KR20170047228A - Zwitter ion compound and ion conductor - Google Patents
Zwitter ion compound and ion conductor Download PDFInfo
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- KR20170047228A KR20170047228A KR1020177003918A KR20177003918A KR20170047228A KR 20170047228 A KR20170047228 A KR 20170047228A KR 1020177003918 A KR1020177003918 A KR 1020177003918A KR 20177003918 A KR20177003918 A KR 20177003918A KR 20170047228 A KR20170047228 A KR 20170047228A
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- 239000010416 ion conductor Substances 0.000 title claims abstract description 29
- -1 ion compound Chemical class 0.000 title description 60
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 33
- 150000008040 ionic compounds Chemical class 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000011664 nicotinic acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
- 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 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002051 biphasic effect Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 2
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VWEYDBUEGDKEHC-UHFFFAOYSA-N 3-methyloxathiolane 2,2-dioxide Chemical compound CC1CCOS1(=O)=O VWEYDBUEGDKEHC-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 150000001993 dienes Chemical group 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- CITYCXHDERIVTC-UHFFFAOYSA-N propane-1-sulfonate tributylazanium Chemical compound CCCS([O-])(=O)=O.CCCC[NH+](CCCC)CCCC CITYCXHDERIVTC-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
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- 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
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- General Health & Medical Sciences (AREA)
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Abstract
본 발명은, 하기 식 (I) 로 나타내는 쌍성 이온 화합물, 및 이 쌍성 이온 화합물을 함유하는 이온 전도체 (식 중, R1 ∼ R3 은, 각각 독립적으로, 탄소수 1 ∼ 5 의 알킬기, 탄소수 3 ∼ 8 의 시클로알킬기, 탄소수 2 ∼ 10 의 알케닐기, 또는 치환 혹은 무치환의 탄소수 6 ∼ 20 의 아릴기를 나타내고, X 는, 탄소수 2 ∼ 5 의 알킬렌기를 나타낸다) 이다. 본 발명에 의하면, 이온 전도성 및 내열성이 우수한, 신규 쌍성 이온 화합물, 및 이 쌍성 이온 화합물을 함유하는 이온 전도체가 제공된다.The present invention relates to a bistable ionic compound represented by the following formula (I) and an ion conductor containing the bithonic ionic compound (wherein R 1 to R 3 each independently represents an alkyl group having 1 to 5 carbon atoms, A cycloalkyl group having 2 to 8 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and X represents an alkylene group having 2 to 5 carbon atoms. According to the present invention, there is provided a novel binary ionic compound having excellent ion conductivity and heat resistance, and an ionic conductor containing this binary ionic compound.
Description
본 발명은, 이온 전도성 및 내열성이 우수한, 신규 쌍성 (雙性) 이온 화합물, 및 이 쌍성 이온 화합물을 함유하는 이온 전도체에 관한 것이다.The present invention relates to a novel twin ionic compound having excellent ion conductivity and heat resistance and an ionic conductor containing this bithonic ionic compound.
최근, 카티온 부위와 아니온 부위를 동일 분자 내에 갖는 쌍성 이온 화합물은, 이온 전도체의 재료나 각종 첨가제 등으로서 주목을 끌고 있다.In recent years, biphasic ionic compounds having cationic sites and anionic sites in the same molecule have attracted attention as materials for ionic conductors and various additives.
예를 들어, 특허문헌 1, 2 에는, 쌍성 이온염과 프로톤 공여체로 이루어지는 프로톤 전도체, 및 이 프로톤 전도체로 이루어지는 프로톤 전도층을 갖는 연료 전지 등이 기재되어 있다.For example, Patent Documents 1 and 2 disclose proton conductors composed of a biphasic ion salt and a proton donor, and a fuel cell having a proton conduction layer made of the proton conductor.
특허문헌 3 에는, 리튬염과 쌍성 이온형 이온 액체를 함유하는 전해액, 및 이 전해액을 사용하는 리튬 이온 2 차 전지가 기재되어 있다.Patent Literature 3 discloses an electrolytic solution containing a lithium salt and a bionic ion liquid, and a lithium ion secondary battery using the electrolytic solution.
특허문헌 4 에는, 대전 방지제 등으로서 사용하는 쌍성 이온 화합물이 기재되어 있다.Patent Document 4 describes a bistable ionic compound used as an antistatic agent or the like.
상기와 같이, 쌍성 이온 화합물은, 연료 전지, 리튬 전지 등의 전기 화학 디바이스의 이온 전도성 부재의 재료 등으로서 유용하다.As described above, the bionic ion compound is useful as a material for an ion conductive member of an electrochemical device such as a fuel cell or a lithium battery.
그러나, 종래의 쌍성 이온 화합물은, 내열성이 열등한 경향이 있어, 고온시에 분해될 우려가 있었기 때문에, 구동시에 매우 고온이 되는 전기 화학 디바이스의 제조 재료로는 적합하지 않았다.However, the conventional bithionic ionic compounds tend to be inferior in heat resistance, and are liable to be decomposed at high temperatures, so they are not suitable as materials for producing electrochemical devices which become very hot at the time of driving.
본 발명은, 이러한 실정을 감안하여 이루어진 것으로, 이온 전도성 및 내열성이 우수한, 신규 쌍성 이온 화합물, 및 이 쌍성 이온 화합물을 함유하는 이온 전도체를 제공하는 것을 목적으로 한다.SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a novel binary ionic compound having excellent ion conductivity and heat resistance and an ionic conductor containing this binary ionic compound.
본 발명자들은 상기 과제를 해결하기 위하여 예의 검토한 결과, 인 원자를 함유하는 카티온성기 및 술폰산기를 갖는 쌍성 이온 화합물은, 이온 전도성 및 내열성이 우수한 것을 알아내어, 본 발명을 완성하기에 이르렀다.The present inventors have intensively studied to solve the above problems and found that a cationic group containing a phosphorus atom and a bionic ion compound having a sulfonic acid group are excellent in ion conductivity and heat resistance, and have completed the present invention.
이렇게 하여 본 발명에 의하면, 하기 (1) 의 쌍성 이온 화합물, 및 (2), (3) 의 이온 전도체가 제공된다.Thus, according to the present invention, the bistable ionic compound of the following (1) and the ionic conductors of (2) and (3) are provided.
(1) 하기 식 (I)(1)
[화학식 1][Chemical Formula 1]
(식 중, R1 ∼ R3 은, 각각 독립적으로, 탄소수 1 ∼ 5 의 알킬기, 탄소수 3 ∼ 8 의 시클로알킬기, 탄소수 2 ∼ 10 의 알케닐기, 또는 치환 혹은 무치환의 탄소수 6 ∼ 20 의 아릴기를 나타내고, X 는, 탄소수 2 ∼ 5 의 알킬렌기를 나타낸다) 로 나타내는 쌍성 이온 화합물.(Wherein R 1 to R 3 are each independently an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms And X represents an alkylene group having 2 to 5 carbon atoms.
(2) 상기 (1) 에 기재된 쌍성 이온 화합물과, 주기율표 제 1 족 또는 제 2 족의 금속의 염을 함유하는 이온 전도체.(2) An ion conductor containing the bistable ionic compound described in (1) above and a salt of a metal of Group 1 or Group 2 of the periodic table.
(3) 상기 금속의 염이 리튬염인 (2) 에 기재된 이온 전도체.(3) The ion conductor according to (2), wherein the salt of the metal is a lithium salt.
본 발명에 의하면, 이온 전도성 및 내열성이 우수한, 신규 쌍성 이온 화합물, 및 이 쌍성 이온 화합물을 함유하는 이온 전도체가 제공된다.According to the present invention, there is provided a novel binary ionic compound having excellent ion conductivity and heat resistance, and an ionic conductor containing this binary ionic compound.
이하, 본 발명을, 1) 쌍성 이온 화합물, 및 2) 이온 전도체로 항목 분류하여 상세하게 설명한다.Hereinafter, the present invention will be described in detail as 1) a binary ion compound and 2) an ion conductor.
본 발명에 있어서, 쌍성 이온 화합물의 「이온 전도성」이란, 수송되는 이온을 함유하는 염과 혼합하여 얻어진 혼합물에 있어서의 이온의 이동이 용이한 것을 의미하고, 이온 전도체의 「이온 전도성」이란, 이온 전도체에 있어서의 이온의 이동이 용이한 것을 의미한다.In the present invention, the " ionic conductivity " of a bionic ion compound means that ions are easily transferred in a mixture obtained by mixing with a salt containing a transported ion, and the " ionic conductivity " It means that the movement of ions in the conductor is easy.
1) 쌍성 이온 화합물1) Binary ionic compound
본 발명의 쌍성 이온 화합물은, 상기 식 (I) 로 나타내는 화합물이다.The bifunctional ionic compound of the present invention is a compound represented by the above formula (I).
식 (I) 중, R1 ∼ R3 은, 각각 독립적으로, 탄소수 1 ∼ 5 의 알킬기, 탄소수 3 ∼ 8 의 시클로알킬기, 탄소수 2 ∼ 10 의 알케닐기, 또는 치환 혹은 무치환의 탄소수 6 ∼ 20 의 아릴기를 나타낸다.In formula (I), R 1 to R 3 each independently represent an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted group having 6 to 20 carbon atoms ≪ / RTI >
R1 의 알킬기의 탄소수는, 1 ∼ 5, 바람직하게는 2 ∼ 4 이다.The alkyl group of R < 1 > has 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms.
R1 의 알킬기로는, 메틸기, 에틸기, n-프로필기, n-부틸기, n-펜틸기 등의 직사슬 알킬기；이소프로필기, s-부틸기, t-부틸기, 이소부틸기 등의 분기사슬 알킬기를 들 수 있다.Examples of the alkyl group represented by R 1 include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl and n-pentyl groups, isopropyl, And branched-chain alkyl groups.
R1 의 시클로알킬기의 탄소수는, 3 ∼ 8, 바람직하게는 5 ∼ 7 이다.The cycloalkyl group of R < 1 > has 3 to 8 carbon atoms, preferably 5 to 7 carbon atoms.
R1 의 시클로알킬기로는, 시클로프로필기, 시클로부틸기, 시클로펜틸기, 시클로헥실기, 시클로헵틸기, 시클로옥틸기를 들 수 있다.Examples of the cycloalkyl group represented by R 1 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
R1 의 알케닐기의 탄소수는, 2 ∼ 10, 바람직하게는 3 ∼ 8 이다.The alkenyl group of R < 1 > has 2 to 10 carbon atoms, preferably 3 to 8 carbon atoms.
R1 의 알케닐기로는, 비닐기, 알릴기, 1-부테닐기, 2-부테닐기, 1-펜테닐기 등을 들 수 있다.Examples of the alkenyl group for R 1 include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group and a 1-pentenyl group.
R1 의 아릴기의 탄소수는, 6 ∼ 20, 바람직하게는 6 ∼ 10 이다.The aryl group of R < 1 > has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms.
R1 의 무치환의 아릴기로는, 페닐기, 1-나프틸기, 2-나프틸기 등을 들 수 있다.Examples of the unsubstituted aryl group for R 1 include a phenyl group, a 1-naphthyl group and a 2-naphthyl group.
치환 아릴기의 치환기로는, 메틸기, 에틸기 등의 탄소수 1 ∼ 6 의 알킬기；메톡시기, 에톡시기 등의 탄소수 1 ∼ 6 의 알콕시기；등을 들 수 있다.Examples of the substituent of the substituted aryl group include an alkyl group having 1 to 6 carbon atoms such as methyl group and ethyl group; and an alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group.
이것들 중에서도, 이온 전도성 및 내열성이 우수한 점에서, R1 은, 탄소수 1 ∼ 5 의 알킬기가 바람직하고, 탄소수 2 ∼ 4 의 알킬기가 보다 바람직하다.Of these, R 1 is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 2 to 4 carbon atoms, from the viewpoint of excellent ion conductivity and heat resistance.
식 (I) 중, X 는, 탄소수 2 ∼ 5 의 알킬렌기를 나타낸다.In the formula (I), X represents an alkylene group having 2 to 5 carbon atoms.
X 의 탄소수 2 ∼ 5 의 알킬렌기로는, 에틸렌기, 트리메틸렌기, 테트라메틸렌기, 펜타메틸렌기 등의 직사슬형 알킬렌기；프로판-1,2-디일기, 부탄-1,3-디일기 등의 분기사슬상 알킬렌기；를 들 수 있다.Examples of the alkylene group having 2 to 5 carbon atoms for X include a linear alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group and a pentamethylene group; a propane-1,2-diyl group, And branched alkylene groups such as dienes.
본 발명의 쌍성 이온 화합물의 제조 방법은 특별히 한정되지 않는다. 예를 들어, 하기 식에 나타내는 바와 같이, 쌍성 이온 화합물 (IV) 은, 대응하는 포스핀 화합물 (II) 과 술톤 화합물 (III) 을 반응시킴으로써 얻을 수 있다.The method for producing the zwitterionic compound of the present invention is not particularly limited. For example, as shown in the following formula, the biphasic ionic compound (IV) can be obtained by reacting the corresponding phosphine compound (II) with the sultone compound (III).
[화학식 2](2)
(상기 식 중, R1, R2, R3 은 상기와 동일한 의미를 나타내고, n 은 0, 1, 2 또는 3 이다)(Wherein R 1 , R 2 and R 3 have the same meanings as defined above, and n is 0, 1, 2 or 3)
상기 포스핀 화합물 (II) 로는, 트리에틸포스핀, 트리(n-프로필)포스핀, 트리(n-부틸)포스핀 등의 트리알킬포스핀；트리시클로펜틸포스핀, 트리시클로헥실포스핀 등의 트리시클로알킬포스핀；을 들 수 있다.Examples of the phosphine compound (II) include trialkylphosphines such as triethylphosphine, tri (n-propyl) phosphine and tri (n-butyl) phosphine, tricyclopentylphosphine, tricyclohexylphosphine Of tricycloalkylphosphine.
상기 술톤 화합물 (III) 로는, 1,2-에탄술톤, 1,3-프로판술톤, 1,4-부탄술톤, 2,4-부탄술톤, 1,5-펜탄술톤을 들 수 있다.Examples of the sultone compound (III) include 1,2-ethane sultone, 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone and 1,5-pentane sultone.
포스핀 화합물 (II) 이나 술톤 화합물 (III) 은, 공지 화합물이며, 공지된 방법으로 제조하고, 입수할 수 있다. 또, 포스핀 화합물 (II) 이나 술톤 화합물 (III) 로서 시판품을 사용할 수도 있다.The phosphine compound (II) or the sultone compound (III) is a known compound and can be prepared by a known method. A commercially available product may also be used as the phosphine compound (II) or the sultone compound (III).
포스핀 화합물 (II) 과 술톤 화합물 (III) 의 반응에 있어서, 술톤 화합물 (III) 의 사용량은, 포스핀 화합물 (II) 에 대하여, 바람직하게는 0.8 ∼ 1.2 당량, 보다 바람직하게는 0.9 ∼ 1.1 당량이다. 술톤 화합물 (III) 의 사용량을 상기 범위로 함으로써, 미반응물을 제거하는 공정을 생략하거나, 제거에 걸리는 시간을 단축하거나 할 수 있다.The amount of the sultone compound (III) to be used in the reaction of the phosphine compound (II) and the sultone compound (III) is preferably 0.8 to 1.2 equivalents, more preferably 0.9 to 1.1 equivalents, relative to the phosphine compound (II) Equivalent. By setting the amount of the sultone compound (III) to fall within the above range, the step of removing unreacted materials can be omitted or the time required for removal can be shortened.
포스핀 화합물 (II) 과 술톤 화합물 (III) 의 반응은, 무용매로 실시해도 되고, 불활성 용매의 존재 하에 실시해도 된다.The reaction of the phosphine compound (II) with the sultone compound (III) may be carried out in the absence of a solvent or in the presence of an inert solvent.
사용하는 불활성 용매로는, 테트라하이드로푸란, 디글라임 등의 에테르계 용매；아세토니트릴, 프로피오니트릴 등의 니트릴계 용매；아세톤, 메틸에틸케톤 등의 케톤계 용매；톨루엔, 자일렌 등의 방향족 탄화수소계 용매；클로로포름 등의 할로겐화 탄화수소계 용매；등을 들 수 있다.Examples of the inert solvent to be used include ether solvents such as tetrahydrofuran and diglyme; nitrile solvents such as acetonitrile and propionitrile; ketone solvents such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and xylene; A halogenated hydrocarbon solvent such as chloroform, and the like.
불활성 용매를 사용하는 경우, 그 사용량은 특별히 제한되지 않지만, 포스핀 화합물 (II) 1 질량부에 대하여, 통상 100 질량부 이하인 것이 바람직하다.When an inert solvent is used, the amount to be used is not particularly limited, but is preferably 100 parts by mass or less based on 1 part by mass of the phosphine compound (II).
반응 온도는, 특별히 한정되지 않지만, 통상, -20 ∼ 200 ℃, 바람직하게는 0 ∼ 100 ℃, 보다 바람직하게는 10 ∼ 60 ℃ 의 범위이다. 또, 상압 조건 하에서 반응을 실시해도 되고, 가압 조건 하에서 반응을 실시해도 된다.The reaction temperature is not particularly limited, but is usually in the range of -20 to 200 占 폚, preferably 0 to 100 占 폚, and more preferably 10 to 60 占 폚. The reaction may be carried out under atmospheric pressure or under pressure.
반응 시간은, 특별히 한정되지 않지만, 통상, 12 ∼ 336 시간, 바람직하게는 24 ∼ 168 시간이다.The reaction time is not particularly limited, but is usually 12 to 336 hours, preferably 24 to 168 hours.
반응은 산소에 의한 산화나, 공기 중의 수분에 의한 술톤 화합물 (III) 의 가수 분해에 의한 수율의 저하를 방지하는 관점에서, 질소 분위기 하에서 실시하는 것이 바람직하다.The reaction is preferably carried out in a nitrogen atmosphere, from the viewpoint of preventing oxidation by oxygen and reduction in yield due to hydrolysis of the sultone compound (III) by moisture in the air.
반응의 진행은, 예를 들어 가스 크로마토그래피, 고속 액체 크로마토그래피, 박층 크로마토그래피, NMR, IR 등의 통상적인 분석 수단에 의해 확인할 수 있다.The progress of the reaction can be confirmed by conventional analytical means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR and IR.
반응 종료 후, 얻어진 쌍성 이온 화합물은, 용제 세정, 재결정, 칼럼 크로마토그래피 등의 공지된 정제 방법에 의해 정제할 수 있다.After completion of the reaction, the obtained bistable ionic compound can be purified by a known purification method such as solvent washing, recrystallization, column chromatography and the like.
본 발명의 쌍성 이온 화합물은, 카티온성기로서 상기 포스포늄기를, 아니온성기로서 술폰산기 (-SO3-) 를 갖는다.The bithion ionic compound of the present invention has the phosphonium group as a cationic group and a sulfonic acid group (-SO 3 -) as an anionic group.
이와 같은 구조를 갖는 본 발명의 쌍성 이온 화합물은, 이온 전도성 및 내열성이 우수하다.The bionic ion compound of the present invention having such a structure is excellent in ion conductivity and heat resistance.
본 발명의 쌍성 이온 화합물의 이온 전도성은, 예를 들어, 리튬염과 혼합하여 얻어진 혼합물의 이온 전도도를 측정함으로써 평가할 수 있다.The ionic conductivity of the bithionic ionic compound of the present invention can be evaluated, for example, by measuring the ionic conductivity of a mixture obtained by mixing with a lithium salt.
예를 들어, 본 발명의 쌍성 이온 화합물과, 리튬비스 (트리플루오로메탄술포닐)이미드 (LiTFSI) 의 혼합물 (혼합 비율：쌍성 이온 화합물 1 몰에 대하여, LiTFSI 1 몰) 의 60 ℃ 에 있어서의 이온 전도도는, 통상, 10-8 ∼ 10-2 S/㎝, 바람직하게는 10-7 ∼ 10-2 S/㎝, 특히 바람직하게는 10-6 ∼ 10-2 S/㎝ 이다.For example, a mixture of a mixture of a bithion ion compound of the present invention and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) (mixing ratio: 1 mole of LiTFSI relative to 1 mole of a bithionic compound) The ionic conductivity is usually 10 -8 to 10 -2 S / cm, preferably 10 -7 to 10 -2 S / cm, and particularly preferably 10 -6 to 10 -2 S / cm.
본 발명의 쌍성 이온 화합물의 내열성은, 예를 들어, 열 중량 분석을 실시했을 때의 중량 감소에 따라 평가할 수 있다.The heat resistance of the bithion ionic compound of the present invention can be evaluated, for example, by weight reduction when thermogravimetric analysis is carried out.
예를 들어, 실시예에 기재된 조건으로 열 중량 분석을 실시했을 때에, 중량 감소 비율이 5 ％ 에 도달했을 때의 온도는, 통상, 300 ∼ 600 ℃, 바람직하게는 400 ∼ 500 ℃ 이다.For example, when thermogravimetric analysis is carried out under the conditions described in the examples, the temperature at which the weight loss rate reaches 5% is usually 300 to 600 ° C, preferably 400 to 500 ° C.
본 발명의 쌍성 이온 화합물의 유리 전이 온도는, 특별히 한정되지 않지만, 통상, -100 ∼ ＋150 ℃, 바람직하게는 -80 ∼ ＋50 ℃, 특히 바람직하게는 -60 ∼ ＋20 ℃ 이다.The glass transition temperature of the bist ionic compound of the present invention is not particularly limited, but is usually -100 to +150 占 폚, preferably -80 to +50 占 폚, particularly preferably -60 to +20 占 폚.
유리 전이 온도가 상기 범위 내에 있는 쌍성 이온 화합물을 사용함으로써, 이온 전도성이 우수한 이온 전도체를 효율적으로 얻을 수 있다.By using a bistable ionic compound having a glass transition temperature falling within the above range, an ion conductor having excellent ion conductivity can be efficiently obtained.
본 발명의 쌍성 이온 화합물의 융점은, 특별히 한정되지 않지만, 통상, 0 ∼ 250 ℃, 바람직하게는 20 ∼ 200 ℃ 이다. 융점이 상기 범위 내에 있는 쌍성 이온 화합물을 사용함으로써, 쌍성 이온 화합물이 잘 결정화되지 않는 이온 전도체를 효율적으로 얻을 수 있다.The melting point of the bithionic ion compound of the present invention is not particularly limited, but is usually from 0 to 250 캜, preferably from 20 to 200 캜. By using a bionic ion compound having a melting point within the above range, it is possible to efficiently obtain an ion conductor whose bistable ionic compound does not crystallize well.
이들 특성을 갖는 점에서, 본 발명의 쌍성 이온 화합물은, 연료 전지의 프로톤 전도체, 리튬 이온 2 차 전지의 리튬 이온 전도체, 대전 방지제, 분산제 등으로서 바람직하게 사용할 수 있다.In view of these properties, the bithion ionic compound of the present invention can be preferably used as a proton conductor of a fuel cell, a lithium ion conductor of a lithium ion secondary battery, an antistatic agent, a dispersant and the like.
2) 이온 전도체2) ion conductor
본 발명의 이온 전도체는, 본 발명의 쌍성 이온 화합물과, 주기율표 제 1 족 또는 제 2 족의 금속의 염을 함유한다.The ion conductor of the present invention contains a bithion ion compound of the present invention and a salt of a metal of Group 1 or Group 2 of the periodic table.
이온 전도체는, 그 내부를, 이들 금속의 염 유래의 금속 이온이 비교적 자유롭게 이동 가능한 물질이다.The ion conductor is a material in which the metal ions derived from the salt of these metals are relatively freely movable.
상기 금속의 염을 구성하는 금속 이온으로는, 리튬 이온, 나트륨 이온, 칼륨 이온 등의 알칼리 금속 이온；마그네슘 이온；칼슘 이온, 스트론튬 이온 등의 알칼리 토금속 이온；을 들 수 있다.Examples of the metal ion constituting the salt of the metal include alkali metal ions such as lithium ion, sodium ion and potassium ion; magnesium ions; and alkaline earth metal ions such as calcium ion and strontium ion.
상기 금속의 염을 구성하는 음이온으로는, 비스(플루오로메탄술포닐)이미드 이온, 비스(트리플루오로메탄술포닐)이미드 이온, 비스(펜타플루오로에탄술포닐)이미드 이온, 트리스(트리플루오로메탄술포닐)메티드 이온, 트리플루오로메탄술폰산 이온, 헥사플루오로인산 이온, 테트라플루오로보레이트 이온, 테트라시아노보레이트 이온, 과염소산 이온, 헥사플루오로비산 이온 등을 들 수 있다.Examples of the anion constituting the salt of the metal include bis (fluoromethanesulfonyl) imide ion, bis (trifluoromethanesulfonyl) imide ion, bis (pentafluoroethanesulfonyl) (Trifluoromethanesulfonyl) methide ion, trifluoromethanesulfonic acid ion, hexafluorophosphate ion, tetrafluoroborate ion, tetracyanoborate ion, perchlorate ion, hexafluoroborate ion, etc. .
상기 금속의 염으로는, 리튬염, 나트륨염, 칼륨염, 마그네슘염이 바람직하고, 리튬염이 보다 바람직하다.As the salt of the metal, a lithium salt, a sodium salt, a potassium salt, and a magnesium salt are preferable, and a lithium salt is more preferable.
리튬염으로는, 리튬비스(플루오로메탄술포닐)이미드 (LiN(SO2CH2F)2), 리튬비스(트리플루오로메탄술포닐)이미드 (LiN(SO2CF3)2), 리튬비스(펜타플루오로에탄술포닐)이미드 (LiN(SO2C2F5)2), 리튬트리스(트리플루오로메탄술포닐)메티드 (LiC(SO2CF3)3), 트리플루오로메탄술폰산리튬 (LiCF3SO3), 헥사플루오로인산리튬 (LiPF6), 리튬테트라플루오로보레이트 (LiBF4), 리튬테트라시아노보레이트 (LiB(CN)4), 과염소산리튬 (LiClO4), 헥사플루오로비산리튬 (LiAsF6) 등을 들 수 있다.Examples of the lithium salt include lithium bis (fluoromethanesulfonyl) imide (LiN (SO 2 CH 2 F) 2 ), lithium bis (trifluoromethanesulfonyl) imide (LiN (SO 2 CF 3 ) 2 ) , lithium bis (pentafluoro ethane sulfonyl) imide (LiN (SO 2 C 2 F 5) 2), ( methanesulfonyl trifluoromethyl) lithium tris methide (LiC (SO 2 CF 3) 3), tree (LiCF 3 SO 3 ), lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium tetracyanoborate (LiB (CN) 4 ), lithium perchlorate (LiClO 4 ), Lithium hexafluoroarsenate (LiAsF 6 ), and the like.
본 발명에 있어서, 주기율표 제 1 족 또는 제 2 족의 금속의 염은, 일종 단독으로, 혹은 2 종 이상을 조합하여 사용할 수 있다.In the present invention, salts of metals of Group 1 or Group 2 of the periodic table can be used singly or in combination of two or more.
이온 전도체 중의 상기 금속의 염의 함유량은, 쌍성 이온 화합물 1 몰에 대하여, 통상, 0.1 ∼ 100 몰, 바람직하게는 0.5 ∼ 30 몰이다.The salt content of the metal in the ion conductor is usually 0.1 to 100 moles, preferably 0.5 to 30 moles, per 1 mole of the bistable ionic compound.
본 발명의 이온 전도체의 60 ℃ 에 있어서의 이온 전도도는, 통상, 10-8 ∼ 10-2 S/㎝, 바람직하게는 10-6 ∼ 10-2 S/㎝ 이다.The ionic conductivity of the ion conductor of the present invention at 60 캜 is generally 10 -8 to 10 -2 S / cm, preferably 10 -6 to 10 -2 S / cm.
본 발명의 이온 전도체의 유리 전이 온도는, 통상, -100 ∼ ＋50 ℃, 바람직하게는 -90 ∼ ＋30 ℃ 이다.The glass transition temperature of the ion conductor of the present invention is usually -100 to +50 캜, preferably -90 to +30 캜.
본 발명의 이온 전도체는, 각종 전기 화학 디바이스의 전해질층이나 전극 중의 성분으로서 사용할 수 있다.The ion conductor of the present invention can be used as a component in an electrolyte layer or an electrode of various electrochemical devices.
그 중에서도, 리튬염을 함유하는 리튬 이온 전도체는, 리튬 이온 2 차 전지의 전해질층이나 전극 중의 성분으로서 바람직하게 사용된다.Among them, a lithium ion conductor containing a lithium salt is preferably used as a component in an electrolyte layer or an electrode of a lithium ion secondary battery.
본 발명의 이온 전도체는, 본 발명의 쌍성 이온 화합물을 함유하는 것이며, 이온 전도성 및 내열성이 우수하다. 따라서, 본 발명의 이온 전도체를 사용함으로써, 안전성이 높은 전기 화학 디바이스를 얻을 수 있다.The ion conductor of the present invention contains the bithion ion compound of the present invention and is excellent in ion conductivity and heat resistance. Therefore, by using the ion conductor of the present invention, an electrochemical device having high safety can be obtained.
실시예Example
이하, 실시예를 들어 본 발명을 더욱 상세하게 설명한다. 단, 본 발명은, 이하의 실시예에 전혀 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples at all.
각 예 중의 부 및 ％ 는, 특별히 언급이 없는 한, 질량 기준이다.Parts and% in each example are on a mass basis unless otherwise specified.
[실시예 1][Example 1]
적하 깔때기를 구비한 2 구 가지형 플라스크에, 질소 분위기 하, 트리부틸포스핀 6.0 g (29.7 m㏖), 및 클로로포름 10 ㎖ 를 넣고, 내용물을 교반하면서, 25 ℃ 에서, 1,3-프로판술톤 3.6 g (29.7 m㏖) 을 천천히 첨가하고, 첨가 종료 후, 전체 용량을 40 ℃ 에서 168 시간 교반하였다.6.0 g (29.7 mmol) of tributylphosphine and 10 ml of chloroform were placed in a two-necked flask equipped with a dropping funnel under nitrogen atmosphere and 1,3-propane sultone 3.6 g (29.7 mmol) was slowly added, and after the addition was completed, the total volume was stirred at 40 占 폚 for 168 hours.
반응 종료 후, 반응액으로부터 용매를 감압 증류 제거하고, 잔류물을 아세트산에틸로 세정하고, 건조시킴으로써 무색 결정을 얻었다 (수량：8.8 g, 수율 91.0 ％).After completion of the reaction, the solvent was distilled off from the reaction mixture under reduced pressure, and the residue was washed with ethyl acetate and dried to obtain colorless crystals (yield: 8.8 g, yield: 91.0%).
얻어진 무색 결정의 1H-NMR 스펙트럼 데이터를 하기에 나타낸다. 1 H-NMR spectrum data of the obtained colorless crystals are shown below.
[실시예 2][Example 2]
적하 깔때기를 구비한 2 구 가지형 플라스크에, 질소 분위기 하, 트리에틸포스핀/THF (테트라하이드로푸란) 용액 (농도 1 ㏖/ℓ) 50 ㎖, 및 클로로포름 20 ㎖ 를 넣고, 내용물을 교반하면서, 25 ℃ 에서, 1,3-프로판술톤 6.1 g (50 m㏖) 을 천천히 첨가하고, 첨가 종료 후, 전체 용량을 40 ℃ 에서 168 시간 교반하였다.In a two-necked flask equipped with a dropping funnel, 50 ml of a triethylphosphine / THF (tetrahydrofuran) solution (concentration 1 mol / l) and 20 ml of chloroform were placed under a nitrogen atmosphere, At 25 占 폚, 6.1 g (50 mmol) of 1,3-propanesultone was added slowly, and after the addition was completed, the total volume was stirred at 40 占 폚 for 168 hours.
반응 종료 후, 석출물을 여과 채취하고, 이것을 아세트산에틸로 세정하고, 건조시킴으로써 무색 결정 (수량：11.1 g, 수율 92.5 ％) 을 얻었다.After completion of the reaction, the precipitate was collected by filtration, washed with ethyl acetate and dried to obtain colorless crystals (yield: 11.1 g, yield: 92.5%).
얻어진 무색 결정의 1H-NMR 스펙트럼 데이터를 하기에 나타낸다. 1 H-NMR spectrum data of the obtained colorless crystals are shown below.
[비교예 1][Comparative Example 1]
냉각관, 적하 깔때기를 구비한 3 구 플라스크에, 트리부틸아민 2 g (10.8 m㏖), 아세톤 5 ㎖ 를 넣고, 내용물을 교반하면서, 25 ℃ 에서, 1,3-프로판술톤 1.32 g (10.8 m㏖) 을 천천히 첨가하고, 첨가 종료 후, 48 시간 환류를 실시하였다.2 g (10.8 mmol) of tributylamine and 5 ml of acetone were placed in a three-necked flask equipped with a reflux condenser, a cooling tube and a dropping funnel. While stirring the contents, 1.32 g ㏖) was added slowly, and after completion of the addition, the mixture was refluxed for 48 hours.
반응 종료 후, 침전물을 여과 채취하고, 얻어진 침전물을 아세톤으로 세정함으로써, 목적물인 트리부틸암모늄프로판술포네이트를 얻었다 (수량：1.23 g, 수율 37.0 ％).After completion of the reaction, the precipitate was collected by filtration, and the obtained precipitate was washed with acetone to obtain tributylammonium propane sulfonate (yield: 1.23 g, yield: 37.0%).
얻어진 무색 결정의 1H-NMR 스펙트럼 데이터를 하기에 나타낸다. 1 H-NMR spectrum data of the obtained colorless crystals are shown below.
실시예 1 ∼ 2 및 비교예 1 에서 얻은 쌍성 이온 화합물에 대하여, 각각 이하의 측정을 실시하였다.The following measurements were carried out on the bistable ionic compounds obtained in Examples 1 and 2 and Comparative Example 1, respectively.
(시차 주사 열량 분석)(Differential scanning calorimetry)
시차 주사 열량 분석 장치 (SII 나노테크놀로지사 제조, DSC7020) 를 사용하여, N2 가스 유량이 40 ㎖/분, 승온 속도가 10 ℃/분의 조건에서, 실시예 및 비교예에서 얻은 쌍성 이온 화합물을 -100 ℃ 에서 ＋250 ℃ 까지 승온시켜, 유리 전이 온도 및 융점을 측정하였다. 결과를 제 1 표에 나타낸다.(Manufactured by SII Nanotechnology Co., Ltd., DSC7020) at a flow rate of N 2 gas of 40 ml / min and a temperature raising rate of 10 ° C / min, the zwitterionic compound obtained in Examples and Comparative Examples The temperature was raised from -100 ° C to +250 ° C, and the glass transition temperature and melting point were measured. The results are shown in Table 1.
(열 중량 분석)(Thermogravimetric analysis)
열 중량 분석 장치 (시마즈 제작소사 제조, DTG-60) 를 사용하여, N2 가스 유량이 100 ㎖/분, 승온 속도가 10 ℃/분의 조건에서, 실시예 및 비교예에서 얻은 쌍성 이온 화합물을 25 ℃ 에서 600 ℃ 까지 승온시켰다. 중량 감소 비율이 5 ％ 에 도달했을 때의 온도를 제 1 표에 나타낸다.(Manufactured by Shimadzu Corporation, DTG-60) at a flow rate of N 2 gas of 100 ml / min and a rate of temperature increase of 10 ° C / min, the zwitterionic compound obtained in Examples and Comparative Examples And the temperature was raised from 25 占 폚 to 600 占 폚. Table 1 shows the temperatures when the weight loss ratio reaches 5%.
(이온 전도도 측정)(Ion conductivity measurement)
실시예 및 비교예에서 얻은 쌍성 이온 화합물과, 리튬비스(트리플루오로메탄술포닐)이미드를 1：1 (몰비) 의 배합으로 메탄올에 용해시켰다. 얻어진 용액으로부터, 이배퍼레이터에 의해 메탄올을 증류 제거 후, 잔류물을, 감압 하, 120 ℃ 에서 24 시간 건조시키고, 리튬 이온 전도체를 얻었다.Binary ionic compounds obtained in Examples and Comparative Examples and lithium bis (trifluoromethanesulfonyl) imide were dissolved in methanol in a ratio of 1: 1 (molar ratio). From the obtained solution, methanol was distilled off by a distributor, and the residue was dried under reduced pressure at 120 占 폚 for 24 hours to obtain a lithium ion conductor.
백금 전극판에, 직경 8 ㎜ 의 구멍이 뚫린 300 ㎛ 두께의 폴리테트라플루오로에틸렌제 스페이서를 2 액 경화형 에폭시 수지로 접착하였다. 이어서, 이 구멍 안에, 리튬 이온 전도체를 각각 충전시킨 후, 상기 폴리테트라플루오로에틸렌제 스페이서의 위에, 다른 1 장의 백금 전극판을 중첩시킴으로써, 백금 전극판/리튬 이온 전도체/백금 전극판의 층 구조를 갖는 측정용 시료를 얻었다.A spacer made of polytetrafluoroethylene having a thickness of 300 탆 and having a hole of 8 mm in diameter was bonded to the platinum electrode plate with a two-liquid curing type epoxy resin. Then, the lithium ion conductors were filled in the holes, and another one platinum electrode plate was superimposed on the polytetrafluoroethylene spacer to obtain a layer structure of the platinum electrode plate / lithium ion conductor / platinum electrode plate Was obtained.
얻어진 측정용 시료를, 도요 시스템사 제조 전지 평가용 셀에 장착하고, Solartron 사 제조 임피던스 애널라이저 1260 을 사용하여, 온도：60 ℃ (무가습 조건), 측정 주파수：5 ∼ 1 ㎒, 인가 전압：100 mV 의 조건에서 임피던스를 측정하였다. 항온조에는 에스펙사 제조 SH-241 을 사용하였다.The measurement sample thus obtained was mounted on a cell for evaluation of battery manufactured by Toyo Systems Co., and measurement was carried out by using an impedance analyzer 1260 manufactured by Solartron under the conditions of temperature: 60 占 폚 (no humidification condition) mV. < tb > < TABLE > SH-241 manufactured by Especa was used as a thermostatic chamber.
상기 측정에 의해 얻어진 저항값을 사용하여, 하기 식으로부터 이온 전도도를 산출하였다.Using the resistance value obtained by the measurement, the ion conductivity was calculated from the following equation.
결과를 제 1 표에 나타낸다.The results are shown in Table 1.
[수학식 1][Equation 1]
σ：이온 전도도 (S/㎝), d：전극간 거리 (㎝), R：저항 (Ω), S：단면적 (㎠)R: Resistance (?), S: Cross-sectional area (cm 2), I: Conductivity (S /
제 1 표로부터, 이하를 알 수 있다.From the first table, the following can be known.
실시예 1, 2 의 쌍성 이온 화합물은, 중량 감소 비율이 5 ％ 에 도달했을 때의 온도가 높고, 내열성이 우수하다.The bistable ionic compounds of Examples 1 and 2 have a high temperature when the weight loss ratio reaches 5% and are excellent in heat resistance.
또, 실시예 1, 2 의 쌍성 이온 화합물을 사용하여 얻어진 이온 전도체는, 이온 전도도가 높다.The ionic conductors obtained by using the bistable ionic compounds of Examples 1 and 2 have high ionic conductivity.
Claims (3)
[화학식 1]
(식 중, R1 ∼ R3 은, 각각 독립적으로, 탄소수 1 ∼ 5 의 알킬기, 탄소수 3 ∼ 8 의 시클로알킬기, 탄소수 2 ∼ 10 의 알케닐기, 또는 치환 혹은 무치환의 탄소수 6 ∼ 20 의 아릴기를 나타내고, X 는, 탄소수 2 ∼ 5 의 알킬렌기를 나타낸다)
로 나타내는 쌍성 이온 화합물.(I)
[Chemical Formula 1]
(Wherein R 1 to R 3 are each independently an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms Group, and X represents an alkylene group having 2 to 5 carbon atoms)
≪ / RTI >
상기 금속의 염이 리튬염인 이온 전도체.3. The method of claim 2,
Wherein the salt of the metal is a lithium salt.
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