JP2013182887A - 電解質及びそれを含むリチウム空気電池 - Google Patents
電解質及びそれを含むリチウム空気電池 Download PDFInfo
- Publication number
- JP2013182887A JP2013182887A JP2013037102A JP2013037102A JP2013182887A JP 2013182887 A JP2013182887 A JP 2013182887A JP 2013037102 A JP2013037102 A JP 2013037102A JP 2013037102 A JP2013037102 A JP 2013037102A JP 2013182887 A JP2013182887 A JP 2013182887A
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- JP
- Japan
- Prior art keywords
- electrolyte
- lithium
- formula
- ion conductive
- lithium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 131
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 70
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000126 substance Substances 0.000 claims abstract description 34
- 239000002608 ionic liquid Substances 0.000 claims abstract description 32
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 31
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 31
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 20
- 150000001450 anions Chemical class 0.000 claims abstract description 13
- 239000007784 solid electrolyte Substances 0.000 claims description 41
- 239000012528 membrane Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 26
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 20
- 230000001681 protective effect Effects 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 16
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- -1 pyrrolidinium cation Chemical class 0.000 claims description 13
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 10
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 7
- 239000005518 polymer electrolyte Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000011244 liquid electrolyte Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229910010238 LiAlCl 4 Inorganic materials 0.000 claims description 5
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 5
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 5
- 229910013372 LiC 4 Inorganic materials 0.000 claims description 5
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 5
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 5
- 150000001768 cations Chemical group 0.000 claims description 5
- 229910010093 LiAlO Inorganic materials 0.000 claims description 4
- 229910015044 LiB Inorganic materials 0.000 claims description 4
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 3
- 229910013131 LiN Inorganic materials 0.000 claims description 3
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 claims description 3
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 3
- 210000004027 cell Anatomy 0.000 description 56
- 230000000052 comparative effect Effects 0.000 description 41
- 239000002241 glass-ceramic Substances 0.000 description 30
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 26
- 239000013078 crystal Substances 0.000 description 20
- 239000011521 glass Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- 229910052751 metal Chemical class 0.000 description 7
- 239000002184 metal Chemical class 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 210000001787 dendrite Anatomy 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002847 impedance measurement Methods 0.000 description 4
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JYVXNLLUYHCIIH-UHFFFAOYSA-N (+/-)-mevalonolactone Natural products CC1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 239000002227 LISICON Substances 0.000 description 1
- 229910019271 La0.55Li0.35TiO3 Inorganic materials 0.000 description 1
- 229910008576 Li2O—Al2O3—TiO2—SiO2—P2O5 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013375 LiC Inorganic materials 0.000 description 1
- 229910013398 LiN(SO2CF2CF3)2 Inorganic materials 0.000 description 1
- 229910012305 LiPON Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- FVXHSJCDRRWIRE-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] FVXHSJCDRRWIRE-UHFFFAOYSA-H 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- JYVXNLLUYHCIIH-ZCFIWIBFSA-N R-mevalonolactone, (-)- Chemical compound C[C@@]1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-ZCFIWIBFSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- URZWHNFFWSYUMB-UHFFFAOYSA-B aluminum lithium silicon(4+) titanium(4+) tetraphosphate Chemical compound P(=O)([O-])([O-])[O-].[Si+4].[Ti+4].[Al+3].[Li+].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] URZWHNFFWSYUMB-UHFFFAOYSA-B 0.000 description 1
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- IEFUHGXOQSVRDQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-methyl-1-propylpiperidin-1-ium Chemical compound CCC[N+]1(C)CCCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F IEFUHGXOQSVRDQ-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229940057061 mevalonolactone Drugs 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- GHZRKQCHJFHJPX-UHFFFAOYSA-N oxacycloundecan-2-one Chemical compound O=C1CCCCCCCCCO1 GHZRKQCHJFHJPX-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
一具現例によれば、化学式1のR1およびR2のパーフルオロアルキル基は−CF3である。
ポリ酸化エチレン(H−[O−CH2CH2]18−OH、重合度は18、重量平均分子量:約60万、以下、PEO18で表示)1モル、LiTFSI(LiN(SO2CF3)2)1モル及び下記化学式14の化合物0.4モルを混合して電解質を製造した。
化学式14の化合物の含量が0.80モルに変わったことを除き、実施例1と同一の方法によって実施して電解質を製造した。
化学式14の化合物の含量が1.20モルに変わったことを除き、実施例1と同一の方法によって実施して電解質を製造した。
化学式14の化合物の含量が1.60モルに変わったことを除き、実施例1と同一の方法によって実施して電解質を製造した。
化学式14の化合物の含量が2.00モルに変わったことを除き、実施例1と同一の方法によって実施して電解質を製造した。
化学式14の化合物の含量が1.44モルに変わったことを除き、実施例1と同一の方法によって実施して電解質を製造した。
化学式14の化合物の含量が1.44モルに変わり、ポリ酸化エチレン、LiTFSI及び化学式15の化合物の総重量100重量部に、BaTiO3 10重量部がさらに付加されたことを除き、実施例1と同一の方法によって実施して電解質を製造した。
化学式14の化合物の含量が2.40モルに変わったことを除き、実施例1と同一の方法によって実施して電解質を製造した。
化学式14の化合物が付加されていないことを除き、実施例1と同一の方法によって実施して電解質を製造した。
化学式20の化合物0.96モルが使われたことを除き、比較例2と同一の方法によって実施して電解質を製造した。
化学式20の化合物1.44モルが使われたことを除き、比較例2と同一の方法によって実施して電解質を製造した。
化学式20の化合物2.00モルが使われたことを除き、比較例2と同一の方法によって実施して電解質を製造した。
評価用セル1ないし6及び比較セル1ないし5を、下記積層構造を有するように製作した。
Li/実施例1の電解質(PEO18LiTFSI−0.40PP13FSI)/Li積層構造
[セル2]
Li/実施例2の電解質(PEO18LiTFSI−0.80PP13FSI)/Li積層構造
[セル3]
Li/実施例3の電解質(PEO18LiTFSI−1.20PP13FSI)/Li積層構造
[セル4]
Li/実施例4の電解質(PEO18LiTFSI−1.60PP13FSI)/Li積層構造
[セル5]
Li/実施例5の電解質(PEO18LiTFSI−2.00PP13FSI)/Li積層構造
[セル6]
Li/実施例8の電解質(PEO18LiTFSI−2.40PP13FSI)/Li積層構造
[比較セル1]
Li/比較例1の電解質(PEO18LiTFSI)/Li積層構造
[比較セル2]
Li/比較例2の電解質(PEO18LiTFSI−0.48PP13TFSI)/Li積層構造
[比較セル3]
Li/比較例3の電解質(PEO18LiTFSI−0.96PP13TFSI)/Li積層構造
[比較セル4]
Li/比較例4の電解質(PEO18LiTFSI−1.44PP13TFSI)/Li積層構造
[比較セル5]
Li/比較例5の電解質(PEO18LiTFSI−2.00PP13TFSI)/Li積層構造
Li/実施例6の電解質(PEO18LiTFSI−1.44PP13FSI)/Li積層構造
[セル8]
Li/実施例7の電解質(PEO18LiTFSI−1.44PP13FSI−BaTiO3)/Li積層構造
[セル9]
Li/実施例7の電解質(PEO18LiTFSI−1.44PP13FSI−BaTiO3)/LATP/1MLiCl(aq.)/Pt積層構造
[比較セル1]
Li/比較例1の電解質(PEO18LiTFSI)/Li積層構造
11,21 正極
12 電解質
22 第1電解質
23 保護膜
24 第2電解質
25 保護負極
Claims (20)
- 前記パーフルオロアルキル基が、
CF3であることを特徴とする請求項1に記載の電解質。 - 前記イオン性液体が、
アンモニウム陽イオン、イミダゾリウム陽イオン、ピロリジニウム陽イオン、ピペリジニウム陽イオンまたはホスホニウム陽イオンを含むことを特徴とする請求項1または2に記載の電解質。 - 前記イオン性液体の含量が、
リチウムイオン伝導性高分子1モルを基準にして、0.1ないし2モルであることを特徴とする請求項1から7の何れか一項に記載の電解質。 - 前記リチウム塩が、
LiPF6、LiBF4、LiSbF6、LiAsF6、LiN(SO2C2F5)2、LiN(SO2F2)2、Li(CF3SO2)2N、LiC4F9SO3、LiClO4、LiAlO2、LiAlCl4、LiN(CxF2x+1SO2)(CyF2y+1SO2)(ここで、x及びyは0ないし10の整数)、LiF、LiBr、LiCl、LiI及びLiB(C2O4)2(リチウムビスオキサレートボラート)からなる群から選択された一つ以上であることを特徴とする請求項1から8の何れか一項に記載の電解質。 - 前記リチウム塩の含量が、
リチウムイオン伝導性高分子の酸素のモル数に対するリチウムイオンのモル数の比Li/Oが、1/6ないし1/54であることを特徴とする請求項1から9の何れか一項に記載の電解質。 - 無機フィラーがさらに含まれることを特徴とする請求項1から10の何れか一項に記載の電解質。
- 前記無機フィラーが、
BaTiO3、SiO2、TiO2、ZrO2及びゼオライトからなる群から選択された一つ以上であることを特徴とする請求項11に記載の電解質。 - 前記無機フィラーの含量が、
リチウムイオン伝導性高分子、リチウム塩及びイオン性液体の総重量100重量部に対して、0.1ないし20重量部であることを特徴とする請求項11または12に記載の電解質。 - 正極と、第1電解質と、負極と、を含み、
前記第1電解質が、
請求項1ないし13のうちいずれか1項に記載の電解質であるリチウム空気電池。 - 前記パーフルオロアルキル基が、
CF3であることを特徴とする請求項14に記載のリチウム空気電池。 - 前記第1電解質と正極との間に保護膜がさらに含まれることを特徴とする請求項14または15に記載のリチウム空気電池。
- 前記保護膜が、
無機固体電解質膜、高分子固体電解質膜、ゲル型高分子電解質膜及びリチウムイオン伝導性固体電解質膜のうちから選択された一つ以上であることを特徴とする請求項16に記載のリチウム空気電池。 - 前記正極と保護膜との間に、
第2電解質がさらに含まれることを特徴とする請求項16または17に記載のリチウム空気電池。 - 前記第2電解質が、
セパレータ、液体電解質、無機固体電解質、高分子固体電解質、リチウムイオン伝導性固体電解質及びゲル型高分子電解質のうちから選択された一つ以上であることを特徴とする請求項18に記載のリチウム空気電池。 - 前記第2電解質が、
非水系溶媒及びリチウム塩を含む液体電解質であることを特徴とする請求項18または19に記載のリチウム空気電池。
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Also Published As
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JP6300446B2 (ja) | 2018-03-28 |
KR20130099706A (ko) | 2013-09-06 |
US20130224609A1 (en) | 2013-08-29 |
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