JP2022542350A - リチウム-硫黄電池用電解質及びこれを含むリチウム-硫黄電池 - Google Patents
リチウム-硫黄電池用電解質及びこれを含むリチウム-硫黄電池 Download PDFInfo
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- JP2022542350A JP2022542350A JP2022503966A JP2022503966A JP2022542350A JP 2022542350 A JP2022542350 A JP 2022542350A JP 2022503966 A JP2022503966 A JP 2022503966A JP 2022503966 A JP2022503966 A JP 2022503966A JP 2022542350 A JP2022542350 A JP 2022542350A
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- Prior art keywords
- lithium
- ether
- electrolyte
- sulfur
- carbonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 102
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 81
- -1 ether compound Chemical class 0.000 claims abstract description 74
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims abstract description 23
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 110
- 239000007774 positive electrode material Substances 0.000 claims description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 35
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 35
- 239000011593 sulfur Substances 0.000 claims description 33
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims description 18
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 17
- 239000007773 negative electrode material Substances 0.000 claims description 13
- ACBQROXDOHKANW-UHFFFAOYSA-N bis(4-nitrophenyl) carbonate Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC(=O)OC1=CC=C([N+]([O-])=O)C=C1 ACBQROXDOHKANW-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- GWQOOADXMVQEFT-UHFFFAOYSA-N 2,5-Dimethylthiophene Chemical compound CC1=CC=C(C)S1 GWQOOADXMVQEFT-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- CPULIKNSOUFMPL-UHFFFAOYSA-N 2,4-dimethylthiophene Chemical compound CC1=CSC(C)=C1 CPULIKNSOUFMPL-UHFFFAOYSA-N 0.000 claims description 6
- NWZIYQNUCXUJJJ-UHFFFAOYSA-N 2-butylfuran Chemical compound CCCCC1=CC=CO1 NWZIYQNUCXUJJJ-UHFFFAOYSA-N 0.000 claims description 6
- HLPIHRDZBHXTFJ-UHFFFAOYSA-N 2-ethylfuran Chemical compound CCC1=CC=CO1 HLPIHRDZBHXTFJ-UHFFFAOYSA-N 0.000 claims description 6
- KJRRQXYWFQKJIP-UHFFFAOYSA-N 3-methylfuran Chemical compound CC=1C=COC=1 KJRRQXYWFQKJIP-UHFFFAOYSA-N 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 6
- 239000006182 cathode active material Substances 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- CWHJIJJSDGEHNS-UHFFFAOYSA-N 13-(chloromethyl)-2,3-dihydroxy-4,6a,11,11,14b-pentamethyl-2,3,4a,5,6,7,8,9,10,12,12a,13,14,14a-tetradecahydro-1h-picene-4,8a-dicarboxylic acid Chemical compound C1C(O)C(O)C(C)(C(O)=O)C2CCC3(C)C(CCC4(CCC(CC44)(C)C)C(O)=O)=C4C(CCl)CC3C21C CWHJIJJSDGEHNS-UHFFFAOYSA-N 0.000 claims description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- 229910018091 Li 2 S Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- CAQYAZNFWDDMIT-UHFFFAOYSA-N 1-ethoxy-2-methoxyethane Chemical compound CCOCCOC CAQYAZNFWDDMIT-UHFFFAOYSA-N 0.000 claims description 4
- BZYUMXXOAYSFOW-UHFFFAOYSA-N 2,3-dimethylthiophene Chemical compound CC=1C=CSC=1C BZYUMXXOAYSFOW-UHFFFAOYSA-N 0.000 claims description 4
- CPLJMYOQYRCCBY-UHFFFAOYSA-N 2-Propylfuran Chemical compound CCCC1=CC=CO1 CPLJMYOQYRCCBY-UHFFFAOYSA-N 0.000 claims description 4
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 claims description 4
- BTXIJTYYMLCUHI-UHFFFAOYSA-N 2-propylthiophene Chemical compound CCCC1=CC=CS1 BTXIJTYYMLCUHI-UHFFFAOYSA-N 0.000 claims description 4
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 claims description 4
- QIXRWIVDBZJDGD-UHFFFAOYSA-N benzyl (4-nitrophenyl) carbonate Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC(=O)OCC1=CC=CC=C1 QIXRWIVDBZJDGD-UHFFFAOYSA-N 0.000 claims description 4
- DQPSUGZZTADITQ-UHFFFAOYSA-N bis(2-nitrophenyl) carbonate Chemical compound [O-][N+](=O)C1=CC=CC=C1OC(=O)OC1=CC=CC=C1[N+]([O-])=O DQPSUGZZTADITQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 150000003464 sulfur compounds Chemical class 0.000 claims description 4
- JRRDISHSXWGFRF-UHFFFAOYSA-N 1-[2-(2-ethoxyethoxy)ethoxy]-2-methoxyethane Chemical compound CCOCCOCCOCCOC JRRDISHSXWGFRF-UHFFFAOYSA-N 0.000 claims description 3
- YZWVMKLQNYGKLJ-UHFFFAOYSA-N 1-[2-[2-(2-ethoxyethoxy)ethoxy]ethoxy]-2-methoxyethane Chemical compound CCOCCOCCOCCOCCOC YZWVMKLQNYGKLJ-UHFFFAOYSA-N 0.000 claims description 3
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 claims description 3
- KIAMPLQEZAMORJ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxyethoxy)ethoxy]ethane Chemical compound CCOCCOCCOCCOCC KIAMPLQEZAMORJ-UHFFFAOYSA-N 0.000 claims description 3
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 claims description 3
- YVBAUDVGOFCUSG-UHFFFAOYSA-N 2-Pentylfuran Natural products CCCCCC1=CC=CO1 YVBAUDVGOFCUSG-UHFFFAOYSA-N 0.000 claims description 3
- JCCCMAAJYSNBPR-UHFFFAOYSA-N 2-ethylthiophene Chemical compound CCC1=CC=CS1 JCCCMAAJYSNBPR-UHFFFAOYSA-N 0.000 claims description 3
- XWNTYHBAQIEAGN-UHFFFAOYSA-N 2-methyl-2h-pyran Chemical compound CC1OC=CC=C1 XWNTYHBAQIEAGN-UHFFFAOYSA-N 0.000 claims description 3
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 claims description 3
- HYDWALOBQJFOMS-UHFFFAOYSA-N 3,6,9,12,15-pentaoxaheptadecane Chemical compound CCOCCOCCOCCOCCOCC HYDWALOBQJFOMS-UHFFFAOYSA-N 0.000 claims description 3
- SCRLLDUEKYMHDB-UHFFFAOYSA-N 3-methylpyran Chemical compound CC1=CO[CH][CH][CH]1 SCRLLDUEKYMHDB-UHFFFAOYSA-N 0.000 claims description 3
- OOARNVHTYGBULA-UHFFFAOYSA-N 4-methyl-2h-pyran Chemical compound CC1=CCOC=C1 OOARNVHTYGBULA-UHFFFAOYSA-N 0.000 claims description 3
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 claims description 3
- YHLVIDQQTOMBGN-UHFFFAOYSA-N methyl prop-2-enyl carbonate Chemical compound COC(=O)OCC=C YHLVIDQQTOMBGN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 claims description 2
- AABTWRKUKUPMJG-UHFFFAOYSA-N 2,4-dimethylfuran Chemical compound CC1=COC(C)=C1 AABTWRKUKUPMJG-UHFFFAOYSA-N 0.000 claims description 2
- WVUICGOYGDHVBH-ONEGZZNKSA-N 2-[(e)-2-nitroethenyl]furan Chemical compound [O-][N+](=O)\C=C\C1=CC=CO1 WVUICGOYGDHVBH-ONEGZZNKSA-N 0.000 claims description 2
- MNDZHERKKXUTOE-UHFFFAOYSA-N 2-butylthiophene Chemical compound CCCCC1=CC=CS1 MNDZHERKKXUTOE-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000002019 disulfides Chemical class 0.000 claims description 2
- OFJLSOXXIMLDDL-UHFFFAOYSA-N ethyl (4-nitrophenyl) carbonate Chemical compound CCOC(=O)OC1=CC=C([N+]([O-])=O)C=C1 OFJLSOXXIMLDDL-UHFFFAOYSA-N 0.000 claims description 2
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 59
- 230000000052 comparative effect Effects 0.000 description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 31
- 239000011230 binding agent Substances 0.000 description 22
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical class [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 9
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- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 8
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- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting 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
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TXQBMQNFXYOIPT-UHFFFAOYSA-N octyl nitrate Chemical class CCCCCCCCO[N+]([O-])=O TXQBMQNFXYOIPT-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- JNTOKFNBDFMTIV-UHFFFAOYSA-N propyl nitrate Chemical class CCCO[N+]([O-])=O JNTOKFNBDFMTIV-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- XLABPPWWFVQMBZ-UHFFFAOYSA-O pyridin-1-ium;nitrate Chemical class [O-][N+]([O-])=O.C1=CC=[NH+]C=C1 XLABPPWWFVQMBZ-UHFFFAOYSA-O 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003577 thiophenes Chemical class 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
- 229910052723 transition metal Inorganic materials 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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
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- H01M4/381—Alkaline or alkaline earth metals elements
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- 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
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- H01M4/5815—Sulfides
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
Description
[実施例1]
0.75M LiFSIと3.0重量%の硝酸リチウムを2-メチルフランとジメトキシエタン(2-methylfuran:DME=1:2(体積比))からなる有機溶媒に溶解させた溶液を製造した。次いで、電解質全体100重量%に対して1.4重量%の含量になるように上記溶液にビス(4-ニトロフェニル)カーボネートを添加して電解質を製造した。
正極活物質として硫黄-炭素複合体(S:C=75:25(重量比))87.5重量%、導電材としてデンカブラック5.0重量%、バインダーとしてスチレンブタジエンゴム/カルボキシメチルセルロース(SBR:CMC=70:30(重量比))7.5重量%を混合して正極スラリー組成物を製造した。
2-メチルフランとジメトキシエタンの体積比を1:4で、ビス(4-ニトロフェニル)カーボネートの含量を2.0重量%に変更したことを除いては、上記実施例1と同様の方法で電解質を製造した。
実施例1の電解質の代わりに実施例3の電解質を使ったことを除いては、上記実施例2と同様の方法でリチウム-硫黄電池を製造した。
ビス(4-ニトロフェニル)カーボネートを添加しないことを除いては、上記実施例1と同様の方法で電解質を製造した。
有機溶媒としてジメトキシエタンのみを使用し、ビス(4-ニトロフェニル)カーボネートの含量を1.3重量%に変更したことを除いては、上記実施例1と同様の方法で電解質を製造した。
有機溶媒として2-メチルフランのみを使用し、ビス(4-ニトロフェニル)カーボネートを添加しないことを除いては、上記実施例1と同様の方法で電解質を製造した。しかし、図1に示すように、リチウム塩が溶解されずに析出されていて電池に適用することが不可能だった。
1.0M LiTFSIと2.4重量%の硝酸リチウムを1,3-ジオキソランとジメトキシエタン(DOL:DME=1:1(体積比))からなる有機溶媒に溶解させて電解質を製造した。
1.0M LiTFSIと2.4重量%の硝酸リチウムを1,3-ジオキソランとジメトキシエタン(DOL:DME=1:1(体積比))からなる有機溶媒に溶解させた溶液を製造した。次いで、電解質全体100重量%に対して1.2重量%の含量になるように上記溶液にビス(4-ニトロフェニル)カーボネートを添加して電解質を製造した。
有機溶媒としてジメトキシエタンのみを使用し、ビス(4-ニトロフェニル)カーボネートを添加しないことを除いては、上記実施例1と同様の方法で電解質を製造した。
実施例1の電解質の代わりに比較例1の電解質を使ったことを除いては、上記実施例2と同様に行ってリチウム-硫黄電池を製造した。
実施例1の電解質の代わりに比較例2の電解質を使ったことを除いては、上記実施例2と同様に行ってリチウム-硫黄電池を製造した。
実施例1の電解質の代わりに比較例4の電解質を使ったことを除いては、上記実施例2と同様に行ってリチウム-硫黄電池を製造した。
実施例1の電解質の代わりに比較例5の電解質を使ったことを除いては、上記実施例2と同様に行ってリチウム-硫黄電池を製造した。
実施例1の電解質の代わりに比較例6の電解質を使ったことを除いては、上記実施例2と同様に行ってリチウム-硫黄電池を製造した。
45μm厚さのリチウム金属薄膜2個を負極で使用し、上記実施例1及び比較例1で製造した電解質100μlをそれぞれ注入してLi/Li対称セル(symmetric cell)を製造した。
実施例2及び4と比較例7ないし11で製造した電池に対し、充放電測定装置(LAND CT-2001A、武漢(Wuhan)社製品)を使って性能を評価した。
Claims (15)
- リチウム塩、非水系有機溶媒及び添加剤を含み、
前記非水系有機溶媒は、エーテル化合物及び酸素原子または硫黄原子を含むヘテロ環化合物を含み、
前記ヘテロ環化合物は一つ以上の二重結合を含み、
前記添加剤はカーボネート化合物を含むリチウム-硫黄電池用電解質。 - 前記カーボネート化合物は、ビス(4-ニトロフェニル)カーボネート、ビス(2-ニトロフェニル)カーボネート、2-(メチルスルホニル)エチル4-ニトロフェニルカーボネート、ベンジル4-ニトロフェニルカーボネート、2-(トリメチルシルリル)エチル4-ニトロフェニルカーボネート、ビニレンカーボネート、フルオロエチレンカーボネート、ビニルエチレンカーボネート及びアリルメチルカーボネートからなる群から選択される1種以上を含む、請求項1に記載のリチウム-硫黄電池用電解質。
- 前記カーボネート化合物は、リチウム-硫黄電池用電解質全体100重量%を基準にして0.1ないし10重量%で含まれる、請求項1に記載のリチウム-硫黄電池用電解質。
- 前記エーテル化合物は線状エーテル化合物を含む、請求項1に記載のリチウム-硫黄電池用電解質。
- 前記線状エーテル化合物は、ジメチルエーテル、ジエチルエーテル、ジプロピルエーテル、メチルエチルエーテル、メチルプロピルエーテル、エチルプロピルエーテル、ジメトキシエタン、ジエトキシエタン、エチレングリコールエチルメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテル、トリエチレングリコールメチルエチルエーテル、テトラエチレングリコールジメチルエーテル、テトラエチレングリコールジエチルエーテル、テトラエチレングリコールメチルエチルエーテル、ポリエチレングリコールジメチルエーテル、ポリエチレングリコールジエチルエーテル及びポリエチレングリコールメチルエチルエーテルからなる群から選択される1種以上を含む、請求項4に記載のリチウム-硫黄電池用電解質。
- 前記ヘテロ環化合物は3ないし15員のヘテロ環化合物である、請求項1に記載のリチウム-硫黄電池用電解質。
- 前記ヘテロ環化合物は、炭素数1ないし4のアルキル基、炭素数3ないし8の環状アルキル基、炭素数6ないし10のアリール基、ハロゲン基、ニトロ基、アミン基及びスルホニル基からなる群から選択される1種以上に置換または非置換されたヘテロ環化合物;または炭素数3ないし8の環状アルキル基及び炭素数6ないし10のアリール基からなる群から選択される1種以上とヘテロ環化合物の多重環化合物を含む、請求項1に記載のリチウム-硫黄電池用電解質。
- 前記ヘテロ環化合物は、フラン、2-メチルフラン、3-メチルフラン、2-エチルフラン、2-プロピルフラン、2-ブチルフラン、2,3-ジメチルフラン、2,4-ジメチルフラン、2,5-ジメチルフラン、ピラン、2-メチルピラン、3-メチルピラン、4-メチルピラン、ベンゾフラン、2-(2-ニトロビニル)フラン、チオフェン、2-メチルチオフェン、2-エチルチオフェン、2-プロピルチオフェン、2-ブチルチオフェン、2,3-ジメチルチオフェン、2,4-ジメチルチオフェン及び2,5-ジメチルチオフェンからなる群から選択される1種以上を含む、請求項1に記載のリチウム-硫黄電池用電解質。
- 前記非水系有機溶媒は、エーテル化合物100体積比に対してヘテロ環化合物を0.1ないし100体積比で含む、請求項1に記載のリチウム-硫黄電池用電解質。
- 前記非水系有機溶媒は、エーテル化合物100体積比に対してヘテロ環化合物を25以上ないし100未満の体積比で含む、請求項9に記載のリチウム-硫黄電池用電解質。
- 前記非水系有機溶媒は、環状エーテル化合物、エステル化合物、アミド化合物、線状カーボネート化合物及び環状カーボネート化合物からなる群から選択される1種以上をさらに含む、請求項1に記載のリチウム-硫黄電池用電解質。
- 正極活物質を含む正極;
負極活物質を含む負極;及び
請求項1に記載の電解質を含むリチウム-硫黄電池。 - 前記正極活物質は硫黄元素及び硫黄化合物からなる群から選択される1種以上を含む、請求項12に記載のリチウム-硫黄電池。
- 前記正極活物質は、無機硫黄、Li2Sn(n≧1)、ジスルフィド化合物、有機硫黄化合物及び炭素-硫黄ポリマー((C2Sx)n、x=2.5ないし50、n≧2)からなる群から選択される1種以上を含む、請求項12に記載のリチウム-硫黄電池。
- 前記負極活物質は、リチウム金属及びリチウム合金からなる群から選択される1種以上を含む、請求項12に記載のリチウム-硫黄電池。
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