mass is preferable, 2.5 parts by mass to 15.0 parts by mass is more preferable, and 5.0 parts by mass to 10.0 parts by mass is even more preferable.
- the electrolyte for non-aqueous secondary batteries of the present invention is an organic solvent containing a chain carbonate compound; lithium bis(trifluoromethanesulfonyl)imide (LiTFSI); and additives.
- LiTFSI lithium bis(trifluoromethanesulfonyl)imide
- the electrolytic solution for non-aqueous secondary batteries of the present invention further contains lithium bis(trifluoromethanesulfonyl)imide (LiTFSI: Li(CF 3 SO 2 ) 2 N) as a lithium salt.
- LiTFSI lithium bis(trifluoromethanesulfonyl)imide
- This lithium salt is an organic lithium salt having a sulfonyl group (perfluoroalkanesulfonyl group).
- organic lithium salt having a sulfonyl group is not particularly limited as long as it is conventionally used in electrolyte solutions for non-aqueous secondary batteries.
- (Pentafluoroethanesulfonyl) imide Li(C 2 F 5 SO 2 ) 2 N, etc.
- These organic lithium salts having a sulfonyl group may be used singly or in combination of two or more. may be used.
- the lithium salt is preferably an organic lithium salt having a sulfonyl group rather than an inorganic lithium salt ( LiPF6 , LiBF4 , etc.).
- an organic lithium salt having boron atoms may be added.
- the lithium salt is preferably an organic lithium salt having a boron atom.
- non-aqueous secondary battery of the present invention uses a lithium-free metal sulfide as a positive electrode active material, the influence of reactivity with sulfur on charge-discharge cycle characteristics is taken into account.
- LiTFSI LiTFSI as the lithium salt, good charge-discharge cycle characteristics are obtained.
- the content of the chain carbonate compound is preferably 2 to 4 times the content of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in molar ratio.
- the concentration of the lithium salt described above is preferably 2 to 4 times the molar ratio of the chain carbonate from the viewpoint of charge-discharge cycle characteristics and internal resistance. 2 to 3 times is more preferable.
- Such other additives include, for example, tetrabutylammonium hexafluorophosphate, tetrabutylammonium perchlorate, tetramethylammonium tetrafluoroborate, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabromide methylammonium, tetraethylammonium bromide, tetrabutylammonium bromide, biphenyl, trialkyl phosphate (trimethyl phosphate etc.) and the like. These other additives may be used alone or in combination of two or more.
- Non-Aqueous Secondary Battery of the present invention comprises the above electrolyte for non-aqueous secondary batteries.
- the non-aqueous secondary battery of the present invention can comprise a positive electrode, a negative electrode and a separator in addition to the electrolyte for non-aqueous secondary batteries.
- (2-1) Positive Electrode As the positive electrode, a configuration in which a positive electrode mixture layer containing a positive electrode active material, a binder, etc. is formed on one or both sides of a positive electrode current collector can be adopted.
- This positive electrode mixture layer is prepared by adding a binder to a positive electrode active material and a conductive aid added as necessary, and dispersing this in an organic solvent to prepare a positive electrode mixture layer forming paste (in this case, The binder may be dissolved or dispersed in an organic solvent in advance), applied to the surface (one side or both sides) of a positive electrode current collector made of metal foil or the like, and dried to form a positive electrode mixture layer, It can be manufactured through a process of processing as necessary.
- the above lithium-free metal sulfide is used as the positive electrode active material.
- the details of the lithium-free metal sulfide follow those explained above.
- a conductive aid graphite; carbon black (acetylene black, ketjen black, etc.); amorphous carbon materials such as carbon materials with amorphous carbon generated on the surface, as in ordinary non-aqueous secondary batteries. fibrous carbon (vapor-grown carbon fiber, carbon fiber obtained by carbonizing pitch after spinning, etc.); carbon nanotube (various multilayer or single-wall carbon nanotubes); As the conductive aid for the positive electrode, one may be used alone, or two or more may be used in combination.
- binders examples include polyvinylidene fluoride (PVDF), polytetrafluoroethylene, polyacrylic acid, styrene-butadiene rubber, polyimide, polyvinyl alcohol, and water-soluble carboxymethylcellulose.
- PVDF polyvinylidene fluoride
- polyacrylic acid examples include acrylic acid, styrene-butadiene rubber, polyimide, polyvinyl alcohol, and water-soluble carboxymethylcellulose.
- the organic solvent used in producing the positive electrode mixture is not particularly limited, and examples thereof include N-methylpyrrolidone (NMP). can be done.
- NMP N-methylpyrrolidone
- the positive electrode active material is about 70% to 95% by weight and the binder is about 1% to 30% by weight.
- the positive electrode active material is about 50% to 90% by weight, the binder is about 1% to 20% by weight, and the conductive aid is 1% to 40% by weight. % is preferable.
- the thickness of the positive electrode mixture layer is preferably about 1 ⁇ m to 100 ⁇ m per side of the current collector.
- the positive electrode current collector for example, aluminum foil, stainless steel, nickel, titanium or alloys thereof, punched metal, expanded metal, mesh, etc. can be used. Foil is preferably used.
- Negative Electrode As the negative electrode, a structure in which a negative electrode mixture layer containing a negative electrode active material, a binder, etc. is formed on one or both sides of a negative electrode current collector can be adopted.
- This negative electrode mixture layer is formed by mixing a binder with a negative electrode active material and a conductive aid that is added as necessary and forming it into a sheet, which is formed on the surface (one side) of a negative electrode current collector made of a metal foil or the like. or both sides).
- the negative electrode active material is not particularly limited, and for example, graphite (natural graphite, artificial graphite, etc.), difficult-to-sinter carbon, lithium metal, tin, silicon, alloys containing these, SiO, etc. can be used.
- lithium metal, lithium alloys, etc. can be used for metallic lithium primary batteries and metallic lithium secondary batteries, and materials capable of doping and dedoping lithium ions (graphite (natural graphite, artificial graphite, etc.), difficult-to-sinter carbon, etc.), etc. can be used as the active material.
- These negative electrode active materials may be used alone or in combination of two or more.
- a conductive aid graphite; carbon black (acetylene black, ketjen black, etc.); amorphous carbon materials such as carbon materials with amorphous carbon generated on the surface, as in ordinary non-aqueous secondary batteries. fibrous carbon (vapor-grown carbon fiber, carbon fiber obtained by carbonizing pitch after spinning, etc.); carbon nanotube (various multilayer or single-wall carbon nanotubes);
- the conductive aid for the negative electrode it may be used alone, or two or more of them may be used in combination. If the negative electrode active material has high conductivity, it may not be used.
- binders examples include polyvinylidene fluoride (PVDF), polytetrafluoroethylene, polyacrylic acid, styrene-butadiene rubber, polyimide, polyvinyl alcohol, and water-soluble carboxymethylcellulose.
- PVDF polyvinylidene fluoride
- polyacrylic acid examples include acrylic acid, styrene-butadiene rubber, polyimide, polyvinyl alcohol, and water-soluble carboxymethylcellulose.
- the negative electrode active material is about 70% to 95% by weight and the binder is about 1% to 30% by weight.
- the negative electrode active material is about 50% to 90% by weight, the binder is about 1% to 20% by weight, and the conductive aid is 1% to 40% by weight. % is preferable.
- the thickness of the negative electrode mixture layer is preferably about 1 ⁇ m to 100 ⁇ m per side of the current collector.
- the negative electrode current collector for example, a foil, punched metal, expanded metal, mesh, mesh, etc. made of aluminum, copper, stainless steel, nickel, titanium, or alloys thereof can be used, and the thickness is usually 5 ⁇ m to 5 ⁇ m.
- a copper foil with a thickness of about 30 ⁇ m is preferably used.
- the positive electrode and the negative electrode described above can be used, for example, in the form of a laminated electrode body in which a separator is interposed and laminated, or in the form of a wound electrode body in which this is spirally wound.
- separator it is preferable to use a separator that has sufficient strength and can hold a large amount of electrolytic solution. From this point of view, polyethylene, polypropylene, ethylene-propylene with a thickness of 10 ⁇ m to 50 ⁇ m and an aperture ratio of 30% to 70%. Microporous films, non-woven fabrics, etc. containing one or more copolymers are preferred.
- non-aqueous secondary battery of the present invention a cylindrical shape (square cylindrical shape, cylindrical shape, etc.) using a stainless steel can, an aluminum can, or the like as an outer can can be adopted. Also, a soft package battery in which a laminated film integrated with a metal foil is used as an outer package can be employed.
- Synthesis Example 1 Synthesis of vanadium sulfide (positive electrode active material)
- vanadium sulfide (III) V 2 S 3 : manufactured by Kojundo Chemical Laboratory Co., Ltd.
- sulfur manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
- the vacuum-sealed sample was sintered in a tubular furnace at 400°C for 5 hours.
- the calcined sample was calcined in vacuum at 200°C for 8 hours to desulfurize surplus sulfur and synthesize crystalline vanadium sulfide VS 4 (c-VS 4 ).
- crystalline VS 4 (c-VS 4 ) was mechanically milled (ball diameter of 4 mm and rotation speed of 270 rpm), a low-crystalline vanadium sulfide VS 4 (a-VS 4 ) was synthesized and used as a positive electrode active material.
- the powder XRD measurement of the obtained a-VS 4 showed no clear peaks other than the minimum peak of V 2 O 3 , which is an extremely small amount of impurity, and it was found to be completely amorphous.
- Synthesis example 2 Synthesis of molybdenum sulfide (positive electrode active material) Zhang, M. Xue, and J. Chen, ACS Appl. Mater. Interface, 9, 38606-38611 (2017).).
- ammonium molybdate tetrahydrate (NH4) 6Mo7O24.4H2O : manufactured by FUJIFILM Wako Pure Chemical Industries , Ltd.) and hydroxylamine chloride ( NH2OH.HCl : FUJIFILM Wako Pure Chemical Industries , Ltd.) Co., Ltd.) was weighed into a volumetric flask so that the weight ratio was 4:3, and a mixture of ammonium sulfide ((NH 4 ) 2 S: Fuji Film Wako Pure Chemical Co., Ltd.) and ion-exchanged water was dripped. After that, the mixture was held at 50° C. for 1 hour and then at 90° C. for 4 hours to obtain a precipitate.
- ammonium molybdate tetrahydrate (NH4) 6Mo7O24.4H2O : manufactured by FUJIFILM Wako Pure Chemical Industries , Ltd.) and hydroxylamine chloride ( NH2OH.HCl : FU
- Amorphous MoS 5.7 was synthesized by heat-treating the dried sample at 220°C for 1 hour in an electric furnace in an Ar atmosphere.
- EMC Ethyl methyl carbonate
- LiTFSI Lithium bis(trifluoromethanesulfonyl)imide
- FEC Fluoroethylene carbonate
- VC Vinylene carbonate
- DMC Dimethyl carbonate
- DEC Diethyl carbonate
- Example 1 FEC 2.5 wt%/EMC:LiTFSI (solvent 2:1 molar ratio) LiTFSI was added to the EMC solvent so that the concentration was (2:1 molar ratio), and 2.5 parts by mass of FEC was added to 100 parts by mass of the mixed electrolyte to obtain the non-aqueous secondary battery of Example 1. obtained an electrolytic solution for
- Example 2 FEC 5 wt%/EMC:LiTFSI (solvent 2:1 molar ratio) LiTFSI was added to the EMC solvent so that the concentration was (2:1 molar ratio), and 5 parts by mass of FEC was added to 100 parts by mass of the mixed electrolyte, and the non-aqueous secondary battery of Example 2 obtained an electrolytic solution for
- Example 3 FEC 10 wt%/EMC:LiTFSI (solvent 2:1 molar ratio) LiTFSI was added to the EMC solvent so that the concentration was (2:1 molar ratio), and 10 parts by mass of FEC was added to 100 parts by mass of the mixed electrolyte. obtained an electrolytic solution for
- Example 4 VC2.5 wt%/EMC:LiTFSI (solvent 2:1 molar ratio) LiTFSI was added to the EMC solvent so that the concentration was (2:1 molar ratio), and 2.5 parts by mass of VC was added to 100 parts by mass of the mixed electrolyte. obtained an electrolytic solution for
- Example 5 VC5 wt%/EMC:LiTFSI (solvent 2:1 molar ratio) LiTFSI was added to the EMC solvent so that the concentration was (2:1 molar ratio), and 5 parts by mass of VC was added to 100 parts by mass of the mixed electrolyte. obtained an electrolytic solution for
- Example 6 VC10 wt%/EMC:LiTFSI (solvent 2:1 molar ratio) LiTFSI was added to the EMC solvent so that the concentration was (2:1 molar ratio), and 10 parts by mass of VC was added to 100 parts by mass of the mixed electrolyte. obtained an electrolytic solution for
- Example 7 10 wt% FEC/EMC:LiTFSI (solvent 3:1 molar ratio) LiTFSI was added to the EMC solvent so that the concentration was (3:1 molar ratio), and 10 parts by mass of FEC was added to 100 parts by mass of the mixed electrolyte. obtained an electrolytic solution for
- Example 8 FEC 10 wt%/EMC:LiTFSI (solvent 4:1 molar ratio) LiTFSI was added to the EMC solvent so that the concentration was (4:1 molar ratio), and 10 parts by mass of FEC was added to 100 parts by mass of the mixed electrolyte, and the non-aqueous secondary battery of Example 6 obtained an electrolytic solution for
- Example 9 10 wt% FEC/DMC:LiTFSI (solvent 2:1 molar ratio) LiTFSI was added to the DMC solvent so that the concentration was (2:1 molar ratio), and 10 parts by mass of FEC was added to 100 parts by mass of the mixed electrolyte. An electrolyte was obtained.
- Example 10 10 wt% FEC/DEC:LiTFSI (solvent 2:1 molar ratio) LiTFSI was added to the DEC solvent so that the concentration was (2:1 molar ratio), and 10 parts by mass of FEC was added to 100 parts by mass of the mixed electrolyte to obtain the non-aqueous secondary battery of Example 10. obtained an electrolytic solution for
- Example 11 FEC 5% by mass + VC 5% by mass/EMC: LiTFSI (solvent 2:1 molar ratio) LiTFSI was added to the EMC solvent so that the concentration was (2:1 molar ratio), and FEC was further mixed. 5 parts by mass and 5 parts by mass of VC were added to 100 parts by mass of the electrolyte to obtain an electrolyte for a non-aqueous secondary battery of Example 11.
- LiTFSI solvent 2:1 molar ratio
- Example 12 FEC 10 wt%/EMC:LiTFSI (solvent 3:1 molar ratio) LiTFSI was added to the EMC solvent so that the concentration was (3:1 molar ratio), and 10 parts by mass of FEC was added to 100 parts by mass of the mixed electrolyte, and the non-aqueous secondary battery of Example 12 obtained an electrolytic solution for
- Comparative Example 1 No additive/EMC:LiTFSI (solvent 2:1 molar ratio) LiTFSI was added to the EMC solvent at a concentration of (2:1 molar ratio) to obtain an electrolytic solution for a non-aqueous secondary battery of Comparative Example 1.
- Comparative Example 2 No additive/EMC:LiTFSI (solvent 3:1 molar ratio) LiTFSI was added to the EMC solvent at a concentration of (3:1 molar ratio) to obtain an electrolytic solution for a non-aqueous secondary battery of Comparative Example 2.
- Test example 1 Initial internal resistance evaluation (initial) The VS4 powder obtained in Synthesis Example 1 was used in the non-aqueous secondary battery electrolytes obtained in Examples 1 to 11 and Comparative Example 1 as a positive electrode active material.
- the MoS5.7 powder obtained in Synthesis Example 2 was used as the positive electrode active material in the non-aqueous secondary battery electrolytes obtained in Example 12 and Comparative Example 2.
- the working electrode positive electrode was prepared by mixing 10 mg of the VS4 powder obtained in Synthesis Example 1 with 1 mg of Ketjenblack and polytetrafluoroethylene (PTFE ) was added, mixed in a mortar for 8 minutes, and then pasted on an aluminum mesh.
- PTFE polytetrafluoroethylene
- Lithium metal was used as the counter electrode (negative electrode).
- Polypropylene was used as the separator.
- Table 1 shows the results of the initial internal resistance characteristics.
- Test example 2 Charge/discharge test (after 100 cycles) The VS4 powder obtained in Synthesis Example 1 was used in the non-aqueous secondary battery electrolytes obtained in Examples 1 to 11 and Comparative Example 1 as a positive electrode active material.
- the MoS5.7 powder obtained in Synthesis Example 2 was used as the positive electrode active material in the non-aqueous secondary battery electrolytes obtained in Example 12 and Comparative Example 2.
- the working electrode positive electrode
- the working electrode was prepared by adding 10 mg of VS4 powder obtained in Synthesis Example 1, 1 mg of Ketjenblack, and polytetrafluoroethylene ( 1 mg of PTFE) was added, mixed in a mortar for 8 minutes, and then attached to an aluminum mesh.
- Lithium metal was used as the counter electrode (negative electrode).
- Polypropylene was used as the separator.
- Table 1 shows the results of charge-discharge cycle characteristics (capacity retention rate at 100 cycles).
- the capacity retention rate is the ratio of the capacity measured after 100 cycles when the capacity at the start of the cycle test (first cycle) is taken as 100. The higher the capacity retention rate, the better the life characteristics as a battery. indicates that
- the initial internal resistance is not determined by a particular threshold.
- Examples 1 to 11 of the present invention When VS4 is used as the active material in the stage before the charge/discharge cycle, the resistance of Examples 1 to 11 of the present invention is lower than that of Comparative Example 1 by 25% or more. Examples 1 to 11 of the present invention suggest that a battery system with high energy efficiency can be realized because electric energy used for charging is not wasted due to resistance heating or the like.
- Example 12 to which the present invention is applied suggests that a battery system with high energy efficiency can be realized as in the case of using VS4.
- the capacity maintenance rate is not determined based on a particular threshold.
- Examples 1 to 11 of the present invention show a higher capacity retention rate than Comparative Example 1 by 50% or more. Examples 1 to 11 of the present invention suggest that a battery system with high energy efficiency and excellent life characteristics can be realized.
- Example 12 to which the present invention is applied shows a higher capacity retention rate than Comparative Example 2 by 40% or more.
- Example 12 to which the present invention is applied suggests that a battery system with high energy efficiency and excellent life characteristics can be realized.
- the electrolytic solution for non-aqueous secondary batteries of the present invention and non-aqueous secondary batteries using the same can be used for various known applications. Specific examples include laptop computers, mobile phones, electric vehicles, power sources for load leveling, and natural energy storage power sources.
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Abstract
Description
非水二次電池用電解液であって、
前記非水二次電池は、正極活物質としてリチウム非含有遷移金属硫化物を使用する非水二次電池であり、
前記電解液は、
鎖状カーボネート化合物を含む有機溶媒と、
リチウムビス(トリフルオロメタンスルホニル)イミド(LiTFSI)と、
添加剤とを含有する、
非水二次電池用電解液。
前記添加剤は、ビニレンカーボネート(VC)、及びフルオロエチレンカーボネート(FEC)から成る群から選ばれる少なくとも1種である、前記項1に記載の非水二次電池用電解液。
前記リチウムビス(トリフルオロメタンスルホニル)イミド(LiTFSI)の含有量に対して、前記鎖状カーボネート化合物の含有量は、モル比で2倍~4倍である、前記項1又は2に記載の非水二次電池用電解液。
前記電解液の総量を100重量%として、前記添加剤の含有量は、2.5重量%~10重量%である、前記項1~3のいずれか1項に記載の非水二次電池用電解液。
前記鎖状カーボネート化合物は、ジメチルカーボネート(DMC)、ジエチルカーボネート(DEC)、エチルメチルカーボネート(EMC)から成る群から選ばれる少なくとも1種である、前記項1~4のいずれか1項に記載の非水二次電池用電解液。
前記リチウム非含有遷移金属硫化物は、バナジウム硫化物、及びモリブデン硫化物から成る群から選ばれる少なくとも1種である、前記項1~5のいずれか1項に記載の非水二次電池用電解液。
前記項1~6のいずれか1項に記載の非水二次電池用電解液を備える、非水二次電池。
リチウムイオン二次電池である、前記項7に記載の非水二次電池。
本発明は、非水二次電池用電解液であって、
前記非水二次電池は、正極活物質としてリチウム非含有遷移金属硫化物を使用する非水二次電池であり、
前記電解液は、
鎖状カーボネート化合物を含む有機溶媒と、
リチウムビス(トリフルオロメタンスルホニル)イミド(LiTFSI)と、
添加剤とを含有する。
本発明において、遷移金属硫化物としては、リチウムを含むものについては、アルゴンガス雰囲気等の不活性雰囲気下での取り扱いが必要となるため、リチウム非含有遷移金属硫化物を使用する。このようなリチウム非含有遷移金属硫化物としては、本発明の非水二次電池用電解液が使用される非水二次電池において、正極活物質として使用されるリチウムを含有しない遷移金属硫化物であり、リチウムイオン二次電池の正極活物質として知られているリチウム非含有遷移金属硫化物であれば特に制限されない。具体的には、バナジウム硫化物(リチウム非含有バナジウム硫化物:国際公開第2018/181698号)、ニオブ硫化物及びチタンニオブ硫化物(リチウム非含有ニオブ硫化物及びリチウム非含有チタンニオブ硫化物:国際公開第2015/049986号)、モリブデン硫化物(リチウム非含有モリブデン硫化物)、鉄硫化物(リチウム非含有鉄硫化物)等が挙げられる。なお、国際公開第2018/181698号及び国際公開第2015/049986号の記載は、参照により引用する(incorporate by reference)。
M1Sx (2)
[式中、M1は遷移金属を示す。xは2.1~10を示す。]
で表される組成を有することが好ましい。なお、M1として複数の遷移金属を含む場合は、硫黄と遷移金属の総量との組成比(S/M1)をモル比で2.1~10とすることが好ましい。
測定装置:D8ADVANCE(BrukerAXS)
X線源:CuKα40kV/40mA
測定条件:2θ=10°~80°、0.1°ステップ、走査速度0.02°/秒
で測定する。
本発明の非水二次電池用電解液は、
鎖状カーボネート化合物を含む有機溶媒と、
リチウムビス(トリフルオロメタンスルホニル)イミド(LiTFSI)と、
添加剤とを含有する。
鎖状カーボネート化合物としては、リチウムイオン二次電池の電解液において有機溶媒として使用し得るものであれば特に制限はなく、例えば、鎖状カーボネート化合物が、ジメチルカーボネート(DMC)、ジエチルカーボネート(DEC)、エチルメチルカーボネート(EMC)等が挙げられる。これらの鎖状カーボネート化合物は、単独で用いることもでき、2種以上を組合せて用いることもできる。
本発明の非水二次電池用電解液は、
鎖状カーボネート化合物を含む有機溶媒と、
リチウムビス(トリフルオロメタンスルホニル)イミド(LiTFSI)と、
添加剤とを含有する。
本発明の非水二次電池用電解液は、
鎖状カーボネート化合物を含む有機溶媒と、
リチウムビス(トリフルオロメタンスルホニル)イミド(LiTFSI)と、
添加剤とを含有する。
本発明の非水二次電池用電解液においては、本発明の効果を損なわない範囲(例えば、0.01mol/L~0.2mol/L、特に0.02mol/L~0.1mol/L)であれば、上記以外の成分、例えば他の添加剤を含ませることもできる。
本発明の非水二次電池は、上記した非水二次電池用電解液を備える。その他の構成及び構造については、従来から知られている非水二次電池で採用されている構成及び構造を適用し得る。通常は、本発明の非水二次電池は、上記の非水二次電池用電解液の他、正極、負極及びセパレータを備え得る。
正極としては、正極活物質、結着剤等を含有する正極合剤層を、正極集電体の片面又は両面に形成した構成を採用し得る。
負極としては、負極活物質、結着剤等を含有する負極合剤層を、負極集電体の片面又は両面に形成した構成を採用し得る。
上記した正極と負極は、例えば、セパレータを介在させつつ積層した積層電極体や、さらにこれを渦巻状に巻回した巻回電極体の形で用いることができる。
市販の硫化バナジウム(III)(V2S3:(株)高純度化学研究所製)及び硫黄(富士フイルム和光純薬(株)製)を、モル比が1:6となるよう、アルゴンガス雰囲気のグローブボックス内(露点-80℃)で秤量し、真空中にてガラス管内に封管を行った。
モリブデン硫化物は、既報(X. Wang, K. Du, C. Wang, L. Ma, B. Zhao, J. Yang, M. Li, X. Zhang, M. Xue, and J. Chen, ACS Appl. Mater. Interface, 9, 38606-38611 (2017).)に記述される手法に準じる手法で合成した。
EMC:エチルメチルカーボネート
LiTFSI:リチウムビス(トリフルオロメタンスルホニル)イミド
FEC:フルオロエチレンカーボネート
VC:ビニレンカーボネート
DMC:ジメチルカーボネート
DEC:ジエチルカーボネート
EMC溶媒に、LiTFSIを濃度が(2:1モル比)となるように添加し、さらに、FECを混合電解液100質量部に対して2.5質量部添加し、実施例1の非水二次電池用電解液を得た。
EMC溶媒に、LiTFSIを濃度が(2:1モル比)となるように添加し、さらに、FECを混合電解液100質量部に対して5質量部添加し、実施例2の非水二次電池用電解液を得た。
EMC溶媒に、LiTFSIを濃度が(2:1モル比)となるように添加し、さらに、FECを混合電解液100質量部に対して10質量部添加し、実施例3の非水二次電池用電解液を得た。
EMC溶媒に、LiTFSIを濃度が(2:1モル比)となるように添加し、さらに、VCを混合電解液100質量部に対して2.5質量部添加し、実施例4の非水二次電池用電解液を得た。
EMC溶媒に、LiTFSIを濃度が(2:1モル比)となるように添加し、さらに、VCを混合電解液100質量部に対して5質量部添加し、実施例5の非水二次電池用電解液を得た。
EMC溶媒に、LiTFSIを濃度が(2:1モル比)となるように添加し、さらに、VCを混合電解液100質量部に対して10質量部添加し、実施例6の非水二次電池用電解液を得た。
EMC溶媒に、LiTFSIを濃度が(3:1モル比)となるように添加し、さらに、FECを混合電解液100質量部に対して10質量部添加し、実施例7の非水二次電池用電解液を得た。
EMC溶媒に、LiTFSIを濃度が(4:1モル比)となるように添加し、さらに、FECを混合電解液100質量部に対して10質量部添加し、実施例6の非水二次電池用電解液を得た。
DMC溶媒に、LiTFSIを濃度が(2:1モル比)となるように添加し、さらにFECを混合電解液100質量部に対して10質量部添加し、実施例9の非水二次電池用電解液を得た。
DEC溶媒に、LiTFSIを濃度が(2:1モル比)となるように添加し、さらに、FECを混合電解液100質量部に対して10質量部添加し、実施例10の非水二次電池用電解液を得た。
EMC溶媒に、LiTFSIを濃度が(3:1モル比)となるように添加し、さらに、FECを混合電解液100質量部に対して10質量部添加し、実施例12の非水二次電池用電解液を得た。
EMC溶媒に、LiTFSIを濃度が(2:1モル比)となるように添加し、比較例1の非水二次電池用電解液を得た。
EMC溶媒に、LiTFSIを濃度が(3:1モル比)となるように添加し、比較例2の非水二次電池用電解液を得た。
実施例1~11、及び比較例1で得た非水二次電池用電解液に、合成例1で得たVS4粉末を正極活物質として用いた。
実施例1~11、及び比較例1で得た非水二次電池用電解液に、合成例1で得たVS4粉末を正極活物質として用いた。
Claims (8)
- 非水二次電池用電解液であって、
前記非水二次電池は、正極活物質としてリチウム非含有遷移金属硫化物を使用する非水二次電池であり、
前記電解液は、
鎖状カーボネート化合物を含む有機溶媒と、
リチウムビス(トリフルオロメタンスルホニル)イミド(LiTFSI)と、
添加剤とを含有する、
非水二次電池用電解液。 - 前記添加剤は、ビニレンカーボネート(VC)、及びフルオロエチレンカーボネート(FEC)から成る群から選ばれる少なくとも1種である、請求項1に記載の非水二次電池用電解液。
- 前記リチウムビス(トリフルオロメタンスルホニル)イミド(LiTFSI)の含有量に対して、前記鎖状カーボネート化合物の含有量は、モル比で2倍~4倍である、請求項1又は2に記載の非水二次電池用電解液。
- 前記電解液の総量を100重量%として、前記添加剤の含有量は、2.5重量%~10重量%である、前記項1~3のいずれか1項に記載の非水二次電池用電解液。
- 前記鎖状カーボネート化合物は、ジメチルカーボネート(DMC)、ジエチルカーボネート(DEC)、エチルメチルカーボネート(EMC)から成る群から選ばれる少なくとも1種である、請求項1~4のいずれか1項に記載の非水二次電池用電解液。
- 前記リチウム非含有遷移金属硫化物は、バナジウム硫化物、及びモリブデン硫化物から成る群から選ばれる少なくとも1種である、請求項1~5のいずれか1項に記載の非水二次電池用電解液。
- 請求項1~6のいずれか1項に記載の非水二次電池用電解液を備える、非水二次電池。
- リチウムイオン二次電池である、請求項7に記載の非水二次電池。
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