WO2004051679A1 - 難燃性電解液電解コンデンサ - Google Patents
難燃性電解液電解コンデンサ Download PDFInfo
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- WO2004051679A1 WO2004051679A1 PCT/JP2003/015079 JP0315079W WO2004051679A1 WO 2004051679 A1 WO2004051679 A1 WO 2004051679A1 JP 0315079 W JP0315079 W JP 0315079W WO 2004051679 A1 WO2004051679 A1 WO 2004051679A1
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- WO
- WIPO (PCT)
- Prior art keywords
- group
- electrolytic capacitor
- phosphazene derivative
- formula
- capacitor according
- Prior art date
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- 239000003990 capacitor Substances 0.000 title claims abstract description 56
- 239000003792 electrolyte Substances 0.000 title claims abstract description 32
- 239000003063 flame retardant Substances 0.000 title abstract description 7
- 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 title abstract description 6
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 43
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 32
- 150000002367 halogens Chemical class 0.000 claims description 31
- -1 tenorel Chemical compound 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
- 239000011737 fluorine Substances 0.000 claims description 21
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910052711 selenium Inorganic materials 0.000 claims description 14
- 239000011669 selenium Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 125000005647 linker group Chemical group 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 239000011135 tin Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052699 polonium Inorganic materials 0.000 claims description 5
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 238000002048 anodisation reaction Methods 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 150000002596 lactones Chemical class 0.000 claims 1
- 238000007743 anodising Methods 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 description 31
- 125000003545 alkoxy group Chemical group 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000011888 foil Substances 0.000 description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 9
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000000962 organic group Chemical group 0.000 description 8
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000004714 phosphonium salts Chemical group 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 125000003652 trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 238000009835 boiling Methods 0.000 description 2
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
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- OHXSFWVRSAGWHH-UHFFFAOYSA-N [Sb].F Chemical compound [Sb].F OHXSFWVRSAGWHH-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- SYEOWUNSTUDKGM-UHFFFAOYSA-N beta-methyladipic acid Natural products OC(=O)CC(C)CCC(O)=O SYEOWUNSTUDKGM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- OLKRIVQBFQVHRL-UHFFFAOYSA-M but-2-enedioate;hydron;tetraethylazanium Chemical compound OC(=O)C=CC([O-])=O.CC[N+](CC)(CC)CC OLKRIVQBFQVHRL-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000001629 suppression Effects 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
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- XOGCTUKDUDAZKA-UHFFFAOYSA-N tetrapropylphosphanium Chemical compound CCC[P+](CCC)(CCC)CCC XOGCTUKDUDAZKA-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- TZWFFXFQARPFJN-UHFFFAOYSA-N triethyl(methyl)phosphanium Chemical compound CC[P+](C)(CC)CC TZWFFXFQARPFJN-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229950002929 trinitrophenol Drugs 0.000 description 1
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
Definitions
- the present invention relates to an electrolytic capacitor, and particularly to a flame-retardant electrolytic capacitor.
- An electrolytic capacitor is a capacitor in which an insulating oxide layer is formed by electrolytic oxidation on the surface of aluminum or tantalum metal foil, and this insulating oxide layer is used as a dielectric.
- the capacitance is large due to the large relative dielectric constant of the coating.
- the structure of a general aluminum electrolytic capacitor element using aluminum is composed of a strip-shaped anode foil provided with an insulating oxide layer by anodic oxidation and a strip-shaped cathode foil having no insulating oxide layer. It is wound in a cylindrical shape with a separator interposed therebetween, or a separator is alternately stacked or folded with a separator sandwiched between a cathode and an anode.
- the electrolytic capacitor element After being impregnated with an electrolytic solution, the electrolytic capacitor element is housed in an outer case, and the opening of the outer case is sealed with a sealing material to form an electrolytic capacitor.
- an electrolytic capacitor solution a solution in which boric acid, carboxylic acid, or the like, or an ammonium salt thereof, or the like is dissolved in an organic solvent such as ethylene glycol, N, N-dimethylformamide, and ⁇ -petit mouth ratataton is used. ing.
- flame retardants for plastics include phosphorus compounds, halogenated compounds, antimony oxide, and the like.
- the basic performance of the electrolyte (operating temperature range, conductivity, It is important not to reduce spark voltage, compatibility with electrodes, etc.).
- solid materials cannot be included in electrolytes because they reduce conductivity and halides corrode electrodes.
- there is a technology for improving the flame retardancy of electrolytic capacitors by incorporating a non-halogen phosphate ester into the electrolytic solution see Japanese Patent No. 2611262).
- a powerful electrolytic capacitor does not have sufficient flame retardancy, and there is a need for an electrolytic capacitor with further improved flame retardancy. Disclosure of the invention
- An object of the present invention is to provide a flame-retardant electrolyte electrolytic capacitor having a high level of safety even when the electrolyte leaks to the outside by imparting a higher level of flame retardancy to the electrolyte than before. Is to do.
- the present inventors have conducted intensive studies to achieve the above object, and as a result, by blending the phosphazene derivative and Z or its isomer with the electrolyte, the flame retardancy of the electrolyte has been further improved than before. However, they found that the safety of the electrolytic capacitor was significantly improved, and completed the present invention.
- the electrolytic capacitor of the present invention is an electrolytic capacitor comprising an anode provided with an insulating oxide layer by anodic oxidation, a cathode, a separator, and an electrolytic solution containing a solute in an organic solvent.
- the electrolyte is characterized by containing 3% by mass or more of a phosphazene derivative and an isomer of Z or a phosphazene derivative.
- the electrolytic solution is the phosphazene Contains at least 5% by mass of isomers of derivatives and / or phosphazene derivatives.
- the electrolytic solution contains the phosphazene derivative and / or its isomer in an amount of 10% by mass or more.
- the phosphazene derivative is preferably a phosphazene derivative having a viscosity of 10 OmPa ⁇ s (100 cP) or less at 25 ° C. and represented by the following formula (I) or (II).
- R 2 and! 3 independently represent a monovalent substituent or a halogen element.
- X 1 represents carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth. , oxygen, sulfur, selenium,.
- Y ⁇ Upsilon 2 and Upsilon 3 represents a substituent containing at least one element selected from the group consisting of tellurium and polonium are independently divalent connecting group, a bivalent element or Represents a single bond.
- R 4 independently represents a monovalent substituent or a halogen element.
- N represents 3 to 15 J
- phosphazene derivatives represented by the above formula ⁇ are particularly preferable.
- R 5 independently represents a monovalent substituent or fluorine, at least one of all R 5 is a monovalent substituent containing fluorine or fluorine, and n represents 3 to 8. And not all R 5 are fluorine.
- phosphazene derivative a phosphazene derivative which is solid at 25 ° C. and represented by the following formula (V) is also preferable.
- the isomer of the phosphazene derivative is represented by the following formula (VI):
- the isomer of the phosphazene derivative represented by (VII) is preferred.
- R 7 , 8 and 19 independently represent a monovalent substituent or a halogen element.
- X 2 is a substituent containing at least one element selected from the group consisting of carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, zeolite, selenium, tenorel, and polonium.
- Y 7 and Y 8 independently represent a divalent linking group, a divalent element, or a single bond.
- the electrolytic solution contains an organic solvent having a relative dielectric constant at 25 of 30 or more.
- the electrolytic solution contains ⁇ -petit mouth ratatone and / or ethylene dalicol.
- the anode is aluminum
- the total proportion of elements selected from the group consisting of tantalum and niobium is 95% by mass or more.
- the electrolytic capacitor of the present invention comprises an anode provided with an insulating oxide layer by anodic oxidation, a cathode, a separator, and an electrolyte containing a solute in an organic solvent.
- the electrolytic solution includes an organic solvent, a solute, and a phosphazene derivative and / or an isomer of the phosphazene derivative.
- the reason that the electrolytic solution contains the phosphazene derivative and Z or an isomer thereof is as follows. That is, conventionally, when the internal pressure of the electrolytic capacitor rises due to heat, overvoltage, etc., the electrolyte leaks from the sealing portion or the explosion-proof valve operates, so that the electrolyte blows out and the jetted electrolyte ignites Bow I was at risk of fire.
- the above-mentioned phosphazene derivative and phosphorus constituting the isomer thereof have the effect of suppressing the chain decomposition of the polymer material constituting the electrolytic capacitor. By including the isomer, the risk of the ignition-ignition can be effectively reduced.
- phosphazene and its isomers containing halogen function as scavengers for active radicals in the event of combustion, and the organic substituents generate carbides (chars) on the separator during combustion, thus reducing the amount of oxygen.
- halogen eg, fluorine
- the phosphazene derivative and its isomer preferably have a substituent containing a halogen element in the molecular structure.
- the safety of the electrolytic solution can be more effectively improved.
- halides cannot be added to the electrolyte that directly contacts the electrodes because they corrode the electrodes.
- the phosphorus element in the molecular structure traps the haegent radical to form a stable phosphorus halide, and the halogen is not dissociated, so that the electrode is corroded.
- the phosphazene derivative and its isomer have a high decomposition potential and a wide potential window, the electrolytic solution does not decompose when using the electrolytic capacitor, and the electric characteristics do not deteriorate.
- the content of the halogen element in the phosphazene derivative and its isomer is preferably 2 to 80% by mass, and more preferably 2 to 60% by mass. / 0 is more preferable, and 2 to 50% by mass is further preferable. If the content is less than 2% by mass, the effect of including a halogen element may not be sufficiently exhibited, while if it exceeds 80% by mass, the electrical conductivity may decrease.
- the halogen element fluorine, chlorine, bromine and the like are preferable, and fluorine is particularly preferable.
- the phosphazene derivative has a viscosity of not more than 100 OmPas (100 cP) at 25 ° C, more preferably not more than 10 OmPas, and the formula (I) Alternatively, a phosphazene derivative represented by the formula (II) is preferable.
- RR 2 and R 3 are not particularly limited as long as they are monovalent substituents or halogen elements.
- the monovalent substituent include an alkoxy group, a phenoxy group, an alkyl group, a carboxyl group, an acyl group, an aryl group and the like.
- an alkoxy group is particularly preferred because of its low viscosity.
- preferred examples of the halogen element include fluorine, chlorine, and bromine.
- 1 ⁇ to 1 3 may be all the same type of substituents, it may be some of them are different types of substituents.
- alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, and an alkoxy-substituted alkoxy group such as a methoxyethoxy group and a methoxyxetoxy group.
- 1 to! ⁇ 3 are preferably all methoxy, ethoxy, methoxetoxy, or methoxyethoxyethoxy groups, and are particularly low-viscosity. Particularly preferred is a group or an ethoxy group.
- Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pen. And a tyl group.
- Examples of the acryl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isoptyryl group, and a valeryl group.
- Examples of the aryl group include a phenyl group, a tolyl group and a naphthyl group.
- the hydrogen element in these monovalent substituents is preferably substituted with a halogen element, and the halogen element preferably includes fluorine, chlorine, bromine and the like.
- the divalent linking group represented by Y 2 and 3 include, in addition to a CH 2 group, oxygen, sulfur, selenium, nitrogen, boron, aluminum, scandium, gallium, and itium.
- divalent linking groups containing at least one element selected from the group consisting of iron, cobalt, and nickel.
- CH 2 groups and the group consisting of oxygen, sulfur, selenium, and nitrogen A divalent linking group containing at least one selected element is preferred.
- Y 2 and 3 may be a divalent element such as oxygen, sulfur, selenium, or a single bond.
- a divalent linking group containing sulfur and / or selenium, a sulfur element, and a selenium element are particularly preferable.
- Y i Y 3 may be all the same type or some may be different types.
- X 1 is an organic material containing at least one element selected from the group consisting of carbon, silicon, nitrogen, phosphorus, oxygen and sulfur from the viewpoint of harmfulness, environmental considerations, and the like. Groups are preferred. Among these organic groups, an organic group having a structure represented by the following formula (VI11), (IX) or (X) is more preferable.
- R 10 to R 14 represent a monovalent substituent or a halogen element.
- Y 1Q to Y 14 represent a divalent linking group, a divalent element, or a single bond, and Z represents a divalent group or a divalent element.
- each of R 10 to R 14 is the same monovalent substituent or halogen element as described for the scale 1 to! ⁇ 3 in the formula (I). Preferably, these may be of the same type in the same organic group, or some may be of different types.
- R 10 and R 11 in the formula (VIII), and R 13 and R 14 in the formula (X) may be bonded to each other to form a ring.
- the groups represented by Y 1Q to Y 14 are the same divalent linkages as described for Y 1 to Y 3 in the formula (I). Similarly, a group or a divalent element may be mentioned. Similarly, a group containing an element of sulfur, sulfur, or selenium is particularly preferable because the risk of ignition and ignition of the electrolytic solution is reduced. These may be of the same type within the same organic group, or some may be of different types.
- ⁇ represents, for example, a CH 2 group, a CHR (R represents an alkyl group, an alkoxyl group, a phenyl group, etc .; the same applies hereinafter), an NR group, oxygen, sulfur, Selenium, boron, aluminum, scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, germanium, zirconium, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum , Tenorenore, Polonium, Tungsten, Iron, Koba Belt, or the like divalent group containing at least one element selected from the group consisting of nickel.
- a divalent group containing at least one element selected from the following is preferable. Particularly, in the case of a divalent group containing an element of sulfur and / or selenium, the risk of ignition and ignition of the electrolyte is reduced.
- Z may be a divalent element such as oxygen, sulfur, and selenium.
- an organic group containing phosphorus as represented by the formula (VIII) is particularly preferable, since the risk of ignition and ignition can be particularly effectively reduced. Further, when the organic group is an organic group containing sulfur as represented by the formula (IX), it is particularly preferable from the viewpoint of reducing the interface resistance of the electrolytic solution.
- R 4 is not particularly limited as long as it is a monovalent substituent or a halogen element.
- the monovalent substituent include an alkoxy group, a phenoxy group, an alkyl group, a carboxy group, an acyl group, an aryl group and the like. Among these, an alkoxy group, a phenoxy group and the like are particularly preferable.
- preferred examples of the halogen element include fluorine, chlorine, and bromine.
- the alkoxy group include a methoxy group, an ethoxy group, a methoxyethoxy group, and a propoxy group.
- a methoxy group, an ethoxy group, and a methoxyethoxy group are particularly preferable.
- the hydrogen element in these substituents is preferably substituted with a halogen element.
- halogen element fluorine, chlorine, bromine and the like are preferred.
- Equation (1) ( ⁇ ), (VI II) scale 1 ⁇ ! ⁇ 4 in-a), R 1 0 ⁇ R 1 4 , Y ⁇ Y 3 ⁇ 1 0 ⁇ 1 4, by appropriately selecting the ⁇
- This makes it possible to synthesize a phosphazene derivative having more suitable viscosity, solubility suitable for addition and mixing, and the like.
- the above phosphazene derivatives may be used alone or in combination of two or more.
- the phosphazene derivative represented by the formula (I ⁇ ) is particularly preferable.
- ⁇ is preferably 3 to 4, and more preferably 3.
- the value of ⁇ is small, the boiling point is low, and the ignition Can be improved.
- the value of n increases, so that it can be used stably even at high temperatures. It is also possible to select and use a plurality of phosphazenes in a timely manner to obtain the desired performance by utilizing the above properties.
- the phosphazene derivative represented by the formula (IV) is also particularly preferable.
- Examples of the monovalent substituent in the formula (IV) include an alkyl group, an acyl group, an aryl group, and a carboxyl group in addition to the alkoxy group, and are particularly excellent in improving the safety of the electrolytic solution. Groups are preferred.
- Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a butoxy group and the like, and an a // oxy group-substituted alkoxy group such as a methoxetoxy group.
- a methoxy group, an ethoxy group, and an ⁇ -propoxy group are particularly preferred from the viewpoint of improving the safety of the electrolytic solution.
- a methoxy group is preferable from the viewpoint of reducing the viscosity of the electrolytic solution.
- ⁇ is preferably 3 to 4 from the viewpoint that excellent safety can be imparted to the electrolytic solution.
- the monovalent substituent is preferably substituted by fluorine.
- R 5 in the formula (IV) is not fluorine, at least one monovalent substituent contains fluorine.
- the content of fluorine in the phosphazene derivative represented by the formula (IV) is preferably 3 to 70% by weight, more preferably 7 to 45% by weight / 0 .
- As the phosphazene derivative a phosphazene derivative which is solid at 25 ° C.
- R 6 is not particularly limited as long as it is a monovalent substituent or a halogen element.
- the monovalent substituent include an alkoxy group, an alkyl group, a carboxyl group, an acyl group, and an aryl group. And the like.
- the halogen element for example, a halogen element such as fluorine, chlorine, bromine, and iodine is preferably exemplified.
- an alkoxy group is particularly preferable in that the increase in the viscosity of the electrolytic solution can be suppressed.
- the alkoxy group is preferably a methoxy group, an ethoxy group, a methoxetoxy group, a propoxy group (isopropoxy group, n-propoxy group), a phenoxy group, a trifluoroethoxy group, or the like, and suppresses an increase in the viscosity of the electrolyte.
- Methoxy, ethoxy, and propoxy groups (iso A propoxy group, an n-propoxy group), a phenoxy group, a trifluoroethoxy group and the like are more preferred.
- the monovalent substituent preferably contains the aforementioned halogen element.
- n is particularly preferably 3 or 4 from the viewpoint that the increase in the viscosity of the electrolytic solution can be suppressed.
- R 6 is an n-propoxy group and n is 4; a structure of formula (V) in which R 6 is a trifluoroethoxy group and n is 3 or 4; A structure in which R 6 is a phenoxy group and n is 3 or 4 is particularly preferred because it can suppress an increase in the viscosity of the electrolyte solution.
- the isomer of the phosphazene derivative is preferably an isomer of the phosphazene derivative represented by the above formula (VI) and represented by the above formula (VI I).
- R 7 , R 8 and R 9 in the formula (VI) are not particularly limited as long as they are monovalent substituents or halogen elements, and are the same as those described for R 3 in the above formula (I). Any of the above substituents or halogen elements are preferred.
- the divalent linking group or the divalent element represented by Y 7 and Y 8 is the same as the divalent linking group or the same as described for Y i Y 3 in the formula (I). Any of divalent elements and the like are preferably exemplified.
- the substituent represented by X 2 the same substituents as those described for X 1 in the formula (I) are preferable, and deviations are also suitably mentioned.
- the isomer represented by the formula (VI) is an isomer of the phosphazene derivative represented by the formula (VI I).
- the content (volume / 0 ) of the isomer in the electrolytic solution can be measured by the following measuring method.
- the peak area of the sample is determined by gel permeation chromatography (GPC) or high performance liquid chromatography, and the molar ratio is obtained by comparing the peak area with the previously determined area per mole of the isomer. It can also be measured by considering the specific gravity and converting the volume.
- phosphazene derivative represented by the formula (VII) those having a relatively low viscosity and capable of satisfactorily dissolving the supporting salt are preferable.
- the flash point of the phosphazene derivative and its isomer is not particularly limited, but is preferably 100 ° C or higher, more preferably 150 ° C or higher, and more preferably 230 ° C or higher, from the viewpoint of suppression of ignition and ignition. Are more preferred, and those which do not ignite are most preferred.
- the flash point is, specifically, a temperature at which a flame spreads on the surface of a substance and covers at least 75% of the surface of the substance.
- the flash point refers to a degree of tendency to form a combustible mixture with air. It is a measure to measure. If the phosphazene derivative and its isomer have a flash point at 100 ° C. or higher, ignition and the like are suppressed, and the risk of ignition and burning over the electrolyte surface can be reduced.
- the ratio of the phosphazene derivative and / or its isomer in the electrolyte depends on the required performance of the electrolytic capacitor, but the most flame-retardant electrolyte is used when the total amount of the solvent is phosphazene derivative and / or Z or its isomer. A capacitor is obtained. Further, in order to improve the flame retardancy by adding a conventional electrolyte as a cosolvent, it is necessary to use 3% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more. I do.
- organic solvent used in the above electrolyte examples include alcohol solvents such as ethylene glycol, propylene glycol, glycerin, and methyl sorbent; N-methylformamide, N-ethylformamide, ⁇ , ⁇ -dimethylformamide, ⁇ , ⁇ -jetylformamide. ⁇ , ⁇ -methylacetamide, ⁇ -ethynoleacetamide, ⁇ , ⁇ -dimethyl Amide solvents such as acetoamide, N, N-getylacetamide, and N-methylpyrrolidinone; ⁇ -petit mouth ratatone,] 3-petitium ratatone, ⁇ -valero ratatone, ⁇ -valero ratatone, etc.
- alcohol solvents such as ethylene glycol, propylene glycol, glycerin, and methyl sorbent
- ratatone solvents ethylene Carbonate solvents such as carbonate, propylene carbonate and butylene carbonate; nitrinole solvents such as 3-methoxypropionitolinole; carbamate solvents such as ⁇ -methyloxazolidinone; ⁇ , ⁇ , -dimethylimidazolidinone and the like
- Surea solvent a sulfolane solvent such as sulfolane and 3-methylsulfolane.
- 10% by mass or less of water may be added to the electrolytic solution of the electrolytic capacitor of the present invention.
- those having a relative dielectric constant of 30 or more at 25 ° C. are preferred, and y-petit mouth ratataton and ethylene glycol are particularly preferred.
- alkali metal salts of inorganic acids and organic acids ammonium salts, amine salts, quaternary ammonium salts, quaternary phosphonium salts, and the like can be used.
- the inorganic acids include boric acid, carbonic acid, keic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, nitric acid, sulfuric acid, sulfurous acid, thiocyanic acid, cyanic acid, borofluoric acid, and hydrofluoric acid Arsenic hydrofluoric acid, antimony hydrofluoric acid, perchloric acid and the like.
- the organic acids include formic acid, acetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, pendecanedioic acid, dodecanedioic acid, and brassic acid , Tetradecandioic acid, Pentadecandioic acid, Dimethylmalonic acid, Getylmalonic acid, Dipropylmalonic acid, 3,3-Dimethyldaltaric acid, 3-Methyladipic acid, 1,6-Decanedicarboxylic acid, 1,2-Cyclohexane Dicarboxylic acid, maleic acid, citraconic acid, benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, salicylic acid, ⁇ _resorcinic acid, ⁇ -nitrobenzoic acid, phenol, picric acid, methanesulfonic acid, benzen
- Alkali metals include lithium, sodium, potassium and the like.
- the amine include methylamine, ethylamine, propynoleamine, and butylamine. Tilamine, ethylenediamine, monoethanolamine, dimethylamine, getylamine, dipropylamine, ethynolemethinoleamine, dipheninoleamine, ethanolamine, trimethinoleamine, triethylamine, triptylamine, 1,8-diazabicyclo (5.4. 0) -Pendene-17, triethanolamine and the like.
- the quaternary ammoniums include getyl ammonium, trietinole ammonium, tripropyl ammonium, ethanol non-ammonium, jetano one-ammonium, triethanol-one-ammonium, silk mouth ammonium, piperamen, 1,5-Diazabicyclo (4.3.0) none-2,5,1,8-diazabicyclo (5.4.0) indesenium-7, tetramethylammonium, methyltriethylammonium, dimethyl Jethylammonium, trimethylethylammonium, tetraethynoleammonium, tetrabutylammonium, N, N-dimethylpyrrolidinium, N-methyl-N-ethylpyrrolidinium, N, N- Dimethylbiperidinium, Benzinoletrimethinoleammonium, N-ethynolepirimem, N, N, -dimethyl Chillimidazolym
- Examples of the quaternary phosphonium include tetramethinolephosphonium, methyltriethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium and the like.
- the amount of solute is below the saturation concentration, preferably between 0.1 and 40% by weight.
- the organic solvent other than the alcohol, and the phosphazene derivative and its isomer used in the present invention do not dissolve the alkali metal salt or ammonium salt in a small amount. Therefore, when using organic solvents other than alcohols and mixed solvents of phosphazene derivatives and / or isomers thereof, amine salts, quaternary ammonium salts, and quaternary phosphonium salts may be used. preferable. Among them, those using a quaternary ammonium salt or a quaternary phosphonium salt as a solute are particularly preferred in view of solubility and conductivity.
- the anode of the electrolytic capacitor of the present invention has an insulating oxide layer provided by anodic oxidation on a surface of a valve metal such as an anode or a tantalum, and an anode is formed of aluminum. Use a damper or the like. These may be subjected to etching or sintering in order to increase the contact area with the electrolyte. Where the anode is the aluminum in the anode
- the total proportion of -Pa, tantalum and niobium is 95% by mass or more.
- a separator is provided between the anode and the cathode to prevent a short circuit.
- the separator include a paper separator such as manila paper and kraft paper, a polyolefin separator such as polypropylene and polyethylene, and an engineering plastic separator such as polyphenylene sulfide and polybutylene terephthalate.
- the electrolytic capacitor of the present invention can be manufactured by a known method.
- the electrolytic capacitor of the present invention includes an anode foil made of aluminum whose surface is oxidized to be a dielectric, an aluminum cathode foil opposed to the dielectric surface of the anode foil, an anode foil and a cathode. It can be manufactured by sealing a wound element composed of a foil and a separator interposed between the foil and an electrolytic solution in a case.
- the electrolytic capacitor of the present invention is characterized in that the above-mentioned phosphazene derivative is contained in the electrolytic solution.
- the electrolytic solution was impregnated in an electrolytic capacitor element, housed in an outer case, and the opening of the outer case was sealed with a sealing material to produce an aluminum electrolytic capacitor.
- the mass of the aluminum electrode was 1.18 g
- the mass of the separator was 0.36 g
- the mass of the electrolyte was 0.82 g
- the size of the electrolytic capacitor was 12.2 ⁇ X 2 Omm. is there.
- the spark voltage, the capacitance, the dielectric loss tangent, and the leakage current of the aluminum-electrolytic capacitor thus manufactured were measured by a known method. Table 1 shows the results.
- Ph OF phenoxypentaf / reolocyclotriphosphazene, in formula (II), n is 3, one of the six R 4 is a phenoxy group (PhO one), and five are fluorine.
- TFEOF Tetrafluoroethoxypentafluorosuccinic triphosphazene.
- n is 3, cyclic phosphazene in which one of six R 4 is a tetrafluoroethoxy group, and five are fluorine.
- Industrial applicability is 3, cyclic phosphazene in which one of six R 4 is a tetrafluoroethoxy group, and five are fluorine.
- an electrolytic capacitor having high safety even when the electrolytic solution leaks to the outside by including the phosphazene derivative and / or an isomer of the phosphazene derivative in the electrolytic solution. .
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03775897A EP1569253A4 (en) | 2002-12-03 | 2003-11-26 | ELECTROLYTIC CAPACITOR WITH FLAME-RESISTANT ELECTRIC |
AU2003284452A AU2003284452A1 (en) | 2002-12-03 | 2003-11-26 | Flame-retardant electrolyte electrolytic capacitor |
US10/537,289 US7315441B2 (en) | 2002-12-03 | 2003-11-26 | Flame-retardant electrolyte electrolytic capacitor |
JP2004556842A JPWO2004051679A1 (ja) | 2002-12-03 | 2003-11-26 | 難燃性電解液電解コンデンサ |
KR1020057010017A KR100760497B1 (ko) | 2002-12-03 | 2003-11-26 | 난연성 전해질 전해 축전기 |
CNA2003801048915A CN1720597A (zh) | 2002-12-03 | 2003-11-26 | 阻燃电解质电解电容器 |
Applications Claiming Priority (2)
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JP2002-351699 | 2002-12-03 | ||
JP2002351699 | 2002-12-03 |
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WO2004051679A1 true WO2004051679A1 (ja) | 2004-06-17 |
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PCT/JP2003/015079 WO2004051679A1 (ja) | 2002-12-03 | 2003-11-26 | 難燃性電解液電解コンデンサ |
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Country | Link |
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US (1) | US7315441B2 (ja) |
EP (1) | EP1569253A4 (ja) |
JP (1) | JPWO2004051679A1 (ja) |
KR (1) | KR100760497B1 (ja) |
CN (1) | CN1720597A (ja) |
AU (1) | AU2003284452A1 (ja) |
WO (1) | WO2004051679A1 (ja) |
Cited By (1)
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CN114694978A (zh) * | 2020-12-29 | 2022-07-01 | 山东海科创新研究院有限公司 | 一种热致激发主动安全机制阻燃微胶囊及其制备方法、超级电容器 |
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WO2011153330A1 (en) * | 2010-06-02 | 2011-12-08 | Florida State University Research Foundation, Inc. | High energy density electrochemical capacitors |
US10333178B2 (en) * | 2014-04-17 | 2019-06-25 | Gotion Inc. | Electrolyte compositions containing esters of dicarboxylic acids |
CN107564735A (zh) * | 2017-08-23 | 2018-01-09 | 吴江佳亿电子科技有限公司 | 超级电容器用的阻燃有机电解液、其制备方法及超级电容器 |
CN112908702A (zh) * | 2021-02-03 | 2021-06-04 | 广州金立电子有限公司 | 一种电解电容器用电解液 |
Citations (2)
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JP2001335590A (ja) * | 2000-05-26 | 2001-12-04 | Nippon Chem Ind Co Ltd | スルホニル基含有ホスファゼン誘導体及びその製造方法 |
JP2002249742A (ja) * | 2000-12-07 | 2002-09-06 | Nitto Denko Corp | 接着性多孔質膜、それより得られる高分子ゲル電解質とそれらの応用 |
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GB2041646A (en) * | 1979-02-02 | 1980-09-10 | Pye Ltd | Electrolytic capacitors |
JP2611262B2 (ja) * | 1987-10-08 | 1997-05-21 | 三菱化学株式会社 | 難燃性電解コンデンサ |
US5780185A (en) * | 1993-06-07 | 1998-07-14 | Honda Giken Kogyo Kabushiki Kaisha | Cathode materials for lithium batteries and methods for producing the same |
EP0890963A3 (en) * | 1997-07-09 | 1999-11-17 | Mitsubishi Chemical Corporation | Electric double-layer capacitor |
US6152970A (en) * | 1998-09-29 | 2000-11-28 | General Electric Company | Drying an ultracapacitor |
EP1096521A3 (en) * | 1999-10-27 | 2001-11-21 | Asahi Glass Co., Ltd. | Electric double layer capacitor |
US6452782B1 (en) * | 1999-11-25 | 2002-09-17 | Bridgestone Corporation | Non-aqueous electrolyte electric double-layer capacitor, deterioration inhibitor for non-aqueous electrolyte electric double-layer capacitor and additive for non-aqueous electrolyte electric double-layer capacitor |
US6469888B1 (en) * | 1999-11-25 | 2002-10-22 | Bridgestone Corporation | Non-aqueous electrolyte electric double-layer capacitor |
EP1329975B1 (en) * | 2000-09-07 | 2018-04-25 | Bridgestone Corporation | Non-aqueous liquid electrolyte secondary cell and non-aqueous liquid electrolyte electric double layer capacitor |
AU2001284429A1 (en) * | 2000-09-07 | 2002-03-22 | Bridgestone Corporation | Additive for non-aqueous liquid electrolyte, non-aqueous liquid electrolyte secondary cell and non-aqueous liquid electrolyte electric double layer capacitor |
EP1329974B1 (en) * | 2000-09-07 | 2018-05-02 | Bridgestone Corporation | Non-aqueous liquid electrolyte secondary cell and non-aqueous liquid electrolyte electric double layer capacitor |
US7067219B2 (en) * | 2000-09-07 | 2006-06-27 | Bridgestone Corporation | Additive for nonaqueous-electrolyte secondary battery |
EP1324358A3 (en) * | 2001-12-11 | 2003-12-17 | Asahi Glass Co., Ltd. | Electric double layer capacitor |
-
2003
- 2003-11-26 JP JP2004556842A patent/JPWO2004051679A1/ja not_active Withdrawn
- 2003-11-26 AU AU2003284452A patent/AU2003284452A1/en not_active Abandoned
- 2003-11-26 KR KR1020057010017A patent/KR100760497B1/ko not_active IP Right Cessation
- 2003-11-26 WO PCT/JP2003/015079 patent/WO2004051679A1/ja active Application Filing
- 2003-11-26 EP EP03775897A patent/EP1569253A4/en not_active Withdrawn
- 2003-11-26 CN CNA2003801048915A patent/CN1720597A/zh active Pending
- 2003-11-26 US US10/537,289 patent/US7315441B2/en not_active Expired - Fee Related
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JP2001335590A (ja) * | 2000-05-26 | 2001-12-04 | Nippon Chem Ind Co Ltd | スルホニル基含有ホスファゼン誘導体及びその製造方法 |
JP2002249742A (ja) * | 2000-12-07 | 2002-09-06 | Nitto Denko Corp | 接着性多孔質膜、それより得られる高分子ゲル電解質とそれらの応用 |
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Cited By (1)
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CN114694978A (zh) * | 2020-12-29 | 2022-07-01 | 山东海科创新研究院有限公司 | 一种热致激发主动安全机制阻燃微胶囊及其制备方法、超级电容器 |
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US20060098391A1 (en) | 2006-05-11 |
EP1569253A4 (en) | 2008-01-16 |
JPWO2004051679A1 (ja) | 2006-04-06 |
AU2003284452A1 (en) | 2004-06-23 |
US7315441B2 (en) | 2008-01-01 |
EP1569253A1 (en) | 2005-08-31 |
KR20050084117A (ko) | 2005-08-26 |
KR100760497B1 (ko) | 2007-09-20 |
CN1720597A (zh) | 2006-01-11 |
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