JP6464725B2 - Electrolyte for metal-air battery - Google Patents
Electrolyte for metal-air battery Download PDFInfo
- Publication number
- JP6464725B2 JP6464725B2 JP2014258889A JP2014258889A JP6464725B2 JP 6464725 B2 JP6464725 B2 JP 6464725B2 JP 2014258889 A JP2014258889 A JP 2014258889A JP 2014258889 A JP2014258889 A JP 2014258889A JP 6464725 B2 JP6464725 B2 JP 6464725B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- air battery
- electrolyte
- ionic liquid
- air
- 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.)
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- 239000003792 electrolyte Substances 0.000 title claims description 39
- 239000008151 electrolyte solution Substances 0.000 claims description 50
- 239000002608 ionic liquid Substances 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical group 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 description 41
- 238000003786 synthesis reaction Methods 0.000 description 41
- 239000011777 magnesium Substances 0.000 description 26
- 239000011734 sodium Substances 0.000 description 23
- 229910018071 Li 2 O 2 Inorganic materials 0.000 description 22
- -1 pyrrolidinium cation Chemical class 0.000 description 18
- 229940021013 electrolyte solution Drugs 0.000 description 17
- 230000037427 ion transport Effects 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 10
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- ZOSPVHQYAGHQPI-UHFFFAOYSA-M 1-(2-methoxyethyl)-1-methylpyrrolidin-1-ium chloride Chemical compound [Cl-].COCC[N+]1(CCCC1)C ZOSPVHQYAGHQPI-UHFFFAOYSA-M 0.000 description 4
- XTIGGAHUZJWQMD-UHFFFAOYSA-N 1-chloro-2-methoxyethane Chemical compound COCCCl XTIGGAHUZJWQMD-UHFFFAOYSA-N 0.000 description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000011356 non-aqueous organic solvent Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- ZKLQIVPPHFQZOK-UHFFFAOYSA-N 1-(2-methoxyethyl)pyrrolidine Chemical compound COCCN1CCCC1 ZKLQIVPPHFQZOK-UHFFFAOYSA-N 0.000 description 2
- GTHWJSPEAAGERR-UHFFFAOYSA-M 1-(methoxymethyl)-1-methylpyrrolidin-1-ium;chloride Chemical compound [Cl-].COC[N+]1(C)CCCC1 GTHWJSPEAAGERR-UHFFFAOYSA-M 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 229910020808 NaBF Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-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
- 239000007788 liquid Substances 0.000 description 2
- 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 2
- 239000002905 metal composite material Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001472 pulsed field gradient Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- JRRDISHSXWGFRF-UHFFFAOYSA-N 1-[2-(2-ethoxyethoxy)ethoxy]-2-methoxyethane Chemical compound CCOCCOCCOCCOC JRRDISHSXWGFRF-UHFFFAOYSA-N 0.000 description 1
- YZWVMKLQNYGKLJ-UHFFFAOYSA-N 1-[2-[2-(2-ethoxyethoxy)ethoxy]ethoxy]-2-methoxyethane Chemical compound CCOCCOCCOCCOCCOC YZWVMKLQNYGKLJ-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- BELGHMWMXFCZTP-UHFFFAOYSA-N 3-ethyl-1,3-oxazolidin-2-one Chemical compound CCN1CCOC1=O BELGHMWMXFCZTP-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- GDKSTFXHMBGCPG-UHFFFAOYSA-N 4,4-dimethyl-1,3-dioxane Chemical compound CC1(C)CCOCO1 GDKSTFXHMBGCPG-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- 229910018921 CoO 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- LYKZLSOWKOVLKF-UHFFFAOYSA-N FS(=O)(=O)[N-]S(=O)(=O)F.COC[N+]1(CCCC1)C Chemical compound FS(=O)(=O)[N-]S(=O)(=O)F.COC[N+]1(CCCC1)C LYKZLSOWKOVLKF-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 description 1
- ROYOLNQPXVHWNE-UHFFFAOYSA-N [Co].[Ca].[La] Chemical compound [Co].[Ca].[La] ROYOLNQPXVHWNE-UHFFFAOYSA-N 0.000 description 1
- GGGMJWBVJUTTLO-UHFFFAOYSA-N [Co]=O.[Sr].[La] Chemical compound [Co]=O.[Sr].[La] GGGMJWBVJUTTLO-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- GPCXOTFNQZKHSR-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[La+3].[K+].[Mn](=O)(=O)([O-])[O-] Chemical compound [Mn](=O)(=O)([O-])[O-].[La+3].[K+].[Mn](=O)(=O)([O-])[O-] GPCXOTFNQZKHSR-UHFFFAOYSA-N 0.000 description 1
- JOCCKLUWAJCUFY-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[La+3].[Na+].[Mn](=O)(=O)([O-])[O-] Chemical compound [Mn](=O)(=O)([O-])[O-].[La+3].[Na+].[Mn](=O)(=O)([O-])[O-] JOCCKLUWAJCUFY-UHFFFAOYSA-N 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- ZPIRDTOMKBAWBG-UHFFFAOYSA-N [Rb+].[Mn](=O)(=O)([O-])[O-].[La+3].[Mn](=O)(=O)([O-])[O-] Chemical compound [Rb+].[Mn](=O)(=O)([O-])[O-].[La+3].[Mn](=O)(=O)([O-])[O-] ZPIRDTOMKBAWBG-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
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- 239000012300 argon atmosphere Substances 0.000 description 1
- HBTKRUXLKWRXSK-UHFFFAOYSA-N bis(fluorosulfonyl)azanide 1-(2-methoxyethyl)-1-methylpyrrolidin-1-ium Chemical compound FS(=O)(=O)[N-]S(F)(=O)=O.COCC[N+]1(C)CCCC1 HBTKRUXLKWRXSK-UHFFFAOYSA-N 0.000 description 1
- NLMPZJBZQUPZSN-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-(2-methoxyethyl)-1-methylpyrrolidin-1-ium Chemical compound COCC[N+]1(C)CCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F NLMPZJBZQUPZSN-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
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- 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
- 229910021320 cobalt-lanthanum-strontium oxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 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
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 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
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 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
- 230000007774 longterm Effects 0.000 description 1
- 229960004995 magnesium peroxide Drugs 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001524 potential step chrono-amperometry Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920006027 ternary co-polymer Polymers 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
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
Description
本発明は、金属空気電池用電解液に関し、さらに詳述すると、特定のイオン液体を含む金属空気電池用電解液に関する。 The present invention relates to a metal-air battery electrolyte, and more particularly to a metal-air battery electrolyte containing a specific ionic liquid.
近年、デジタルカメラ、スマートフォン、タブレット機器などの携帯電子機器の普及がめざましく、これに伴って、それらの機器の電源として用いられる、充電により繰り返し使用できる二次電池の需要が大きく伸びるとともに、その高容量化、高エネルギー密度化の要望がますます高まりつつある。
中でも、金属空気電池は、空気極で大気中の酸素を正極活物質とした酸化還元反応を利用し、負極で金属の酸化還元反応を利用して充放電を行う電池であり、エネルギー密度が高いことから、現在汎用されているリチウムイオン二次電池に優る高容量電池として期待されている（特許文献１参照）。
In recent years, portable electronic devices such as digital cameras, smartphones, and tablet devices have become widespread. Along with this, the demand for secondary batteries that can be used repeatedly for charging, which are used as power sources for such devices, has greatly increased. The demand for higher capacity and higher energy density is increasing.
In particular, a metal-air battery is a battery that uses the redox reaction using oxygen in the atmosphere as the positive electrode active material at the air electrode and performs charge / discharge using the metal redox reaction at the negative electrode, and has a high energy density. Therefore, it is expected as a high-capacity battery superior to lithium ion secondary batteries that are currently widely used (see Patent Document 1).
金属空気電池の非水電解質溶媒としては、一般的に有機溶媒が用いられているが、有機溶媒は揮発性があるとともに、水との混和性もあるため、長期の電池作動時には、正極側から電解液が揮発することによって電池抵抗が増大したり、水分が電池内部に浸入することによって負極である金属リチウムが腐食されたりする場合がある。
揮発性による電解液の減少および水分の電池内部への混入が抑制され、電池の長期の安定作動が可能なリチウム空気電池を提供することを目的として、非水電解質として、疎水性のイオン液体を用いた電解液を有する空気電池が提案されている（特許文献２〜５参照）。
As a non-aqueous electrolyte solvent for metal-air batteries, organic solvents are generally used. However, organic solvents are volatile and miscible with water. The battery resistance may increase due to volatilization of the electrolytic solution, or the lithium metal as the negative electrode may be corroded due to moisture entering the battery.
For the purpose of providing a lithium-air battery capable of long-term stable operation of the battery, in which a decrease in the electrolyte due to volatility and the entry of moisture into the battery is suppressed, a hydrophobic ionic liquid is used as a non-aqueous electrolyte. An air battery having the electrolytic solution used has been proposed (see
イオン液体を電解液として用いることで、電解液の揮発による減少や水分の電池内部への混入の抑制に一定の効果が得られるものの、イオン液体を電解液として用いた空気電池においては、イオン液体の耐電圧性および粘度や、電解液中のイオン電導率等の点でさらなる改良の余地がある。 Although the use of an ionic liquid as an electrolytic solution can provide a certain effect in the reduction of the electrolytic solution due to volatilization and the suppression of moisture mixing into the battery, in an air battery using the ionic liquid as an electrolytic solution, the ionic liquid There is room for further improvement in terms of withstand voltage and viscosity, and ionic conductivity in the electrolyte.
本発明は、このような事情に鑑みてなされたものであり、イオン液体を含み、良好な酸素供給能および金属イオン輸率を発揮する金属空気電池用電解液を提供することを目的とする。 This invention is made | formed in view of such a situation, and it aims at providing the electrolyte solution for metal air batteries which contains an ionic liquid and exhibits favorable oxygen supply capability and a metal ion transport number.
本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、所定のピロリジニウムカチオンを有するイオン液体が、耐電圧性に優れるとともに酸素供給能および金属イオン輸率が良好であることから、金属空気電池用電解液として好適であることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have found that an ionic liquid having a predetermined pyrrolidinium cation is excellent in voltage resistance and has good oxygen supply ability and metal ion transport number. Thus, the present invention was completed by finding it suitable as an electrolyte for metal-air batteries.
すなわち、本発明は、
１． 式（１）で示されるイオン液体を含むことを特徴とする金属空気電池用電解液、
２． 前記Ｘ-が、ＢＦ4 -、ＰＦ6 -、ＣＦ3ＳＯ3 -、ＣＦ3ＣＯ2 -、（ＣＦ3ＳＯ2）2Ｎ-または（ＦＳＯ2）2Ｎ-を表す１の金属空気電池用電解液、
３． 前記Ｒ1が、メチル基またはエチル基を表す１または２の金属空気電池用電解液、
４． 前記Ｒ1およびＲ2が、共にメチル基を表す３の金属空気電池用電解液、
５． 前記ｎが、１〜３の整数を表す１〜４のいずれかの金属空気電池用電解液、
６． 前記イオン液体が、式（２）で示される２の金属空気電池用電解液、
７． 前記Ｘ-が、（ＣＦ3ＳＯ2）2Ｎ-または（ＦＳＯ2）2Ｎ-である６の金属空気電池用電解液、
８． 前記イオン液体が、式（３）で示される２の金属空気電池用電解液、
９． 前記Ｘ-が、（ＣＦ3ＳＯ2）2Ｎ-または（ＦＳＯ2）2Ｎ-である８の金属空気電池用電解液、
１０． 前記ｎが、２である９の金属空気電池用電解液、
１１． 有機溶媒を含まない１〜１０のいずれかの金属空気電池用電解液、
１２． 金属塩を含む１〜１１のいずれかの金属空気電池用電解液、
１３． 前記金属塩が、前記Ｘ-と同一のアニオンを有する１２の金属空気電池用電解液、
１４． 前記金属塩が、リチウム塩、ナトリウム塩またはマグネシウム塩である１２または１３の金属空気電池用電解液、
１５． 空気極と負極と、これら各極間に介在する電解質層を有し、前記電解質層が、１〜１４のいずれかの金属空気電池用電解液を含むことを特徴とする金属空気電池
を提供する。
That is, the present invention
1. An electrolytic solution for a metal-air battery, comprising an ionic liquid represented by the formula (1):
2. For the metal-air battery according to claim 1, wherein X − represents BF 4 − , PF 6 − , CF 3 SO 3 − , CF 3 CO 2 − , (CF 3 SO 2 ) 2 N − or (FSO 2 ) 2 N − . Electrolyte,
3. 1 or 2 metal-air battery electrolyte for which R 1 represents a methyl group or an ethyl group,
4). 3. an electrolyte for a metal-air battery, wherein R 1 and R 2 both represent a methyl group,
5. The electrolytic solution for metal-air batteries according to any one of 1 to 4, wherein n represents an integer of 1 to 3,
6). The ionic liquid is an electrolyte for a metal-air battery represented by formula (2),
7). 6. An electrolyte for a metal-air battery, wherein X − is (CF 3 SO 2 ) 2 N − or (FSO 2 ) 2 N − .
8). The ionic liquid is an electrolytic solution for metal-air battery of 2 represented by formula (3),
9. 8. An electrolyte for a metal-air battery, wherein X − is (CF 3 SO 2 ) 2 N − or (FSO 2 ) 2 N − ,
10. 9 is an electrolyte for a metal-air battery, wherein n is 2.
11. 1 to 10 electrolytic solution for metal-air battery, which does not contain an organic solvent,
12 1 to 11 metal-air battery electrolyte containing a metal salt,
13. 12 metal-air battery electrolytes in which the metal salt has the same anion as X − ,
14 12 or 13 metal-air battery electrolyte, wherein the metal salt is a lithium salt, a sodium salt or a magnesium salt,
15. Provided is a metal-air battery comprising an air electrode, a negative electrode, and an electrolyte layer interposed between these electrodes, wherein the electrolyte layer contains any one of the electrolyte solutions for metal-air batteries 1-14. .
本発明の電解液に用いられるイオン液体は比較的粘度が低く、電解液とした場合に良好な酸素供給能および金属イオン輸率を発揮するとともに、耐電圧性が良好であるため、電解液の電位が高電圧領域になる金属空気電池においても劣化が少ない。
また、本発明の電解液に用いられるイオン液体は、金属塩や金属酸化物の溶解能に優れているため、有機溶媒を使用しない、あるいは使用する場合でもその量を極めて少量とすることができるため、安全性に優れた金属空気電池を提供することができる。
The ionic liquid used in the electrolytic solution of the present invention has a relatively low viscosity, and when used as an electrolytic solution, exhibits good oxygen supply ability and metal ion transport number, and has a good voltage resistance. There is little deterioration even in a metal-air battery in which the potential is in a high voltage region.
In addition, since the ionic liquid used in the electrolytic solution of the present invention is excellent in the ability to dissolve metal salts and metal oxides, the amount of the ionic liquid can be made extremely small even when an organic solvent is not used or is used. Therefore, a metal-air battery excellent in safety can be provided.
以下、本発明についてさらに詳しく説明する。
本発明に係る金属空気電池用電解液は、式（１）で示されるイオン液体を含む。
Hereinafter, the present invention will be described in more detail.
The electrolytic solution for a metal-air battery according to the present invention includes an ionic liquid represented by the formula (1).
Ｒ1は、炭素数１〜３のアルキル基を表し、その具体例としては、直鎖、分岐、環状のいずれでもよく、例えば、メチル、エチル、ｎ−プロピル、ｉ−プロピル、ｃ−プロピル基等が挙げられるが、直鎖状のアルキル基が好ましく、中でもメチル基、エチル基がより好ましく、メチル基がより一層好ましい。
Ｒ2は、メチル基またはエチル基を表すが、メチル基が好ましい。
Ａは、メチレン基またはエチレン基を表す。
ｎは１〜５の整数を表すが、１〜３が好ましく、Ａがメチレン基の場合は１がより好ましく、Ａがエチレン基の場合は２または３がより好ましく、２がより一層好ましい。
R 1 represents an alkyl group having 1 to 3 carbon atoms, and specific examples thereof may be linear, branched or cyclic, for example, methyl, ethyl, n-propyl, i-propyl, c-propyl group A linear alkyl group is preferable, and a methyl group and an ethyl group are more preferable, and a methyl group is still more preferable.
R 2 represents a methyl group or an ethyl group, and is preferably a methyl group.
A represents a methylene group or an ethylene group.
n represents an integer of 1 to 5, preferably 1 to 3, 1 is more preferable when A is a methylene group, 2 or 3 is more preferable when A is an ethylene group, and 2 is even more preferable.
中でもカチオン構造としては、より熱安定性に優れているという点から、下記（Ａ）の構造が好ましく、より低粘度という点から、下記（Ｂ）の構造が好ましい。 Among these, as the cationic structure, the following structure (A) is preferable from the viewpoint of more excellent thermal stability, and the following structure (B) is preferable from the viewpoint of lower viscosity.
Ｘ-は１価のアニオンであり、イオン液体を形成し得るアニオンであれば特に限定されるものではないが、本発明では、ＢＦ4 -、ＰＦ6 -、ＣＦ3ＳＯ3 -、ＣＦ3ＣＯ2 -、（ＣＦ3ＳＯ2）2Ｎ-または（ＦＳＯ2）2Ｎ-が好ましく、耐電圧性、金属塩の溶解能、低粘度性等を考慮すると、中でも、ＢＦ4 -、（ＣＦ3ＳＯ2）2Ｎ-、（ＦＳＯ2）2Ｎ-がより好ましく、特に低粘度性という点から、（ＣＦ3ＳＯ2）2Ｎ-、（ＦＳＯ2）2Ｎ-がより一層好ましい。 X − is a monovalent anion and is not particularly limited as long as it is an anion capable of forming an ionic liquid, but in the present invention, BF 4 − , PF 6 − , CF 3 SO 3 − , CF 3 CO 2 − , (CF 3 SO 2 ) 2 N − or (FSO 2 ) 2 N − is preferable, and BF 4 − , (CF 3 ) are particularly preferable in consideration of voltage resistance, metal salt solubility, low viscosity, and the like. SO 2 ) 2 N − and (FSO 2 ) 2 N − are more preferable, and (CF 3 SO 2 ) 2 N − and (FSO 2 ) 2 N − are even more preferable from the viewpoint of low viscosity.
耐電圧性や粘度等を考慮すると、式（２）または（３）で示されるイオン液体が好ましく、金属塩等の溶解能や酸素供給能などを考慮すると、式（３）で示されるイオン液体がより好ましい。 The ionic liquid represented by the formula (2) or (3) is preferable in view of the voltage resistance and viscosity, and the ionic liquid represented by the formula (3) is considered in consideration of the dissolving ability of the metal salt and the oxygen supply ability. Is more preferable.
本発明で用いられるイオン液体は、国際公開第２００２／０７６９２４号記載の方法や、中国特許出願公開第１０１７４７２４３号明細書等により製造することができ、例えば、定法に従って製造したＮ−アルコキシアルキル−Ｎ−アルキルピロリジニウムハライド（例えば、クロライド、ブロマイド等）と、所望のアニオンのアルカリ金属（例えば、ナトリウム、カリウム等）塩とを水や有機溶媒中でアニオン交換反応させて得ることができる。また、陰イオン交換樹脂を用いてハライド塩を水酸化物塩に変換した後、アニオンに対応する酸との中和反応によって合成するなどのその他公知の方法でも合成できる。 The ionic liquid used in the present invention can be produced by the method described in International Publication No. 2002/076924 or the specification of Chinese Patent Application No. 10147243, for example, N-alkoxyalkyl-N produced according to a conventional method. -An alkylpyrrolidinium halide (for example, chloride, bromide, etc.) and an alkali metal (for example, sodium, potassium, etc.) salt of a desired anion can be obtained by anion exchange reaction in water or an organic solvent. Moreover, after converting a halide salt into a hydroxide salt using an anion exchange resin, it can also be synthesized by other known methods such as synthesis by a neutralization reaction with an acid corresponding to an anion.
本発明で好適に用いることができるイオン液体としては下記のものが挙げられるが、これらに限定されるものではない。 Examples of the ionic liquid that can be suitably used in the present invention include, but are not limited to, the following.
本発明の金属空気電池用電解液は、上述したイオン液体に加え、金属塩や金属酸化物を含んでいてもよく、さらに、非水系有機溶媒を含んでいてもよい。
金属塩や金属酸化物としては、空気電池に使用可能な公知の化合物を使用することができるが、使用するイオン液体のアニオンＸ-と同一のアニオンを有する金属塩が好適であり、具体的な金属種としても空気電池に使用できる限り特に限定されるものではなく、リチウム、ナトリウム、カリウム、マグネシウム、カルシウム、アルミニウム、亜鉛、鉄等が挙げられるが、リチウム、ナトリウム、マグネシウムが好ましい。
金属塩や金属酸化物の濃度は、特に限定されるものではないが、電解液中に０．１〜４．０ｍｏｌ／Ｌが好ましく、０．５〜２．０ｍｏｌ／Ｌがより好ましい。
The electrolytic solution for metal-air batteries of the present invention may contain a metal salt or a metal oxide in addition to the ionic liquid described above, and may further contain a non-aqueous organic solvent.
As the metal salt or metal oxide, a known compound that can be used for an air battery can be used, but a metal salt having the same anion as the anion X − of the ionic liquid to be used is preferable, The metal species is not particularly limited as long as it can be used for an air battery, and lithium, sodium, potassium, magnesium, calcium, aluminum, zinc, iron and the like can be mentioned, but lithium, sodium and magnesium are preferable.
Although the density | concentration of a metal salt and a metal oxide is not specifically limited, 0.1-4.0 mol / L is preferable in an electrolyte solution, and 0.5-2.0 mol / L is more preferable.
リチウム塩の具体例としては、ＬｉＰＦ6、Ｌｉ［ＰＦ3（Ｃ2Ｆ5）3］、Ｌｉ［ＰＦ3（ＣＦ3）3］、ＬｉＢＦ4、Ｌｉ［ＢＦ2（ＣＦ3）2］、Ｌｉ［ＢＦ2（Ｃ2Ｆ5）2］、Ｌｉ［ＢＦ3（ＣＦ3）］、Ｌｉ［ＢＦ3（Ｃ2Ｆ5）］、Ｌｉ［Ｂ（ＣＯＯＣＯＯ）2］、ＬｉＣＦ3ＳＯ3、ＬｉＣ4Ｆ9ＳＯ3、Ｌｉ［（ＣＦ3ＳＯ2）2Ｎ］、Ｌｉ［（Ｃ2Ｆ5ＳＯ2）2Ｎ］、Ｌｉ［（ＣＦ3ＳＯ2）（Ｃ4Ｆ9ＳＯ2）Ｎ］、Ｌｉ［（ＣＮ）2Ｎ］、Ｌｉ［（ＣＦ3ＳＯ2）3Ｃ］、Ｌｉ［（ＦＳＯ2）2Ｎ］、Ｌｉ［（ＣＮ）3Ｃ］などが挙げられるが、これらの中でも、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3、Ｌｉ［（ＣＦ3ＳＯ2）2Ｎ］、Ｌｉ［（ＦＳＯ2）2Ｎ］が好ましい。
リチウム酸化物の具体例としては、Ｌｉ2Ｏ、Ｌｉ2Ｏ2（過酸化リチウム）等が挙げられる
Specific examples of the lithium salt include LiPF 6 , Li [PF 3 (C 2 F 5 ) 3 ], Li [PF 3 (CF 3 ) 3 ], LiBF 4 , Li [BF 2 (CF 3 ) 2 ], Li [BF 2 (C 2 F 5 ) 2 ], Li [BF 3 (CF 3 )], Li [BF 3 (C 2 F 5 )], Li [B (COOCOO) 2 ], LiCF 3 SO 3 , LiC 4 F 9 SO 3, Li [( CF 3 SO 2) 2 N], Li [(C 2
Specific examples of the lithium oxide include Li 2 O and Li 2 O 2 (lithium peroxide).
ナトリウム塩の具体例としては、ＮａＰＦ6、Ｎａ［ＰＦ3（Ｃ2Ｆ5）3］、Ｎａ［ＰＦ3（ＣＦ3）3］、ＮａＢＦ4、Ｎａ［ＢＦ2（ＣＦ3）2］、Ｎａ［ＢＦ2（Ｃ2Ｆ5）2］、Ｎａ［ＢＦ3（ＣＦ3）］、Ｎａ［ＢＦ3（Ｃ2Ｆ5）］、Ｎａ［Ｂ（ＣＯＯＣＯＯ）2］、ＮａＣＦ3ＳＯ3、ＮａＣ4Ｆ9ＳＯ3、Ｎａ［（ＣＦ3ＳＯ2）2Ｎ］、Ｎａ［（Ｃ2Ｆ5ＳＯ2）2Ｎ］、Ｎａ［（ＣＦ3ＳＯ2）（Ｃ4Ｆ9ＳＯ2）Ｎ］、Ｎａ［（ＣＮ）2Ｎ］、Ｎａ［（ＣＦ3ＳＯ2）3Ｃ］、Ｎａ［（ＦＳＯ2）2Ｎ］、Ｎａ［（ＣＮ）3Ｃ］等が挙げられるが、これらの中でも、ＮａＰＦ6、ＮａＢＦ4、ＮａＣＦ3ＳＯ3、Ｎａ［（ＣＦ3ＳＯ2）2Ｎ］、Ｎａ［（ＦＳＯ2）2Ｎ］が好ましい。
ナトリウム酸化物の具体例としては、Ｎａ2Ｏ、Ｎａ2Ｏ2（過酸化ナトリウム）等が挙げられる
Specific examples of the sodium salt include NaPF 6 , Na [PF 3 (C 2 F 5 ) 3 ], Na [PF 3 (CF 3 ) 3 ], NaBF 4 , Na [BF 2 (CF 3 ) 2 ], Na [BF 2 (C 2 F 5 ) 2], Na [BF 3 (CF 3)], Na [BF 3 (C 2 F 5)], Na [B (COOCOO) 2],
Specific examples of sodium oxide include Na 2 O and Na 2 O 2 (sodium peroxide).
マグネシウム塩の具体例としては、Ｍｇ（ＰＦ6）2、Ｍｇ［ＰＦ3（Ｃ2Ｆ5）3］2、Ｍｇ［ＰＦ3（ＣＦ3）3］2、Ｍｇ（ＢＦ4）2、Ｍｇ［ＢＦ2（ＣＦ3）2］2、Ｍｇ［ＢＦ2（Ｃ2Ｆ5）2］2、Ｍｇ［ＢＦ3（ＣＦ3）］2、Ｍｇ［ＢＦ3（Ｃ2Ｆ5）］2、Ｍｇ［Ｂ（ＣＯＯＣＯＯ）2］2、Ｍｇ（ＣＦ3ＳＯ3）2、Ｍｇ（Ｃ4Ｆ9ＳＯ3）2、Ｍｇ［（ＣＦ3ＳＯ2）2Ｎ］2、Ｍｇ［（Ｃ2Ｆ5ＳＯ2）2Ｎ］2、Ｍｇ［（ＣＦ3ＳＯ2）（Ｃ4Ｆ9ＳＯ2）Ｎ］2、Ｍｇ［（ＣＮ）2Ｎ］2、Ｍｇ［（ＣＦ3ＳＯ2）3Ｃ］2、Ｍｇ［（ＦＳＯ2）2Ｎ］2、Ｍｇ［（ＣＮ）3Ｃ］2等が挙げられるが、これらの中でも、Ｍｇ（ＰＦ6）2、Ｍｇ（ＢＦ4）2、Ｍｇ（ＣＦ3ＳＯ3）2、Ｍｇ［（ＣＦ3ＳＯ2）2Ｎ］2、Ｍｇ［（ＦＳＯ2）2Ｎ］2が好ましい。
マグネシウム酸化物の具体例としては、ＭｇＯ、ＭｇＯ2（過酸化マグネシウム）等が挙げられる。
Specific examples of the magnesium salt include Mg (PF 6 ) 2 , Mg [PF 3 (C 2 F 5 ) 3 ] 2 , Mg [PF 3 (CF 3 ) 3 ] 2 , Mg (BF 4 ) 2 , Mg [ BF 2 (CF 3 ) 2 ] 2 , Mg [BF 2 (C 2 F 5 ) 2 ] 2 , Mg [BF 3 (CF 3 )] 2 , Mg [BF 3 (C 2 F 5 )] 2 , Mg [ B (COOCOO) 2 ] 2 , Mg (CF 3 SO 3 ) 2 , Mg (C 4 F 9 SO 3 ) 2 , Mg [(CF 3 SO 2 ) 2 N] 2 , Mg [(C 2 F 5 SO 2 ) 2 N] 2 , Mg [(CF 3 SO 2 ) (C 4 F 9 SO 2 ) N] 2 , Mg [(CN) 2 N] 2 , Mg [(CF 3 SO 2 ) 3 C] 2 , Mg [(FSO 2 ) 2 N] 2 , Mg [(CN) 3 C] 2, etc., among these, Mg (PF 6 ) 2 , Mg (BF 4 ) 2 , Mg (CF 3 SO 3 ) 2, Mg [(CF 3 SO 2 2 N] 2, Mg [( FSO 2) 2 N] 2 are preferred.
Specific examples of the magnesium oxide include MgO, MgO 2 (magnesium peroxide) and the like.
非水系有機溶媒としては、例えば、ジブチルエーテル、１，２−ジメトキシエタン、１，２−エトキシメトキシエタン、メチルジグライム、メチルトリグライム、メチルテトラグライム、エチルグライム、エチルジグライム、ブチルジグライム、エチルセルソルブ、エチルカルビトール、ブチルセルソルブ、ブチルカルビトール等の鎖状エーテル類；テトラヒドロフラン、２−メチルテトラヒドロフラン、１，３−ジオキソラン、４，４−ジメチル−１，３−ジオキサン等の複素環式エーテル類；γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、３−メチル−１，３−オキサゾリジン−２−オン、３−エチル−１，３−オキサゾリジン−２−オン等のラクトン類；Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ−メチルピロリジノン等のアミド類；ジエチルカーボネート、ジメチルカーボネート、エチルメチルカーボネート、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート等のカーボネート類；１，３−ジメチル−２−イミダゾリジノン等のイミダゾリン類、アセトニトリル、プロピオニトリル等のニトリル類などが挙げられ、これらは単独で、または２種以上混合して用いることができる。 Examples of the non-aqueous organic solvent include dibutyl ether, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, methyl diglyme, methyl triglyme, methyl tetraglyme, ethyl glyme, ethyl diglyme, butyl diglyme, Chain ethers such as ethyl cellosolve, ethyl carbitol, butyl cellosolve, butyl carbitol; heterocycles such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4,4-dimethyl-1,3-dioxane Formula ethers; Lactones such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, 3-methyl-1,3-oxazolidine-2-one, 3-ethyl-1,3-oxazolidine-2-one; N-methylformamide, N, N-dimethylformamide, N Amides such as methylacetamide and N-methylpyrrolidinone; Carbonates such as diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, propylene carbonate, ethylene carbonate and butylene carbonate; Imidazolines such as 1,3-dimethyl-2-imidazolidinone , Nitriles such as acetonitrile and propionitrile, and the like can be used alone or in admixture of two or more.
なお、本発明で用いる上記イオン液体は、それ自体比較的粘度が低く、また金属塩の溶解能も良好であるため、非水系有機溶媒を用いる場合でも、その使用量は電解液中に１０質量％以下が好ましく、５質量％以下がより好ましく、０質量％（すなわち、液体成分はイオン液体のみ）であることが最適である。 The ionic liquid used in the present invention has a relatively low viscosity per se and has a good ability to dissolve a metal salt. Therefore, even when a non-aqueous organic solvent is used, the amount used is 10 mass in the electrolyte. % Or less, more preferably 5% by mass or less, and most preferably 0% by mass (that is, the liquid component is only an ionic liquid).
本発明に係る金属空気電池は、空気極と負極と、これら各極間に介在する電解質層を有し、電解質層が、上述した金属空気電池用電解液を含むものである。
この場合、上記金属空気電池用電解液以外の電池構成材料としては、従来公知のものから適宜選択して用いればよく、特に限定されるものではないが、その一例を挙げると次のとおりである。
The metal-air battery according to the present invention includes an air electrode, a negative electrode, and an electrolyte layer interposed between these electrodes, and the electrolyte layer includes the above-described electrolyte for a metal-air battery.
In this case, battery constituent materials other than the above-described metal-air battery electrolyte may be appropriately selected from conventionally known ones, and are not particularly limited, but examples thereof are as follows. .
空気極（正極）は、正極集電体と、この上に形成される正極層とを含んで構成される。
正極集電体の具体例としては、アルミニウム箔、アルミニウム合金箔、ステンレス箔等が挙げられ、これらの発泡体や不織布状などの三次元多孔質体を集電体に用いることもできる。
正極層は、炭素質材料と、バインダーポリマーと、必要に応じて酸化還元触媒とを含む組成物をフィルム状に圧延して製膜して乾燥したり、さらに上記各成分に加え溶媒を含む組成物を集電体上に塗布し、これを乾燥・圧延したりすることで作製できる。
炭素質材料の具体例としては、ケッチェンブラック、アセチレンブラック、チャンネルブラック、ファーネスブラック、メソポーラスカーボン等のカーボンブラック、活性炭、カーボン炭素繊維等が挙げられる。
The air electrode (positive electrode) includes a positive electrode current collector and a positive electrode layer formed thereon.
Specific examples of the positive electrode current collector include an aluminum foil, an aluminum alloy foil, a stainless steel foil, and the like. A three-dimensional porous body such as a foam or a nonwoven fabric can be used as the current collector.
The positive electrode layer is a composition containing a carbonaceous material, a binder polymer, and if necessary, a composition containing a redox catalyst, rolled into a film and dried, and further containing a solvent in addition to the above components It can be produced by applying an object on a current collector and drying and rolling it.
Specific examples of the carbonaceous material include ketjen black, acetylene black, channel black, furnace black, carbon black such as mesoporous carbon, activated carbon, carbon carbon fiber, and the like.
バインダーポリマーとしては、公知の材料から適宜選択して用いることができ、その具体例としては、ポリフッ化ビニリデン（ＰＶｄＦ）、ポリビニルピロリドン、ポリテトラフルオロエチレン、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体〔Ｐ（ＶＤＦ−ＨＦＰ）〕、フッ化ビニリデン−塩化３フッ化エチレン共重合体〔Ｐ（ＶＤＦ−ＣＴＦＥ）〕、ポリビニルアルコール、エチレン−プロピレン−ジエン三元共重合体、スチレン−ブタジエンゴム、カルボキシメチルセルロース（ＣＭＣ）等が挙げられる。 The binder polymer can be appropriately selected from known materials and used. Specific examples thereof include polyvinylidene fluoride (PVdF), polyvinylpyrrolidone, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, Vinylidene fluoride-hexafluoropropylene copolymer [P (VDF-HFP)], vinylidene fluoride-trichloroethylene copolymer [P (VDF-CTFE)], polyvinyl alcohol, ethylene-propylene-diene ternary Copolymers, styrene-butadiene rubber, carboxymethyl cellulose (CMC) and the like can be mentioned.
酸化還元触媒の具体例としては、コバルトフタロシアニン、コバルトポルフィリン、酸化セリウム（ＣｅＯ2）、酸化アルミニウム（Ａｌ2Ｏ3）、酸化チタン（ＴｉＯ2）、酸化銀（ＡｇＯ）、タングステン酸リチウム（Ｌｉ2ＷＯ4）、モリブデン酸リチウム（Ｌｉ2ＭｏＯ4）、マンガンコバルト酸リチウム（ＬｉＭｎxＣｏyＯ4）、ランタンカルシウムコバルト複合酸化物（ＬａxＣａyＣｏＯ3-z）、ランタンストロンチウムコバルト酸化物（ＬａxＳｒyＣｏＯ3-z）、ランタンマンガン酸ナトリウム（ＮａxＬａyＭｎＯ3）、ランタンマンガン酸カリウム（ＫxＬａyＭｎＯ3-z）、ランタンマンガン酸ルビジウム（ＲｂxＬａyＭｎＯ3-z）、銅マンガン複合酸化物（ＣｕxＭｎyＯ4）、マンガン酸化物（ＭｎＯx）などが挙げられる。
溶媒は、バインダーポリマーの種類に応じて選定されるものであるが、一般的には、Ｎ−メチル−２−ピロリドンや水が用いられる。
Specific examples of the redox catalyst include cobalt phthalocyanine, cobalt porphyrin, cerium oxide (CeO 2 ), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), silver oxide (AgO), and lithium tungstate (Li 2). WO 4 ), lithium molybdate (Li 2 MoO 4 ), lithium manganese cobaltate (LiMn x Co y O 4 ), lanthanum calcium cobalt composite oxide (La x Ca y CoO 3 -z), lanthanum strontium cobalt oxide ( La x Sr y CoO 3-z ), sodium lanthanum manganate (Na x La y MnO 3) , potassium lanthanum manganate (K x La y MnO 3- z), lanthanum manganate rubidium (Rb x La y MnO 3- z), copper-manganese composite oxide (Cu x Mn y O 4) , manganese oxide (MnO x) And the like.
The solvent is selected according to the type of the binder polymer, but generally N-methyl-2-pyrrolidone or water is used.
一方、負極は、負極集電体と、この上に形成される負極層とを含んで構成される。
負極集電体の具体例としては、銅箔、銅合金箔、ニッケル箔、ニッケル合金箔、ステンレス箔等が挙げられる。
負極層は、負極活物質と、バインダーポリマーとを含む組成物をフィルム状に圧延して製膜して乾燥したり、さらに上記各成分に加え溶媒を含む組成物を集電体上に塗布し、これを乾燥・圧延したりすることで作製できる。
負極活物質としては、金属、金属酸化物、金属硫化物、金属窒化物、金属複合酸化物、合金材料、または炭素質材料等を用いることができ、その具体例としては、リチウム、ナトリウム、カリウム等のアルカリ金属；マグネシウム、カルシウム等の第２族金属；アルミニウム等の第１３族元素；亜鉛、鉄等の遷移金属；スズ酸化物、ケイ素酸化物、リチウムチタン酸化物、ニオブ酸化物、タングステン酸化物等の金属酸化物；リチウムコバルト窒化物、リチウム鉄窒化物、リチウムマンガン窒化物等の金属窒化物；スズ硫化物、チタン硫化物等の金属硫化物；リチウム複合酸化物等の金属複合酸化物；リチウムアルミニウム合金、リチウムスズ合金、リチウム鉛合金、リチウムケイ素合金等の合金材料；黒鉛、コークス、炭素繊維、球状炭素等の炭素質材料などが挙げられる。
バインダーポリマーおよび溶媒としては、上記と同様のものが挙げられる。
On the other hand, the negative electrode includes a negative electrode current collector and a negative electrode layer formed thereon.
Specific examples of the negative electrode current collector include copper foil, copper alloy foil, nickel foil, nickel alloy foil, and stainless steel foil.
The negative electrode layer is formed by rolling a composition containing a negative electrode active material and a binder polymer into a film and drying it, or by applying a composition containing a solvent in addition to the above components onto a current collector. This can be produced by drying and rolling.
As the negative electrode active material, metals, metal oxides, metal sulfides, metal nitrides, metal composite oxides, alloy materials, carbonaceous materials, and the like can be used. Specific examples thereof include lithium, sodium, potassium Alkali metals such as;
Examples of the binder polymer and the solvent include the same ones as described above.
本発明の金属空気電池は、正極および負極の間にセパレータを備えていてもよい。
セパレータの具体例としては、ポリエチレン、ポリプロピレン等のポリオレフィン系セパレータ、ポリエチレンテレフタレート等のポリエステル系セパレータ、ポリアミド系セパレータ、ポリイミド系セパレータ、セルロース系セパレータ、ガラス繊維系セパレータなどが挙げられる。
The metal-air battery of the present invention may include a separator between the positive electrode and the negative electrode.
Specific examples of the separator include polyolefin separators such as polyethylene and polypropylene, polyester separators such as polyethylene terephthalate, polyamide separators, polyimide separators, cellulose separators, and glass fiber separators.
金属空気電池の外装材としては、特に限定されるものではなく、金属缶、樹脂、ラミネートパック等、空気電池の外装材として通常用いられる材料を使用することができる。
なお、外装材には、通常、正極層を覆う位置などに酸素を取り込むための空気孔が設けられる。
本発明の金属空気電池は、例えば、正負極間に、セパレータを介在させてなる電池構造体を積層、折畳、または捲回し、これを電池缶またはラミネートパック等の電池容器に収容した後、本発明の金属空気電池用電解液を充填し、電池缶であれば封缶して、一方、ラミネートパックであればヒートシール（熱溶着）して得ることができる。
The outer packaging material of the metal-air battery is not particularly limited, and materials usually used as the outer packaging material of the air battery, such as a metal can, a resin, and a laminate pack, can be used.
Note that the exterior material is usually provided with air holes for taking in oxygen at a position covering the positive electrode layer.
The metal-air battery of the present invention, for example, after laminating, folding, or winding a battery structure in which a separator is interposed between positive and negative electrodes, and accommodating this in a battery container such as a battery can or a laminate pack, It can be obtained by filling the electrolytic solution for metal-air battery of the present invention and sealing it if it is a battery can, and heat sealing (thermal welding) if it is a laminate pack.
以下、合成例、実施例および比較例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。
なお、実施例で使用した分析装置は下記のとおりである。
［１］1Ｈ−ＮＭＲおよび7Ｌｉ−ＮＭＲスペクトル
装置：日本電子（株）製 ＡＬ−４００
溶媒：重ジメチルスルホキシド
［２］粘度計
装置：ＢＲＯＯＫ ＦＩＥＬＤ社製 プログラマブルレオメーター
［３］電気伝導率
装置：東亜ディーケーケー（株）製 電気伝導率計ＣＭ−３０Ｒ
［４］電位窓
装置：北斗電工（株）製 スタンダードボルタンメトリツールＨＳＶ−１００
［５］磁場勾配ＮＭＲ
装置：バリアン社製 ＩＮＯＶＡ３００
Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
The analyzers used in the examples are as follows.
[1] 1 H-NMR and 7 Li-NMR spectrum apparatus: AL-400 manufactured by JEOL Ltd.
Solvent: Heavy dimethyl sulfoxide [2] Viscometer device: BROOK FIELDEL, Inc. Programmable rheometer [3] Electrical conductivity device: Toa DKK Corporation Electric conductivity meter CM-30R
[4] Potential window device: Standard voltammetric tool HSV-100 manufactured by Hokuto Denko Co., Ltd.
[5] Magnetic field gradient NMR
Apparatus: INOVA300 manufactured by Varian
［１］イオン液体の合成
［合成例１］ＭＥＭＰ・ＦＳＡの合成
ピロリジン（和光純薬工業（株）製）１．５１質量部と塩化２−メトキシエチル（関東化学（株）製）１．００質量部とを混合し、還流しながら１時間反応させた。反応後、反応液は２層に分離したが、しばらく放冷すると下層は固化した。デカンテーションにより上層のみ回収し、減圧蒸留により精製し、目的物であるＮ−２−メトキシエチルピロリジン（沸点７６℃／蒸気圧４５ｍｍＨｇ）０．９６質量部を得た（収率７０％）。
得られたＮ−２−メトキシエチルピロリジン１．００質量部、およびこれに対して２倍容量のトルエン（和光純薬工業（株）製）を混合し、オートクレーブ中に入れ、系内を窒素置換した。密閉系にした後、室温撹拌下で塩化メチルガス（日本特殊化学工業（株）製）約１．００質量部を加えた。塩化メチルガス導入時には温度および内圧の上昇が見られ、最高時で温度は約５３℃、内圧は５．５ｋｇｆ／ｃｍ2（約５．４×１０5Ｐａ）まで上昇した。そのまま加熱せずに反応させ、２日後に塩化メチルガス約０．７５質量部を加えた。さらに１日反応させた後、加圧を解除し、系中に生成した結晶を減圧濾過にてろ別し、真空ポンプを用いて乾燥させ、Ｎ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライド１．２９質量部を得た（収率９２％）。
得られたＮ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライド１．００質量部に当倍容量のイオン交換水を加え、撹拌して溶解させた。この溶液をカリウムビス（フルオロスルホニル）アミド（関東化学（株）製）１．２９質量部を当倍容量のイオン交換水に溶かした溶液に撹拌下で加えた。室温で反応させ、３時間以上経過した後に、２層に分離した反応液を分液し、下層の有機層を２回イオン交換水で洗浄後、真空ポンプを用いて乾燥させ、目的物であるＮ−２−メトキシエチル−Ｎ−メチルピロリジニウムビス（フルオロスルホニル）アミド（ＭＥＭＰ・ＦＳＡ）１．５０質量部を得た（収率８３％）。なお２５℃での粘度は、３５ｃＰであった。
Pyrrolidine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.51 parts by mass and 2-methoxyethyl chloride (manufactured by Kanto Chemical Co., Ltd.) 1.00 parts by mass were mixed and reacted for 1 hour while refluxing. After the reaction, the reaction solution was separated into two layers, but the lower layer solidified when allowed to cool for a while. Only the upper layer was recovered by decantation, and purified by distillation under reduced pressure to obtain 0.96 parts by mass of the target product, N-2-methoxyethylpyrrolidine (boiling point 76 ° C./vapor pressure 45 mmHg) (yield 70%).
1.00 parts by mass of the obtained N-2-methoxyethylpyrrolidine and 2 times volume of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed and placed in an autoclave, and the system is purged with nitrogen did. After making it a closed system, about 1.00 parts by mass of methyl chloride gas (manufactured by Nippon Specialty Chemicals Co., Ltd.) was added with stirring at room temperature. When methyl chloride gas was introduced, the temperature and internal pressure increased. At the maximum, the temperature increased to about 53 ° C., and the internal pressure increased to 5.5 kgf / cm 2 (about 5.4 × 10 5 Pa). The reaction was continued without heating, and about 0.75 parts by mass of methyl chloride gas was added after 2 days. After further reaction for 1 day, the pressure was released, and the crystals formed in the system were filtered off under reduced pressure, dried using a vacuum pump, and N-2-methoxyethyl-N-methylpyrrolidinium chloride. 1.29 parts by mass were obtained (yield 92%).
To 1.00 parts by mass of the obtained N-2-methoxyethyl-N-methylpyrrolidinium chloride, an equivalent volume of ion-exchanged water was added and dissolved by stirring. This solution was added with stirring to a solution prepared by dissolving 1.29 parts by mass of potassium bis (fluorosulfonyl) amide (manufactured by Kanto Chemical Co., Inc.) in an equivalent volume of ion-exchanged water. After reacting at room temperature for 3 hours or more, the reaction solution separated into two layers is separated, and the lower organic layer is washed twice with ion-exchanged water and then dried using a vacuum pump. N-2-methoxyethyl-N-methylpyrrolidinium bis (fluorosulfonyl) amide (MEMP • FSA) 1.50 parts by mass was obtained (yield 83%). The viscosity at 25 ° C. was 35 cP.
［合成例２］ＭＥＭＰ・ＴＦＳＡの合成
合成例１記載と同様の合成法で得たＮ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライド１．００質量部に、当倍容量のイオン交換水を加えて撹拌して溶解させた。この溶液をリチウムビス（トリフルオロメタンスルホニル）アミド（関東化学（株）製）１．６８質量部を当倍容量のイオン交換水に溶かした溶液に撹拌下で加えた。室温で反応させ、３時間以上経過した後に、２層に分離した反応液を分液し、下層の有機層を２回イオン交換水で洗浄後、真空ポンプを用いて乾燥させ、目的物であるＮ−２−メトキシエチル−Ｎ−メチルピロリジニウムビス（トリフルオロメタンスルホニル）アミド（ＭＥＭＰ・ＴＦＳＡ）１．５０質量部を得た（収率８３％）。なお２５℃での粘度は、５０ｃＰであった。 To 1.00 parts by mass of N-2-methoxyethyl-N-methylpyrrolidinium chloride obtained by the same synthesis method as described in Synthesis Example 1, this volume of ion-exchanged water was added and dissolved by stirring. This solution was added with stirring to a solution obtained by dissolving 1.68 parts by mass of lithium bis (trifluoromethanesulfonyl) amide (manufactured by Kanto Chemical Co., Inc.) in an equivalent volume of ion-exchanged water. After reacting at room temperature for 3 hours or more, the reaction solution separated into two layers is separated, and the lower organic layer is washed twice with ion-exchanged water and then dried using a vacuum pump. 1.50 parts by mass of N-2-methoxyethyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) amide (MEMMP · TFSA) was obtained (yield 83%). The viscosity at 25 ° C. was 50 cP.
［合成例３］ＭＭＭＰ・ＦＳＡの合成
Ｎ−メチルピロリジン（和光純薬工業（株）製）１４．４質量部をテトラヒドロフラン（和光純薬工業（株）製）２００質量部に溶かした溶液を氷冷し、撹拌下、クロロメチルメチルエーテル（東京化成工業（株）製）１７．１質量部を加えた。一晩反応させた後、析出した固体を、桐山ロートを用い減圧濾過した。得られた白色固体を、真空ポンプを用いて乾燥させ、中間体Ｎ−メトキシメチル−Ｎ−メチルピロリジニウムクロライド２６．７質量部を得た（収率９６％）。
得られたＮ−メトキシメチル−Ｎ−メチルピロリジニウムクロライド８．５８質量部をイオン交換水１０質量部に溶解させた。この溶液をカリウムビス（フルオロスルホニル）アミド（関東化学（株）製）１２．５質量部をイオン交換水５質量部に溶かした溶液に撹拌下で加えた。室温で撹拌を一晩継続させた後、２層に分かれた反応液を分液し、下層の有機層をイオン交換水で４回洗浄後、真空ポンプを用いて乾燥させ、目的物であるＮ−メトキシメチル−Ｎ−メチルピロリジニウムビス（フルオロスルホニル）アミド（ＭＭＭＰ・ＦＳＡ））を１０．２質量部得た（収率６３％）。なお２５℃での粘度は、２０ｃＰであった。
A solution prepared by dissolving 14.4 parts by mass of N-methylpyrrolidine (manufactured by Wako Pure Chemical Industries, Ltd.) in 200 parts by mass of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was ice-cooled, and chloromethyl methyl ether was stirred. 17.1 parts by mass (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After reacting overnight, the precipitated solid was filtered under reduced pressure using a Kiriyama funnel. The obtained white solid was dried using a vacuum pump to obtain 26.7 parts by mass of an intermediate N-methoxymethyl-N-methylpyrrolidinium chloride (yield 96%).
The obtained N-methoxymethyl-N-methylpyrrolidinium chloride 8.58 parts by mass was dissolved in 10 parts by mass of ion-exchanged water. This solution was added with stirring to a solution prepared by dissolving 12.5 parts by mass of potassium bis (fluorosulfonyl) amide (manufactured by Kanto Chemical Co., Ltd.) in 5 parts by mass of ion-exchanged water. After stirring overnight at room temperature, the reaction solution separated into two layers was separated, and the lower organic layer was washed four times with ion-exchanged water and then dried using a vacuum pump. 10.2 parts by mass of (methoxymethyl-N-methylpyrrolidinium bis (fluorosulfonyl) amide (MMMP · FSA)) was obtained (yield 63%). The viscosity at 25 ° C. was 20 cP.
［合成例４］ＭＭＭＰ・ＴＦＳＡの合成
Ｎ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライドを、合成例３と同様の合成法で得たＮ−２−メトキシメチル−Ｎ−メチルピロリジニウムクロライドに代えた以外は、合成例２と同様にして目的物であるＮ−２−メトキシメチル−Ｎ−メチルピロリジニウムビス（トリフルオロメタンスルホニル）アミド（ＭＭＭＰ・ＴＦＳＡ）を得た。なお２５℃での粘度は、４２ｃＰであった。 Synthesis Example 2 except that N-2-methoxyethyl-N-methylpyrrolidinium chloride was replaced with N-2-methoxymethyl-N-methylpyrrolidinium chloride obtained by the same synthesis method as in Synthesis Example 3. In the same manner as described above, N-2-methoxymethyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) amide (MMMP · TFSA) was obtained as the target product. The viscosity at 25 ° C. was 42 cP.
［合成例５］ＭＥＭＰ２・ＦＳＡの合成
原料をトリエチレングリコールモノメチルエーテルから２−（２−メトキシエトキシ）エタノール（関東化学（株）製）に代えた以外は、特開２００５−１４５９２７号公報記載の方法と同様にして１−ヨード−（２−メトキシエトキシ）エチルを合成した。
さらに、原料の塩化２−メトキシエチルを１−ヨード−（２−メトキシエトキシ）エチルに代えた以外は、合成例１と同様にして目的物であるＭＥＭＰ２・ＦＳＡを得た。
1-iodo- () in the same manner as described in JP-A-2005-145927 except that the raw material was changed from triethylene glycol monomethyl ether to 2- (2-methoxyethoxy) ethanol (manufactured by Kanto Chemical Co., Inc.). 2-Methoxyethoxy) ethyl was synthesized.
Furthermore, MEMP2 · FSA, which is the target product, was obtained in the same manner as in Synthesis Example 1 except that 2-methoxyethyl chloride as a raw material was replaced with 1-iodo- (2-methoxyethoxy) ethyl.
［合成例６］ＭＥＭＰ２・ＴＦＳＡの合成
原料をトリエチレングリコールモノメチルエーテルから２−（２−メトキシエトキシ）エタノール（関東化学（株）製）に代えた以外は、特開２００５−１４５９２７号公報記載の方法と同様にして１−ヨード−（２−メトキシエトキシ）エチルを合成した。
さらに、原料の塩化２−メトキシエチルを１−ヨード−（２−メトキシエトキシ）エチルに変更した以外は、合成例２と同様にして目的物であるＭＥＭＰ２・ＴＦＳＡを得た。
1-iodo- () in the same manner as described in JP-A-2005-145927 except that the raw material was changed from triethylene glycol monomethyl ether to 2- (2-methoxyethoxy) ethanol (manufactured by Kanto Chemical Co., Inc.). 2-Methoxyethoxy) ethyl was synthesized.
Furthermore, MEMP2 · TFSA, which is the target product, was obtained in the same manner as in Synthesis Example 2 except that the raw material 2-methoxyethyl chloride was changed to 1-iodo- (2-methoxyethoxy) ethyl.
［合成例７］ＭＥＭＰ３・ＴＦＳＡの合成
特開２００５−１４５９２７号公報記載の方法と同様にして１−ヨード−２−（２−（２−メトキシエトキシ）エトキシ）エチルを合成した。
続いて、原料の塩化２−メトキシエチルを１−ヨード−２−（２−（２−メトキシエトキシ）エトキシ）エチルに変更した以外は、合成例２と同様にして目的物であるＭＥＭＰ３・ＴＦＳＡを得た。
1-iodo-2- (2- (2-methoxyethoxy) ethoxy) ethyl was synthesized in the same manner as described in JP-A-2005-145927.
Subsequently, MEMP3 · TFSA, which is the target product, was prepared in the same manner as in Synthesis Example 2 except that the raw material 2-methoxyethyl chloride was changed to 1-iodo-2- (2- (2-methoxyethoxy) ethoxy) ethyl. Obtained.
合成例１〜３で得られた各イオン液体のそれぞれに、リチウムビス（フルオロスルホニル）アミド（Ｌｉ・ＦＳＡ、関東化学（株）製）を添加してＬｉ・ＦＳＡ濃度が１ｍｏｌ／Ｌの溶液を調製し、それらについて、電気伝導率を測定した。測定は電気伝導率計（ＣＭ−３０Ｒ、東亜ディーケーケー（株）製）を用い、２５℃の恒温槽内で計測した。結果を表１に示す。 Lithium bis (fluorosulfonyl) amide (Li · FSA, manufactured by Kanto Chemical Co., Inc.) was added to each of the ionic liquids obtained in Synthesis Examples 1 to 3 to obtain a solution with a Li · FSA concentration of 1 mol / L. They were prepared and their electrical conductivity was measured. The measurement was performed in a thermostatic bath at 25 ° C. using an electric conductivity meter (CM-30R, manufactured by Toa DKK Co., Ltd.). The results are shown in Table 1.
また、合成例１，３で得られた各イオン液体について電位窓を測定した。その結果を図１に示す。
図１に示されるように、いずれのイオン液体とも広い電位窓を有することがわかる。
Further, the potential window was measured for each ionic liquid obtained in Synthesis Examples 1 and 3. The result is shown in FIG.
As shown in FIG. 1, it can be seen that any ionic liquid has a wide potential window.
［２］Ｌｉ2Ｏ2溶解性評価用電解液の調製
［実施例１−１］
合成例１で得られたＭＥＭＰ・ＦＳＡを溶媒として、過酸化リチウム（Ｌｉ2Ｏ2、（株）高純度化学研究所製）を、０．５ｍｏｌ／ｋｇの濃度で２５℃のＡｒ雰囲気下で秤量混合して１０日間浸漬し、上澄み液を分離してＬｉ2Ｏ2溶解性評価用電解液を調製した。
[2] Preparation of electrolyte solution for evaluating Li 2 O 2 solubility [Example 1-1]
Using MEMP • FSA obtained in Synthesis Example 1 as a solvent, lithium peroxide (Li 2 O 2 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) was added at a concentration of 0.5 mol / kg in an Ar atmosphere at 25 ° C. The mixture was weighed and immersed for 10 days, and the supernatant was separated to prepare an electrolytic solution for evaluating Li 2 O 2 solubility.
［実施例１−２］
ＭＥＭＰ・ＦＳＡを合成例２で得られたＭＥＭＰ・ＴＦＳＡに代えた以外は、実施例１−１と同様にしてＬｉ2Ｏ2溶解性評価用電解液を調製した。
[Example 1-2]
An electrolyte solution for evaluating Li 2 O 2 solubility was prepared in the same manner as in Example 1-1 except that MEMP · FSA was replaced with MEMP · TFSA obtained in Synthesis Example 2.
［実施例１−３］
ＭＥＭＰ・ＦＳＡを合成例３で得られたＭＭＭＰ・ＦＳＡに代えた以外は、実施例１−１と同様にしてＬｉ2Ｏ2溶解性評価用電解液を調製した。
[Example 1-3]
An electrolyte solution for evaluating Li 2 O 2 solubility was prepared in the same manner as in Example 1-1 except that MEMP · FSA was replaced with MMMP · FSA obtained in Synthesis Example 3.
［実施例１−４］
ＭＥＭＰ・ＦＳＡを合成例４で得られたＭＭＭＰ・ＴＦＳＡに代えた以外は、実施例１−１と同様にしてＬｉ2Ｏ2溶解性評価用電解液溶解性評価用電解液を調製した。
[Example 1-4]
An electrolyte solution for solubility evaluation for Li 2 O 2 solubility evaluation was prepared in the same manner as in Example 1-1 except that MEMP · FSA was replaced with MMMP · TFSA obtained in Synthesis Example 4.
［実施例１−５］
ＭＥＭＰ・ＦＳＡを合成例５で得られたＭＥＭＰ２・ＦＳＡに代えた以外は、実施例１−１と同様にしてＬｉ2Ｏ2溶解性評価用電解液溶解性評価用電解液を調製した。
[Example 1-5]
An electrolyte solution for solubility evaluation for Li 2 O 2 solubility evaluation was prepared in the same manner as in Example 1-1, except that MEMP · FSA was replaced with
［実施例１−６］
ＭＥＭＰ・ＦＳＡを合成例６で得られたＭＥＭＰ２・ＴＦＳＡに代えた以外は、実施例１−１と同様にしてＬｉ2Ｏ2溶解性評価用電解液溶解性評価用電解液を調製した。
[Example 1-6]
An electrolyte solution for evaluating Li 2 O 2 solubility was prepared in the same manner as Example 1-1 except that MEMP · FSA was replaced with
［実施例１−７］
ＭＥＭＰ・ＦＳＡを合成例７で得られたＭＥＭＰ３・ＴＦＳＡに代えた以外は、実施例１−１と同様にしてＬｉ2Ｏ2溶解性評価用電解液溶解性評価用電解液を調製した。
[Example 1-7]
An electrolyte solution for evaluating Li 2 O 2 solubility was prepared in the same manner as in Example 1-1 except that MEMP · FSA was replaced with
［比較例１−１］
１−メチル−３−プロピルピペリジニウムビス（トリフルオロメタンスルホニル）アミド（ＰＰ１３・ＴＦＳＡ，関東化学（株）製）を溶媒として、過酸化リチウム（Ｌｉ2Ｏ2溶解性評価用電解液、（株）高純度化学研究所製）を０．５ｍｏｌ／ｋｇの濃度で２５℃のＡｒ雰囲気下で秤量混合して１０日間浸漬し、上澄み液を分離してＬｉ2Ｏ2溶解性評価用電解液溶解性評価用電解液を調製した。
[Comparative Example 1-1]
1-methyl-3-propylpiperidinium bis (trifluoromethanesulfonyl) amide (PP13 / TFSA, manufactured by Kanto Chemical Co., Ltd.) as a solvent, lithium peroxide (Li 2 O 2 solubility evaluation electrolyte, ) High purity chemical laboratory) was weighed and mixed at a concentration of 0.5 mol / kg in an Ar atmosphere at 25 ° C. and soaked for 10 days. The supernatant was separated and dissolved in an electrolyte for evaluating Li 2 O 2 solubility. An electrolyte for evaluating the properties was prepared.
上記実施例１−１〜１−７、比較例１−１で調製したＬｉ2Ｏ2溶解性評価用電解液を用いて、各イオン液体のＬｉ2Ｏ2溶解濃度を以下の手法により比較した。
２重管およびリチウム化合物の溶解濃度が既知の基準物質（エチルメチルカーボネートにＬｉＰＦ6を１ｍｏｌ／Ｌの濃度で溶解させたもの）を準備し、調製したＬｉ2Ｏ2溶解性評価用電解液を２重管の外管に、基準物質を２重管の内管に入れ、２５℃で7Ｌｉ−ＮＭＲ測定を行った。基準物質について測定したＬｉＰＦ6のピークに対する、評価用イオン液体について得られたＬｉ2Ｏ2溶解性評価用電解液のピークの積分比を計測し、ピーク積分比と２重管の内管および外管に入れた液量比とを用いて計算し、評価用電解液中のＬｉ2Ｏ2濃度を算出した。その結果を図２に示す。
Using the electrolyte solutions for evaluating Li 2 O 2 solubility prepared in Examples 1-1 to 1-7 and Comparative Example 1-1, the Li 2 O 2 dissolution concentration of each ionic liquid was compared by the following method. .
A reference material having a known double tube and lithium compound dissolution concentration (LiPF 6 dissolved in ethyl methyl carbonate at a concentration of 1 mol / L) was prepared, and the prepared electrolyte for evaluating Li 2 O 2 solubility was prepared. The reference substance was put in the inner tube of the double tube in the outer tube of the double tube, and 7 Li-NMR measurement was performed at 25 ° C. The integral ratio of the Li 2 O 2 solubility evaluation electrolyte obtained for the evaluation ionic liquid with respect to the LiPF 6 peak measured for the reference material was measured, and the peak integration ratio and the inner and outer pipes of the double tube were measured. calculated using the liquid volume ratio was placed in the tube was calculated Li 2 O 2 concentration in the ratings for the electrolyte solution. The result is shown in FIG.
図２に示されるように、ＰＰ１３・ＴＦＳＡはＬｉ2Ｏ2を溶解することができなかったが、ＭＥＭＰ・ＦＳＡ、ＭＥＭＰ・ＴＦＳＡ、ＭＭＭＰ・ＦＳＡ、ＭＭＭＰ・ＴＦＳＡ、ＭＥＭＰ２・ＦＳＡ、ＭＥＭＰ２・ＴＦＳＡ、ＭＥＭＰ３・ＴＦＳＡは、それぞれＬｉ2Ｏ2濃度が、０．７ｍｍｏｌ／ｋｇ、０．６ｍｍｏｌ／ｋｇ、０．８ｍｍｏｌ／ｋｇ、０．７ｍｍｏｌ／ｋｇ、８．４ｍｍｏｌ／ｋｇ、８．２ｍｍｏｌ／ｋｇ、８．７ｍｍｏｌ／ｋｇであった。エーテル基の数が多くなるほどＬｉ2Ｏ2の溶解濃度が増加し、特にエーテル基が２以上で顕著にＬｉ2Ｏ2溶解濃度が増加した。 As shown in FIG. 2, PP13 • TFSA could not dissolve Li 2 O 2 , but MEMP • FSA, MEMP • TFSA, MMMP • FSA, MMMP • TFSA, MEMP2 • FSA, MEMP2 • TFSA, MEMP3 · TFSA has a Li 2 O 2 concentration of 0.7 mmol / kg, 0.6 mmol / kg, 0.8 mmol / kg, 0.7 mmol / kg, 8.4 mmol / kg, 8.2 mmol / kg, 8 respectively. 0.7 mmol / kg. Increased concentration of dissolved Li 2 O 2 as the number of ether groups is increased significantly Li 2 O 2 dissolved concentration is increased, especially with an ether group is 2 or more.
［３］酸素供給能の測定
［実施例２−１〜２−７および比較例２−１］
合成例１〜７で得られた各イオン液体（実施例２−１〜２−７）およびＰＰ１３・ＴＦＳＡ（比較例２−１）の各イオン液体について、以下の電気化学測定を行って酸素供給能を求めた。
作用電極としてグラッシーカーボン（径３ｍｍ）、参照電極としてＡｇ／Ａｇ＋、および対極としてＮｉを備えた気密性を有する三電極式の測定セル、並びに測定装置としてポテンショスタット／ガルバノスタット（Ｓｏｌａｒｔｒｏｎ社製）を用意した。各イオン液体を入れた測定セルを、２５℃、１気圧の恒温槽にて３時間静置し、測定セル内の雰囲気をアルゴン雰囲気で置換した後、純酸素で３０分間、イオン液体をバブリングしながら酸素雰囲気に置換した。次いで、２５℃、酸素雰囲気、１気圧の条件下で、スイープ電圧１０ｍＶ／ｓで−１．７〜１．３Ｖｖ．ｓ．Ａｇ／Ａｇ＋の範囲で、サイクリックボルタンメトリー（ＣＶ）測定を行った。次いで、サイクリックボルタンメトリー（ＣＶ）から拡散律速状態と推定された電位を使用して、ポテンシャルステップクロノアンペロメトリー測定を行い、下記コットレル（Ｃｏｔｔｒｅｌｌ）の式を用いて、時間ｔの平方根の逆数に対して測定した限界電流密度ｉから、Ｃ×Ｄ1/2で表される酸素供給能を算出した。結果を図３に示す。
[3] Measurement of oxygen supply capacity [Examples 2-1 to 2-7 and Comparative example 2-1]
For each ionic liquid (Examples 2-1 to 2-7) obtained in Synthesis Examples 1 to 7 and each ionic liquid of PP13 · TFSA (Comparative Example 2-1), the following electrochemical measurement was performed to supply oxygen. I asked Noh.
Glassy carbon (
図３に示されるように、酸素供給能（１０-9ｍｏｌ・ｃｍ-2・ｓ-0.5）は、ＭＥＭＰ・ＦＳＡが１０．３、ＭＥＭＰ・ＴＦＳＡが１０．１、ＭＭＭＰ・ＦＳＡが１０．７、ＭＭＭＰ・ＴＦＳＡが１０．３、ＭＥＭＰ２・ＦＳＡが１３．０、ＭＥＭＰ２・ＴＦＳＡが１２．４、ＭＥＭＰ３・ＴＦＳＡが７．２、ＰＰ１３・ＴＦＳＡが８．０を示した。
ＭＥＭＰ２・ＦＳＡとＭＥＭＰ２・ＴＦＳＡがより高い酸素供給能を有しており、２つのエーテル基を有する構造が、リチウム空気電池用の電解液として適していることがわかった。
As shown in FIG. 3, the oxygen supply capacity (10 −9 mol · cm −2 · s −0.5 ) is 10.3 for MEMP · FSA, 10.1 for MEMP · TFSA, 10.7 for MMMP · FSA. MMMP · TFSA was 10.3, MEMP2 · FSA was 13.0, MEMP2 · TFSA was 12.4, MEMP3 · TFSA was 7.2, and PP13 · TFSA was 8.0.
It was found that MEMP2 · FSA and MEMP2 · TFSA have higher oxygen supply capacity, and the structure having two ether groups is suitable as an electrolyte for a lithium-air battery.
［４］リチウムイオン輸率評価用電解液の調製
［実施例３−１］
合成例１で得られたＭＥＭＰ・ＦＳＡを溶媒として、リチウムビス（トリフルオロメタンスルホニル）アミド（関東化学（株）製）を、０．３５ｍｏｌ／ｋｇの濃度で６０℃のＡｒ雰囲気下で秤量混合して６時間撹拌し、リチウムイオン輸率評価用電解液を調製した。
[4] Preparation of electrolyte for evaluating lithium ion transport number [Example 3-1]
Using MEMP • FSA obtained in Synthesis Example 1 as a solvent, lithium bis (trifluoromethanesulfonyl) amide (manufactured by Kanto Chemical Co., Inc.) was weighed and mixed in an Ar atmosphere of 60 ° C. at a concentration of 0.35 mol / kg. For 6 hours to prepare an electrolyte solution for lithium ion transport number evaluation.
［実施例３−２］
ＭＥＭＰ・ＦＳＡを合成例２で得られたＭＥＭＰ・ＴＦＳＡに代えた以外は、実施例３−１と同様にしてリチウムイオン輸率評価用電解液を調製した。
[Example 3-2]
An electrolytic solution for lithium ion transport number evaluation was prepared in the same manner as in Example 3-1, except that MEMP • FSA was replaced with MEMP • TFSA obtained in Synthesis Example 2.
［実施例３−３］
ＭＥＭＰ・ＦＳＡを合成例３で得られたＭＭＭＰ・ＦＳＡに代えた以外は、実施例３−１と同様にしてリチウムイオン輸率評価用電解液を調製した。
[Example 3-3]
An electrolytic solution for lithium ion transport number evaluation was prepared in the same manner as in Example 3-1, except that MEMP • FSA was replaced with MMMP • FSA obtained in Synthesis Example 3.
［実施例３−４］
ＭＥＭＰ・ＦＳＡを合成例４で得られたＭＭＭＰ・ＴＦＳＡに代えた以外は、実施例３−１と同様にしてリチウムイオン輸率評価用電解液を調製した。
[Example 3-4]
An electrolytic solution for lithium ion transport number evaluation was prepared in the same manner as in Example 3-1, except that MEMP • FSA was replaced with MMMP • TFSA obtained in Synthesis Example 4.
［実施例３−５］
ＭＥＭＰ・ＦＳＡを合成例５で得られたＭＥＭＰ２・ＦＳＡに代えた以外は、実施例３−１と同様にしてリチウムイオン輸率評価用電解液を調製した。
[Example 3-5]
An electrolytic solution for lithium ion transport number evaluation was prepared in the same manner as in Example 3-1, except that MEMP · FSA was replaced with MEMP2 · FSA obtained in Synthesis Example 5.
［実施例３−６］
ＭＥＭＰ・ＦＳＡを合成例６で得られたＭＥＭＰ２・ＴＦＳＡに代えた以外は、実施例３−１と同様にしてリチウムイオン輸率評価用電解液を調製した。
[Example 3-6]
An electrolytic solution for lithium ion transport number evaluation was prepared in the same manner as in Example 3-1, except that MEMP · FSA was replaced with MEMP2 · TFSA obtained in Synthesis Example 6.
［実施例３−７］
ＭＥＭＰ・ＦＳＡを合成例７で得られたＭＥＭＰ３・ＴＦＳＡに代えた以外は、実施例３−１と同様にしてリチウムイオン輸率評価用電解液を調製した。
[Example 3-7]
An electrolytic solution for lithium ion transport number evaluation was prepared in the same manner as in Example 3-1, except that MEMP · FSA was replaced with MEMP3 · TFSA obtained in Synthesis Example 7.
［比較例３−１］
１−メチル−３−プロピルピペリジニウムビス（トリフルオロメタンスルホニル）アミド（ＰＰ１３・ＴＦＳＡ，関東化学（株）製）を溶媒として、０．３５ｍｏｌ／ｋｇの濃度で６０℃のＡｒ雰囲気下で秤量混合して６時間撹拌し、リチウムイオン輸率評価用電解液を調製した。
[Comparative Example 3-1]
1-Methyl-3-propylpiperidinium bis (trifluoromethanesulfonyl) amide (PP13.TFSA, manufactured by Kanto Chemical Co., Ltd.) as a solvent, and weighed and mixed at a concentration of 0.35 mol / kg in an Ar atmosphere at 60 ° C. And it stirred for 6 hours and prepared the electrolyte solution for lithium ion transport number evaluation.
上記実施例３−１〜３−７、比較例３−１で調製した各電解液のリチウムイオン輸率について、磁場勾配ＮＭＲ（バリアン社製、ＩＮＯＶＡ３００）を用い、６０℃で7Ｌｉ（カチオン）、1Ｈ（カチオン）、19Ｆ（アニオン）の拡散係数（ＤLi、ＤH、ＤF）を算出し、リチウムイオン輸率ｔLiを下記式にて決定した。 About the lithium ion transport number of each electrolyte solution prepared in Examples 3-1 to 3-7 and Comparative Example 3-1, 7 Li (cation) was used at 60 ° C. using magnetic field gradient NMR (Varian, INOVA300). , 1 H (cation), 19 F (anion) diffusion coefficients (D Li , D H , D F ) were calculated, and the lithium ion transport number t Li was determined by the following formula.
ｔLi＝（リチウムイオンの拡散量）／（カチオンの拡散量＋アニオンの拡散量）
＝ＣLiTFSA×ＤLi／｛ＣLiTFSA×ＤLi＋［ＣLiTFSA＋（１０００−ＣLiTFSA×（ＬｉＴＦＳＡの分子量））／（イオン液体の分子量）］×ＤF＋（１０００−ＣLiTFSA×（ＬｉＴＦＳＡの分子量））／（イオン液体の分子量）×ＤH｝
（式中、ＣLiTFSAは、ＬｉＴＦＳＡの濃度を表す。）
t Li = (Lithium ion diffusion amount) / (Cation diffusion amount + Anion diffusion amount)
= C LiTFSA × D Li / {C LiTFSA × D Li + [C LiTFSA + (1000-C LiTFSA × (molecular weight of LiTFSA)) / (molecular weight of ionic liquid)] × D F + (1000-C LiTFSA × (LiTFSA Molecular weight)) / (molecular weight of ionic liquid) × D H }
(In the formula, C LiTFSA represents the concentration of LiTFSA.)
各電解液の６０℃におけるリチウムイオン輸率を比較したグラフを図４に示す。
図４に示されるように、リチウムイオン輸率は、ＭＥＭＰ・ＦＳＡ、ＭＥＭＰ・ＴＦＳＡ、ＭＭＭＰ・ＦＳＡ、ＭＭＭＰ・ＴＦＳＡ、ＭＥＭＰ２・ＦＳＡ、ＭＥＭＰ２・ＴＦＳＡ、ＭＥＭＰ３・ＴＦＳＡおよびＰＰ１３・ＴＦＳＡについて、それぞれ３．８％、３．６％、４．０％、３．８％、５．０％、４．７％、５．１％および３．５％であった。この結果より、２つ以上のエーテル基を有するカチオンのイオン液体にＬｉＴＦＳＡを溶解させた電解液が、特にリチウム空気電池用電解液として適していることがわかる。
The graph which compared the lithium ion transport number in 60 degreeC of each electrolyte solution is shown in FIG.
As shown in FIG. 4, the lithium ion transport number is 3 for MEMP • FSA, MEMP • TFSA, MMMP • FSA, MMMP • TFSA, MEMP2 • FSA, MEMP2 • TFSA, MEMP3 • TFSA, and PP13 • TFSA, respectively. 8%, 3.6%, 4.0%, 3.8%, 5.0%, 4.7%, 5.1%, and 3.5%. From this result, it can be seen that an electrolytic solution obtained by dissolving LiTFSA in a cationic ionic liquid having two or more ether groups is particularly suitable as an electrolytic solution for a lithium air battery.
Claims (15)
前記電解質層が、請求項１〜１４のいずれか１項記載の金属空気電池用電解液を含むことを特徴とする金属空気電池。 Having an air electrode, a negative electrode, and an electrolyte layer interposed between these electrodes,
The metal-air battery, wherein the electrolyte layer includes the metal-air battery electrolyte solution according to any one of claims 1 to 14.
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