CN102264926A - 五元环阴离子盐及其作为电解质的用途 - Google Patents
五元环阴离子盐及其作为电解质的用途 Download PDFInfo
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- CN102264926A CN102264926A CN2009801381915A CN200980138191A CN102264926A CN 102264926 A CN102264926 A CN 102264926A CN 2009801381915 A CN2009801381915 A CN 2009801381915A CN 200980138191 A CN200980138191 A CN 200980138191A CN 102264926 A CN102264926 A CN 102264926A
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- Prior art keywords
- salt
- compound
- charged ion
- och
- carbon atom
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- -1 anion salt Chemical class 0.000 title claims abstract description 36
- 239000003792 electrolyte Substances 0.000 title claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims description 71
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 239000002608 ionic liquid Substances 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 10
- 150000002460 imidazoles Chemical class 0.000 claims description 9
- 125000002524 organometallic group Chemical group 0.000 claims description 9
- 150000002892 organic cations Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001767 cationic compounds Chemical group 0.000 claims description 6
- 229910001411 inorganic cation Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 5
- 150000003053 piperidines Chemical class 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 5
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 claims description 4
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical class CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 230000005518 electrochemistry Effects 0.000 claims description 4
- 150000003217 pyrazoles Chemical class 0.000 claims description 4
- 150000001449 anionic compounds Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- YMRPKBLFDBUOAJ-UHFFFAOYSA-N 5-butyl-2-methyl-1h-imidazole Chemical class CCCCC1=CN=C(C)N1 YMRPKBLFDBUOAJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000005495 cold plasma Effects 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- XTPRURKTXNFVQT-UHFFFAOYSA-N hexyl(trimethyl)azanium Chemical compound CCCCCC[N+](C)(C)C XTPRURKTXNFVQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002082 metal nanoparticle Substances 0.000 claims description 2
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- DLXHXAPHMVWFGO-UHFFFAOYSA-N triethyl(2-methoxyethyl)azanium Chemical compound CC[N+](CC)(CC)CCOC DLXHXAPHMVWFGO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 2
- 150000001450 anions Chemical class 0.000 abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- 159000000002 lithium salts Chemical class 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 229910003002 lithium salt Inorganic materials 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 150000001721 carbon Chemical group 0.000 description 11
- 150000008040 ionic compounds Chemical class 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000031709 bromination Effects 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001241 acetals Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000007096 poisonous effect Effects 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 0 *C(NC1C#N)NC1C#N Chemical compound *C(NC1C#N)NC1C#N 0.000 description 2
- TWAYCBAMBSDJDT-UHFFFAOYSA-N 1-$l^{1}-oxidanylpyrrolidine-2,5-dione Chemical compound [O-][N+]1C(=O)CCC1=O TWAYCBAMBSDJDT-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- IVANFNGOSJTZFM-UHFFFAOYSA-N 2h-triazole-4,5-dicarbonitrile Chemical compound N#CC1=NNN=C1C#N IVANFNGOSJTZFM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000006501 nitrophenyl group Chemical group 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- ZJIFDEVVTPEXDL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) hydrogen carbonate Chemical group OC(=O)ON1C(=O)CCC1=O ZJIFDEVVTPEXDL-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- XGDRLCRGKUCBQL-UHFFFAOYSA-N 1h-imidazole-4,5-dicarbonitrile Chemical group N#CC=1N=CNC=1C#N XGDRLCRGKUCBQL-UHFFFAOYSA-N 0.000 description 1
- FIGYYXIYTVBRJV-UHFFFAOYSA-N 1h-imidazole;lithium Chemical compound [Li].C1=CNC=N1 FIGYYXIYTVBRJV-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical group C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- MBVGJZDLUQNERS-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound FC(F)(F)C1=NC(C#N)=C(C#N)N1 MBVGJZDLUQNERS-UHFFFAOYSA-N 0.000 description 1
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical compound OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- FMYCPRQGKSONCP-UHFFFAOYSA-N Acetal R Chemical compound CCCOC(C)OCCC1=CC=CC=C1 FMYCPRQGKSONCP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- DTIODQURVIMKJN-UHFFFAOYSA-N FC(C(=O)O)F.[Cl] Chemical compound FC(C(=O)O)F.[Cl] DTIODQURVIMKJN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
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- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
Description
技术领域
本发明涉及用于制备用于电池的电解质的离子化合物。
背景技术
在非水介质(特别是非质子介质,更常称作“质子惰性”介质)中的电解质溶液在技术上很重要,因为它们可以拓展电池可以没有副反应(比如溶剂分解)地操作的电势范围,所述电势在水中不超过1.3V的值。
能够溶解盐的介质主要是极性有机溶剂或溶剂化聚合物,特别是那些包括分布在大分子链中的醚基的介质,其结构可以是直链或支链,梳状,具有或不具有交联结点。具有-CH2CH2O-重复单元的聚醚因其高溶剂化能力而特别有价值。
也已知离子液体,所述产品是在低温下熔融的盐,由至少一种具有离域电荷的阳离子(比如(乙基)(甲基)咪唑鎓(EMI)、(甲基)(丙基)吡咯烷鎓或二乙基甲基(2-甲氧基乙基)铵)和阴离子组成,优选阴离子本身也具有在大体积上离域的电荷,以减小阳离子和阴离子之间的相互作用,由此可以实现低固化温度。
旨在引入电解质所需的离子型导电性的溶解物选自金属盐和选自通过一种或多种元素(比如N、O、S、P、As或I)的自由电子对和质子或有机基团结合以形成阳离子而获得的“鎓”盐。可以提到铵、鏻、锍、碘鎓、吡啶鎓、咪唑鎓、噁唑鎓和噻唑鎓离子。在金属中,特别重要的是碱金属和碱土金属盐,特别是锂盐。锂离子实际上具有非常丰富的电化学性,可以形成具有高能量密度的电池,这在现代技术中非常重要。作为非水电解质的其它应用,可以提到电致变色系统和超级电容。
充当阳离子对电荷的阴离子选自那些显示离域负电荷的阳离子,因为质子惰性电解质不能和负电荷形成氢原子,且离域是在这些条件下获得可感知的分解的仅有方法。在最著名的阴离子中,可以提及ClO4 -、BF4 -、PF6 -、AsF6 -或SbF6 -。ClO4 -阴离子可以形成爆炸性混合物。来源于As和Sb的阴离子是有毒和不常见的。BF4 -阴离子相对轻微分离。LiPF6阴离子的盐在锂发电机中最广为使用,不过具有大的劣势:i)它们非常易于水解,释放HF,HF有毒且对电极材料有腐蚀性。HF从正极释放阳离子(Mn、Fe等)并使它们迁移到负极,它们在那里被还原(Mn°、Fe°等),这显著增大该电极的界面阻抗,减小可用功率和寿命;ii)酸/碱平衡释放非常强的能够特别对酯或醚(由所述酯或醚可以形成电解质溶剂)诱发碳阳离子化学破坏的路易斯酸;iii)在强加热的不受控反应(“失控反应”)的情况下,LiPF6可以充当氟化剂,得到单氟乙醇或单氟乙酸衍生物,它们非常有毒。
也已知无氟的配位阴离子,特别是双(草酸)硼酸根离子[B(C2O4)2]-,其采用便宜的元素;然而,它的锂盐的导电性有限。所述阴离子的刚性及其大尺寸在包括碳酸乙烯酯的标准电解质中产生不利的相图(低温下的导电性差)。此外,该阴离子在高温(65℃)下对氧化具有非常有限的稳定性,这引起自放电和气体释放的问题。
已知其它显示高电化学稳定性和高导电性的阴离子,包括液体和聚合物。其中,形成阴离子液体的阴离子最有效。主要的种类是磺酰亚胺[(RFSO2)2N]-,它的最重要的代表符合RF=CF3(TFSI)。一方面,这些盐的劣势是由于将所述盐用于电池或超级电容(带有具有由铝制成的集流体的电极)时在超过3.6V vs.Li+:Li°时缺乏铝的钝化。另一个劣势是高制备成本,这和CF3SO2合成纤维的价格有关。[(FSO2)2N]-阴离子就铝的腐蚀而言,具有较良好的性质,但制备非常昂贵,且锂盐的稳定性有限(130℃)。通常,当形成包括共价阴离子的盐作为可溶性铝盐(比如,例如,TFSI盐[(CF3SO2)2N]3Al,它稳定且非常易溶)的电解质,所述电解质不能钝化金属表面时,似乎铝的腐蚀在3.6伏特以上不可避免。另一方面,配位阴离子(比如PF6 -)不形成(PF6)3Al但形成AlF3盐,它不溶且钝化。
其它阴离子(“Hückel阴离子”)基于应用于包括五个原子的环的Hückel(4n+2)规则(它预言了芳香族系统的稳定性),其负电荷非常有利。这些阴离子中最著名的是4,5-二氰基三唑(DCTA):
根据是否考虑腈基的C≡N键的电子,这个纯共价阴离子可看作6“π”电子构型或10“π”电子构型,各个这些构型稳定。DCTA盐在最高300℃热稳定。此外,DCTA阴离子不包括氟且它易于从工业前驱体二氨基顺丁烯腈(DAMN)制造:
然而,这个阴离子的劣势在于其锂盐相对适度的导电率(EC-DMC 50/50中2.9mS.cm-1),特别是氧化电势为3.7V vs.Li+:Li°,这以完全不能接受的方式将它的用途限制于电极材料比如过渡金属氧化物,LixTMO2(0<x<1),TM=Mn、Ni或Co,磷酸锰LiMnPO4或它和磷酸铁LiMn1-yFeyPO4(0<y<1)的固溶体。即使对于电势为3.5V vs.Li+:Li°的磷酸铁(y=1),为电极充电结束时的安全边界也太小。
阴离子的盐符合下式:
其中R是吸电子基,例如已知全氟烷基磺酰基或全氟烷基羰基,特别是从EP-0 850 933-A已知。然而,尽管R基的吸引力高,和阳离子产生非常强的相互作用的氧(C=O和O=S=O)的存在限制分解。另外,C=O或S=O基团和环共轭,且“π”电子数是4的倍数。由此带来的是系统“抗芳香”且它们因此对于氧化和对于还原具有较低的稳定性。此外,这类化合物的制备非常难且不能从DAMN开始在单个阶段中进行。
M.Bukowska等人[Polish J.Chem.,78,417-422(2004)]描述了2-三氟甲基-4,5-二氰基咪唑的合成。相应的锂盐可以通过和碳酸锂反应而获得。
发明内容
本发明的目的在于提供可在锂电化学装置中用作电解质的盐,所述盐在高温和大于4V vs.Li+:Li°的电势下稳定。
根据本发明的化合物(I)具有化合价为m(1≤m≤3)的阳离子M和m个符合下式的阴离子:
其中Rf是-CFZ′Z″基团,其中:
-Z′是F或具有1到3个碳原子的全氟烷基,
-Z″是H、F或Cl基、具有1到5个碳原子的任选地氟化或全氟化的烷氧基、具有1到5个碳原子的任选地氟化或全氟化的氧杂烷氧基(oxaalcoxy)或具有1到5个碳原子的任选地氟化或全氟化的烷基;当M是Li且Z’是F时Z”不是F。
可以提到下列Rf基团作为实例:CF2H、CF2Cl、C2F5、CF2CF2H、C3F7、C4F9、CF2OCH3、CF2OC2H5、CF2OC2H4OCH3、CF2OC2H4OC2H5、CF2OCH2OCF3、CF(CF3)OCH3、CF(CF3)OC2H5、CF(CF3)OC2H4OCH3、CF(CF3)OC2H4OC2H5和CF(CF3)OCH2CF3。
阳离子选自无机阳离子、有机金属阳离子和有机阳离子。
无机阳离子可以选自碱金属阳离子、碱土金属阳离子和铵离子。特别优选Li+、Na+、K+、NH4 +、Ca++和Ba++离子。
有机金属阳离子可以选自二茂铁、二茂钛和二茂锆离子。可以特别提到二茂铁阳离子[C5H5)2Fe]+、二茂钛阳离子[C5H5)2Ti]2+和二茂锆离子[C5H5)2Zr]2+。
有机阳离子可以选自铵、鏻、锍、碘鎓、吡啶鎓、咪唑鎓、吡唑鎓、乙酰铵、噁唑鎓、噻唑鎓、吡咯烷鎓和哌啶鎓离子。可以特别提到符合下式的阳离子,其中:
-R1到R37各自表示H或1到20个碳原子的烷基、芳基或氧杂烷基(oxaalkyle);
-R5到R13各自表示芳基、烷基芳基或二烷基氨基R37R38N,其中R37和R38基团是具有1到20个碳原子的烷基;
-或者相邻的碳原子共同带有的两个R基团形成双基(biradical),形成脂肪环或芳香环。
吡咯烷鎓和吡啶鎓离子是季铵的两个重要实例,其中氮的两个取代基共同成环。
在一个具体实施方案中,本发明的离子化合物包括和提供化合物的电中性所需的阴离子的数量有关的有机聚阳离子部分。聚阳离子部分包括至少两个各自带有阳离子基团的重复单元。根据一个替代形式,聚阳离子部分的重复单元可以是带有阳离子侧基的单元,例如上述阳离子之一,所述阳离子中的R基团之一是与重复单元键合而形成聚阳离子基团链的双基。根据另一替代形式,阳离子基团形成聚阳离子基团链的一部分,阳离子基团上的两个R取代基是和相邻的阳离子基团成键的双基。
阳离子是有机或有机金属阳离子的本发明离子化合物可用于电致变色系统(其中它可以充当对电极),特别是低吸收性的二茂铁/二茂铁离子系统。这样的化合物也可用于将电信号转化为机械运动的电化学致动器,特别是包括聚噻吩或聚苯胺型的共轭聚合物的致动器,其掺杂/去掺杂大体积阳离子带来可通过施加的电流控制的机械运动。
其中的阳离子是有机或有机金属阳离子且在小于100℃的温度下是液体的本发明离子化合物形成离子液体,所述离子液体可用作碱金属盐的溶剂,特别是在电化学发电机中。这样的化合物由于它不可燃而在该用途中特别有优势。
其中的阳离子是阳离子或有机金属阳离子的本发明离子化合物也可用于进行金属的电化学沉积,所述金属比如铝、钽、铌、锡、铜、铬、铂、钯和锌。这些金属作为腐蚀防护或作为催化剂是重要的,特别是以纳米颗粒的形式。金属的纳米颗粒特别易于通过将金属盐溶于离子液体并向溶液表面发送电子束或施加冷等离子体以获得金属盐的还原而获得。这个金属纳米颗粒的制备方法对于本发明的离子化合物是特定的,所述离子化合物的阳离子是有机或有机金属阳离子,因为它们没有蒸汽压。
其中的阳离子是有机或有机金属阳离子的本发明离子化合物也可用于从溶于液体离子化合物的半导体前躯体(例如氯化物或溴化物)制备半导体(比如Si、Ge或它们的固溶体)。
本发明的另一主题是包括离子化合物和溶剂的电解质组合物,其特征在于所述离子化合物具有化合价为m(1≤m≤3)的阳离子M和m个符合下式的阴离子:
其中Rf是-CFZ′Z″基团,其中:
-Z′是F或具有1到3个碳原子的全氟烷基,
-Z″是H、F或Cl基、具有1到5个碳原子的任选地氟化或全氟化的烷氧基、具有1到5个碳原子的任选地氟化或全氟化的氧杂烷氧基或具有1到5个碳原子的任选地氟化或全氟化的烷基,
-所述阳离子是无机阳离子,特别是碱金属阳离子、碱土金属阳离子或铵阳离子,优选为锂离子或钠离子。
溶剂选自任选地通过聚合物凝胶化的液体有机溶剂、任选地通过液体溶剂增塑的溶剂化聚合物、非溶剂化聚合物和极性液体或离子液体的混合物、和离子液体。
术语“液体有机溶剂”理解为表示能够溶解本发明的盐的极性液体或极性液体的混合物。作为极性液体的实例,可以特别提到线性醚和环醚、酯、腈、硝化衍生物、酰胺、砜、环砜烷、烷基磺酰胺和部分卤代烃。特别优选的溶剂是二甲氧基乙烷、甘醇二甲醚、四氢呋喃、二氧六环、甲基四氢呋喃、甲酸甲酯、甲酸乙酯、碳酸亚丙酯、碳酸亚乙酯、碳酸烷基酯(特别是碳酸二甲酯、碳酸二乙酯和碳酸甲基丙基酯)、丁内酯、乙腈、苯并腈、硝基甲烷、硝基苯、二甲基甲酰胺、二乙基甲酰胺、N-甲基吡咯烷酮、二甲砜、四亚甲基砜、二甲亚砜和具有5到10个碳原子的四烷基磺酰胺、或它们的混合物。
术语“离子液体”理解为表示熔点≤100℃的无机或有机阳离子的盐或盐的混合物。作为离子液体的实例,可以特别提到有机阳离子和选自BF4 -、CF3SO3 -、TFSI、FSI、C(CN)3 -和N(CN)2 -的阴离子的盐。另外可以提到具有有机阳离子或有机金属阳离子的本发明化合物,特别是铵、鏻、锍、碘鎓、吡啶鎓、咪唑鎓、吡唑鎓、乙酰铵、噁唑鎓、噻唑鎓、吡咯烷鎓或哌啶鎓阳离子的盐,更特别是选自(乙基)(甲基)咪唑鎓、(丁基)(甲基)咪唑鎓、(甲基)(丙基)吡咯烷鎓、(甲基)(丁基)吡咯烷鎓、(甲基)(丙基)哌啶鎓、丁基吡啶鎓、(2-甲氧基乙基)三乙基铵和己基三甲基铵阳离子的阳离子的盐。
术语“溶剂化聚合物”理解为表示具有足量能够和上述金属盐形成络合物的官能团的聚合物。这样的聚合物可选自带有或不带有接枝的离子基的交联或非交联的溶剂化聚合物。作为溶剂化聚合物的实例,可以提到具有线性、冠状或嵌段结构的形成或不形成网络的聚醚,所述聚醚基于聚(环氧乙烷)或共聚物,所述共聚物包括环氧乙烷或环氧丙烷或烯丙基缩水甘油醚单元、聚磷腈、基于通过异氰酸酯交联的聚乙二醇的交联网络或带有可以并入可交联基团的通过缩聚获得的网络。也可提到嵌段共聚物,其中一些嵌段带有具有氧化还原性的官能团。
离子化合物在根据本发明的液体电解质组合物(其中溶剂为极性有机溶剂型或离子液体型)中的浓度优选在10-3mol/l和3.5mol/l之间。
在包括聚合物溶剂(其中聚合物由氧亚烷基重复单元组成)的电解质组合物中,离子化合物的浓度优选为使得每摩尔离子化合物的氧原子(或重复单元)数在1和200之间。
出乎意料地,就导电性和电化学稳定性而言,本发明化合物具有比那些其它常规Hückel阴离子的化合物好得多的性质。特别地,本发明的盐的阴离子具有大于4.5V vs.Li+/Li°的阳极稳定性。如果认为DCTA型阴离子和本发明的盐的阴离子根据下列反应方案通过和DAMN的缩合而源于[ZO2]-酸,则这个抗氧化性完全例外。
Q对于现有技术的DCTA型化合物是N,对于本发明化合物是CRf,特别是CF3C。
因此可以通过比较DCTA和本发明阴离子的酸性前躯体,即亚硝酸NO2 -(其pKa为3.4)(对于DCTA型化合物)和三氟乙酸CF3CO2(其在25℃的pKa为0.23,对于Rf是CF3的本发明化合物),来比较它们的酸性和氧化电势。根据这些数值,可以设想本发明的阴离子Rf=CF3的氧化电势将向阳极电势漂移56×(3.4-0.23)=178mV,即漂移至≈4V vs.Li+:Li°。这个电势无法满足LixTMO2(0<x<1)型氧化物或磷酸锰LiMnPO4或LiMn1-yFeyPO4(0<y<1)的电化学操作。人们认为使用这些阴极材料的电化学发电机需要4.3V的电解质的阳极稳定性。
实际上,本发明的多种化合物(Rf分别为CF3、CF2Cl、CF2OCH3、CF2OCF3、C2F5、C2F4H、C3F7或C4F9)进行的伏安循环显示本发明的化合物的氧化电势大于4.3V,远在理论预测之上。
意外地,本发明的化合物的锂盐在低于4.6V的电势下不腐蚀铝,这使它们成为集流体是铝片的锂电池的优良候选,所述铝片具有重量和成本的优势。
本发明的几种化合物的令人感兴趣的优势是起始材料的低成本。对于Rf=CF3,三氟乙酸是从制备冷却剂(比如,例如CF3CH2F)衍生的工业产品。
本发明的电解质组合物在电化学装置中具有特别的用途,所述装置通过阳极和阴极之间的锂离子交换而操作。它们特别是锂电池、锂离子电池、超级电容和电致变色装置。那么所使用的离子化合物优选为锂盐。
本发明的化合物(I)可以通过包括下列步骤的方法获得:
-包括制备酸的第一阶段
-第二阶段,在此期间将所述酸转化成阳离子M的盐。
化合物(3)可以通过DAMN和提供Rf基团的反应物之间的反应获得。
在第一个实施方案中,第一阶段根据下列反应方案进行:
其中Rf具有上面给出的含义,且Y表示RfC(=O)O、Cl、F、CF3SO3、OCH3、OC2H5、OCH2CF3、OC6H4NO2(硝基苯基)、咪唑基或琥珀酰亚胺基氧基。
在第二个实施方案中,根据下列反应方案从醛(4)O=CHRf开始进行第一阶段:
Rf具有上面给出的含义。
在第三个实施方案中,根据下列反应方案从乙缩醛(6)开始进行方法的第一阶段:
当醛RfCHO或它的乙缩醛RfCH(OH)(OR′)、RfCH(OH)2和RfCH(OR′)(OR″)在市场上有售时(例如当R′和R″是CH3、C2H5、n-C3H7或i-C3H7时),第二个和第三个实施方案是有优势的。
在使用醛或乙缩醛的方法中,可将溴替换为具有对于化合物(5)具有类似环化强度的另一种氧化剂。例如,可在低温下将溴替换为氯,或者替换为酰亚胺,比如N-氯琥珀酰亚胺或N-溴琥珀酰亚胺、次氯酸盐或N,N’-二氯三聚氰酸的钠盐。
在第一阶段结束获得的酸化合物(3)可以通过本领域技术人员已知的方法和技术转化成所需的阳离子M的盐。可以特别提到化合物(3)和阳离子M的碳酸盐、碳酸氢盐、乙酸盐、甲基碳酸盐或氢氧化物的反应。当阳离子M是有机阳离子时,转化可以在两个阶段中进行:酸化合物(3)转化成钠或钾盐,然后所述钠盐或钾盐和化学当量的有机阳离子化合物(例如氯化物、溴化物或烷基硫酸盐)在质子惰性溶剂(例如乙腈)中反应,所述钠或钾盐不溶于所述质子惰性溶剂。
其中Rf的R′基团是F,且R″基团和Y基团各自表示烷氧基或氧杂烷氧基OZ1的化合物(2)(由化合物2′表示)可以通过化合物HOZ1(8)和四氟环氧乙烷(7)根据下列反应方案的反应而获得:
所关注的化合物(2’)特别是那些Z1是烷基或烷氧基烷基的化合物,所述基团任选地是氟化或全氟化的。作为基团OZ1的实例,可以提到OCH3、OC2H5、OC2H4OCH3、OC2H4OC2H5、OCH2CF3和OCF3基团。
将所述反应改成在碱性介质中可以从阴离子CF3O-开始获得CF3OCF2CO2H″的衍生物。这个替代方案可以制备Rf基团是CF2OCF3的化合物。
其中Rf的R′基团是CF3且R”基团和Y基团各自表示烷氧基或氧杂烷氧基OZ2的化合物(2)(由化合物2”表示)可以通过化合物HOZ2(8)和环氧乙烷(10)根据下列反应方案的反应而获得:
所关注的化合物(2”)特别是那些包括OZ2基团的化合物,OZ2基团比如OCH3、OC2H5、OC2H4OCH3、OC2H4OC2H5或OCH2CF3基团。
其中Rf基团是CF3、CF2H、CF2Cl、C2F5、HC2F4、C3F7或C4F9的化合物O=C(Rf)Y在市场上以酸、酸酐或酯的形式有售,由此可以形成二氰基咪唑环。
符合O=C(Rf)Y式的化合物(2)可以通过本领域技术人员已知的方法从相应的酸O=C(Rf)OH通过和适当试剂的反应而制备。例如,如果Y是Cl,则所述试剂是氯化剂(例如SOCl2);如果Y是咪唑基,则所述试剂是羰基咪唑;如果Y是硝基苯基,则所述试剂是硝基苯基碳酸酯;或者,如果Y是琥珀酰亚胺基氧基,则所述试剂是琥珀酰亚胺基碳酸酯。
本发明通过下列实施例加以说明,然而本发明不限于所述实施例。
实施例1
将2.42g三氟乙酸酐引入反应器,所述反应器包含1.14g DAMN在11ml二氧六环中的溶液。将所述混合物维持在氩下并在回流下搅拌直到反应物完全消失。在真空下除去溶剂和三氟乙酸后,将固体残余物溶于50ml乙醚。用在90ml水中包含1g碳酸锂的悬浮液萃取乙醚溶液,然后用乙醚洗涤锂盐的水溶液。在旋转蒸发器中除去水后,在100℃的真空下将暗色的残余物干燥。随后用乙腈(4×10ml)萃取暗色的固体并过滤得到的溶液。随后除去乙腈并通过层析在矾土上使用乙腈/苯2/1混合物作为洗脱剂纯化粗盐。干燥后,以无色固体的形式获得1.45g(产率71%)2-三氟甲基-4,5-二氰基咪唑锂。重结晶后获得二溶剂(di-solvate)形式的锂盐(LiTDCI)。通过150℃真空下的处理获得纯产品。
通过在搅拌下将680mg聚(环氧乙烷)(其摩尔质量Mw为105)、200mg聚(环氧乙烷)(其摩尔质量Mw为5×106)、和LiTDCI溶于13ml乙腈,直到获得微乳白色且粘稠的溶液,而制备几个聚合物电解质样品。
由此分别使用180mg、320mg和240mg LiTDCI制备三个样品。
使各个溶液进入位于PTFE覆盖的玻璃片上的直径为50cm的玻璃环。在干空气流下蒸发乙腈后,获得弹性且透明的络合物膜。
测量这些电解质和温度有关的导电率。随温度(用1000/T(K)表示)变化的导电率C(欧姆-1.cm-1)示于图1。曲线和样品之间的对应关系在下表中给出:
LiTDCI含量 | 样品 | 曲线 |
480mg | P(EO)8LiTDCI | O/Li=8/1 |
320mg | P(EO)12LiTDCI | O/Li=12/1 |
240mg | P(EO)16LiTDCI | O/Li=16/1 |
LiTDCI的导电率可以和Li[CF3SO2)2N](LiTFSI)的导电率相比拟,后者是聚合物电解质的导电率的参比盐。
实施例2
将10.5ml(53.8mmol)五氟丙酸酐加入4.84g(44.8mmol)二氨基顺丁烯腈在47ml二氧六环中的溶液。在氩下在回流下加热该混合物直到沉淀物消失[通过薄层色谱(TLC)证实,大约6小时]。将得到的混合物置于90℃真空下1小时,然后在120℃的高真空线上干燥1小时以除去溶剂和酸。将固体残余物溶于40ml乙醚并用3g(40.5mmol)碳酸锂在100ml水中的悬浮物萃取得到的溶液三次。用50ml乙醚洗涤含水的盐溶液两次。随后,将充当脱色剂的活性碳加入含水溶液并将浆料加热1小时。通过滤纸过滤除去活性碳后,在80℃真空下将溶液干燥2小时。随后,将残余物溶于无水乙腈并再次滤除固体残余物。将乙腈溶液置于90℃真空1小时。从乙腈/苯1/1混合物重结晶得到晶体,将所述晶体置于120℃的高真空线的真空下4小时。获得5.12g 4,5-二氰基-2-(五氟乙基)咪唑[LiPDCI]的无色晶体(产率:47.2%)。
实施例3
将10.8g DAMN和22g氯二氟乙酸酐(ClF2CO)2O加入100ml二甘醇二甲醚并在保护性氮气氛下进行回流,反应持续48小时。过滤反应产物并用12g碳酸钠处理,并蒸发溶液。在80ml水和25g氨基磺酸中吸收固体残余物。用三份50ml乙醚萃取2-氯二氟乙基-4,5-二氰基咪唑以及反应副产品氯二氟乙酸的混合物。将各份合并并蒸发。通过在Büchi烘箱中在90℃低真空下升华而提纯粗2-氯二氟甲基-4,5-二氰基咪唑。
通过使5g咪唑的酸形式和略微化学当量过量的碳酸锂(1.1g)在乙腈中反应而获得锂盐。离心分离悬浮液并以吸湿性白色粉末的形式获得锂盐Li[CClF2C3N2(CN)2]。
实施例4
将16.2g商品化羰二咪唑加入75ml二甘醇二甲醚中的9.6g商品化二氟乙酸。几分钟后发生CO2逸出。将10.8g DAMN加入获得的清液。在氮气氛下在回流下维持反应24小时。在减压下蒸发二甘醇二甲醚并加入100ml 2M HCl。用三份30ml乙醚萃取2-二氟甲基-4,5-二氰基咪唑。将合并的萃取物蒸发后,通过在低真空下在115℃真空下升华而提纯产品。如先前的实施例,在乙腈中从轻微过量的碳酸锂获得锂盐。
实施例5
通过16g乙氧基六氟丙烯C3F6O在-30℃在75ml无水甲醇中的缩合制备3,3,3-三氟甲氧基-2-氟-2-甲氧基丙酸的甲酯。通过用水稀释将酯分离,用二氯甲烷萃取并蒸馏。用2.4g氢氧化钠在乙醇中将8.5gCF3C(OCH3)FC(=O)OCH3水解,将溶剂蒸发并在乙腈中将固体吸收,其中仅CF3C(OCH3)FCO2Na可溶。随后通过过滤和蒸发乙醇将所述盐分离。
在50mg作为催化剂的二甲基甲酰胺(DMF)的存在下在0℃使9.9g所述钠盐和4.95g三光气(CCl3O)2C=O在二氧六环中反应。加入5.40g DAMN并在氮气氛下使混合物回流24小时。在碳酸锂的作用下将咪唑A5转化成锂盐B5。
实施例6
在30ml水中,通过3.84g实施例1的锂盐对4.75g(乙基)(甲基)咪唑鎓硫酸乙酯N2O4SC8H16的作用而制备离子液体。用二氯甲烷萃取分离的离子液体并用水洗涤三次。蒸发溶剂后,获得符合下式的液体油:
这个液体没有可检测的蒸汽压且在最高375℃下稳定。
实施例7
通过16.6g乙氧基四氟乙烯C2F4O在-30℃在250ml无水甲氧基乙醇中的缩合获得二氟(2-甲氧基乙氧基)乙酸的2-甲氧基乙基酯。
通过蒸馏将酯CH3O-C2H4O-F2C-C(=O)-OCH2CH2OCH3分离。用乙醇中的3g氢氧化钾将11.4g酯水解,将溶剂和得到的甲氧基乙醇蒸发然后在70℃真空下将固体干燥。在乙腈中吸收固体,其中仅钾盐CH3O-C2H4O-CF2-CO2K可溶。通过过滤和蒸发回收该盐。
在0℃使6.6g钾盐、4g亚硫酰氯SOCl2和50mg作为催化剂的二甲基甲酰胺(DMF)在35ml二甘醇二甲醚中反应。1小时后,加入3.6g DAMN并在氮气氛下使混合物回流24小时。在碳酸锂的作用下将在实施例5中萃取和提纯的咪唑A7转化成锂盐B7。
实施例8
通过27.5g 1-溴丁烷和15.8g吡啶在40℃下没有溶剂的24小时Menshutkin反应制备溴化丁基吡啶鎓。获得的固体在50℃低真空下干燥。
在25ml水中,通过4.84g实施例2的锂盐(CN)2C3N2C2F5Li对4.35g溴化丁基吡啶鎓的作用而制备离子液体。用二氯甲烷萃取分离的离子液体并用水洗涤三次。蒸发溶剂后,获得符合下式的液体油:
这个液体没有可检测的蒸汽压且在最高375℃下稳定。
实施例9
通过12.4g 1-溴丙烷和8.5g N-甲基吡咯烷在常温下的反应而制备溴化(丙基)(甲基)吡咯烷鎓。
在25ml水中,通过3.84g根据实施例1获得的盐(CN)2C3N2CF3Li对4.18g溴化(丙基)(甲基)吡咯烷鎓的作用而制备离子液体。用二氯甲烷萃取分离的离子液体并用水洗涤三次。蒸发溶剂后,获得符合下式的液体油:
这个液体没有可检测的蒸汽压且在最高375℃下稳定。
实施例10
将18g商品化的五氟丙醛半缩醛C2F5CH(OH)OCH3加入50ml乙腈中的10.8g DAMN。在搅拌下将混合物维持在50℃24小时。随后,将反应混合物冷却至-10℃并逐滴加入乙腈中的16g溴化物。将溶剂蒸发。在Büchi烘箱中在100℃真空下通过升华提纯粗2-五氟乙基-4,5-二氰基咪唑。如上所述在碳酸锂的作用下制备锂盐。
实施例11
实施例1的锂盐LiTDCI和实施例2的盐LiPDCI的导电率可以和用于锂电池的已知的现有技术的各种盐的导电率相比。在20℃,从各种盐在碳酸乙烯酯/碳酸甲酯(EC/DMC)50/50v/v混合物中的1M溶液进行测量。
盐 | 导电率(mS.cm-1) |
LiPF6 | 10.8 |
LiTFSI | 9.0 |
LiTDCI | 6.7 |
LiPDCI | 6.3 |
LiDCTA | 2.9 |
该表显示LiTDCI和LiPDCI的性能显著好于LiDCTA的性能,导电率大于两倍。
实施例12
组装三个“Swagelok”型电池:
Li/EC-DMC电解质中的1M盐/LiFePO4
所述电池包括锂阳极、由盐在EC/DMC 50/50混合物中的1M溶液组成的液体电解质和由包括Pt集电体上的15重量%的碳SP的LiFePO4的混合物组成的阴极。
所述盐分别是实施例1的盐LiTDCI、实施例2的盐LiPDCI、以及作为比较的盐LiPF6。
根据下列方法针对各个电池证实其根据所需的功率保持其容量的能力。在22℃用不同的施加电流操作几次各个电池,记录为了获得完全放电所需的时间相对于为了完全放电所需的理论时间的函数。结果通过图2的Ragone曲线表示,其中纵坐标上的″%C″表示剩余容量的百分比,相对于横坐标上表示的放电率t(xc)。T(xc)表示时间的倒数,以小时计。
这些曲线显示其中的电解质的盐是根据本发明的化合物的电池具有可以和其中的电解质是LiPF6的电池相比的性能,LiPF6被认为是当前用于液体电解质锂电池中最具导电性的盐之一。
实施例13
为了试验铝相对于各种电解质组合物的耐腐蚀性,将铝集流体用于阴极组装和实施例12的电池类似的电池。
所述盐分别是实施例1的盐LiTDCI、实施例2的盐LiPDCI、以及作为比较的盐LiPF6和盐LiTFSI。
在10mV/分钟的条件下对各个电池进行循环伏安法处理。
结果在图3中给出,其中纵座标给出了以mA计的氧化电流Iox,相对于以伏特计的P(电势,vs.Li+/Li)
正如所料,LiPF6没有可感知的腐蚀性,另一方面,LiTFSI经证明非常具有腐蚀性。本发明的盐LiTDCI和LiPDCI在4.6V vs.Li+:Li°氧化前没有腐蚀性。应当记得大多数氧化物或Li1-xFexPO4型电极材料在4.3V vs.Li+:Li°结束它们的再充电,这显示本发明化合物的优势,它在这个电势下不腐蚀铝。
实施例14
组装三个“纽扣电池”型电池
Li/盐+POE电解质/LiFePO4
所述电池包括锂阳极;由盐在聚(环氧乙烷)POE中的固溶体组成的聚合物电解质;和由40%LiFePO4、10%碳SP和50%PEO(以在不锈钢制成的集电体上的重量分数计)组成的正极。
根据实施例1的步骤制备各个电解质,以形成厚度≈100μm的膜,调整聚合物以及锂盐的用量以获得O/Li比值=20。
所述盐分别是实施例1的盐LiTDCI,实施例2的盐LiPDCI,以及作为比较的盐LiTFSI。
根据下列方法针对各个电池证实其根据所需的功率保持其容量的能力。在80℃用不同的施加电流操作几次各个电池,记录为了获得完全放电所需的时间相对于为了完全放电所需的理论时间的函数。结果通过图4的Ragone曲线表示,其中纵坐标上的″%C″表示剩余容量的百分比,相对于横坐标上表示的放电率t(xc)。T(xc)表示时间的倒数,以小时计。
这些曲线显示其中的电解质的盐是根据本发明的化合物的电池具有可以和其中的电解质是LiTFSI的电池相比的性能,LiTFSI被认为是当前用于聚合物电解质锂电池中最具导电性的盐之一。
Claims (17)
1.一种化合物,其包括化合价为m(1≤m≤3)的无机阳离子、有机阳离子或有机金属阳离子M和m个符合下式的阴离子
其中Rf是-CFZ′Z”基团,其中:
-Z′是F或具有1到3个碳原子的全氟烷基,
-Z”是H、F或Cl基、具有1到5个碳原子的任选地氟化或全氟化的烷氧基、具有1到5个碳原子的任选地氟化或全氟化的氧杂烷氧基或具有1到5个碳原子的任选地氟化或全氟化的烷基;当Z’是F且M是Li时,Z”不是F。
2.权利要求1的化合物,其特征在于Rf选自CF2H、CF2Cl、C2F5、CF2CF2H、C3F7、C4F9、CF2OCH3、CF2OC2H5、CF2OC2H4OCH3、CF2OC2H4OC2H5、CF2OCH2OCF3、CF(CF3)OCH3、CF(CF3)OC2H5、CF(CF3)OC2H4OCH3、CF(CF3)OC2H4OC2H5和CF(CF3)OCH2CF3.
3.权利要求1的化合物,其特征在于所述阳离子是选自碱金属阳离子、碱土金属阳离子和铵离子的无机阳离子。
4.权利要求1的化合物,其特征在于所述阳离子是二茂铁离子、二茂钛离子或二茂锆离子。
5.权利要求1的化合物,其特征在于所述阳离子是选自铵、鏻、锍、碘鎓、吡啶鎓、咪唑鎓、吡唑鎓、乙酰铵、噁唑鎓、噻唑鎓、吡咯烷鎓和哌啶鎓离子的有机阳离子。
7.权利要求6的电解质组合物,其特征在于Rf选自CF3、CF2H、CF2Cl、C2F5、CF2CF2H、C3F7、C4F9、CF2OCH3、CF2OC2H5、CF2OC2H4OCH3、CF2OC2H4OC2H5、CF2OCH2OCF3、CF(CF3)OCH3、CF(CF3)OC2H5、CF(CF3)OC2H4OCH3和CF(CF3)OC2H4OC2H5。
8.权利要求6的电解质组合物,其特征在于所述电解质的盐的阳离子是锂离子。
9.权利要求6的电解质组合物,其特征在于所述溶剂选自任选地通过聚合物凝胶的液体有机溶剂、任选地通过液体溶剂增塑的溶剂化聚合物、和离子液体。
11.权利要求10的电解质组合物,其特征在于形成离子液体的化合物的阳离子选自(乙基)(甲基)咪唑鎓、(丁基)(甲基)咪唑鎓、(甲基)(丙基)吡咯烷鎓、(甲基)(丁基)吡咯烷鎓、(甲基)(丙基)哌啶鎓、丁基吡啶鎓、(2-甲氧基乙基)三乙基铵和己基三甲基铵阳离子。
12.权利要求9的电解质组合物,其特征在于所述溶剂是极性液体或极性液体混合物且盐的浓度为10-3mol/l到3.5mol/l。
13.权利要求9的电解质组合物,其特征在于所述溶剂是包括氧亚烷基重复单元的溶剂化聚合物,且盐的浓度使得每摩尔盐的氧原子(或重复单元)数在1和200之间。
14.权利要求9的电解质组合物,其特征在于所述溶剂是离子液体,且盐的浓度为10-3mol/l到3.5mol/l。
15.权利要求4或5的化合物作为电致变色系统的对电极或电化学致动器中的材料的用途。
16.电解质组合物,其包括碱金属盐在权利要求4或5的化合物中的溶液,所述化合物在小于100℃的温度下是液体。
17.金属纳米颗粒的制备方法,其包括将所述金属的盐溶于溶剂,且然后向溶液表面发送电子束或施加冷等离子体,以获得金属盐的还原,其特征在于所述溶剂是权利要求4或5的化合物,所述化合物在小于100℃的温度下是液体。
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CN113354587B (zh) * | 2021-05-19 | 2022-07-05 | 江苏理文化工有限公司 | 一种咪唑基含氟锂盐的干燥方法 |
CN113277982B (zh) * | 2021-05-19 | 2022-07-05 | 江苏理文化工有限公司 | 一种连续制备2-三氟甲基-4,5-二氰基咪唑锂盐的方法及反应装置 |
CN113582930A (zh) * | 2021-08-26 | 2021-11-02 | 如鲲(山东)新材料科技有限公司 | 一种4,5-二氰基-2-三氟甲基-咪唑盐的制备方法 |
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Publication number | Publication date |
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CN102264926B (zh) | 2014-06-25 |
PL2334831T3 (pl) | 2016-07-29 |
WO2010023413A1 (fr) | 2010-03-04 |
EP2928003A1 (fr) | 2015-10-07 |
ES2547057T3 (es) | 2015-10-01 |
PL2928003T3 (pl) | 2017-10-31 |
EP2928003B1 (fr) | 2016-12-28 |
EP2334831A1 (fr) | 2011-06-22 |
EP2334831B1 (fr) | 2015-06-17 |
US8927160B2 (en) | 2015-01-06 |
US20150315155A1 (en) | 2015-11-05 |
ES2622108T3 (es) | 2017-07-05 |
FR2935382B1 (fr) | 2010-10-08 |
JP2012500833A (ja) | 2012-01-12 |
FR2935382A1 (fr) | 2010-03-05 |
US20110311884A1 (en) | 2011-12-22 |
US9452987B2 (en) | 2016-09-27 |
CN104262259A (zh) | 2015-01-07 |
JP5469668B2 (ja) | 2014-04-16 |
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