JP2007153856A - Ordinary temperature molten salt and method for producing the same - Google Patents
Ordinary temperature molten salt and method for producing the same Download PDFInfo
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- JP2007153856A JP2007153856A JP2005355444A JP2005355444A JP2007153856A JP 2007153856 A JP2007153856 A JP 2007153856A JP 2005355444 A JP2005355444 A JP 2005355444A JP 2005355444 A JP2005355444 A JP 2005355444A JP 2007153856 A JP2007153856 A JP 2007153856A
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- polymerizable functional
- cation
- functional group
- temperature molten
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- 150000003839 salts Chemical class 0.000 title claims abstract description 107
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- -1 halogen ions Chemical class 0.000 claims abstract description 122
- 125000000524 functional group Chemical group 0.000 claims abstract description 47
- 150000001768 cations Chemical class 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 150000002891 organic anions Chemical class 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 5
- 150000001639 boron compounds Chemical class 0.000 claims description 4
- 150000003464 sulfur compounds Chemical class 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 description 27
- 239000003792 electrolyte Substances 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000005041 acyloxyalkyl group Chemical group 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004255 ion exchange chromatography Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- SDXKWPVFZWZYNK-UHFFFAOYSA-N (4-ethenylphenyl)methanesulfonic acid Chemical compound OS(=O)(=O)CC1=CC=C(C=C)C=C1 SDXKWPVFZWZYNK-UHFFFAOYSA-N 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- JYVPKRHOTGQJSE-UHFFFAOYSA-M hexyl(trimethyl)azanium;bromide Chemical compound [Br-].CCCCCC[N+](C)(C)C JYVPKRHOTGQJSE-UHFFFAOYSA-M 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001958 silver carbonate Inorganic materials 0.000 description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- GWQYPLXGJIXMMV-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1 GWQYPLXGJIXMMV-UHFFFAOYSA-M 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YRXGMKXSRJAWIW-UHFFFAOYSA-N 2-(prop-2-enoxymethoxy)ethenesulfonic acid Chemical compound OS(=O)(=O)C=COCOCC=C YRXGMKXSRJAWIW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- BRNDFMNCOYQXBB-UHFFFAOYSA-N 2-methylpent-1-ene-1-sulfonic acid Chemical compound CCCC(C)=CS(O)(=O)=O BRNDFMNCOYQXBB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- ATBDZSAENDYQDW-UHFFFAOYSA-N 3-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C=C)=C1 ATBDZSAENDYQDW-UHFFFAOYSA-N 0.000 description 1
- HACHQKIXHAWKLE-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene-1-sulfonic acid Chemical compound OS(=O)(=O)C=CCOCC=C HACHQKIXHAWKLE-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HPECXVHZSGHAFK-UHFFFAOYSA-N C(C)[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC.C(C=C)(=O)N Chemical compound C(C)[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC.C(C=C)(=O)N HPECXVHZSGHAFK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 1
- 125000005085 alkoxycarbonylalkoxy group Chemical group 0.000 description 1
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 1
- 125000003806 alkyl carbonyl amino group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005157 alkyl carboxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical group C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 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
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical class OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- XKCNGNVSRKVSDD-UHFFFAOYSA-N ethane;phosphoric acid Chemical compound CC.OP(O)(O)=O XKCNGNVSRKVSDD-UHFFFAOYSA-N 0.000 description 1
- 125000006627 ethoxycarbonylamino group Chemical group 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000004672 ethylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- BICAGYDGRXJYGD-UHFFFAOYSA-N hydrobromide;hydrochloride Chemical compound Cl.Br BICAGYDGRXJYGD-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- 239000011855 lithium-based material Substances 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
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical class [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 229910052748 manganese Chemical group 0.000 description 1
- 239000011572 manganese Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000006626 methoxycarbonylamino group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 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
- 125000004676 n-butylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006252 n-propylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- FDVWKHPUNHWEJY-UHFFFAOYSA-N oct-1-ene-1-sulfonic acid Chemical compound CCCCCCC=CS(O)(=O)=O FDVWKHPUNHWEJY-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000004962 sulfoxyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Secondary Cells (AREA)
Abstract
Description
本発明は、常温溶融塩及びその製造方法に関するものである。 The present invention relates to a room temperature molten salt and a method for producing the same.
常温溶融塩は、カチオンとアニオンとの組み合せにより構成され、常温において液体状態を保つものであり、イオン性液体とも呼ばれている。この常温溶融塩は、不揮発性、不燃性、熱安定性、化学的安定性、高イオン伝導性及び電気分解耐性などの特性に優れており、電池やコンデンサ、化学反応の溶媒などへの応用が広く研究されている。
常温溶融塩の合成方法としては、目的とする常温溶融塩を構成するカチオン部を有する化合物とアニオン部を有する化合物とを用いて、前記カチオン部を有する化合物をイオン交換する方法が最も一般的である（例えば、特許文献１参照。）。しかしながら、この方法により得られた常温溶融塩は、その製造過程で生じる副反応物由来の不純物を含み、この不純物の混入を防ぐことが難しい。また、前記不純物の除去においては、前記常温溶融塩は不揮発性であることから、蒸留などによる精製も困難で、不純物を取り除くことは容易ではない。このような常温溶融塩をリチウム二次電池などの電解質に用いた場合、含まれるイオン性の不純物が抵抗成分として作用し、二次電池性能の悪化の原因となってしまう。
また、このようなイオン性不純物を取り除くために、アルミナ粉末を用いることも提案されている（例えば、特許文献２参照。）。この方法により、イオン性不純物の低減が達成されるが、活性アルミナの処理を行うことが必要であり、精製のために余分な工程を必要とする。
この様な背景から、容易に製造できる高純度の常温溶融塩が求められていた。
The most common method for synthesizing a room temperature molten salt is to ion-exchange the compound having a cation moiety using a compound having a cation moiety and a compound having an anion moiety constituting the target room temperature molten salt. (For example, refer to Patent Document 1). However, the room temperature molten salt obtained by this method contains impurities derived from by-products in the production process, and it is difficult to prevent the contamination of these impurities. Further, in removing the impurities, since the room temperature molten salt is non-volatile, purification by distillation or the like is difficult, and it is not easy to remove the impurities. When such a room temperature molten salt is used in an electrolyte such as a lithium secondary battery, the ionic impurities contained act as a resistance component and cause deterioration of secondary battery performance.
In order to remove such ionic impurities, it has also been proposed to use alumina powder (see, for example, Patent Document 2). Although this method achieves reduction of ionic impurities, it requires treatment of activated alumina and requires an extra step for purification.
From such a background, a high purity room temperature molten salt that can be easily produced has been demanded.
本発明によれば、高純度、特に、ハロゲンイオンの少ない、常温溶融塩を提供することができる。 According to the present invention, it is possible to provide a room temperature molten salt with high purity, in particular, low halogen ions.
本発明者らは、上記の目的を達成するために鋭意検討を重ねた結果、重合性官能基を有するオニウムカチオンと重合性官能基を有する有機アニオンからなる塩モノマーの重合性を消失させることによって、高純度の常温溶融塩が得られることを見出し、さらに検討を進めて本発明を完成させるに至った。
すなわち、本発明は、
（１）重合性官能基を有するオニウムカチオンと重合性官能基を有する有機アニオンとからなる塩モノマーの重合性官能基の重合性を消失させてなる常温溶融塩、
（２）前記常温溶融塩は、ハロゲンイオンの含有量が２００ｐｐｍ以下である第（１）項記載の常温溶融塩、
（３）重合性官能基を有するオニウムカチオンと重合性官能基を有する有機アニオンとからなる塩モノマーの重合性官能基に、重合性官能基未含有化合物を付加反応させる工程を含むことを特徴とする常温溶融塩の製造方法、
（４）前記重合性官能基未含有化合物は、ハロゲン酸、低級アルコール類、アミン化合物、硫黄化合物又はホウ素化合物である第（３）項記載の常温溶融塩の製造方法、
である。
As a result of intensive studies to achieve the above object, the present inventors have eliminated the polymerizability of a salt monomer composed of an onium cation having a polymerizable functional group and an organic anion having a polymerizable functional group. The present inventors have found that a high-purity room-temperature molten salt can be obtained, and have further studied and completed the present invention.
That is, the present invention
(1) A room temperature molten salt in which the polymerizable functional group of the salt monomer composed of an onium cation having a polymerizable functional group and an organic anion having a polymerizable functional group is lost.
(2) The room temperature molten salt according to the item (1), wherein the halogen ion content is 200 ppm or less,
(3) The method includes a step of adding a polymerizable functional group-free compound to a polymerizable functional group of a salt monomer composed of an onium cation having a polymerizable functional group and an organic anion having a polymerizable functional group. Manufacturing method of room temperature molten salt,
(4) The method for producing a room temperature molten salt according to (3), wherein the polymerizable functional group-free compound is a halogen acid, a lower alcohol, an amine compound, a sulfur compound or a boron compound,
It is.
本発明によれば、高純度で、特にハロゲンイオンの含有量が少ない常温溶融塩が得られ、その製造工程は余分な処理を必要としないものである。
本発明の常温溶融塩によれば、優れたイオン伝導性を有する電解質が得られ、これを用いた電池は優れた電池特性を示すため、リチウム二次電池への適用が可能である。また、優れたイオン伝導度を示すことから、キャパシタ、エレクトロクロミック素子等、電気化学素子全般への適用も可能である。
According to the present invention, a room temperature molten salt with high purity and particularly low halogen ion content can be obtained, and the production process does not require extra processing.
According to the room temperature molten salt of the present invention, an electrolyte having excellent ionic conductivity is obtained, and a battery using the electrolyte exhibits excellent battery characteristics, and thus can be applied to a lithium secondary battery. In addition, since it exhibits excellent ionic conductivity, it can be applied to general electrochemical devices such as capacitors and electrochromic devices.
本発明は、重合性官能基を有するオニウムカチオンと重合性官能基を有する有機アニオンからなる塩モノマーを用い、前記塩モノマーを構成する前記重合性官能基の重合性を消失させることにより得られた常温溶融塩に関するものである。これにより、高純度で、特にハロゲンイオンの含有量が少ない常温溶融塩が得られる。前記ハロゲンイオンとしては、Ｃｌ-、Ｂｒ-、Ｉ-などが挙げられ、本発明の方法により、好ましくは２００ｐｐｍ以下の含有量に抑えることが可能となる。 The present invention was obtained by using a salt monomer composed of an onium cation having a polymerizable functional group and an organic anion having a polymerizable functional group, and eliminating the polymerizable property of the polymerizable functional group constituting the salt monomer. It relates to room temperature molten salt. As a result, a room temperature molten salt with high purity and particularly low halogen ion content is obtained. Examples of the halogen ion include Cl − , Br − , I − and the like, and it is possible to suppress the content to 200 ppm or less by the method of the present invention.
本発明に用いる塩モノマーを構成する重合性官能基を有するオニウムカチオンとしては、フルオニウム（Ｆ+）、オキソニウム（Ｏ+）、スルホニウム（Ｓ+）、アンモニウム（Ｎ+）、ホスホニウム（Ｐ+）などがカチオン種として挙げられる。汎用性、作業性の点から、ホスホニウムカチオン、スルホニウムカチオン、アンモニウムカチオンがより好ましく、中でも、アンモニウムカチオンが最も好ましい。 Examples of the onium cation having a polymerizable functional group constituting the salt monomer used in the present invention include fluonium (F + ), oxonium (O + ), sulfonium (S + ), ammonium (N + ), phosphonium (P + ) and the like. Are mentioned as cationic species. From the viewpoint of versatility and workability, a phosphonium cation, a sulfonium cation, and an ammonium cation are more preferable, and among them, an ammonium cation is most preferable.
前記スルホニウムカチオンとしては、具体的には、硫黄原子が３つの置換基Ｒで置換されたカチオンが挙げられる。３つの置換基Ｒの内、少なくとも一つは重合性官能基を含む基である。置換基Ｒは、置換または無置換の、アルキル基：ＣnＨ2n+1−、アリール基：（Ｒ’）n−Ｃ6Ｈ5-n−、アラルキル基：（Ｒ’）m−Ｃ6Ｈ5-m−ＣnＨ2n−、アルケニル基：Ｒ’−ＣＨ＝ＣＨ−Ｒ’−、アラルケニル基：（Ｒ’）n−Ｃ6Ｈ5-n−ＣＨ＝ＣＨ−Ｒ’−、アルコキシアルキル基：Ｒ’−Ｏ−ＣnＨ2n−、アシルオキシアルキル基：Ｒ’−ＣＯＯ−ＣnＨ2n−などを例示することができる。また、置換基Ｒはヘテロ原子やハロゲン原子を含んでも良い。また、３つのＲは各々異なっても、同一であってもかまわない。前記スルホニウムカチオンで置換基Ｒにおける、Ｒ’は水素、または置換もしくは無置換の炭素数２０以下のアルキル基などであり、複数ある場合は互いに異なっても良く、ｍは１以上５以下の整数であり、ｎは１以上２０以下の整数である。Ｒ、Ｒ’において置換された場合の置換基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ネオペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基およびｎ−デシル基などの直鎖または分岐のアルキル基、シクロヘキシル基および４−メチルシクロヘキシル基などの環状のアルキル基、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、イソブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基およびｎ−ヘキシルオキシ基等の直鎖または分岐のアルコキシ基、シクロヘキシルオキシ基などの環状のアルコキシ基、メトキシメトキシ基、メトキシエトキシ基、エトキシエトキシ基、メトキシプロポキシ基、エトキシプロポキシ基、プロポキシプロポキシ基等のアルコキシアルコキシ基、フェニル基、ｐ−トリル基、ｍ−トリル基、ｏ−トリル基、ｐ−クロロフェニル基、ｍ−クロロフェニル基およびｏ−クロロフェニル基等のアリール基、フェノキシ基、ｍ−メチルフェノキシ基、ｏ−メチルフェノキシ基、ｐ−クロロフェノキシ基、ｍ−クロロフェノキシ基、ｏ−クロロフェノキシ基およびｐ−ｎ−ブチルフェノキシ基等のアリールオキシ基、フェニルチオ基、ｐ−メチルフェニルチオ基、ｍ−メチルフェニルチオ基，ｏ−メチルフェニルチオ基、ｏ−エチルフェニルチオ基、ｐ−プロピルフェニルチオ基および２，４，６−トリメチルフェニルチオ基等のアリールチオ基、メチルカルボニルアミノ基、エチルカルボニルアミノ基、ｎ−プロピルカルボニルアミノ基、イソプロピルカルボニルアミノ基およびｎ−ブチルカルボニルアミノ基等のアルキルカルボニルアミノ基、メトキシカルボニルアミノ基、エトキシカルボニルアミノ基、ｎ−プロポキシカルボニルアミノ基、イソプロポキシカルボニルアミノ基およびｎ−ブトキシカルボニルアミノ基等のアルコキシカルボニルアミノ基、メチルカルボニル基、エチルカルボニル基、ｎ−プロピルカルボニル基、イソプロピルカルボニル基およびｎ−ブチルカルボニル基等のアルキルカルボニル基、メチルカルボキシ基、エチルカルボキシ基、ｎ−プロピルカルボキシ基、イソプロピルカルボキシ基およびｎ−ブチルカルボキシ基等のアルキルカルボキシ基、メトキシカルボキシ基、エトキシカルボキシ基、ｎ−プロポキシカルボキシ基、イソプロポキシカルボキシ基およびｎ−ブトキシカルボキシ基等のアルコキシカルボキシ基、メトキシカルボニルメトキシ基、エトキシカルボニルエトキシ基、エトキシカルボニルメトキシ基、ｎ−プロポキシカルボニルメトキシ基、イソプロポキシカルボニルメトキシ基およびｎ−ブトキシカルボニルメトキシ基等のアルコキシカルボニルアルコキシ基等を挙げることができ、これらの置換基は、ハロゲン原子やヘテロ原子が含まれていても良い。さらに、前記置換基として、シアノ基や、フッ素、塩素および臭素などのハロゲン原子も挙げることができる。 Specific examples of the sulfonium cation include a cation in which a sulfur atom is substituted with three substituents R. At least one of the three substituents R is a group containing a polymerizable functional group. Substituent R is a substituted or unsubstituted, alkyl group: C n H 2n + 1 - , an aryl group: (R ') n -C 6 H 5-n -, an aralkyl group: (R') m -C 6 H 5-m -C n H 2n -, alkenyl group: R'-CH = CH-R'- , aralkenyl group: (R ') n -C 6 H 5-n -CH = CH-R'-, alkoxy Examples thereof include an alkyl group: R′—O—C n H 2n —, an acyloxyalkyl group: R′—COO—C n H 2n —, and the like. The substituent R may contain a hetero atom or a halogen atom. Further, the three Rs may be different or the same. R ′ in the substituent R in the sulfonium cation is hydrogen or a substituted or unsubstituted alkyl group having 20 or less carbon atoms, and when there are a plurality thereof, they may be different from each other, and m is an integer of 1 or more and 5 or less. Yes, n is an integer of 1-20. Examples of the substituent when R and R ′ are substituted include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. Group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and other linear or branched alkyl groups, cyclohexyl group and 4-methylcyclohexyl group Linear or branched alkoxy such as alkyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group and n-hexyloxy group Group, cyclic alkoxy group such as cyclohexyloxy group, methoxymethoxy group, methoxyethoxy group, ethoxy group Alkoxyalkoxy groups such as ciethoxy group, methoxypropoxy group, ethoxypropoxy group, propoxypropoxy group, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-chlorophenyl group, m-chlorophenyl group and o- Aryl such as chlorophenyl, aryl such as phenoxy, m-methylphenoxy, o-methylphenoxy, p-chlorophenoxy, m-chlorophenoxy, o-chlorophenoxy and pn-butylphenoxy Oxy group, phenylthio group, p-methylphenylthio group, m-methylphenylthio group, o-methylphenylthio group, o-ethylphenylthio group, p-propylphenylthio group and 2,4,6-trimethylphenylthio An arylthio group such as a group, a methylcarbonylamino group, Alkylcarbonylamino groups such as tilcarbonylamino group, n-propylcarbonylamino group, isopropylcarbonylamino group and n-butylcarbonylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, isopropoxycarbonyl Alkoxycarbonylamino groups such as amino group and n-butoxycarbonylamino group, alkylcarbonyl groups such as methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group and n-butylcarbonyl group, methylcarboxy group, ethyl Alkylcarboxy groups such as carboxy group, n-propylcarboxy group, isopropylcarboxy group and n-butylcarboxy group, methoxycarboxy group, ethoxy group Alkoxy group such as boxy group, n-propoxycarboxy group, isopropoxycarboxy group and n-butoxycarboxy group, methoxycarbonylmethoxy group, ethoxycarbonylethoxy group, ethoxycarbonylmethoxy group, n-propoxycarbonylmethoxy group, isopropoxycarbonyl Examples thereof include alkoxycarbonylalkoxy groups such as methoxy group and n-butoxycarbonylmethoxy group, and these substituents may contain a halogen atom or a hetero atom. Furthermore, examples of the substituent include a cyano group and halogen atoms such as fluorine, chlorine and bromine.
前記ホスホニウムカチオンとしては、具体的には、燐原子が４つの置換基Ｒで置換されたカチオンが挙げられる。４つの置換基Ｒの内、少なくとも一つは重合性官能基を含む基である。置換基Ｒは、置換または無置換の、アルキル基：ＣnＨ2n+1−、アリール基：（Ｒ’）n−Ｃ6Ｈ5-n−、アラルキル基：（Ｒ’）m−Ｃ6Ｈ5-m−ＣnＨ2n−、アルケニル基：Ｒ’−ＣＨ＝ＣＨ−Ｒ’−、アラルケニル基：（Ｒ’）n−Ｃ6Ｈ5-n−ＣＨ＝ＣＨ−Ｒ’−、アルコキシアルキル基：Ｒ’−Ｏ−ＣnＨ2n−、アシルオキシアルキル基：Ｒ’−ＣＯＯ−ＣnＨ2n−などを例示することができる。また、置換基Ｒはヘテロ原子やハロゲン原子を含んでも良い。また、４つのＲは各々異なっても、同一であってもかまわない。前記ホスホニウムカチオンで置換基Ｒにおける、Ｒ’は水素、または置換もしくは無置換の炭素数２０以下のアルキル基などであり、複数ある場合は互いに異なっても良く、ｍは１以上５以下の整数であり、ｎは１以上２０以下の整数である。Ｒ、Ｒ’において置換された場合の置換基としては、上記スルホニウムカチオンにおけるそれと同じものが挙げられる。 Specific examples of the phosphonium cation include cations in which a phosphorus atom is substituted with four substituents R. At least one of the four substituents R is a group containing a polymerizable functional group. The substituent R is a substituted or unsubstituted alkyl group: C n H 2n + 1 —, aryl group: (R ′) n —C 6 H 5-n —, aralkyl group: (R ′) m —C 6. H 5-m -C n H 2n -, alkenyl group: R'-CH = CH-R'- , aralkenyl group: (R ') n -C 6 H 5-n -CH = CH-R'-, alkoxy Examples thereof include an alkyl group: R′—O—C n H 2n —, an acyloxyalkyl group: R′—COO—C n H 2n —, and the like. The substituent R may contain a hetero atom or a halogen atom. The four Rs may be different or the same. In the substituent R in the phosphonium cation, R ′ is hydrogen or a substituted or unsubstituted alkyl group having 20 or less carbon atoms, and when there are a plurality thereof, they may be different from each other, and m is an integer of 1 to 5 Yes, n is an integer of 1-20. Examples of the substituent when substituted in R and R ′ include the same as those in the sulfonium cation.
前記アンモニウムカチオンとしては、アミン化合物から生じうるカチオンであって、前記アミン化合物が、脂肪族アミン化合物、芳香族アミン化合物、含窒素複素環式アミン化合物などのすべてのアミン化合物を含むことは言うまでもなく、アミンから生じる正電荷を有するのであれば、特に限定されない。具体的には、窒素原子が４つの置換基Ｒで置換されたカチオンが挙げられる。４つの置換基Ｒの内、少なくとも一つは重合性官能基を含む基である。置換基Ｒは、置換または無置換の、アルキル基：ＣnＨ2n+1、アリール基：（Ｒ’）n−Ｃ6Ｈ5-n−、アラルキル基：（Ｒ’）m−Ｃ6Ｈ5-m−ＣnＨ2n−、アルケニル基：Ｒ’−ＣＨ＝ＣＨ−Ｒ’−、アラルケニル基：（Ｒ’）n−Ｃ6Ｈ5-n−ＣＨ＝ＣＨ−Ｒ’−、アルコキシアルキル基：Ｒ’−Ｏ−ＣnＨ2n−、アシルオキシアルキル基：Ｒ’−ＣＯＯ−ＣnＨ2n−などを例示することができる。また、置換基Ｒはヘテロ原子やハロゲン原子を含んでも良い。また、４つのＲは各々異なっても、同一であってもかまわない。前記アンモニウムカチオンで置換基Ｒにおける、Ｒ’は水素、または置換もしくは無置換の炭素数２０以下のアルキル基などであり、複数ある場合は互いに異なっても良く、ｍは１以上５以下の整数であり、ｎは１以上２０以下の整数である。Ｒ、Ｒ’において置換された場合の置換基としては、上記スルホニウムカチオンにおけるそれと同じものが挙げられる。
上記アンモニウムカチオン以外のアンモニウムカチオンとしては、ピリジニウムカチオン、ピラリジニウムカチオンおよびキノリニウムカチオンなどの芳香族アンモニウムカチオン、ピロリジウムカチオン、ピペリジニウムカチオンおよびピペラジニウムカチオンなどの脂肪族複素環式アンモニウムカチオン、モルホリンカチオンのような窒素以外のヘテロ原子を含む複素環式アンモニウムカチオン、イミダゾリウムカチオンなどの不飽和の含窒素複素環式カチオンなど、のアンモニウムカチオンも挙げることができる。さらに、上記環状のアンモニウムカチオンでは窒素の位置が異なるカチオンや、環上に置換基をもったカチオンでもよく、ヘテロ原子を含む置換基を有するカチオンでもよい。
The ammonium cation is a cation that can be generated from an amine compound, and it goes without saying that the amine compound includes all amine compounds such as aliphatic amine compounds, aromatic amine compounds, and nitrogen-containing heterocyclic amine compounds. As long as it has a positive charge derived from an amine, it is not particularly limited. Specific examples include cations in which a nitrogen atom is substituted with four substituents R. At least one of the four substituents R is a group containing a polymerizable functional group. The substituent R is a substituted or unsubstituted alkyl group: C n H 2n + 1 , aryl group: (R ′) n —C 6 H 5-n —, aralkyl group: (R ′) m —C 6 H 5-m -C n H 2n - , alkenyl group: R'-CH = CH-R'- , aralkenyl group: (R ') n -C 6 H 5-n -CH = CH-R'-, alkoxyalkyl Group: R′—O—C n H 2n —, acyloxyalkyl group: R′—COO—C n H 2n — and the like can be exemplified. The substituent R may contain a hetero atom or a halogen atom. The four Rs may be different or the same. In the substituent R in the ammonium cation, R ′ is hydrogen or a substituted or unsubstituted alkyl group having 20 or less carbon atoms, and when there are a plurality thereof, they may be different from each other, and m is an integer of 1 or more and 5 or less. Yes, n is an integer of 1-20. Examples of the substituent when substituted in R and R ′ include the same as those in the sulfonium cation.
Examples of ammonium cations other than the above ammonium cations include aromatic ammonium cations such as pyridinium cation, pyraridinium cation and quinolinium cation, and aliphatic heterocyclic ammonium such as pyrrolidinium cation, piperidinium cation and piperazinium cation. Mention may also be made of ammonium cations such as cations, heterocyclic ammonium cations containing heteroatoms other than nitrogen such as morpholine cations, and unsaturated nitrogen-containing heterocyclic cations such as imidazolium cations. Further, the cyclic ammonium cation may be a cation having a different nitrogen position, a cation having a substituent on the ring, or a cation having a substituent containing a hetero atom.
前記オニウムカチオンにおける重合性官能基としては、ラジカル重合、イオン重合、配位重合およびレドックス重合などにより重合が可能な官能基であれば、何ら限定されない。これらの官能基の例として、例えば、前記ラジカル重合により重合可能な官能基としては、活性エネルギー線照射もしくは加熱によりラジカル重合が可能なものが挙げられ、その具体例としては、（メタ）アクリロイル基、（メタ）アクリロイルオキシ基、（メタ）アクリルアミド基、アリル基、ビニル基、スチリル基などが挙げられる。 The polymerizable functional group in the onium cation is not particularly limited as long as it is a functional group that can be polymerized by radical polymerization, ionic polymerization, coordination polymerization, redox polymerization, or the like. Examples of these functional groups include, for example, those capable of being polymerized by radical polymerization, those capable of radical polymerization by irradiation with active energy rays or heating, and specific examples thereof include (meth) acryloyl groups. , (Meth) acryloyloxy group, (meth) acrylamide group, allyl group, vinyl group, styryl group and the like.
前記塩モノマーを構成する重合性官能基を有するオニウムカチオンの具体例として、（メタ）アクリロイルオキシエチルトリメチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリエチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリ−ｎ−プロピルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリ−ｉｓｏ−プロピルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリ−ｎ−ブチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリ−ｉｓｏ−ブチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリ−ｔｅｒｔ−ブチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリエチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルジエチル−ｎ−ヘキシルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリデシルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリオクチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルドデシルジメチルアンモニウムカチオン、（メタ）アクリロイルオキシジメチルベンジルアンモニウムカチオン、（メタ）アクリロイルオキシエチルドデシルヘキシルメチルアンモニウムカチオン、ジアリルジメチルアンモニウムカチオン、ビススチリルメチルジメチルアンモニウムカチオン、ビススチリルエチルジメチルアンモニウムカチオン、（メタ）アクリルアミドエチルトリメチルアンモニウムカチオン、（メタ）アクリルアミドプロピルトリメチルアンモニウムカチオン、（メタ）アクリルアミドエチルトリエチルアンモニウムカチオン、（メタ）アクリルアミドエチルトリ−ｎ−プロピルアンモニウムカチオン、（メタ）アクリルアミドエチルトリ−ｉｓｏ−プロピルアンモニウムカチオン、（メタ）アクリルアミドエチルトリ−ｎ−ブチルアンモニウムカチオン、（メタ）アクリルアミドエチルトリ−ｉｓｏ−ブチルアンモニウムカチオン、（メタ）アクリルアミドエチルトリ−ｔｅｒｔ−ブチルアンモニウムカチオン、（メタ）アクリルアミドエチルトリエチルアンモニウムカチオン、（メタ）アクリルアミドエチルジエチル−ｎ−ヘキシルアンモニウムカチオン、（メタ）アクリルアミドエチルトリデシルアンモニウムカチオン、（メタ）アクリルアミドエチルトリオクチルアンモニウムカチオン、（メタ）アクリルアミドエチルドデシルジメチルアンモニウムカチオン、（メタ）アクリルアミドエチルドデシルヘキシルメチルアンモニウムカチオン等の各種アンモニウムカチオン、スチリルメチルメチルピロリジニウムカチオン、ビススチリルメチルピペリジニウムカチオン、Ｎ，Ｎ’−（（メタ）アクリロイルオキシエチルメチル）ピペラジニウムカチオン、（メタ）アクリルアミドエチルメチルモルホリニウムカチオン、（メタ）アクリロイルオキシエチルメチルイミダゾリウムカチオンなどが挙げられる。 Specific examples of the onium cation having a polymerizable functional group constituting the salt monomer include (meth) acryloyloxyethyltrimethylammonium cation, (meth) acryloyloxyethyltriethylammonium cation, (meth) acryloyloxyethyltri-n-propyl. Ammonium cation, (meth) acryloyloxyethyl tri-iso-propylammonium cation, (meth) acryloyloxyethyl tri-n-butylammonium cation, (meth) acryloyloxyethyl tri-iso-butylammonium cation, (meth) acryloyloxy Ethyltri-tert-butylammonium cation, (meth) acryloyloxyethyltriethylammonium cation, (meth) acryloyloxyethyl Diethyl-n-hexylammonium cation, (meth) acryloyloxyethyltridecylammonium cation, (meth) acryloyloxyethyltrioctylammonium cation, (meth) acryloyloxyethyldodecyldimethylammonium cation, (meth) acryloyloxydimethylbenzylammonium cation (Meth) acryloyloxyethyldodecylhexylmethylammonium cation, diallyldimethylammonium cation, bisstyrylmethyldimethylammonium cation, bisstyrylethyldimethylammonium cation, (meth) acrylamidoethyltrimethylammonium cation, (meth) acrylamidopropyltrimethylammonium cation, (Meth) acrylamide Rutriethylammonium cation, (meth) acrylamide ethyltri-n-propylammonium cation, (meth) acrylamideethyltri-iso-propylammonium cation, (meth) acrylamideethyltri-n-butylammonium cation, (meth) acrylamideethyltri -Iso-butylammonium cation, (meth) acrylamidoethyltri-tert-butylammonium cation, (meth) acrylamidoethyltriethylammonium cation, (meth) acrylamidoethyldiethyl-n-hexylammonium cation, (meth) acrylamidoethyltridecylammonium cation Cation, (meth) acrylamide ethyl trioctyl ammonium cation, (meth) acrylamide ethyl Various ammonium cations such as decyldimethylammonium cation, (meth) acrylamidoethyldodecylhexylmethylammonium cation, styrylmethylmethylpyrrolidinium cation, bisstyrylmethylpiperidinium cation, N, N ′-((meth) acryloyloxyethylmethyl And piperazinium cation, (meth) acrylamidoethylmethylmorpholinium cation, (meth) acryloyloxyethylmethylimidazolium cation, and the like.
また、塩モノマーを構成する有機アニオンとしては、重合性官能基を有するアニオンであれば、特に限定されないが、例えば、アルコラートおよびフェノラートなどの水酸基含有有機化合物のプロトンが脱離したアニオン：ＲＯ-アニオン、チオレートおよびチオフェノラートなどのプロトンが脱離したアニオン：ＲＳ-アニオン、スルホン酸アニオン：ＲＳＯ3 -、カルボン酸アニオン：ＲＣＯＯ-、リン酸および亜リン酸の水酸基の一部が有機基で置換している含リン誘導体アニオン：Ｒx（ＯＲ）y（Ｏ）zＰ-、（但し、ｘ、ｙ、ｚは０以上の整数で、かつ、ｘ＋ｙ＋２ｚ＝３またはｘ＋ｙ＋２ｚ＝５）、置換ボレートアニオン：Ｒx（ＯＲ）yＢ-、（但し、ｘ、ｙは０以上の整数で、かつ、ｘ＋ｙ＝４）、置換アルミニウムアニオン：Ｒx（ＯＲ）yＡｌ-、（但し、ｘ、ｙは０以上の整数で、かつ、ｘ＋ｙ＝４）、カルボアニオン（ＥＡ）3Ｃ-、窒素アニオン（ＥＡ）2Ｎ-などが挙げられる。ＥＡは水素原子または電子吸引基を示す。 Further, the anion as an organic anion constituting the salt monomer, as long as the anion having a polymerizable functional group is not particularly limited, for example, a proton of the hydroxyl group-containing organic compounds such as alcoholates and phenolates are eliminated: RO - anion Anion from which protons such as thiolate and thiophenolate are eliminated: RS − anion, sulfonic acid anion: RSO 3 − , carboxylate anion: RCOO − , and a part of hydroxyl groups of phosphoric acid and phosphorous acid are replaced by organic groups Phosphorus-containing derivative anion: R x (OR) y (O) z P − , where x, y and z are integers of 0 or more and x + y + 2z = 3 or x + y + 2z = 5), substituted borate anion : R x (oR) y B -, ( provided that, x, y is 0 or an integer, and, x + y = 4), substituted aluminum anion : R x (OR) y Al - like -, (wherein, x, y is 0 or an integer, and, x + y = 4), carbanions (EA) 3 C -, nitrogen anion (EA) 2 N It is done. EA represents a hydrogen atom or an electron withdrawing group.
前記有機アニオンとしては、特に、スルホキシル基、カルボキシル基、ホスフォキシル基およびスルホンイミド基由来のアニオンである、ＲＳＯ3 -、ＲＣＯＯ-、ＲＰＯ3 2-、および（ＲＯ2Ｓ）2Ｎ-が好ましい。ここで、Ｒは、水素、置換または無置換の、アルキル基ＣnＨ2n+1、アリール基（Ｒ’）n−Ｃ6Ｈ5-n−、アラルキル基（Ｒ’）m−Ｃ6Ｈ5-m−ＣnＨ2n−、アルケニル基Ｒ’−ＣＨ＝ＣＨ−Ｒ’−、アラルケニル基（Ｒ’）n−Ｃ6Ｈ5-n−ＣＨ＝ＣＨ−Ｒ’−、アルコキシアルキル基Ｒ’−Ｏ−ＣnＨ2n−、アシルオキシアルキル基Ｒ’−ＣＯＯ−ＣnＨ2n−であり、これらは環構造を有していてもよく、また、ヘテロ原子を含んでもよい。このＲが分子内に２個以上ある場合は互いに同じであっても異なっていてもかまわない。ただし、置換基Ｒを一つ有するアニオンの場合はそのＲが、複数の置換基Ｒを有する場合は、少なくとも一つが、重合性官能基を含む基であり、同様に、置換基ＥＡを一つ有するアニオンの場合はそのＥＡが、複数の置換基ＥＡを有する場合は、少なくとも一つが、重合性官能基を含む基である。前記Ｒにおける、Ｒ’は水素、または置換もしくは無置換の炭素数２０以下のアルキル基などであり、複数ある場合は互いに異なっても良く、ｍは１以上５以下の整数であり、ｎは１以上２０以下の整数である。また、前述Ｒの炭素上の水素原子の一部または全部がハロゲン原子に置換されているものも含まれる。Ｒ、Ｒ’において置換された場合の置換基としては、上記スルホニウムカチオンにおけるそれと同じものが挙げられる。 As the organic anion, RSO 3 − , RCOO − , RPO 3 2− and (RO 2 S) 2 N − which are anions derived from a sulfoxyl group, a carboxyl group, a phosphoxyl group and a sulfonimide group are particularly preferable. Wherein, R represents hydrogen, a substituted or unsubstituted, alkyl group C n H 2n + 1, aryl groups (R ') n -C 6 H 5-n -, an aralkyl group (R') m -C 6 H 5-m -C n H 2n - , alkenyl group R'-CH = CH-R'-, aralkenyl group (R ') n -C 6 H 5-n -CH = CH-R'-, alkoxyalkyl group R '—O—C n H 2n —, an acyloxyalkyl group R′—COO—C n H 2n —, which may have a ring structure and may contain a heteroatom. When there are two or more Rs in the molecule, they may be the same or different from each other. However, in the case of an anion having one substituent R, when R has a plurality of substituents R, at least one is a group containing a polymerizable functional group, and similarly one substituent EA In the case of an anion having EA, when the EA has a plurality of substituents EA, at least one is a group containing a polymerizable functional group. In R, R ′ is hydrogen or a substituted or unsubstituted alkyl group having 20 or less carbon atoms, and when there are a plurality thereof, they may be different from each other, m is an integer of 1 to 5, and n is 1 It is an integer of 20 or more. Also included are those in which some or all of the hydrogen atoms on the carbon of R are replaced by halogen atoms. Examples of the substituent when substituted in R and R ′ include the same as those in the sulfonium cation.
前記有機アニオンにおける重合性官能基としては、上記重合性官能基を有するオニウムカチオンのそれと同じものを挙げることができる。塩モノマーの場合、少なくとも２つの重合性官能基を有することになるが、それらの重合性官能基は、それぞれ同じでも異なっていてもよい。 Examples of the polymerizable functional group in the organic anion include the same ones as those of the onium cation having the polymerizable functional group. The salt monomer has at least two polymerizable functional groups, and these polymerizable functional groups may be the same or different from each other.
前記塩モノマーを構成する有機アニオンの具体例としては、２−アクリルアミド−２−メチル−１−プロパンスルホン酸、２−［（２−プロペニロキシ）メトキシ］エテンスルホン酸、３−（２−プロペニロキシ）−１−プロペン−１−スルホン酸、ビニルスルホン酸、２−ビニルベンゼンスルホン酸、３−ビニルベンゼンスルホン酸、４−ビニルベンゼンスルホン酸、４−ビニルベンジルスルホン酸、２−メチル−１−ペンテン−１−スルホン酸、１−オクテン−１−スルホン酸、４−ビニルベンゼンメタンスルホン酸、アクリル酸、メタクリル酸、２−アクリルアミド−２−メチル−１−プロパンリン酸、２−（メタ）アクリロイルオキシ−１−エタンリン酸等由来の各種アニオンが挙げられる。 Specific examples of the organic anion constituting the salt monomer include 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-[(2-propenyloxy) methoxy] ethenesulfonic acid, 3- (2-propenyloxy)- 1-propene-1-sulfonic acid, vinylsulfonic acid, 2-vinylbenzenesulfonic acid, 3-vinylbenzenesulfonic acid, 4-vinylbenzenesulfonic acid, 4-vinylbenzylsulfonic acid, 2-methyl-1-pentene-1 -Sulfonic acid, 1-octene-1-sulfonic acid, 4-vinylbenzenemethanesulfonic acid, acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-1-propanephosphoric acid, 2- (meth) acryloyloxy-1 -Various anions derived from ethane phosphate and the like.
本発明に用いる重合性官能基を有するオニウムカチオンと重合性官能基を有する有機アニオンとから構成される塩モノマーとしては、例えば、前記重合性官能基を有する有機アニオンの銀塩などの金属塩と、前記重合性官能基を有するオニウムカチオンのハロゲン化物とを反応させて合成できるが、目的の塩モノマーが得られるのであればこの合成方法に限定されない。ただし、塩モノマーの重合性を消失させる反応を行う前に、塩モノマーの段階で精製を行うことが好ましい。精製の方法としては、公知の方法が適用でき、再結晶、蒸留などを使うことができる。 Examples of the salt monomer composed of an onium cation having a polymerizable functional group and an organic anion having a polymerizable functional group used in the present invention include, for example, metal salts such as silver salts of the organic anion having the polymerizable functional group, These can be synthesized by reacting with a halide of an onium cation having a polymerizable functional group, but the synthesis method is not limited as long as the target salt monomer can be obtained. However, it is preferable to carry out purification at the salt monomer stage before carrying out the reaction for eliminating the polymerizability of the salt monomer. As a purification method, a known method can be applied, and recrystallization, distillation or the like can be used.
本発明において、前記塩モノマーを構成する重合性官能基の重合性を消失させる方法としては、前記塩モノマーの重合性官能基に、重合性官能基未含有化合物を、付加反応させることによって重合性を消失できる。付加反応としては、重合性を消失できるのであれば特に限定はないが、反応が容易に進行するマイケル付加型の反応が好ましく、前記重合性官能基未含有化合物として、例えば、ハロゲン酸、アルコール類、アミン化合物、硫黄化合物およびホウ素化合物などの化合物を用いて、前記塩モノマーと混合し、必要に応じ、加熱することで、塩モノマーの重合性を消失させることができる。塩モノマーと重合性官能基未含有物を反応させる際に、有機溶媒を使用することも可能である。その場合には、アセトニトリル、アルコール類などの極性溶媒を単独、または、混合溶媒として使用することができるが、塩モノマーと付加反応しないものが好ましい。また、加熱の温度としては、３０〜１２０℃が好ましい。このようなマイケル付加型の反応をする前記重合性官能基未含有化合物の具体例としては、塩化水素および臭化水素などのハロゲン酸、１級アルコール及び２級アルコールなどのアルコール類；、メチルアミンおよびエチルアミン等の１級脂肪族アミン化合物、ジメチルアミンおよびジエチルアミン等の２級脂肪族アミン化合物、置換若しくは無置換のベンジルアミンおよびナフチルアミン等の芳香族アミン化合物、シクロエチルアミンおよびシクロブチルアミン等の複素環式アミン化合物などのアミン化合物；、ドデシルメルカプタンなどのアルキルメルカプタン（炭素数２〜３０）などの硫黄化合物、ジアルキルボランなどのホウ素化合物などが挙げられる。付加反応の際に必要に応じて、ナトリウムアルコキシドなどの触媒を添加しても良い。 In the present invention, as a method for eliminating the polymerizable property of the polymerizable functional group constituting the salt monomer, a polymerizable functional group-free compound is added to the polymerizable functional group of the salt monomer for polymerization. Can disappear. The addition reaction is not particularly limited as long as the polymerizability can be lost, but a Michael addition type reaction in which the reaction proceeds easily is preferable. Examples of the polymerizable functional group-free compound include halogen acids and alcohols. The compound of the salt monomer can be eliminated by mixing with the salt monomer using a compound such as an amine compound, a sulfur compound and a boron compound, and heating if necessary. An organic solvent can also be used when the salt monomer and the polymerizable functional group-free product are reacted. In that case, polar solvents such as acetonitrile and alcohols can be used alone or as a mixed solvent, but those which do not undergo an addition reaction with a salt monomer are preferred. The heating temperature is preferably 30 to 120 ° C. Specific examples of the polymerizable functional group-free compound that undergoes such a Michael addition type reaction include halogen acids such as hydrogen chloride and hydrogen bromide, alcohols such as primary alcohol and secondary alcohol; methylamine And primary aliphatic amine compounds such as ethylamine, secondary aliphatic amine compounds such as dimethylamine and diethylamine, aromatic amine compounds such as substituted or unsubstituted benzylamine and naphthylamine, and heterocyclic groups such as cycloethylamine and cyclobutylamine Amine compounds such as amine compounds; sulfur compounds such as alkyl mercaptans (carbon number 2 to 30) such as dodecyl mercaptan; and boron compounds such as dialkylborane. A catalyst such as sodium alkoxide may be added as necessary during the addition reaction.
本発明で得られる常温溶融塩は、リチウム二次電池、キャパシタ、エレクトロクロミック材料などのイオン伝導性電解質として用いることができる。
前記リチウム二次電池用のイオン伝導性電解質は、本発明の常温溶融塩とリチウム塩を混合して得ることができ、これをリチウム二次電池に用いる場合の例について、以下に説明する。
前記リチウム二次電池用のイオン伝導性電解質は、ポリマーとの併用により固形化して利用することも可能である。前記ポリマーとしては、アルキレンオキシド骨格を有するポリマー、（メタ）アクリレートなどのラジカル重合性を有するモノマーを重合して得られるポリマーなどが使用可能である。さらに、このような電解質に、可塑剤、難燃性電解質溶解剤、本発明の常温溶融塩以外の一般的な常温溶融塩を添加しても良い。
前記リチウム塩としては、例えば、ＬｉＰＦ6、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2およびＬｉＣ（ＣＦ3ＳＯ2）3やＬｉイオンを含有するイオン性液体などが挙げられ、これらを単独あるいは２種以上を混合して用いても良い。リチウムイオン伝導性電解質に使用する場合に使用するリチウム塩の添加量は、０．１〜９９ｗｔ％が好ましく、１〜９０ｗｔ％がより好ましい。
前記可塑剤としては、例えば、エチレンカーボネートおよびプロピレンカーボネートなどの環状炭酸エステル、エチルメチルカーボネートおよびジエチルカーボネートなどの鎖状炭酸エステルなどが挙げられ、これらは、それらの混合物を添加することができる。
前記難燃性電解質塩溶解剤としては、自己消火性を示し、かつ、電解質塩が共存した状態で電解質塩を溶解するのに寄与する化合物が挙げられ、一般に非水電解質電池用電解液に添加される難燃性溶媒が利用でき、リン酸エステル、ハロゲン化合物およびフォスファゼンなどが挙げられる。
前記本発明以外の前記常温溶融塩としては、分子中にイオン結合を少なくとも一つ有しており、常温で液体の化合物が挙げられ、公知の化合物が使用できる。
The room temperature molten salt obtained in the present invention can be used as an ion conductive electrolyte for lithium secondary batteries, capacitors, electrochromic materials and the like.
The ion conductive electrolyte for a lithium secondary battery can be obtained by mixing the room temperature molten salt of the present invention and a lithium salt, and an example in which this is used for a lithium secondary battery will be described below.
The ion conductive electrolyte for a lithium secondary battery can be solidified and used in combination with a polymer. As the polymer, a polymer having an alkylene oxide skeleton, a polymer obtained by polymerizing a monomer having radical polymerizability such as (meth) acrylate, and the like can be used. Furthermore, you may add common normal temperature molten salt other than the plasticizer, a flame-retardant electrolyte solubilizer, and the normal temperature molten salt of this invention to such electrolyte.
Examples of the lithium salt include LiPF 6 , LiClO 4 , LiCF 3 SO 3 , LiBF 4 , LiAsF 6 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 and LiC (CF 3 SO 2 ) An ionic liquid containing 3 or Li ion may be used, and these may be used alone or in admixture of two or more. When used for a lithium ion conductive electrolyte, the amount of lithium salt used is preferably 0.1 to 99 wt%, more preferably 1 to 90 wt%.
Examples of the plasticizer include cyclic carbonates such as ethylene carbonate and propylene carbonate, and chain carbonates such as ethyl methyl carbonate and diethyl carbonate, and a mixture thereof can be added thereto.
Examples of the flame retardant electrolyte salt solubilizer include compounds that exhibit self-extinguishing properties and contribute to dissolving the electrolyte salt in the presence of the electrolyte salt, and are generally added to the electrolyte for non-aqueous electrolyte batteries. Flame retardant solvents, such as phosphate esters, halogen compounds and phosphazenes.
Examples of the room temperature molten salt other than the present invention include compounds having at least one ionic bond in the molecule and liquid at room temperature, and known compounds can be used.
上記で得られたリチウム二次電池用のイオン伝導性電解質は、正極及び負極などを組み合わせることによって、二次電池を製造することができる。正極に使用される活物質としては、エネルギー密度が高く、リチウムイオンの可逆的な脱挿入に優れたリチウムを含有する遷移金属酸化物が好ましく、例えば、ＬｉＣｏＯ2などのリチウムコバルト酸化物、ＬｉＭｎ2Ｏ4などのリチウムマンガン酸化物、ＬｉＮｉＯ2などのリチウムニッケル酸化物、これら酸化物の混合物およびＬｉＮｉＯ2のニッケルの一部をコバルトやマンガンに置換したものなどが挙げられる。負極活物質としては、リチウムイオンを挿入、脱離させることのできる材料であれば限定されないが、金属リチウムや炭素系材料などが挙げられ、炭素材料としては、例えば、天然黒鉛、人造黒鉛、メソカーボンマイクロビーズおよびグラファイトなどが挙げられる。 The ion conductive electrolyte for lithium secondary battery obtained above can produce a secondary battery by combining a positive electrode and a negative electrode. The active material used for the positive electrode is preferably a transition metal oxide containing lithium having high energy density and excellent reversible desorption / reinsertion of lithium ions. For example, lithium cobalt oxide such as LiCoO 2 , LiMn 2 Examples thereof include lithium manganese oxides such as O 4 , lithium nickel oxides such as LiNiO 2 , mixtures of these oxides, and nickel in LiNiO 2 partially substituted with cobalt or manganese. The negative electrode active material is not limited as long as it is a material that can insert and desorb lithium ions, and examples thereof include metallic lithium and carbon-based materials. Examples of the carbon material include natural graphite, artificial graphite, and meso Examples thereof include carbon micro beads and graphite.
二次電池を製造する方法の例としては、まず、上記ＬｉＣｏＯ2などの正極活物質、黒鉛などの導電剤、ポリ（ビニリデンフルオライド）などの結着剤を混合して正極合剤を調製し、この正極合剤をＮ−メチル−２−ピロリドン中に分散させて、スラリー状の正極合剤とする。この正極合剤を、厚み２０μｍのアルミニウム箔などからなる正極集電体の両面に均一に塗布し、乾燥後、ロールプレス機で圧縮成形することで正極が得られる。
次に、黒鉛粉末などの負極活物質と、ポリ（ビニリデンフルオライド）などの結着剤を混合して、負極合剤を調製し、この負極合剤をＮ−メチル−２−ピロリドン中に分散させてスラリー状の負極合剤とする。この負極合剤を、厚み１５μｍの銅箔などからなる負極集電体の両面に均一に塗布し、乾燥後、ロールプレス機で圧縮成形することで負極が得られる。このようにして得られた負極と正極とを、厚みが２５μｍのポリエチレン製微多孔性フィルムからなるセパレーターを介して密着させ、巻回して電極巻回体とし、この電極巻回体を、絶縁材料からなる外装フィルムに封入するとともに、上記で得られた電解質を外装フィルム中に注入する。次に、外装フィルムの外周縁部を封口し、正極端子と負極端子とを、外装フィルムの開口部に挟み込むとともに、電極巻回体を外装フィルム中に減圧下にて密閉することにより、二次電池が得られる。
As an example of a method for manufacturing a secondary battery, first, a positive electrode active material such as LiCoO 2 , a conductive agent such as graphite, and a binder such as poly (vinylidene fluoride) are mixed to prepare a positive electrode mixture. The positive electrode mixture is dispersed in N-methyl-2-pyrrolidone to obtain a slurry-like positive electrode mixture. This positive electrode mixture is uniformly applied to both surfaces of a positive electrode current collector made of an aluminum foil having a thickness of 20 μm, etc., dried, and then compression molded with a roll press to obtain a positive electrode.
Next, a negative electrode active material such as graphite powder and a binder such as poly (vinylidene fluoride) are mixed to prepare a negative electrode mixture, and this negative electrode mixture is dispersed in N-methyl-2-pyrrolidone. To make a slurry-like negative electrode mixture. This negative electrode mixture is uniformly applied to both surfaces of a negative electrode current collector made of a copper foil having a thickness of 15 μm, etc., dried, and then compression molded with a roll press to obtain a negative electrode. The negative electrode and the positive electrode thus obtained are brought into close contact with each other through a separator made of a polyethylene microporous film having a thickness of 25 μm, and wound to form an electrode wound body, and this electrode wound body is used as an insulating material. And the electrolyte obtained above is injected into the exterior film. Next, the outer peripheral edge of the exterior film is sealed, the positive electrode terminal and the negative electrode terminal are sandwiched between the openings of the exterior film, and the electrode winding body is hermetically sealed in the exterior film under reduced pressure. A battery is obtained.
（実施例）
以下、実施例により本発明を更に詳しく説明するが、本発明はこれによって何ら限定されるものではない。
(Example)
EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited at all by this.
＜常温溶融塩（１）の合成＞
２−アクリルアミド−２−メチル−１−プロパンスルホン酸１０．３６ｇ（５０ｍｍｏｌ）を、メタノール５００ｍｌ／蒸留水４ｍｌに溶解し、これに炭酸銀８．２８ｇ（３０ｍｍｏｌ）を添加して、室温下で穏やかに４時間連続攪拌し、濾過後、無色透明の溶液を得た。この濾液に、５１ｍｍｏｌのアクリロイルオキシエチルジメチルベンジルアンモニウムクロリドをメタノール１００ｍｌに溶解した溶液を滴下反応させた。反応は定量的に進行した。反応生成物である塩化銀を濾別し、無色透明のメタノール溶液を回収した。この濾液をエバポレーターで減圧濃縮し、冷暗所で終日静置することにより目的物を再結晶させ、無色透明の板状結晶を回収した。得られた塩モノマーは、プロトン核磁気共鳴スペクトル（1Ｈ−ＮＭＲ）により生成物の確認を行い、所望の化合物であることを確認した。
さらに、この塩モノマー１０ｇ（２２ｍｍｏｌ）を１００ｍｌのメタノールに溶解させ、それに４．４４ｇ（２２ｍｍｏｌ）のｎ−ドデシルメルカプタンを添加し、４０℃で６時間反応させた。反応溶液をエバポレーターで減圧濃縮し、溶媒を完全に除去し、常温溶融塩（１）を得た。この常温溶融塩（１）は、プロトン核磁気共鳴スペクトル（1Ｈ−ＮＭＲ）により、重合性官能基が完全に消失していることを確認した。得られた常温溶融塩（１）中に含まれるＣｌ-イオンの含有率をイオンクロマト法により定量すると３３ｐｐｍであった。
<Synthesis of room temperature molten salt (1)>
10.36 g (50 mmol) of 2-acrylamido-2-methyl-1-propanesulfonic acid was dissolved in 500 ml of methanol / 4 ml of distilled water, and 8.28 g (30 mmol) of silver carbonate was added thereto. For 4 hours, and after filtration, a colorless and transparent solution was obtained. A solution obtained by dissolving 51 mmol of acryloyloxyethyldimethylbenzylammonium chloride in 100 ml of methanol was dropped into this filtrate. The reaction proceeded quantitatively. The reaction product silver chloride was removed by filtration, and a colorless and transparent methanol solution was recovered. The filtrate was concentrated under reduced pressure using an evaporator, and allowed to stand all day in a cool dark place to recrystallize the desired product, and colorless and transparent plate crystals were recovered. The obtained salt monomer was confirmed by a proton nuclear magnetic resonance spectrum ( 1 H-NMR) to confirm that it was a desired compound.
Furthermore, 10 g (22 mmol) of this salt monomer was dissolved in 100 ml of methanol, 4.44 g (22 mmol) of n-dodecyl mercaptan was added thereto and reacted at 40 ° C. for 6 hours. The reaction solution was concentrated under reduced pressure using an evaporator, and the solvent was completely removed to obtain a room temperature molten salt (1). This room temperature molten salt (1) confirmed that the polymerizable functional group had completely disappeared by proton nuclear magnetic resonance spectrum ( 1 H-NMR). The content of Cl - ion contained in the obtained room temperature molten salt (1) was 33 ppm as determined by ion chromatography.
＜イオン伝導性電解質（１）の合成＞
上記で得られた０．７ｇの常温溶融塩（１）に、ＬｉＣｌＯ4０．３ｇを完全に溶解させ、得られた溶液を１１０℃で２時間減圧乾燥することにより、イオン伝導性電解質（１）を得た。このイオン伝導性電解質（１）を交流インピーダンス法により、イオン伝導度を測定した。測定の際の周波数範囲は５０Ｈｚ〜３０ＭＨｚ、電圧は０．１Ｖとした。測定の結果、２０℃に於けるイオン伝導度は３．８×１０-3Ｓ／ｃｍであった。
<Synthesis of ion conductive electrolyte (1)>
In 0.7 g of the room temperature molten salt (1) obtained above, 0.3 g of LiClO 4 was completely dissolved, and the resulting solution was dried under reduced pressure at 110 ° C. for 2 hours to obtain an ion conductive electrolyte (1 ) The ion conductivity of this ion conductive electrolyte (1) was measured by an alternating current impedance method. The frequency range during measurement was 50 Hz to 30 MHz, and the voltage was 0.1 V. As a result of the measurement, the ionic conductivity at 20 ° C. was 3.8 × 10 −3 S / cm.
＜二次電池のサイクル特性評価＞
正極活物質として、ＬｉＣｏＯ2を８５重量％、導電剤としての黒鉛を５重量％と、結着剤としてのポリ（ビニリデンフルオライド）を１０重量％とを混合して、正極合剤を調製し、この正極合剤を、Ｎ−メチル−２−ピロリドン中に分散させて、スラリー状の正極合剤とした。この正極合剤を、正極集電体として用いる厚み２０μｍのアルミニウム箔の両面に、均一に塗布し、乾燥後、ロールプレス機で圧縮成形することで正極を得た。
負極活物質として粉砕した黒鉛粉末を９０重量％と、結着剤としてポリ（ビニリデンフルオライド）を１０重量％とを混合して、負極合剤を調製し、この負極合剤を、Ｎ−メチル−２−ピロリドン中に分散させて、スラリー状の負極合剤とした。この負極合剤を、負極集電体として用いる厚み１５μｍの銅箔の両面に、均一に塗布し、乾燥後、ロールプレス機で圧縮成形することで負極を得た。
<Evaluation of cycle characteristics of secondary battery>
A positive electrode mixture was prepared by mixing 85% by weight of LiCoO 2 as a positive electrode active material, 5% by weight of graphite as a conductive agent, and 10% by weight of poly (vinylidene fluoride) as a binder. The positive electrode mixture was dispersed in N-methyl-2-pyrrolidone to obtain a slurry-like positive electrode mixture. This positive electrode mixture was uniformly applied to both surfaces of a 20 μm thick aluminum foil used as a positive electrode current collector, dried, and then compression molded with a roll press to obtain a positive electrode.
A negative electrode mixture was prepared by mixing 90% by weight of pulverized graphite powder as a negative electrode active material and 10% by weight of poly (vinylidene fluoride) as a binder, and this negative electrode mixture was mixed with N-methyl. A slurry-like negative electrode mixture was prepared by dispersing in -2-pyrrolidone. This negative electrode mixture was uniformly applied to both surfaces of a 15 μm thick copper foil used as a negative electrode current collector, dried, and then compression molded with a roll press to obtain a negative electrode.
次に、上記のようにして得られた負極と正極とを、厚みが２５μｍのポリエチレン製微多孔性フィルムからなるセパレーターを介して密着させ、巻回して電極巻回体とした。この電極巻回体を、絶縁材料からなる外装フィルムに封入するとともに、上記で得られたイオン伝導性電解質（１）を、外装フィルム中に注入した。そして外装フィルムの外周縁部を封口し、正極端子と負極端子とを、外装フィルムの開口部に挟み込むとともに、電極巻回体を外装フィルム中に、減圧下にて密閉し、二次電池を得た。
電池の組み立て後、２５℃、５００ｍＡの定電流電圧充電を上限４．２Ｖまで２時間行い、次に５００ｍＡでの放電（１時間率放電）を終止電圧２．５Ｖまで行った。これを１サイクルとして充放電を１００サイクル行い、１サイクル目の放電容量を１００％としたときの１００サイクル目の容量維持率を求めた。１００サイクル後の容量維持率は、９８％であった。
Next, the negative electrode and the positive electrode obtained as described above were brought into close contact with each other through a separator made of a polyethylene microporous film having a thickness of 25 μm and wound to obtain an electrode wound body. While this electrode winding body was enclosed in the exterior film which consists of insulating materials, the ion conductive electrolyte (1) obtained above was inject | poured in the exterior film. Then, the outer peripheral edge of the outer film is sealed, the positive electrode terminal and the negative electrode terminal are sandwiched between the openings of the outer film, and the electrode winding body is sealed in the outer film under reduced pressure to obtain a secondary battery. It was.
After the battery was assembled, constant current voltage charging at 25 ° C. and 500 mA was performed for 2 hours to an upper limit of 4.2 V, and then discharging at 500 mA (1 hour rate discharge) was performed to a final voltage of 2.5 V. Using this as one cycle, 100 cycles of charge / discharge were performed, and the capacity retention rate at the 100th cycle was determined, assuming that the discharge capacity at the first cycle was 100%. The capacity retention rate after 100 cycles was 98%.
＜常温溶融塩（２）の合成＞
２−アクリルアミド−２−メチル−１−プロパンスルホン酸１０．３６ｇ（５０ｍｍｏｌ）を、メタノール５００ｍｌ／蒸留水４ｍｌに溶解し、これに炭酸銀８．２８ｇ（３０ｍｍｏｌ）を添加して、室温下で穏やかに４時間連続攪拌し、濾過後、無色透明の溶液を得た。この濾液に、５１ｍｍｏｌのメタクリルアミドプロピルトリメチルアンモニウムクロリドをメタノール１００ｍｌに溶解した溶液を滴下反応させた。反応は定量的に進行した。反応生成物である塩化銀を濾別し、無色透明のメタノール溶液を回収した。この濾液をエバポレーターで減圧濃縮し、溶媒を完全に除去した。このようにして得られた塩モノマーは、プロトン核磁気共鳴スペクトル（1Ｈ−ＮＭＲ）により生成物の確認を行い、所望の化合物であることを確認した。
<Synthesis of room temperature molten salt (2)>
10.36 g (50 mmol) of 2-acrylamido-2-methyl-1-propanesulfonic acid was dissolved in 500 ml of methanol / 4 ml of distilled water, and 8.28 g (30 mmol) of silver carbonate was added thereto. For 4 hours, and after filtration, a colorless and transparent solution was obtained. A solution obtained by dissolving 51 mmol of methacrylamidopropyltrimethylammonium chloride in 100 ml of methanol was dropped into this filtrate. The reaction proceeded quantitatively. The reaction product silver chloride was removed by filtration, and a colorless and transparent methanol solution was recovered. The filtrate was concentrated under reduced pressure with an evaporator to completely remove the solvent. The salt monomer thus obtained was confirmed by a proton nuclear magnetic resonance spectrum ( 1 H-NMR) to confirm that it was a desired compound.
さらに、この塩モノマー１０ｇ（２６ｍｍｏｌ）を１００ｍｌのメタノールに溶解させ、それに１．８８ｇ（２６ｍｍｏｌ）のジエチルアミンを添加し、６０℃で６時間反応させた。反応溶液をエバポレーターで減圧濃縮し、溶媒を完全に除去し、常温溶融塩（２）を得た。この常温溶融塩（２）は、プロトン核磁気共鳴スペクトル（1Ｈ−ＮＭＲ）により、重合性官能基が完全に消失していることを確認した。得られた常温溶融塩（２）中に含まれるＣｌ-イオンの含有率をイオンクロマト法により定量すると５３ｐｐｍであった。 Further, 10 g (26 mmol) of this salt monomer was dissolved in 100 ml of methanol, and 1.88 g (26 mmol) of diethylamine was added thereto, and reacted at 60 ° C. for 6 hours. The reaction solution was concentrated under reduced pressure using an evaporator, and the solvent was completely removed to obtain a room temperature molten salt (2). This room temperature molten salt (2) confirmed that the polymerizable functional group had completely disappeared by proton nuclear magnetic resonance spectrum ( 1 H-NMR). The content of Cl - ions contained in the obtained room temperature molten salt (2) was 53 ppm as determined by ion chromatography.
＜イオン伝導性電解質（２）の合成＞
実施例１において、常温溶融塩（１）の代わりに、上記で得られた常温溶融塩（２）を使用する以外は、実施例１と同様にして、イオン伝導性電解質（２）を作製し、イオン伝導度を測定した。２０℃に於けるイオン伝導度は５．１×１０-3Ｓ／ｃｍであった。
<Synthesis of ion conductive electrolyte (2)>
In Example 1, an ion conductive electrolyte (2) was prepared in the same manner as in Example 1 except that the room temperature molten salt (2) obtained above was used instead of the room temperature molten salt (1). The ionic conductivity was measured. The ionic conductivity at 20 ° C. was 5.1 × 10 −3 S / cm.
＜二次電池のサイクル特性評価＞
実施例１において、常温溶融塩（１）の代わりに、上記で得られた常温溶融塩（２）を使用する以外は、実施例１と同様にして二次電池を作製し、１００サイクル後の容量維持率を測定したところ、９７％であった。
<Evaluation of cycle characteristics of secondary battery>
In Example 1, a secondary battery was prepared in the same manner as in Example 1 except that the room temperature molten salt (2) obtained above was used instead of the room temperature molten salt (1). The capacity retention rate was measured and found to be 97%.
（比較例１）
トリメチルヘキシルアンモニウムブロマイド１０ｇ（４４．６ｍｍｏｌ）とリチウムビス（トリフルオロメタンスルホン）イミド１２．８ｇ（４４．６ｍｍｏｌ）を蒸留水中で混合攪拌した。直ちにイオン交換反応が起こり、水に不溶な常温溶融塩（３）が水と分離した。常温溶融塩（３）を分取し、蒸留水で３回洗浄を行い、エバポレーターで減圧し、水分を除去した。この常温溶融塩（３）は、プロトン核磁気共鳴スペクトル（1Ｈ−ＮＭＲ）により生成物の確認を行い、所望の化合物であることを確認した。また、得られた常温溶融塩（３）中に含まれるＢｒ-イオンの含有率をイオンクロマト法により定量すると８７０ｐｐｍと高くなった。
この常温溶融塩（３）を用いて、実施例１と同様の方法で、電解質と二次電池を作製し、イオン伝導度と二次電池の容量維持率を測定した。２０℃に於けるイオン伝導度は１．９×１０-3Ｓ／ｃｍと比較的高い結果となったが、二次電池の容量維持率は６８％と低くなった。
(Comparative Example 1)
10 g (44.6 mmol) of trimethylhexylammonium bromide and 12.8 g (44.6 mmol) of lithium bis (trifluoromethanesulfone) imide were mixed and stirred in distilled water. Immediate ion exchange reaction occurred, and room temperature molten salt (3) insoluble in water separated from water. The room temperature molten salt (3) was collected, washed with distilled water three times, and reduced in pressure with an evaporator to remove moisture. This room temperature molten salt (3) was confirmed by a proton nuclear magnetic resonance spectrum ( 1 H-NMR) to confirm that it was a desired compound. Further, when the content of Br − ions contained in the obtained room temperature molten salt (3) was quantified by ion chromatography, it was as high as 870 ppm.
Using this room temperature molten salt (3), an electrolyte and a secondary battery were produced in the same manner as in Example 1, and the ionic conductivity and the capacity retention rate of the secondary battery were measured. The ionic conductivity at 20 ° C. was relatively high at 1.9 × 10 −3 S / cm, but the capacity retention rate of the secondary battery was as low as 68%.
（比較例２）
比較例１のトリメチルヘキシルアンモニウムブロマイドの代わりに１−エチル−３−メチルイミダゾリウムブロマイドを使用する以外は、比較例１と同様にして常温溶融塩（４）を得た。得られた常温溶融塩（４）中に含まれるＢｒ-イオンの含有率をイオンクロマト法により定量すると４５０ｐｐｍと高くなった。
この常温溶融塩（４）を用いて、実施例１と同様の方法で、電解質と二次電池を作製し、イオン伝導度と二次電池の容量維持率を測定した。２０℃に於けるイオン伝導度は２．８×１０-3Ｓ／ｃｍと比較的高い結果となったが、二次電池の容量維持率は７３％と低くなった。
(Comparative Example 2)
A room temperature molten salt (4) was obtained in the same manner as in Comparative Example 1, except that 1-ethyl-3-methylimidazolium bromide was used instead of trimethylhexylammonium bromide in Comparative Example 1. When the content of Br - ions contained in the obtained room temperature molten salt (4) was quantified by ion chromatography, it was as high as 450 ppm.
Using this room temperature molten salt (4), an electrolyte and a secondary battery were produced in the same manner as in Example 1, and the ionic conductivity and the capacity retention rate of the secondary battery were measured. The ionic conductivity at 20 ° C. was relatively high at 2.8 × 10 −3 S / cm, but the capacity retention rate of the secondary battery was as low as 73%.
本発明の常温溶融塩は、イオン伝導性電解質に利用することが可能であり、優れたイオン伝導性を有する電解質が得られることから、これを用いた電池は優れた電池特性を示すため、二次電池への適用が可能であると共に、キャパシタやエレクトロクロミック素子等、電気化学素子全般へも適用可能である。 The room temperature molten salt of the present invention can be used as an ion conductive electrolyte, and an electrolyte having excellent ion conductivity can be obtained. Therefore, a battery using this exhibits excellent battery characteristics. The present invention can be applied to secondary batteries, and can be applied to all electrochemical elements such as capacitors and electrochromic elements.
Claims (4)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009028567A1 (en) * | 2007-08-27 | 2009-03-05 | Bridgestone Corporation | Nonaqueous electrolyte solution for battery and nonaqueous electrolyte battery comprising the same |
| JP2009158245A (en) * | 2007-12-26 | 2009-07-16 | Sumitomo Bakelite Co Ltd | Binder for secondary battery electrode, secondary battery electrode, and secondary battery |
| WO2011024988A1 (en) | 2009-08-31 | 2011-03-03 | 和光純薬工業株式会社 | Ionic liquid containing allylsulfonate anion |
| JP2016178064A (en) * | 2015-03-23 | 2016-10-06 | Tdk株式会社 | Electrolytic solution for lithium ion secondary batteries and lithium ion secondary battery arranged by use thereof |
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2005
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009028567A1 (en) * | 2007-08-27 | 2009-03-05 | Bridgestone Corporation | Nonaqueous electrolyte solution for battery and nonaqueous electrolyte battery comprising the same |
| JP5379688B2 (en) * | 2007-08-27 | 2013-12-25 | 株式会社ブリヂストン | Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery including the same |
| JP2009158245A (en) * | 2007-12-26 | 2009-07-16 | Sumitomo Bakelite Co Ltd | Binder for secondary battery electrode, secondary battery electrode, and secondary battery |
| WO2011024988A1 (en) | 2009-08-31 | 2011-03-03 | 和光純薬工業株式会社 | Ionic liquid containing allylsulfonate anion |
| US8546609B2 (en) | 2009-08-31 | 2013-10-01 | Wako Pure Chemical Industries, Ltd. | Ionic liquid containing allylsulfonate anion |
| JP2016178064A (en) * | 2015-03-23 | 2016-10-06 | Tdk株式会社 | Electrolytic solution for lithium ion secondary batteries and lithium ion secondary battery arranged by use thereof |
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