CN102924495B - 含聚醚链有机卤硅烷及其在非水系锂离子电池电解液中的应用 - Google Patents
含聚醚链有机卤硅烷及其在非水系锂离子电池电解液中的应用 Download PDFInfo
- Publication number
- CN102924495B CN102924495B CN201210389659.1A CN201210389659A CN102924495B CN 102924495 B CN102924495 B CN 102924495B CN 201210389659 A CN201210389659 A CN 201210389659A CN 102924495 B CN102924495 B CN 102924495B
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- China
- Prior art keywords
- organohalosilanes
- polyether chain
- electrolytic solution
- application
- lithium
- 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.)
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 38
- 229920000570 polyether Polymers 0.000 title claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 21
- 239000008151 electrolyte solution Substances 0.000 title claims description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 2
- -1 organic carbonate ester compound Chemical class 0.000 description 50
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 238000004821 distillation Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical group FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000003682 fluorination reaction Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- KEZMLECYELSZDC-UHFFFAOYSA-N 3-chloropropyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(OCC)CCCCl KEZMLECYELSZDC-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- HXVPUKPVLPTVCQ-UHFFFAOYSA-N chloro-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)Cl HXVPUKPVLPTVCQ-UHFFFAOYSA-N 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- WKZJZXUTTGSKDV-UHFFFAOYSA-N fluoro-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)F WKZJZXUTTGSKDV-UHFFFAOYSA-N 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- XYIWPKKMXFMQDN-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propan-1-ol Chemical compound C[Si](Cl)(Cl)CCCO XYIWPKKMXFMQDN-UHFFFAOYSA-N 0.000 description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical group C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004334 fluoridation Methods 0.000 description 2
- JYGXADMDTFJGBT-VWUMJDOOSA-N hydrocortisone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 JYGXADMDTFJGBT-VWUMJDOOSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- QSUPZPHDDZTLHB-UHFFFAOYSA-N 3-chloropropyl-diethoxy-pentylsilane Chemical compound CCCCC[Si](OCC)(OCC)CCCCl QSUPZPHDDZTLHB-UHFFFAOYSA-N 0.000 description 1
- IIFBEYQLKOBDQH-UHFFFAOYSA-N 3-chloropropyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)CCCCl IIFBEYQLKOBDQH-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- GUIUNZALVSPJOZ-UHFFFAOYSA-N CCCC[SiH](Cl)CCCC Chemical group CCCC[SiH](Cl)CCCC GUIUNZALVSPJOZ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- LKHJDAFSSUFVCG-UHFFFAOYSA-N ClCCC[Si](OCC)(OCC)CCC Chemical compound ClCCC[Si](OCC)(OCC)CCC LKHJDAFSSUFVCG-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910008284 Si—F Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- JCHGDLSNQMRKGZ-UHFFFAOYSA-N [SiH4].[I] Chemical compound [SiH4].[I] JCHGDLSNQMRKGZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- DBKNQKMXXOSIOX-UHFFFAOYSA-N butyl(dichloro)silane Chemical group CCCC[SiH](Cl)Cl DBKNQKMXXOSIOX-UHFFFAOYSA-N 0.000 description 1
- LXSKGFLNANWVCO-UHFFFAOYSA-N butyl-(3-chloropropyl)-diethoxysilane Chemical compound CCCC[Si](OCC)(OCC)CCCCl LXSKGFLNANWVCO-UHFFFAOYSA-N 0.000 description 1
- YXMVRBZGTJFMLH-UHFFFAOYSA-N butylsilane Chemical compound CCCC[SiH3] YXMVRBZGTJFMLH-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- SOYVLBDERBHIME-UHFFFAOYSA-N chloro(diethyl)silicon Chemical group CC[Si](Cl)CC SOYVLBDERBHIME-UHFFFAOYSA-N 0.000 description 1
- DNOHLXZVZKTVTE-UHFFFAOYSA-N chloro(dipentyl)silane Chemical group CCCCC[SiH](Cl)CCCCC DNOHLXZVZKTVTE-UHFFFAOYSA-N 0.000 description 1
- QKRFMMNPNXDDGT-UHFFFAOYSA-N chloro(dipropyl)silane Chemical group CCC[SiH](Cl)CCC QKRFMMNPNXDDGT-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- PFMKUUJQLUQKHT-UHFFFAOYSA-N dichloro(ethyl)silicon Chemical group CC[Si](Cl)Cl PFMKUUJQLUQKHT-UHFFFAOYSA-N 0.000 description 1
- MJVFSDBAXDCTOC-UHFFFAOYSA-N dichloro(prop-2-enyl)silicon Chemical group Cl[Si](Cl)CC=C MJVFSDBAXDCTOC-UHFFFAOYSA-N 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229960000890 hydrocortisone Drugs 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 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 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明提供了一种应用范围广的含聚醚链有机卤硅烷,还提供了其在非水系锂离子电池中的应用。所述含聚醚链有机卤硅烷化学结构式如式Ⅰ所示。本发明含聚醚链有机卤硅烷电化学窗口宽,可作为溶剂或添加剂应用于锂离子电池电解液,能在电极表面形成稳定的SEI膜,也可以作为电解质材料应用于任意形状,结构的非水系锂离子电池。也可应用于其它电化学储能器件(如电解电容和超级电容器)。式Ⅰ。
Description
技术领域
本发明涉及化学材料合成和电化学储能技术领域,尤其是涉及一类含聚醚链有机卤硅烷,及其在非水系锂离子电池电解液中的应用。
技术背景
非水系锂离子电池具有高电压、高能量密度、循环寿命长、可存储性等性能,因而被广泛地应用于消费电子产品中,并正积极地向国防工业、空间技术、电动汽车和静置式备用电源等领域发展。
目前,非水系锂离子电池所使用的非水溶剂主要是有机碳酸酯类化合物。另外,电解液中混合有LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、Li2SiF6等电解质。然而,碳酸酯类材料具有很高的可燃性致使锂离子电池在技术上存在巨大的安全隐患。尤其是在要求高安全性、大容量和高倍率放电的混合动力和纯电动汽车应用领域,安全性是制约这些材料应用的重要因素。因此,国内外都在积极地研究开发安全、有效和环境友好的新一代有机电解液材料。
近年,对非水系电解液进行了各种研究。有机硅化合物具有优良的热稳定性、高电导率、无毒性、低可燃性和高分解电压等优点从而引起研究兴趣。Aurbach等人报道了在常规电解液中加入1%的有机硅化合物用作添加剂能明显改善电池的高温性能(J.Electrochem.Soc.,147(2000)1322)。野木荣信等提出了一种包含有机硅化合物的非水系电解液体系,该体系能降低电池电阻(特别是降低首次循环电池电阻),提高电池寿命,提高安全性等(CN102113164A),其在专利中还提到一种氟化有机硅化合物—三甲基氟化硅烷,它在锂离子电池电解液中的使用量建议为0.2%以下或最好是不使用,其原因并没有阐述。West等人在专利中公开了一种含聚烷氧基醚类的有机硅化合物(US2006035154-A1,J.Mater.Chem.,20(2010)8224)。但是,仍然需要对这一领域进行深入研究,以期能开发新型有机硅电解质材料。
发明内容:
本发明的目的是提供一种应用范围广的含聚醚链有机卤硅烷。
本发明还提供了上述含聚醚链有机卤硅烷在非水系锂离子电池中的应用。
本发明含聚醚链有机卤硅烷,其化学结构式如式Ⅰ所示:
式Ⅰ
其中,R1、R2、R3选自相同或不同的-(CH2)xCH3(x=0~5),或卤素取代基,且R1、R2、R3中至少有一个卤素取代基,卤素优选为F或Cl;R4选自C1-C5的烷氧基或叔胺基(-NR5R6,R5、R6为相同或不同C1-C5的烷基);m为1-20的整数,n为0-5的整数。
化学结构中有Si-F键,可以提高电化学性能稳定。化学结构中的聚醚链段提供与锂离子络合点,进行离子传输,从而提高电池性能。
本发明所述的含聚醚链有机卤硅烷可应用于非水系锂离子电池电解液中,具体为,式Ⅰ的含聚醚链有机卤硅烷作为非水溶剂或添加剂应用于非水系锂离子电池。所述非水系锂离子电池电解液包括:氟碱金属锂盐、高介电常数或低沸点的有机溶剂,和化学结构如式Ⅰ所示的含聚醚链有机卤硅烷。
本发明所述的含聚醚链有机卤硅烷电化学窗口宽,可作为溶剂或添加剂应用于锂离子电池电解液,能在电极表面形成稳定的SEI膜,也可以作为电解质材料应用于任意形状,结构的非水系锂离子电池。也可应用于其它电化学储能器件(如电解电容和超级电容器)。本发明合成方法简单,有效,原料易得,操作简单,易于工业化生产。
附图说明:
图1是本发明实施例2化合物的电化学窗口曲线;
图2是表示本发明实施例2化合物的离子电导率随温度变化曲线(1M LiTFSI);
图3是本发明实施例7锂离子电池的循环伏安曲线;
图4为本发明实施例7锂离子电池前两次的0.1C充放电曲线;
图5为本发明实施例7锂离子电池的0.1C充放循环性能曲线;
图6为本发明对比例2锂离子电池的0.1C或0.2C充放循环性能曲线,其中前三次是0.1C充放电。
具体实施方式:
下面通过具体实施例对本发明做进一步说明。
本发明含聚醚链有机卤硅烷的合成方法包含两种:
方法1(反应式1):含聚醚链的醇与金属钠反应生成醇钠盐,醇钠盐与卤硅烷化合物进行成醚反应,最后与氟化试剂进行氟化反应得到相应的含聚醚链有机卤硅烷。
反应式1
方法1中含聚醚链的醇与金属钠的物质的量的比为1:1~10:1,优选为3:1~5:1,所述醇钠盐与卤硅烷化合物和氟化试剂的物质的量的比为1:1:1~1:1:6,优选为1:1:2~1:1:4.5,所述成醚反应温度为80~150℃,反应时间为24小时,氟化反应温度为25~85℃,反应时间为4~30小时。
所述的有机醇选自含聚醚链的烷氧基醇,胺基醇类等,所含的聚醚链的单元数为1-20。例如,乙二醇单甲醚,二乙二醇单甲醚,三乙二醇单甲醚,四乙二醇单甲醚,N,N-甲基乙醇,N,N-甲基二乙氧基乙醇,N,N-甲基三乙氧基乙醇,N,N-甲基四乙氧基乙醇等。
所述的卤硅烷是一种侧链含相同或不同C1-C5的烷基或烷氧基,芳香基或氢基的氯硅烷或碘硅烷。例如,二甲基氯硅烷,二乙基氯硅烷,二丙基氯硅烷,二丁基氯硅烷,二戊基氯硅烷,甲基二氯硅烷,乙基二氯硅烷,丙基二氯硅烷,丁基二氯硅烷,戊基二氯硅烷,三氯硅烷,3-氯丙基三甲氧基硅烷,3-氯丙基三乙氧基硅烷,3-氯丙基二乙氧基甲基硅烷,3-氯丙基二甲基乙氧基硅烷,3-氯乙基三甲氧基硅烷,3-氯乙基二乙氧基甲基硅烷,3-氯丙基三氯硅烷,3-氯丙基二乙氧基丙基硅烷,3-氯丙基二乙氧基丁基硅烷,3-氯丙基二乙氧基戊基硅烷,3-氯丙基二乙氧基烯丙基硅烷,3-氯丙基二乙氧基烯丁基硅烷等。
方法2(反应式2):在铂催化剂的作用下,含聚醚链的端烯烃和卤硅烷进行硅氢化反应,然后与氟化试剂进行氟化反应得到相应的含聚醚链有机卤硅烷。
反应式2
方法2中含聚醚链的端烯烃与卤硅烷、催化剂和氟化试剂的物质的量的比为1:1.05:0.05:1~1:1.05:0.05:6,优选为1:1.05:0.05:2~1:1.05:0.05:4.5,所述硅氢化反应温度为50~100℃,反应时间为24小时,氟化反应温度为20~35℃,反应时间为4~24小时。
所述的铂催化剂选自氯铂酸,氧化铂,铂黑,或Karstedt催化剂。
所述的氟化试剂选自三氟化硼乙醚,氟化钾,氟化锌,氟化锑,以及氟化铯等。
所述的含聚醚链的端烯烃为其合成(见反应式3)是在碱性条件下(氢氧化钾或者氢氧化钠)通过相应含聚醚链的醇和烯丙基溴或者烯丙基氯的成醚反应产生的。首先,醇和过量氢氧化钾反应转化为相应的醇钾盐,然后在冰水浴中缓慢加入烯丙基溴或者烯丙基氯,室温下反应数小时后,通过抽滤、萃取、洗涤、干燥、蒸馏得到相应的含聚醚链的端烯烃。
反应式3
下列实施例中,实施例1-6的化合物结构式如下所示:
实施例1:3-(甲氧基乙氧基)丙基甲基二氟硅烷(F2XMSEOM)的合成
在氩气保护下,取乙二醇单甲醚(61g,0.8mol)加入到250mL两口圆底烧瓶中,然后将金属钠(4.6g,0.2mol)分批加入到反应瓶中,加热至80℃直至钠完全反应后再在此温度下滴加3-氯丙基二乙氧基甲基硅烷(42.1g,0.2mol),然后逐步升温至120℃,反应24h。冷却至室温后抽滤,再减压蒸馏收集3-(甲氧基乙氧基)丙基甲基二(甲氧基乙氧基)硅烷,得到44.5g无色液体产物,b.p.:135℃(3mmHg),产率:60%。在氩气保护下,取98%的三氟化硼乙醚(29.43g,0.203mol)逐步滴入3-(甲氧基乙氧基)丙基甲基二(甲氧基乙氧基)硅烷(21.03g,0.067mol),室温下反应30h后,减压蒸馏收集3-(甲氧基乙氧基)丙基甲基二氟硅烷,得到11.74g无色透明液体,b.p.:34.5℃(3mmHg),产率:87%。
3-(甲氧基乙氧基)丙基甲基二(甲氧基乙氧基)硅烷(TEGS):
1H-NMR(600MHz,CDCl3),δ:3.80(t,4H,Si-O-CH2,J=4.92Hz),3.53(m,4H,Si-O-CCH2),3.45(t,4H,Si-C-C-C-O-CH2-CH2,J=4.95Hz),3.40(t,2H,Si-C-C-CH2,J=7.02Hz),3.36(s,3H,Si-C-C-C-O-C-C-O-CH3),3.35(s,6H,Si-O-C-C-O-CH3),1.65(m,2H,Si-C-CH2),0.62(m,2H,Si-CH2),0.12(s,3H,Si-CH3)。
13C-NMR(300MHz,CDCl3).,δ:73.87,73.84,71.97,69.89,61.81,59.04,58.95,22.84,9.72,-4.96。
3-(甲氧基乙氧基)丙基甲基二氟硅烷:
1H-NMR(600MHz,CDCl3),δ:3.56(m,2H,CH2-O-CH3),3.52(m,2H,Si-C-C-C-O-CH2,J=1.8Hz),3.44(t,2H,Si-C-C-CH2,J=6.36Hz),3.37(s,3H,-O-CH3),1.74(m,2H,Si-C-CH2),0.82(m,2H,Si-CH2),0.33(dd,3H,Si-CH3,J=6.27Hz)。
13C-NMR(300MHz,CDCl3).,δ:72.60,71.85,70.03,58.99,21.87,10.04(t,J=30.64Hz),-4.25(t,J=32.28Hz)。
实施例2:3-(甲氧基二乙氧基)丙基甲基二氟硅烷(F2MSEO2M)的合成
在氩气保护下,取二乙二醇单甲醚(74.4g,0.62mol)加入到250mL两口圆底烧瓶中,然后将金属钠(7g,0.3mol)分批加入到反应瓶中,加热至80℃直至钠完全反应后再在此温度下滴加3-氯丙基二乙氧基甲基硅烷(62.7g,0.29mol),然后逐步升温至120℃,反应24h。冷却至室温后抽滤,再减压蒸馏收集3-(甲氧基二乙氧基)丙基甲基二(甲氧基二乙氧基)硅烷,得到58.8g无色液体产物,b.p.:170℃(3mmHg),产率:65%。在氩气保护下,取46.6%的三氟化硼乙醚(29.43g,0.09mol)逐步滴入40mL溶有3-(甲氧基二乙氧基)丙基甲基二(甲氧基二乙氧基)硅烷(15.9g,0.03mol)的甲苯溶液中,升温至80℃反应24h后,减压蒸馏收集3-(甲氧基乙氧基)丙基甲基二氟硅烷,得到3.47g无色透明液体,b.p.:67℃(3mmHg),产率:40%。
3-(甲氧基二乙氧基)丙基甲基二(甲氧基二乙氧基)硅烷(TDEGS):
1H-NMR(600MHz,CDCl3),δ:3.78(t,4H,Si-O-CH2,J=5.22Hz),3.58(m,8H,Si-C-C-C-O-CH2-CH2-O-CH2-CH2),3.50(m,12H,Si-O-C-CH2-O-CH2-CH2),3.36(t,2H,Si-C-C-CH2,J=6.9Hz),3.32(s,9H,O-CH3),1.59(m,2H,Si-C-CH2),0.57(m,2H,Si-CH2),0.07(s,3H,Si-CH3)。
13C-NMR(300MHz,CDCl3).,δ:73.64,72.28,71.8,70.49,70.38,69.84,61.71,58.84,22.73,9.65,-5.07。
3-(甲氧基二乙氧基)丙基甲基二氟硅烷:
1H-NMR(600MHz,CDCl3),δ:3.63(m,4H,Si-C-C-C-O-C-CH2-O-CH2),3.59(m,2H,Si-C-C-C-O-C-C-O-C-CH2),3.54(m,2H,Si-C-C-C-O-CH2),3.44(t,2H,Si-C-C-CH2,J=6.3Hz),3.36(s,3H,O-CH3),1.72(m,2H,Si-C-CH2),0.82(m,2H,Si-CH2),0.33(t,3H,Si-CH3,J=6.27Hz)。
13C-NMR(300MHz,CDCl3).,δ:72.53,71.94,70.54,70.51,70.09,59.00,21.91,10.05(t,J=30.72Hz),-4.21(t,J=32.49Hz)。
实施例3:3-(甲氧基三乙氧基)丙基甲基二氟硅烷(F2MSEO3M)的合成
在氩气保护下,取三乙二醇单甲醚(149.91g,0.91mol)加入到250mL两口圆底烧瓶中,然后将金属钠(7g,0.304mol)分批加入到反应瓶中,加热至80℃直至钠完全反应后再在此温度下滴加3-氯丙基二乙氧基甲基硅烷(64g,0.304mol),然后逐步升温至130℃,反应24h。冷却至室温后分别滴加200ml甲苯和46.5%的三氟化硼乙醚(186g,0.61mol),然后升温至85摄氏度,反应4h,反应冷却后抽滤,将溶液直接减压蒸馏收集3-(甲氧基三乙氧基)丙基甲基二氟硅烷,得到39g无色透明液体,b.p.:121℃(3mmHg),产率为45%。
3-(甲氧基三乙氧基)丙基甲基二氟硅烷:
1H-NMR(600MHz,CDCl3),δ:3.63(m,8H,CH2-O-CH2CH2-O-CH2,J=1.8Hz),3.56(m,2H,CH2-O-CH3,J=1.8Hz),3.52(m,2H,Si-C-C-C-O-CH2,J=1.8Hz),3.43(t,2H,Si-C-C-CH2,J=6.3Hz),3.36(s,3H,C-O-C-C-O-CH2),1.71(tt,2H,Si-C-CH2,J=7.86Hz),0.81(dd,2H,Si-CH2,J=5.1Hz),0.32(dd,3H,Si-CH2,J=6.3Hz)。
13C-NMR(300MHz,CDCl3).,δ:72.50,71.92,70.58,70.56,70.49,70.48,70.08,58.97,21.90,10.04(t,J=30Hz),-4.22(t,J=30Hz)。
实施例4:3-(甲氧基三乙氧基)丙基二甲基氟硅烷(FDMSEO3M)的合成
在氩气保护下,取三乙二醇烯丙基甲醚(25.14g,0.123mol)加入到250mL两口圆底烧瓶中,然后将氯铂酸(0.1g)加入到反应瓶中,在冰浴下缓慢滴加二甲基氯硅烷(14.0g,0.148mol),然后逐步升温至70℃,反应24h。冷却至室温后,减压蒸馏得到3-(甲氧基三乙氧基)丙基二甲基氯硅烷,19.73g无色透明液体,b.p.:112℃(3mmHg),产率:54%。在氩气保护下,将3-(甲氧基三乙氧基)丙基二甲基氯硅烷(19.73g,0.066mol)溶解于80mL无水乙腈,加入固体氟化钾(7.66g,1.32mol),室温下搅拌18h,经过过滤、蒸除溶剂、减压蒸馏得到3-(甲氧基三乙氧基)丙基二甲基氟硅烷,15.0g无色透明液体,b.p.:98℃(3mmHg),产率:79%。
3-(甲氧基三乙氧基)丙基二甲基氯硅烷(CDMSEO3M):
1H-NMR(600MHz,CDCl3),δ:3.64(m,8H,CH2-O-CH2),3.56(m,4H,CH2-O-CH2,J=1.8Hz),3.46(t,2H,Si-C-C-CH2,J=6.36Hz),3.37(s,3H,-O-CH3),1.69(m,2H,Si-C-CH2),0.83(m,2H,Si-CH2-C),0.40(s,6H,Si-CH3)。
3-(甲氧基三乙氧基)丙基二甲基氟硅烷:
1H-NMR(600MHz,CDCl3),δ:3.63(m,8H,CH2-O-CH2),3.55(m,4H,CH2-O-CH2,J=1.8Hz),3.42(t,2H,Si-C-C-CH2,J=6.84Hz),3.36(s,3H,-O-CH3),1.65(m,2H,Si-C-CH2),0.67(m,2H,Si-CH2-C),0.20(d,6H,Si-CH3,J=7.5Hz)。
13C-NMR(300MHz,CDCl3).,δ:73.51,71.92,70.60,70.58,70.50,70.03,58.98,22.76,12.67(d,J=28.17Hz),-1.5(d,J=29.85Hz)。
实施例5:N,N-甲基二乙氧基丙基三氟硅烷(TFSEN2)的合成
在氩气保护下,取N,N-二甲基二乙氧基乙醇(53.42g,0.40mol)加入到250mL两口圆底烧瓶中,然后将金属钠(2.30g,0.1mol)分批加入到反应瓶中,加热至80℃直至钠完全反应后再在此温度下滴加3-氯丙基三乙氧基硅烷(24.08g,0.1mol),然后逐步升温至150℃,反应24h。冷却至室温后,通过抽滤后直接减压蒸馏得到41.9g无色液体产物N,N-二甲基二乙氧基丙基三(N,N-二甲基二乙氧基)硅烷,b.p.:200℃(3mmHg),产率:70%。在氩气保护下,取46.5%的三氟化硼乙醚(30.9g,0.101mol)逐步滴入3-(甲氧基乙氧基)丙基甲基二(甲氧基乙氧基)硅烷(19g,0.037mol)中,室温下反应30h后,减压蒸馏得到N,N-二甲基二乙氧基丙基三氟硅烷,8g无色透明液体,b.p.:141℃(3mmHg),产率:85%。
N,N-二甲基二乙氧基丙基三(N,N-二甲基二乙氧基)硅烷:
1H-NMR(600MHz,CDCl3),δ:3.82(t,6H,Si-O-CH2,J=2.94Hz),3.46~3.52(m,18H,O-CH2-CH2-O-CH2-,J=6.12Hz),3.33(t,2H,Si-C-C-CH2,J=6.6Hz),2.42(m,8H,CH2-N,J=5.58Hz),2.19(s,24H,N(CH3)2),1.61(dd,2H,Si-C-CH2,J=7.56Hz),0.59(dd,2H,Si-CH2,J=7.08Hz)。
N,N-二甲基二乙氧基丙基三氟硅烷:
1H-NMR(600MHz,CDCl3),δ:3.82(t,2H,Si-C-C-C-O-CH2,J=5.1Hz),3.61(m,4H,CH2-O-CH2C-N,J=4.08Hz),3.47(t,2H,Si-C-C-CH2,J=5.7Hz),3.12(t,2H,N-CH2,J=4.74Hz),2.67(s,6H,N-CH3),1.83(m,2H,Si-C-CH2,J=6.36Hz),1.04(m,2H,Si-CH2,J=3Hz)。
13C-NMR(300MHz,CDCl3).,δ:71.03,70.15,70.05,65.41,57.02,44.47,21.84,4.23(J=37.92Hz)。
实施例6:N,N-二甲基二乙氧基丙基二甲基氟硅烷(FDMSEN2)的合成
用N,N-二甲基二乙氧基烯丙醚代替三乙二醇烯丙基甲醚为反应物,采用与实施例4相同的合成方法,通过减压蒸馏得到产物。其中,中间产物N,N-二甲基二乙氧基丙基二甲基氯硅烷,无色透明液体,b.p.:90℃(3mmHg),产率:80%。产物N,N-二甲基二乙氧基丙基二甲基氟硅烷,无色透明液体,b.p.:83℃(3mmHg),产率:85%。
N,N-二甲基二乙氧基丙基二甲基氯硅烷(CDMSEN2):
1H-NMR(600MHz,CDCl3),δ:3.67(m,2H,Si-C-C-C-O-CH2),3.59(m,4H,N-C-CH2-O-CH2),3.44(t,2H,Si-C-C-CH2,J=6.69Hz),2.66(t,2H,N-CH2,J=5.70Hz),2.38(s,6H,N(CH3)2),1.67(m,2H,Si-C-CH2),0.82(m,2H,Si-CH2),0.40(s,6H,Si-CH3)。
13C-NMR(300MHz,CDCl3).,δ:74.14,73.23,70.43,69.84,45.14,23.39,15.18,1.58,0.26。
N,N-二甲基二乙氧基丙基二甲基氟硅烷:
1H-NMR(600MHz,CDCl3),δ:3.58(m,6H,O-CH2-CH2-O-CH2),3.43(t,2H,Si-C-C-CH2,J=6.78Hz),2.50(t,2H,N-CH2,J=5.91Hz),2.25(s,6H,N(CH3)2),1.66(m,2H,Si-C-CH2),0.68(m,2H,Si-CH2),0.21(d,6H,Si-CH3,J=7.50Hz)。
13C-NMR(300MHz,CDCl3).,δ:73.50,70.38,70.05,69.39,58.81,45.88,22.76,12.67(d,J=28.11Hz),-1.50(d,J=29.82Hz)。
对比例1:3-(甲氧基二乙氧基)丙基甲基二氟硅烷(F2MSEO2M)的合成
用二乙二醇烯丙基甲醚代替三乙二醇烯丙基甲醚为反应物,采用与实施例4相同的合成方法,通过减压蒸馏得到产物。其中,中间产物3-(甲氧基二乙氧基)丙基甲基二氯硅烷,无色透明液体,b.p.:85℃(3mmHg),产率:59%。产物3-(甲氧基二乙氧基)丙基甲基二氟硅烷,无色透明液体,b.p.:67℃(3mmHg),产率:78%。
3-(甲氧基二乙氧基)丙基甲基二氯硅烷(C2MSEO2M):
1H-NMR(600MHz,CDCl3),δ:3.59(m,8H,O-CH2-CH2-O),3.44(t,2H,Si-C-C-CH2,J=6.37Hz),3.37(s,3H,O-CH3,J=5.91Hz),1.78(m,2H,Si-C-CH2),1.17(m,2H,Si-CH2),0.77(s,3H,Si-CH3)。
13C-NMR(300MHz,CDCl3).,δ:72.38,71.94,70.61,70.54,70.07,70.04,59.01,22.73,18.14,5.17。
实施例7:电池制作及测试
本发明化合物应用于锂离子电池时,可按如下步骤制造。
本发明中高介电常数溶剂不特别限制,通常为电池领域常用的非水溶剂-环状碳酸酯,例如碳酸亚乙酯(EC)、碳酸亚丙酯(PC)和-丁内酯(-BL)等,这些碳酸酯也可以混合2种以上来使用,可以提高电池寿命。本发明中低沸点溶剂不特别限制,通常为链状碳酸酯,例如碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、碳酸甲丙酯(MPC)、脂肪酸酯衍生物等。这些链状碳酸酯也可以混合2种以上混合使用,可进一步降低电解液的粘度,提高电解质的溶解度,改善电池的低温负载等低温特性。
本发明中高介电常数溶剂和低沸点的有机溶剂的混合比例,体积比为0:100~100:0,优选为10:90~80:20,特别优选为15:85~50:50。可有效抑制非水电解液的粘度上升,进一步提高电解质的离解度,从而可提高锂离子电池电解液在充放电时的传导率。
本发明的非水电解液的电解质为含氟碱金属盐,例如LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、Li2SiF6等含氟锂盐。上述含氟锂盐可单独使用,也可以混合2种以上使用,其浓度优选为0.1~3mol/L,特别优选为0.5~2mol/L。
本发明的非水电解液中,前述特定含聚醚链有机卤硅烷的含量以体积比来表示,可为1%~100%,优选为2%~80%,进一步优选为5%~70%,最优选为40%~50%。在锂离子电池中,含聚醚链有机卤硅烷的使用可以形成均匀稳定的保护层,且电池的效率可以较现有技术得到提高。另外,含聚醚链有机卤硅烷的电化学窗口较宽,例如实施例2中合成的F2MSEO2M的电化学窗口在0~4.95V,如图1所示,用三电极体系电池:铂为工作电极,金属锂丝为对电极和参比电极。
本发明的锂离子电池的结构包含负极、正极、隔膜和前述的非水电解液。
将正极活性材料、导电剂、粘合剂和溶剂混合以制备正极活性材料组合物。将正极材料组合物直接涂覆在Al集电体上并干燥以制备正极板。正极活性材料可为本领域中通常使用的任何含锂过渡金属金属氧化物,例如LiCoO2、LiMnxO2x(x=1、2)、LiNi1-xMnxO2(0≤x<1)、LiNixCo1-xO2(0<x<1)、LiFePO4等;过渡金属氧化物或过渡金属硫化物,例如MoS2、SnS2、MoO3、V2O5等。在上述正极活性材料中,优选为含锂过渡金属金属氧化物。
类似正极板的制作方法,将负极活性材料、导电剂、粘合剂和溶剂混合以制备正极活性材料组合物。将正极材料组合物直接涂覆在Cu集电体上并干燥以制备正极板。负极活性材料可为金属锂;锂合金;可掺杂和脱掺杂锂离子的碳材料;可掺杂和脱掺杂锂离子的氧化锡、氧化铌、氧化钒、氧化钛;或可掺杂和脱掺杂锂离子的硅。在上述负极活性材料中,优选为可掺杂和脱掺杂锂离子的碳材料。这样的碳材料可以是石墨也可以为非晶碳,例如活性碳、碳纤维、碳黑、天然石墨等。
碳黑可用作导电剂。粘合剂可选自偏二氟乙烯/六氟丙烯共聚物、聚偏二氟乙烯(PVDF)、聚丙烯腈、聚甲基丙烯酸甲酯、聚四氟乙烯及其混合物、或基于丁苯橡胶的聚合物。溶剂可选N-甲基吡咯烷酮(NMP)、丙酮、水等。正/负极活性材料、导电剂、粘合剂和溶剂的量可采用锂离子电池通常使用的用量。隔膜可由在锂离子电池中通常使用的任何材料。隔膜需要对电解质的离子的移动具有低阻抗和对电解液具有良好吸收能力和浸润性。例如,该材料可为选自玻璃纤维、聚酯、聚乙烯、聚四氟乙烯及其组合的无纺物或纺织物。特别优选聚乙烯、或聚丙烯等可卷绕的多孔性隔膜。
本发明的锂离子电池可为圆筒形、硬币型、方形、其它任意的形状。但是电池的形状与基本结构无关,可根据目的而实施设计变更。
在电池性能测试中,所使用的电解液和LiPF6来自东莞市杉杉电池材料有限公司,锂片来自中国锂能,石墨为合肥科晶材料技术有限公司,隔膜为Asashi Chemical Industry公司产品。电解液的配制和电池的组装均在氩气(纯度大于99.999%)气氛下进行。
将LiPF6溶解于PC和含聚醚链有机卤硅烷F2MSEO2M(PC:F2MSEO2M=1:1)中配成浓度为1M的电解液,用金属锂和石墨分别做正、负极组装成硬币式电池(2025),然后在深圳新威电池充放电测试系统中进行充/放电测试,充放电电压0V-3V。以0.1C的恒定电流对实施例7电池充电,然后进行恒流放电,放电倍率为0.1C。另外,用德国ZAHNER电化学工作站进行循环伏安测试。
图3为本发明实施例7锂离子电池的循环伏安曲线,图4为本发明实施例7锂离子电池前两次的0.1C充放电曲线。图5为本发明实施例7锂离子电池的0.1C充放循环性能曲线。
对比例2:
所使用非水电解液的溶剂为PC:DEC:DMC:F2MSEO2M=35:30:30:5,LiPF6浓度为1M,除此以外,按与实施例6相同的方法组装硬币式电池(2025),然后在深圳新威电池充放电测试系统中进行充/放电测试,充放电电压0V-3V。以0.1C或0.2C的恒定电流对实施例7电池充电,然后进行恒流放电,放电倍率为0.1C或0.2C。另外,用德国ZAHNER电化学工作站进行循环伏安测试。
图6为本发明对比例2锂离子电池的0.1C或0.2C充放循环性能曲线。
对本发明所述含聚醚链有机卤硅烷的基本物理性质及电化学性质进行测试。把锂盐LiN(CF3S2O2)2溶解于相应的化合物配成1M浓度的电解液,使用离子电导率仪测试其不同温度下的离子电导率。以F2MSEO2M,CDMSEN2和文献(J.Mater.Chem.,20(2010)8224)中的化合物1S3M2作对比,其结果汇总于表1中。
表1
化合物 | 粘度为/mPa.s | 介电常数 | 离子电导率/mS.cm-1 | 电化学窗口/V |
F2MSEO2M | 1.79 | 9.50 | 1.46 | 4.95 |
CDMSEN2 | 1.89 | 5.65 | - | - |
1S3M2 | 2.10 | 4.44 | 0.90 | - |
“-”表示还未测得,所测数据均是在室温下测得
F2MSEO2M和1S3M2在化学结构上的区别是两个氟取代甲基。从表1中可以得知,氟取代后的化合物F2MSEO2M在室温下的粘度有所降低,离子电导率提高了一点。图1为F2MSEO2M在室温下的电化学窗口为0-4.95V。图2为F2MSEO2M在不同温度下的离子电导率曲线。从以上的基本数据可知:本发明通式[Ⅰ]所示的含聚醚链有机卤硅烷适合作为电解液的共溶剂或者添加剂使用。
化学结构中的聚醚链段提供与锂离子络合点,进行离子传输,从而提高电池性能。聚醚链的单元数决定物质的粘度及对锂盐的溶解性,其中优选为含两个EO单元链的有机卤硅烷,例如F2MSEO2M,其粘度较低,对锂盐的溶解能力好。
实施例7中,电解液的溶剂是由PC和F2MSEO2M的比例为1:1组成,考察是否能改善石墨电极的SEI膜性能。由图3和图4可知,在PC基电解液中,F2MSEO2M的使用可以有效抑制PC分子的共嵌入到石墨层间并使之剥离,在石墨电极片表面形成稳定的SEI膜。图5是实施例7中锂离子电池的在0.1C充放循环性能曲线,电池首次放电比容量为461mAh/g。20个循环后,电池放电比容量为310mAh/g,电池表现出99%以上的效率且循环性能稳定。
对比例2中,向实施例7电解液体系中添加了链状碳酸酯DEC和DMC,降低了PC和F2MSEO2M的浓度,并降低电解液粘度,具体比例为PC:DEC:DMC:F2MSEO2M=35:30:30:5。从图6可知,5%含量F2MSEO2M的仍可以让石墨电极片表面形成稳定的SEI膜,且循环性能稳定。
Claims (3)
1.一种含聚醚链有机卤硅烷,其化学结构式如式Ⅰ所示:
其中,R1、R2、R3选自相同或不同的-(CH2)xCH3,x=0~5,或卤素取代基,所述卤素选自F或Cl,且R1、R2、R3中至少有一个卤素取代基;R4是结构式为-NR5R6的叔胺基,R5、R6选自相同或不同C1-C5的烷基;m为1-20的整数,n为0-5的整数。
2.权利要求1所述的含聚醚链有机卤硅烷在非水系锂离子电池电解液中的应用。
3.如权利要求2所述的含聚醚链有机卤硅烷在非水系锂离子电池电解液中的应用,其特征在于:权利要求1所述含聚醚链有机卤硅烷作为非水溶剂或添加剂应用于锂离子电池。
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