JP2000348761A - Nonaqueous electrolytic solution and secondary battery using it - Google Patents
Nonaqueous electrolytic solution and secondary battery using itInfo
- Publication number
- JP2000348761A JP2000348761A JP11155531A JP15553199A JP2000348761A JP 2000348761 A JP2000348761 A JP 2000348761A JP 11155531 A JP11155531 A JP 11155531A JP 15553199 A JP15553199 A JP 15553199A JP 2000348761 A JP2000348761 A JP 2000348761A
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- aqueous electrolyte
- formula
- battery
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000008151 electrolyte solution Substances 0.000 title abstract description 6
- -1 carbamate compound Chemical class 0.000 claims abstract description 42
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 125000004429 atom Chemical group 0.000 claims abstract description 6
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 57
- 239000003125 aqueous solvent Substances 0.000 claims description 23
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 150000005678 chain carbonates Chemical class 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- PPMCFKAXXHZLMX-UHFFFAOYSA-N 1,3-dioxocan-2-one Chemical compound O=C1OCCCCCO1 PPMCFKAXXHZLMX-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 description 1
- LSUWCXHZPFTZSF-UHFFFAOYSA-N 4-ethyl-5-methyl-1,3-dioxolan-2-one Chemical compound CCC1OC(=O)OC1C LSUWCXHZPFTZSF-UHFFFAOYSA-N 0.000 description 1
- ZMGMDXCADSRNCX-UHFFFAOYSA-N 5,6-dihydroxy-1,3-diazepan-2-one Chemical compound OC1CNC(=O)NCC1O ZMGMDXCADSRNCX-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- CZBRVMVOVWAZND-UHFFFAOYSA-N cyclohexyl n,n-diethylcarbamate Chemical compound CCN(CC)C(=O)OC1CCCCC1 CZBRVMVOVWAZND-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl 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])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 125000006437 ethyl cyclopropyl group Chemical group 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- RCIJMMSZBQEWKW-UHFFFAOYSA-N methyl propan-2-yl carbonate Chemical compound COC(=O)OC(C)C RCIJMMSZBQEWKW-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 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
- 125000001624 naphthyl group Chemical group 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
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 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
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【0001】[0001]
【発明の技術分野】本発明は、過充電防止特性に優れた
非水電解液、およびそれを用いた二次電池に関する。よ
り詳細には、この発明は、特定の非水溶媒を使用するこ
とにより、過充電による電池の急速な発熱等を防止でき
るようにした非水電解液およびそれらを用いた非水電解
液二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte having excellent overcharge prevention properties and a secondary battery using the same. More specifically, the present invention provides a non-aqueous electrolyte which uses a specific non-aqueous solvent to prevent rapid heat generation of a battery due to overcharge, and a non-aqueous electrolyte secondary using the same. Battery.
【0002】[0002]
【発明の技術的背景】非水電解液を用いた電池は、高電
圧でかつ高エネルギー密度を有しており、また貯蔵性な
どの信頼性も高いので、民生用電子機器の電源として広
く用いられている。BACKGROUND OF THE INVENTION A battery using a non-aqueous electrolyte has a high voltage, a high energy density, and a high reliability such as storability, so that it is widely used as a power source for consumer electronic devices. Have been.
【0003】このような電池として非水電解液二次電池
があり、その代表的存在は、リチウムイオン二次電池で
ある。それに用いられる非水溶媒として、誘電率の高い
カーボネート化合物が知られており、各種カーボネート
化合物の使用が提案されている。また電解液として、プ
ロピレンカーボネート、エチレンカーボネートなどの前
記高誘電率カーボネート化合物溶媒と、炭酸ジエチルな
どの低粘度溶媒との混合溶媒に、LiBF4、LiPF6、
LiClO4、LiAsF6、LiCF3SO3、Li2SiF6な
どの電解質を混合した溶液が用いられている。As such a battery, there is a non-aqueous electrolyte secondary battery, a typical example of which is a lithium ion secondary battery. Carbonate compounds having a high dielectric constant are known as non-aqueous solvents used for such a purpose, and the use of various carbonate compounds has been proposed. As an electrolytic solution, LiBF 4 , LiPF 6 , LiPF 6 , a mixed solvent of the high dielectric constant carbonate compound solvent such as propylene carbonate and ethylene carbonate, and a low viscosity solvent such as diethyl carbonate.
A solution in which an electrolyte such as LiClO 4 , LiAsF 6 , LiCF 3 SO 3 , or Li 2 SiF 6 is mixed is used.
【0004】一方で、電池の高容量化を目指して電極の
研究も進められており、リチウムイオン二次電池の負極
として、リチウムの吸蔵、放出が可能な炭素材料が用い
られている。[0004] On the other hand, research on electrodes has been promoted with the aim of increasing the capacity of batteries, and carbon materials capable of occluding and releasing lithium are used as negative electrodes of lithium ion secondary batteries.
【0005】しかしながら、従来の防爆型密閉電池の中
には、過充電状態が長く続くと電流遮断装置や圧カ開放
装置が作勤した後にも引き続き異常な発熱反応が続行
し、電池温度が50〜60℃から300〜400℃に急
速に上昇し、急激に内圧上昇が生じる場合があった。[0005] However, in the conventional explosion-proof sealed batteries, if the overcharge state continues for a long time, an abnormal exothermic reaction continues even after the current interrupting device or the pressure release device is operated, and the battery temperature becomes 50 ° C. In some cases, the temperature rapidly increased from 6060 ° C. to 300 to 400 ° C., and the internal pressure increased rapidly.
【0006】[0006]
【発明が解決しようとする課題】本発明はこのような従
来技術の課題を解決しようとするものであり、電池の過
充電時における圧力開放装置の速やかな作動を促し、電
池電圧の上昇を抑制し、電池温度や電池内圧の急速な上
昇を防止する特性を与える非水電解液の提供を目的とす
る。また、この非水電解液を含む二次電池の提供を目的
とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and promptly operates a pressure relief device when a battery is overcharged, and suppresses a rise in battery voltage. It is another object of the present invention to provide a non-aqueous electrolyte which has characteristics of preventing a rapid rise in battery temperature and battery internal pressure. Another object is to provide a secondary battery including the non-aqueous electrolyte.
【0007】[0007]
【課題を解決するための手段】本発明に係る非水電解液
は、下記一般式[1]で表されるカーバメート化合物を
含有する非水溶媒と電解質とからなる非水電解液に関す
る。Means for Solving the Problems The non-aqueous electrolyte according to the present invention relates to a non-aqueous electrolyte comprising a non-aqueous solvent containing a carbamate compound represented by the following general formula [1] and an electrolyte.
【化4】 ・・・・・・[1]Embedded image ... [1]
【0008】(式[1]中、R1は炭素数3〜12のシ
クロアルキル基であり、R2およびR3は互いに同じであ
っても異なっていてもよく、酸素原子、窒素原子、硫黄
原子から選ばれたすくなくとも1種の原子を含むことが
ある炭素数1〜12の炭化水素基である。)(In the formula [1], R 1 is a cycloalkyl group having 3 to 12 carbon atoms, R 2 and R 3 may be the same or different from each other, and include an oxygen atom, a nitrogen atom, a sulfur atom, It is a C1-C12 hydrocarbon group which may contain at least one atom selected from atoms.)
【0009】また、前記の非水溶媒が、前記一般式
[1]で表されるカーバメート化合物と、下記一般式
[3a]または[3b]で表される環状炭酸エステルお
よび/または鎖状炭酸エステルとから構成されていると
過充電による電池の急速な発熱を防止でき、かつ電池特
性、特に低温特性及びサイクル特性に優れた非水電解液
を提供することができる。Further, the non-aqueous solvent comprises a carbamate compound represented by the above general formula [1] and a cyclic carbonate and / or a chain carbonate represented by the following general formula [3a] or [3b]: With this configuration, rapid heat generation of the battery due to overcharging can be prevented, and a non-aqueous electrolyte having excellent battery characteristics, particularly excellent low-temperature characteristics and cycle characteristics, can be provided.
【化5】 [3a] [3b] (式[3a]または[3b]中、R4およびR5は水素原
子または炭素数1〜6のアルキル基を示し、R4および
R5は同一であっても異なっていてもよい。)Embedded image [3a] [3b] (In the formula [3a] or [3b], R 4 and R 5 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 4 and R 5 are different even if they are the same. May be.)
【0010】さらに、これら非水電解液は、電解質とし
てリチウム塩を用いることが好ましく、このような非水
電解液は一次電池または二次電池用の電解液として有効
に利用することができる。Further, these non-aqueous electrolytes preferably use a lithium salt as an electrolyte, and such a non-aqueous electrolyte can be effectively used as an electrolyte for a primary battery or a secondary battery.
【0011】本発明は、また、負極活物質として金属リ
チウム、リチウム含有合金、リチウムイオンのドープ・
脱ドープが可能な炭素材料のいずれかを含む負極と、正
極活物質としてリチウムと遷移金属の複合酸化物、炭素
材料またはこれらの混合物のいずれかを含む正極と、前
記非水電解液とを含む二次電池に関する。[0011] The present invention also provides a method for doping lithium metal, a lithium-containing alloy, and lithium ion as a negative electrode active material.
A negative electrode including any of the undoped carbon materials, a positive electrode including any of a composite oxide of lithium and a transition metal as the positive electrode active material, a carbon material or a mixture thereof, and the nonaqueous electrolyte Related to secondary batteries.
【0012】[0012]
【発明の具体的説明】次に、本発明に係る非水電解液お
よびこの非水電解液を用いた非水電解液二次電池につい
て具体的に説明する。本発明に係る非水電解液は、カー
バメート化合物を含有する非水溶媒と、電解質とからな
っており、各々について詳述する。Next, the non-aqueous electrolyte according to the present invention and a non-aqueous electrolyte secondary battery using this non-aqueous electrolyte will be described in detail. The non-aqueous electrolyte according to the present invention comprises a non-aqueous solvent containing a carbamate compound and an electrolyte, and each will be described in detail.
【0013】カーバメート化合物 本発明で非水溶媒に含有させるカーバメート化合物とし
ては下記一般式[1]で表される化合物が使用される。 Carbamate Compound As the carbamate compound contained in the non-aqueous solvent in the present invention, a compound represented by the following general formula [1] is used.
【化6】 ……[1] (式[1]中、R1は炭素数3〜12のシクロアルキル
基であり、R2およびR3は互いに同じであっても異なっ
ていてもよく、酸素原子、窒素原子及び硫黄原子から選
ばれたすくなくとも1種の原子を含むことがある(即ち
酸素原子、窒素原子及び硫黄原子から選ばれた少なくと
も1種の原子を含むかあるいは含まない)炭素数1〜1
2の炭化水素基である。)Embedded image ... [1] (In formula [1], R 1 is a cycloalkyl group having 3 to 12 carbon atoms, and R 2 and R 3 may be the same or different from each other, and include an oxygen atom, a nitrogen atom And at least one atom selected from the group consisting of a carbon atom and a sulfur atom (i.e., containing or not containing at least one atom selected from an oxygen atom, a nitrogen atom and a sulfur atom).
2 hydrocarbon groups. )
【0014】R1としては、具体的にはシクロプロピル
基、メチルシクロプロピル基、エチルシクロプロピル
基、シクロブチル基、メチルシクロブチル基、エチルシ
クロブチル基、シクロペンチル基、メチルシクロペンチ
ル基、エチルシクロペンチル基、シクロヘキシル基、メ
チルシクロヘキシル基、エチルシクロヘキシル基、シク
ロヘプチル基、メチルシクロヘプチル基、エチルシクロ
ヘプチル基、シクロオクチル基、メチルシクロオクチル
基、エチルシクロオクチル基などを挙げることができる
が。これらの中では特にシクロペンチル基およびシクロ
ヘキシル基がが好ましい。R2、R3としては、具体的に
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、t-
ブチル基、1-ブテニル基、2-ブテニル基、3-ブテニル
基、2-メチル-2-プロペニル基、1-メチレンプロピル
基、1-メチル-2-プロペニル基、1,2-ジメチルビニル
基、1-ブチニル基、2-ブチニル基、3-ブチニル基、ペン
チル基、1-メチルブチル基、2-メチルブチル基、3-メチ
ルブチル基、1-メチル-2-メチルプロピル基、2,2-ジメ
チルプロピル基、その他、ヘキシル基、オクチル基、ノ
ニル基、デシル基等の炭素数1〜12の直鎖または分岐
アルキル基、フェニル基、トルイル基、メトキシフェニ
ル基、ナフチル基、ピリジル基、R2,R3が直接もしく
は1つ以上の窒素,硫黄および/または酸素原子を介し
て結合したピペリジン、ピペラジン、ピロリジン、モル
フォリンなどを挙げることができるが。これらの中では
炭素数1〜12のアルキル基が好ましく、特にエチル
基、n―プロピル基およびイソプロピル基が好ましい。As R 1 , specifically, cyclopropyl, methylcyclopropyl, ethylcyclopropyl, cyclobutyl, methylcyclobutyl, ethylcyclobutyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, Examples thereof include a cyclohexyl group, a methylcyclohexyl group, an ethylcyclohexyl group, a cycloheptyl group, a methylcycloheptyl group, an ethylcycloheptyl group, a cyclooctyl group, a methylcyclooctyl group, and an ethylcyclooctyl group. Among these, a cyclopentyl group and a cyclohexyl group are particularly preferred. As R 2 and R 3 , specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-
Butyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-2-propenyl group, 1-methylenepropyl group, 1-methyl-2-propenyl group, 1,2-dimethylvinyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-methyl-2-methylpropyl group, 2,2-dimethylpropyl group And other linear or branched alkyl groups having 1 to 12 carbon atoms such as hexyl, octyl, nonyl and decyl, phenyl, toluyl, methoxyphenyl, naphthyl, pyridyl, R 2 and R 3 , Piperidine, piperazine, pyrrolidine, morpholine, etc. directly or via one or more nitrogen, sulfur and / or oxygen atoms. Among these, an alkyl group having 1 to 12 carbon atoms is preferable, and an ethyl group, an n-propyl group and an isopropyl group are particularly preferable.
【0015】前記一般式[1]で表される化合物の中で
好ましい化合物の具体例としては、次式で示される化合
物を挙げることができる。Specific examples of preferred compounds among the compounds represented by the general formula [1] include compounds represented by the following formula.
【化7】 ・・・・・・[2]Embedded image ... [2]
【0016】このような前記一般式[1]で表されるカ
ーバメート化合物は、単独で、若しくは2種類以上を組
み合わせて使用することができ、本発明ではこれらのカ
ーバメート類を非水溶媒に含有させることにより電池の
過充電時における圧力開放装置の速やかな作動を促し、
電池電圧の上昇を抑制し、電池温度や電池内圧の急速な
上昇を防止することができる。These carbamate compounds represented by the above general formula [1] can be used alone or in combination of two or more. In the present invention, these carbamates are contained in a non-aqueous solvent. This facilitates the quick operation of the pressure relief device when the battery is overcharged,
A rise in battery voltage can be suppressed, and a rapid rise in battery temperature and battery internal pressure can be prevented.
【0017】非水溶媒 本発明に係る非水電解液では、前記一般式[1]で表さ
れるカーバメート類を含む化合物を含有する非水溶媒が
使用される。この化合物は、一般に使われる非水溶媒へ
の添加剤として、あるいは非水溶媒を構成する一溶剤と
して使用することができる。カーバメート化合物は全非
水溶媒(カーバメート化合物と他の非水溶媒の合計量)
に対して0.001重量%以上、好ましくは0.01〜
99.5重量%、さらに好ましくは0.01〜70重量
%、特に好ましくは0.05〜30重量%の量で含まれ
ることが望ましい。このような混合割合で前記一般式
[1]で表されるカーバメート化合物が全非水溶媒に含
有されていると、電池が過充電された場合、圧力開放装
置の速やかな作動を促し、電池電圧の上昇を抑制し、電
池温度や電池内圧の急速な上昇を防止しすることができ
る。本発明では特に、上記カーバメート類と下記一般式
[3a]または[3b]で表される環状炭酸エステルお
よび/または鎖状炭酸エステルとを含む非水溶媒を使用
すると、過充電による電池の急速な発熱や電池内圧の上
昇を防止することができ、且つ電池特性、特に低温特性
及びサイクル特性に優れた非水電解液を得ることができ
るの好ましい。 Nonaqueous Solvent In the nonaqueous electrolyte according to the present invention, a nonaqueous solvent containing a compound containing a carbamate represented by the above general formula [1] is used. This compound can be used as an additive to a commonly used non-aqueous solvent or as a solvent constituting a non-aqueous solvent. Carbamate compounds are all non-aqueous solvents (total amount of carbamate compounds and other non-aqueous solvents)
0.001% by weight or more, preferably 0.01 to
It is desirable that it be contained in an amount of 99.5% by weight, more preferably 0.01 to 70% by weight, particularly preferably 0.05 to 30% by weight. When the carbamate compound represented by the general formula [1] is contained in the total non-aqueous solvent at such a mixing ratio, when the battery is overcharged, prompt operation of the pressure relief device is promoted, and the battery voltage is reduced. , And a rapid increase in battery temperature and battery internal pressure can be prevented. In particular, in the present invention, when a non-aqueous solvent containing the above carbamates and a cyclic carbonate and / or a chain carbonate represented by the following general formula [3a] or [3b] is used, the rapid charging of the battery due to overcharging occurs. Preferably, it is possible to prevent heat generation and increase in battery internal pressure, and to obtain a non-aqueous electrolyte having excellent battery characteristics, especially low-temperature characteristics and cycle characteristics.
【0018】環状炭酸エステルとしては、下記に示す一
般式[3a]または[3b]で表される環状炭酸エステ
ルおよび/または鎖状炭酸エステルを挙げることができ
る。Examples of the cyclic carbonate include a cyclic carbonate and / or a chain carbonate represented by the following general formula [3a] or [3b].
【化8】 [3a] [3b] 式[3a]または[3b]中、R4およびR5は水素原子
または炭素数1〜6のアルキル基を示し、R4およびR5
は同一であっても異なっていてもよい。この中でアルキ
ル基としては、炭素数1〜3のアルキル基が好ましく、
具体的には、メチル基、エチル基、n-プロピル基を例示
することができる。Embedded image [3a] [3b] In the formula [3a] or [3b], R 4 and R 5 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 4 and R 5
May be the same or different. Among them, the alkyl group is preferably an alkyl group having 1 to 3 carbon atoms,
Specific examples include a methyl group, an ethyl group, and an n-propyl group.
【0019】前記一般式[3a]または[3b]で表さ
れる環状炭酸エステルの例として具体的には、エチレン
カーボネート、プロピレンカーボネート、1,2‐ブチレ
ンカーボネート、2,3‐ブチレンカーボネート、1,2‐ペ
ンチレンカーボネート、2,3‐ペンチレンカーボネー
ト、ビニレンカーボネートなどが挙げられる。これらの
中で特に好ましい環状炭酸エステルはエチレンカーボネ
ート、プロピレンカーボネートおよびビニレンカーボネ
ートである。また、これら環状炭酸エステルは2種以上
混合して使用してもよい。Specific examples of the cyclic carbonate represented by the general formula [3a] or [3b] include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate and the like. Among these, particularly preferred cyclic carbonates are ethylene carbonate, propylene carbonate and vinylene carbonate. These cyclic carbonates may be used as a mixture of two or more kinds.
【0020】鎖状炭酸エステルとして具体的には、ジメ
チルカーボネート、メチルエチルカーボネート、ジエチ
ルカーボネート、メチルプロピルカーボネート、メチル
イソプロピルカーボネート、エチルプロピルカーボネー
トなどが挙げられる。またこれら鎖状炭酸エステルは2
種以上混合して使用してもよい。Specific examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, and ethyl propyl carbonate. These chain carbonates are 2
You may mix and use more than one kind.
【0021】このような鎖状炭酸エステルが非水溶媒中
に含まれていると、非水電解液の粘度を低くすることが
可能となり、電解質の溶解度をさらに高め、常温または
低温での電気伝導性に優れた電解液とすることできる。
このため電池の充放電効率、および、例えば、低温にお
ける充放電効率や、低温における負荷特性のような低温
特性を改善することができる。When such a chain carbonate is contained in a non-aqueous solvent, the viscosity of the non-aqueous electrolyte can be reduced, the solubility of the electrolyte can be further increased, and the electric conductivity at normal temperature or low temperature can be improved. It is possible to obtain an electrolytic solution having excellent properties.
Therefore, it is possible to improve the charge / discharge efficiency of the battery and low-temperature characteristics such as, for example, the charge / discharge efficiency at low temperatures and the load characteristics at low temperatures.
【0022】非水溶媒として前記一般式[3a]または
[3b]で表される環状炭酸エステルおよび/または鎖
状炭酸エステルを用いる場合は、前記一般式[1]で表
されるカーバメート類は、それを含む全非水溶媒(前記
一般式[1]で表されるカーバメート化合物と、前記一
般式[3a]または[3b]で表される環状炭酸エステ
ルおよび/または鎖状炭酸エステルとの合計量)に対し
て0.001重量%以上、好ましくは0.01〜99.
5重量%、さらに好ましくは0.01〜70重量%、特
に好ましくは0.05〜30重量%の量で含まれている
ことが望ましい。When the cyclic carbonate and / or chain carbonate represented by the general formula [3a] or [3b] is used as the nonaqueous solvent, the carbamates represented by the general formula [1] All nonaqueous solvents containing the same (the total amount of the carbamate compound represented by the general formula [1] and the cyclic carbonate and / or chain carbonate represented by the general formula [3a] or [3b]) ) To 0.001% by weight or more, preferably 0.01 to 99.%.
It is desirable that it be contained in an amount of 5% by weight, more preferably 0.01 to 70% by weight, particularly preferably 0.05 to 30% by weight.
【0023】また、非水溶媒中の、前記一般式[3a]
または[3b]で表される環状炭酸エステルと鎖状炭酸
エステルとの混合割合は、重量比で表して、環状炭酸エ
ステル:鎖状炭酸エステルが、0:100〜100:
0、好ましくは5:95〜95:5、特に好ましくは2
0:80〜85:15である。Further, the above-mentioned general formula [3a] in a non-aqueous solvent
Alternatively, the mixing ratio of the cyclic carbonate and the chain carbonate represented by [3b] is represented by a weight ratio, and the ratio of the cyclic carbonate: chain carbonate is 0: 100 to 100:
0, preferably 5:95 to 95: 5, particularly preferably 2
0:80 to 85:15.
【0024】したがって、本発明に係わる好ましい非水
溶媒は、前記一般式[1]で表されるカーバメート化合
物と、前記一般式[3a]または[3b]で表される環
状炭酸エステル及び/又は前記鎖状炭酸エステルを含む
ものである。またそれらに加えて、通常電池用非水溶媒
として広く使用されている溶媒をさらに混合使用するこ
とも可能である。使用できる溶媒の例として具体的に
は、蟻酸メチル、蟻酸エチル、蟻酸プロピル、酢酸メチ
ル、酢酸エチル、酢酸プロピル、プロピオン酸メチル、
プロピオン酸エチルなどの鎖状エステル;リン酸トリメ
チルなどのリン酸エステル;ジメトキシエタンなどの鎖
状エーテル;テトラヒドロフランなどの環状エーテル;
ジメチルホルムアミドなどのアミド;γ‐ブチロラクト
ンなどの環状エステル;スルホランなどの環状スルホ
ン; N‐メチルオキサゾリジノンなどの環状カーバメー
ト; N‐メチルピロリドンなどの環状アミド; N,N‐ジ
メチルイミダゾリジノンなどの環状ウレアなどを挙げる
ことができる。Therefore, a preferred non-aqueous solvent according to the present invention is a carbamate compound represented by the general formula [1] and a cyclic carbonate represented by the general formula [3a] or [3b] and / or It contains a chain carbonate. In addition, it is also possible to further mix and use a solvent widely used as a non-aqueous solvent for batteries. Specific examples of the solvent that can be used include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate,
Chain esters such as ethyl propionate; phosphate esters such as trimethyl phosphate; chain ethers such as dimethoxyethane; cyclic ethers such as tetrahydrofuran;
Amide such as dimethylformamide; Cyclic ester such as γ-butyrolactone; Cyclic sulfone such as sulfolane; Cyclic carbamate such as N-methyloxazolidinone; Cyclic amide such as N-methylpyrrolidone; Cyclic urea such as N, N-dimethylimidazolidinone And the like.
【0025】非水電解液 本発明の非水電解液は、前述した特定のカーバメート化
合物を含有する非水溶媒と電解質とからなっており、例
えば前述した特定のカーバメート化合物を含有する非水
溶媒に電解質を溶解してなるものである。使用される電
解質としては、通常、非水電解液用電解質として使用さ
れているものであれば、いずれをも使用することができ
る。 Nonaqueous Electrolyte The nonaqueous electrolyte of the present invention comprises a nonaqueous solvent containing the above-mentioned specific carbamate compound and an electrolyte. For example, the nonaqueous solvent containing the above specific carbamate compound contains It is obtained by dissolving an electrolyte. As the electrolyte to be used, any electrolyte which is usually used as an electrolyte for a non-aqueous electrolyte can be used.
【0026】電解質の具体例としては、LiPF6、Li
BF4、LiClO4、LiAsF6、Li 2SiF6、LiC4F
9SO3、LiC8F17SO3などのリチウム塩が挙げられ
る。また、次の一般式で示されるリチウム塩も使用する
ことができる。LiOSO2R6、LiN(SO2R7)(SO2
R8)、LiC(SO2R9)(SO2R10)(SO2R11)、LiN
(SO2OR12)(SO2OR13)(ここで、R6〜R13は、
互いに同一であっても異なっていてもよく、炭素数1〜
6のパーフルオロアルキル基である)。これらのリチウ
ム塩は単独で使用してもよく、また2種以上を混合して
使用してもよい。As a specific example of the electrolyte, LiPF6, Li
BFFour, LiClOFour, LiAsF6, Li TwoSiF6, LiCFourF
9SOThree, LiC8F17SOThreeLithium salts such as
You. In addition, a lithium salt represented by the following general formula is also used.
be able to. LiOSOTwoR6, LiN (SOTwoR7) (SOTwo
R8), LiC (SOTwoR9) (SOTwoRTen) (SOTwoR11), LiN
(SOTwoOR12) (SOTwoOR13) (Where R6~ R13Is
They may be the same or different from each other and have 1 to 1 carbon atoms.
6 is a perfluoroalkyl group). These lithu
Salt may be used alone or as a mixture of two or more.
May be used.
【0027】これらの内、特に、LiPF6、LiBF4、
LiOSO2R6、LiN(SO2R7)(SO2R8)、LiC(S
O2R9)(SO2R10)(SO2R11)、LiN(SO2OR12)
(SO2OR13)が好ましい。Of these, LiPF 6 , LiBF 4 ,
LiOSO 2 R 6 , LiN (SO 2 R 7 ) (SO 2 R 8 ), LiC (S
O 2 R 9 ) (SO 2 R 10 ) (SO 2 R 11 ), LiN (SO 2 OR 12 )
(SO 2 OR 13 ) is preferred.
【0028】このような電解質は、通常、0.1〜3モ
ル/リットル、好ましくは0.5〜2モル/リットルの
濃度で非水電解液中に含まれていることが望ましい。It is desirable that such an electrolyte is usually contained in the non-aqueous electrolyte at a concentration of 0.1 to 3 mol / l, preferably 0.5 to 2 mol / l.
【0029】本発明における非水電解液は、上記特定の
カーバメート化合物を含有する非水溶媒と電解質とを必
須構成成分として含むが、必要に応じて他の添加剤等を
加えてもよい。The non-aqueous electrolyte in the present invention contains a non-aqueous solvent containing the above-mentioned specific carbamate compound and an electrolyte as essential components, but other additives may be added as necessary.
【0030】以上のような本発明に係る非水電解液は、
リチウムイオン二次電池用の非水電解液として好適であ
るばかりでなく、一次電池用の非水電解液としても用い
ることが出来る。The non-aqueous electrolyte according to the present invention as described above comprises:
Not only is it suitable as a non-aqueous electrolyte for lithium ion secondary batteries, but it can also be used as a non-aqueous electrolyte for primary batteries.
【0031】二次電池 本発明に係る非水電解液二次電池は、負極と、正極と、
前記の非水電解液とを基本的に含んで構成されており、
通常負極と正極との間にセパレータが設けられている。The non-aqueous electrolyte secondary battery according to the present invention comprises a negative electrode, a positive electrode,
The non-aqueous electrolyte is basically configured to include,
Usually, a separator is provided between the negative electrode and the positive electrode.
【0032】負極を構成する負極活物質としては、金属
リチウム、リチウム合金、リチウムイオンをドーブ・脱
ドーブすることが可能な炭素材料のいずれを用いること
ができる。これらの中でもリチウムイオンをドーブ・脱
ドーブすることが可能な炭素材料が好ましい。このよう
な炭素材料は、グラファイトであっても非晶質炭素であ
ってもよく、活性炭、炭素繊維、カーボンブラック、メ
ソカーボンマイクロビーズなどが用いられる。As the negative electrode active material constituting the negative electrode, any of lithium metal, a lithium alloy, and a carbon material capable of doping / de-doping lithium ions can be used. Among these, a carbon material capable of doving / de-doping lithium ions is preferable. Such a carbon material may be graphite or amorphous carbon, and activated carbon, carbon fiber, carbon black, mesocarbon microbeads and the like are used.
【0033】正極を構成する正極活物質としては、Mo
S2、TiS2、MnO2、V2O5などの遷移金属酸化物ま
たは遷移金属硫化物、LiCoO2、LiMnO2、LiMn2
O4、LiNiO2などのリチウムと遷移金属とからなる複
合酸化物が挙げられる。これ等の中でも、特にリチウム
と遷移金属とからなる複合酸化物が好ましい。負極がリ
チウム金属またはリチウム合金である場合は、正極とし
て炭素材料を用いることもできる。また、正極として、
リチウムと遷移金属の複合酸化物と炭素材料との混合物
を用いることもできる。As the positive electrode active material constituting the positive electrode, Mo is used.
Transition metal oxides or sulfides such as S 2 , TiS 2 , MnO 2 , V 2 O 5 , LiCoO 2 , LiMnO 2 , LiMn 2
A composite oxide composed of lithium and a transition metal such as O 4 and LiNiO 2 can be used. Among these, a composite oxide composed of lithium and a transition metal is particularly preferable. When the negative electrode is a lithium metal or lithium alloy, a carbon material can be used as the positive electrode. Also, as a positive electrode,
A mixture of a composite oxide of lithium and a transition metal and a carbon material can also be used.
【0034】セパレータは多孔性の膜であって、通常微
多孔性ポリマーフィルムが好適に使用される。特に、多
孔性ポリオレフィンフィルムが好ましく、具体的には多
孔性ポリエチレンフィルム、多孔性ポリプロピレンフィ
ルム、または多孔性のポリエチレンフィルムとポリプロ
ピレンとの多層フィルムを例示することができる。The separator is a porous membrane, and usually a microporous polymer film is suitably used. In particular, a porous polyolefin film is preferable, and specific examples thereof include a porous polyethylene film, a porous polypropylene film, and a multilayer film of a porous polyethylene film and polypropylene.
【0035】このような非水電解液二次電池は、円筒
型、コイン型、角型、その他任意の形状に形成すること
ができる。しかし、電池の基本構造は形状によらず同じ
であり、目的に応じて設計変更を施すことができる。次
に、円筒型およびコイン型電池の構造について説明する
が、各電池を構成する負極活物質、正極活物質およびセ
パレータは、前記したものが共通して使用される。Such a non-aqueous electrolyte secondary battery can be formed in a cylindrical shape, a coin shape, a square shape, or any other shape. However, the basic structure of the battery is the same regardless of the shape, and the design can be changed according to the purpose. Next, the structures of the cylindrical and coin type batteries will be described. The negative electrode active material, the positive electrode active material, and the separator constituting each battery are commonly used.
【0036】例えば、円筒型非水電解液二次電池の場合
には、負極集電体に負極活物質を塗布してなる負極と、
正極集電体に正極活物質を塗布してなる正極とを、非水
電解液を注入したセバレータを介して巻回し、巻回体の
上下に絶縁板を載置した状態で電池缶に収納されてい
る。For example, in the case of a cylindrical non-aqueous electrolyte secondary battery, a negative electrode obtained by applying a negative electrode active material to a negative electrode current collector,
A positive electrode formed by applying a positive electrode active material to a positive electrode current collector is wound through a severator in which a non-aqueous electrolyte is injected, and is housed in a battery can with an insulating plate placed above and below the wound body. ing.
【0037】また、本発明に係る非水電解液二次電池
は、コイン型非水電解液二次電池にも適用することがで
きる。コイン型電池では、円盤状負極、セパレータ、円
盤状正極、およびステンレスの板が、この順序に積層さ
れた状態でコイン型電池缶に収納されている。The non-aqueous electrolyte secondary battery according to the present invention can be applied to a coin-type non-aqueous electrolyte secondary battery. In a coin-type battery, a disk-shaped negative electrode, a separator, a disk-shaped positive electrode, and a stainless steel plate are housed in a coin-type battery can in a state of being stacked in this order.
【0038】[0038]
【実施例】以下、実施例および比較例を通して本発明を
具体的に説明するが、本発明はこれら実施例に限定され
るものではない。EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
【0039】[0039]
【実施例1】<非水電解液の調製>エチレンカーボネー
ト(EC)とジエチルカーボネート(DEC)とを、E
C:DEC=58:42(重量比)の割合で混合した
後、この混合溶媒95重量部に対して下記構造式で表わ
されるシクロヘキシル-N,N-ジエチルカーバメート
(以下CHyECAと略すことがある)を5重量部添加
し、CHyECAの量が非水溶媒全体(ECとDECと
CHyECAとの合計量)に対して5重量%となるよう
非水溶媒を調製した。次に電解質であるLiPF6を非
水溶媒に溶解し、電解質濃度が1.0モル/リットルと
なるように非水電解液を調製した。Example 1 <Preparation of non-aqueous electrolyte> Ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed with E
After mixing at a ratio of C: DEC = 58: 42 (weight ratio), cyclohexyl-N, N-diethylcarbamate (hereinafter sometimes abbreviated as CHyECA) represented by the following structural formula with respect to 95 parts by weight of the mixed solvent. Was added to prepare a non-aqueous solvent such that the amount of CHyECA was 5% by weight based on the total amount of the non-aqueous solvent (the total amount of EC, DEC, and CHyECA). Next, LiPF 6 as an electrolyte was dissolved in a non-aqueous solvent, and a non-aqueous electrolyte was prepared so that the electrolyte concentration was 1.0 mol / L.
【化9】 ・・・・・[2]Embedded image .... [2]
【0040】<負極の作製>大阪ガス(株)製のメソカ
ーボンマイクロビーズ(商品名;MCMB6−28、d
002=0.337nm、密度2.17g/cm3)の
炭素粉末90重量部と、結着剤としてのポリフッ化ビニ
リデン(PVDF)10重量部とを混合し、溶剤のN‐
メチルピロリドンに分散させ、ペースト状の負極合剤ス
ラリーを調製した。次に、この負極合剤スラリーを厚さ
20μmの帯状銅箔製の負極集電体に塗布し、乾燥させ
て帯状の炭素負極を得た。乾燥後の負極合剤の厚さは2
5μmであった。さらに、この帯状電極を直径15mm
の円盤状に打ち抜いた後、圧縮成形して負極電極とし
た。<Preparation of Negative Electrode> Mesocarbon microbeads (trade name: MCMB6-28, d, manufactured by Osaka Gas Co., Ltd.)
002 = 0.337 nm, 90 parts by weight of carbon powder having a density of 2.17 g / cm 3 ) and 10 parts by weight of polyvinylidene fluoride (PVDF) as a binder were mixed, and N-
The paste was dispersed in methylpyrrolidone to prepare a paste-like negative electrode mixture slurry. Next, this negative electrode mixture slurry was applied to a negative electrode current collector made of a 20-μm-thick strip-shaped copper foil, and dried to obtain a strip-shaped carbon negative electrode. The thickness of the negative electrode mixture after drying is 2
It was 5 μm. Furthermore, this strip electrode is 15 mm in diameter.
, And compression molded to form a negative electrode.
【0041】<正極の作製>本庄ケミカル(株)製のL
iCoO2(製品名:HLC−21、平均粒径8μm)
微粒子91重量部と、導電材としてのグラファイト6重
量部と、結着剤としてのポリフッ化ビニリデン(PVD
F)3重量部とを混合して正極合剤を調製し、N‐メチ
ルピロリドンに分散させて正極合剤スラリーを得た。こ
のスラリーを厚さ20μmの帯状アルミニウム箔製正極
集電体に塗布し、乾燥させ、圧縮成形によって帯状正極
を得た。乾燥後の正極合剤の厚さは40μmであった。
その後、この帯状電極を直径15mmの円盤状に打ち抜
くことによって正極電極とした。<Preparation of Positive Electrode> L manufactured by Honjo Chemical Co., Ltd.
iCoO 2 (product name: HLC-21, average particle size 8 μm)
91 parts by weight of fine particles, 6 parts by weight of graphite as a conductive material, and polyvinylidene fluoride (PVD) as a binder
F) was mixed with 3 parts by weight to prepare a positive electrode mixture, and dispersed in N-methylpyrrolidone to obtain a positive electrode mixture slurry. This slurry was applied to a 20-μm-thick aluminum foil positive electrode current collector, dried, and compression-molded to obtain a belt-shaped positive electrode. The thickness of the positive electrode mixture after drying was 40 μm.
Thereafter, the strip-shaped electrode was punched into a disk having a diameter of 15 mm to obtain a positive electrode.
【0042】<電池の作製>このようにして得られた円
盤状負極および円盤状正極、さらに厚さ25μm、直径
19mmの微多孔性ポリプロピレンフィルムからできた
セパレータを用意した。ステンレス製の2032サイズ
の電池缶内に、負極、セパレータ、正極の順序で各々を
積層した後、セパレータに前記非水電解液を注入した。
その後、電池缶内にステンレス製の板(厚さ2.4m
m、直径15.4mm)を収納し、さらにポリプロピレ
ン製のガスケットを介して、電池缶(蓋)をかしめた。
この結果、電池内の気密性が保持でき、直径20mm、
高さ3.2mmのボタン型非水電解液二次電池が得られ
た。<Preparation of Battery> A disk-shaped negative electrode and a disk-shaped positive electrode thus obtained, and a separator made of a microporous polypropylene film having a thickness of 25 μm and a diameter of 19 mm were prepared. After each of the negative electrode, the separator, and the positive electrode were laminated in the order of a 2032-sized stainless steel battery can, the nonaqueous electrolyte was injected into the separator.
Then, a stainless steel plate (2.4 m thick) was placed in the battery can.
m, diameter 15.4 mm), and the battery can (lid) was caulked via a gasket made of polypropylene.
As a result, the airtightness in the battery can be maintained, the diameter is 20 mm,
A button-type nonaqueous electrolyte secondary battery having a height of 3.2 mm was obtained.
【0043】<電池膨張率と電池電圧の測定>過充電時
に電池電圧が上昇すると、電池温度や電池内圧の急速な
上昇が起こる。これを防止するためには、過充電時に、
電池電圧の上昇を抑制し(即ち過充電時の電圧(終了電
圧)が小さく)、かつ圧力開放装置の速やかな作動を促
すため、ガス発生をする(即ち電池膨膨張率が大きい)
非水電解液が好ましい。これら非水電解液を用いた電池
の過充電時の電池電圧とガス発生を以下の方法で評価し
た。作製したボタン型二次電池を用い、室温にて1サイ
クルのみ2.8V−4.2Vで1mAにて充放電を行っ
た。次に、1mAの定電流で12分充電、3分休止を3
0回繰り返した後、電池厚み(これを試験後電池厚みと
する)と電池電圧(これを終了電圧とする)を測定し
た。測定した電池厚みから下式により電池膨張率を算出
した。結果を表1に示した。なお、電池の膨張は、発生
したガスによるものであり、その他部材の膨張によるも
のではない。<Measurement of Battery Expansion Rate and Battery Voltage> When the battery voltage rises during overcharge, a rapid rise in the battery temperature and battery internal pressure occurs. To prevent this, at the time of overcharge,
In order to suppress the rise in battery voltage (that is, the voltage at the time of overcharge (the end voltage) is small) and to promptly operate the pressure relief device, gas is generated (that is, the battery expansion rate is large).
Non-aqueous electrolytes are preferred. The battery voltage and gas generation during overcharging of the battery using these non-aqueous electrolytes were evaluated by the following methods. Using the produced button-type secondary battery, charging and discharging were performed at 2.8 V to 4.2 V and 1 mA at room temperature for only one cycle. Next, charge at a constant current of 1 mA for 12 minutes, and pause for 3 minutes for 3 minutes.
After repeating 0 times, the battery thickness (this was taken as the battery thickness after the test) and the battery voltage (this was taken as the termination voltage) were measured. The battery expansion coefficient was calculated from the measured battery thickness by the following equation. The results are shown in Table 1. The expansion of the battery is due to the generated gas, not to the expansion of other members.
【0044】電池膨張率(%)=〔(試験後電池厚み−試験
前電池厚み)/試験後電池厚み〕×100Battery expansion coefficient (%) = [(battery thickness after test−battery thickness before test) / battery thickness after test] × 100
【0045】[0045]
【比較例1】実施例1において、シクロヘキシル-N,
N-ジエチルカーバメート(CHyECA)を添加しな
かった以外は、実施例1と同様にして、非水電解液の調
製および電池の作製を行い、実施例1と同様にして電池
膨張率と電池電圧を評価した。結果を表1に表わす。Comparative Example 1 In Example 1, cyclohexyl-N,
Except that N-diethylcarbamate (CHyECA) was not added, a non-aqueous electrolyte solution was prepared and a battery was prepared in the same manner as in Example 1. The battery expansion coefficient and battery voltage were measured in the same manner as in Example 1. evaluated. The results are shown in Table 1.
【0046】[0046]
【表1】 [Table 1]
【0047】[0047]
【発明の効果】本発明の非水電解液は、電池の過充電時
における圧力開放装置の速やかな作動を促し、電池電圧
の上昇を抑制し、電池温度や電池内圧の急速な上昇を防
止しすることができる。従って、この非水電解液は、リ
チウムイオン二次電池用の非水電解液として特に好適で
あり、本発明ではこの非水電解液を用いることにより、
電池温度や、電池内圧の急激な上昇を防止することがで
きる二次電池を提供することができた。The non-aqueous electrolyte of the present invention promotes the rapid operation of the pressure relief device at the time of overcharging of the battery, suppresses the rise of the battery voltage, and prevents the rapid rise of the battery temperature and the internal pressure of the battery. can do. Therefore, this non-aqueous electrolyte is particularly suitable as a non-aqueous electrolyte for a lithium ion secondary battery, and in the present invention, by using this non-aqueous electrolyte,
A secondary battery capable of preventing a rapid increase in battery temperature and battery internal pressure was provided.
フロントページの続き (72)発明者 尾身 毅彦 千葉県袖ヶ浦市長浦字拓二号580番32 三 井化学株式会社内 (72)発明者 石田 達麗 千葉県袖ヶ浦市長浦字拓二号580番32 三 井化学株式会社内 (72)発明者 大西 仁志 千葉県袖ヶ浦市長浦字拓二号580番32 三 井化学株式会社内 Fターム(参考) 5H029 AJ12 AK02 AK03 AK05 AK06 AK18 AL06 AL07 AL08 AL12 AM02 AM03 AM04 AM05 AM07 DJ08 EJ11 HJ02 Continuing from the front page (72) Inventor Takehiko Omi 580-32, Takuji, Nagaura-shi, Sodegaura-shi, Chiba (72) Inventor Tatsuri Ishida 580-32-3, Takuji, Nagaura, Sodegaura-shi, Chiba (72) Inventor Hitoshi Onishi 580-32 Takuji, Nagaura-shi, Sodegaura-shi, Chiba F-term (reference) 5H029 AJ12 AK02 AK03 AK05 AK06 AK18 AL06 AL07 AL08 AL12 AM02 AM03 AM04 AM05 AM07 DJ08 EJ11 HJ02
Claims (9)
物を含有する非水溶媒と電解質とからなることを特徴と
する非水電解液。 【化1】 ……[1] (式[1]中、R1は炭素数3〜12のシクロアルキル
基であり、R2およびR3は互いに同じであっても異なっ
ていてもよく、酸素原子、窒素原子及び硫黄原子から選
ばれた少なくとも1種の原子を含むことがある炭素数1
〜12の炭化水素基である。)1. A non-aqueous electrolyte comprising a non-aqueous solvent containing a carbamate compound represented by the general formula [1] and an electrolyte. Embedded image ... [1] (In formula [1], R 1 is a cycloalkyl group having 3 to 12 carbon atoms, and R 2 and R 3 may be the same or different from each other, and include an oxygen atom, a nitrogen atom And 1 carbon atom which may contain at least one atom selected from sulfur atoms
To 12 hydrocarbon groups. )
次の化学式で表されるいずれかの化合物であることを特
徴とする請求項1記載の非水電解液。 【化2】 ……[2]2. A compound represented by the general formula [1]:
The non-aqueous electrolyte according to claim 1, wherein the non-aqueous electrolyte is any compound represented by the following chemical formula. Embedded image ... [2]
れるカーバメート化合物と、一般式[3a]または[3
b]で表される環状炭酸エステルおよび/または鎖状炭
酸エステルとを含むことを特徴とする請求項1記載の非
水電解液。 【化3】 [3a] [3b] (式[3a]または[3b]中、R4およびR5は水素原
子または炭素数1〜6のアルキル基を示し、R4および
R5は同一であっても異なっていてもよい。)3. The method according to claim 1, wherein the non-aqueous solvent comprises a carbamate compound represented by the general formula [1] and a carbamate compound represented by the general formula [3a] or [3]:
2. The non-aqueous electrolyte according to claim 1, comprising a cyclic carbonate and / or a chain carbonate represented by b). Embedded image [3a] [3b] (In the formula [3a] or [3b], R 4 and R 5 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 4 and R 5 are different even if they are the same. May be.)
れる環状炭酸エステルが、エチレンカーボネート、プロ
ピレンカーボネート、ブチレンカーボネート及びビニレ
ンカーボネートからなる群から選ばれた化合物であるこ
とを特徴とする請求項3記載の非水電解液。4. The cyclic carbonate represented by the general formula [3a] or [3b] is a compound selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate and vinylene carbonate. The non-aqueous electrolyte according to claim 3.
ネート、ジエチルカーボネート及びメチルエチルカーボ
ネートからなる群から選ばれた化合物であることを特徴
とする請求項3記載の非水電解液。5. The non-aqueous electrolyte according to claim 3, wherein said chain carbonate is a compound selected from the group consisting of dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate.
合物が、全非水溶媒に対して0.01〜99.5重量%
含まれていることを特徴とする請求項1ないし5記載の
非水電解液。6. The carbamate compound represented by the general formula [1] is contained in an amount of 0.01 to 99.5% by weight based on the total amount of the nonaqueous solvent.
6. The non-aqueous electrolyte according to claim 1, wherein the non-aqueous electrolyte is contained.
る請求項1ないし6記載の非水電解液。7. The non-aqueous electrolyte according to claim 1, wherein the electrolyte is a lithium salt.
電解液を含む二次電池。8. A secondary battery comprising the non-aqueous electrolyte according to claim 1.
含有合金、リチウムイオンのドープ・脱ドープが可能な
炭素材料のいずれかを含む負極と、正極活物質としてリ
チウムと遷移金属の複合酸化物、炭素材料またはこれら
の混合物のいずれかを含む正極と、請求項1ないし7記
載のいずれかの非水電解液とを含むことを特徴とするリ
チウムイオン二次電池。9. A negative electrode containing any of lithium metal, a lithium-containing alloy and a carbon material capable of doping / dedoping lithium ions as a negative electrode active material, a composite oxide of lithium and a transition metal as a positive electrode active material, A lithium ion secondary battery comprising: a positive electrode containing any of the materials or a mixture thereof; and the nonaqueous electrolyte according to any one of claims 1 to 7.
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JP3963611B2 JP3963611B2 (en) | 2007-08-22 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009545129A (en) * | 2006-07-28 | 2009-12-17 | エルジー・ケム・リミテッド | Secondary battery using eutectic mixture and manufacturing method thereof |
US20100196766A1 (en) * | 2007-04-11 | 2010-08-05 | Lg Chem, Ltd. | Secondary battery comprising ternary eutectic mixtures and preparation method thereof |
Families Citing this family (1)
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---|---|---|---|---|
JP2014010976A (en) * | 2012-06-28 | 2014-01-20 | Sony Corp | Electrolyte for nonaqueous secondary battery, nonaqueous secondary battery, battery pack, electric vehicle, power storage system, electric power tool, and electronic apparatus |
-
1999
- 1999-06-02 JP JP15553199A patent/JP3963611B2/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009545129A (en) * | 2006-07-28 | 2009-12-17 | エルジー・ケム・リミテッド | Secondary battery using eutectic mixture and manufacturing method thereof |
US20100196766A1 (en) * | 2007-04-11 | 2010-08-05 | Lg Chem, Ltd. | Secondary battery comprising ternary eutectic mixtures and preparation method thereof |
US8546023B2 (en) * | 2007-04-11 | 2013-10-01 | Lg Chem, Ltd. | Secondary battery comprising ternary eutectic mixtures and preparation method thereof |
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JP3963611B2 (en) | 2007-08-22 |
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