CN102964372B - 卤硅烷功能化碳酸酯电解质材料,其制备方法及在锂离子电池电解液中的应用 - Google Patents
卤硅烷功能化碳酸酯电解质材料,其制备方法及在锂离子电池电解液中的应用 Download PDFInfo
- Publication number
- CN102964372B CN102964372B CN201210358351.0A CN201210358351A CN102964372B CN 102964372 B CN102964372 B CN 102964372B CN 201210358351 A CN201210358351 A CN 201210358351A CN 102964372 B CN102964372 B CN 102964372B
- Authority
- CN
- China
- Prior art keywords
- halosilanes
- acid esters
- carbon acid
- functionalized carbon
- electrolyte
- 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.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- 239000003792 electrolyte Substances 0.000 title claims abstract description 29
- 239000002253 acid Substances 0.000 title claims abstract description 24
- 150000002148 esters Chemical class 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 239000006184 cosolvent Substances 0.000 claims abstract description 5
- -1 halo silicon hydrogen alkane Chemical class 0.000 claims description 59
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 12
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000003682 fluorination reaction Methods 0.000 claims description 8
- KAPMHCGNDQJNRP-UHFFFAOYSA-N 4-(prop-2-enoxymethyl)-1,3-dioxolan-2-one Chemical compound C=CCOCC1COC(=O)O1 KAPMHCGNDQJNRP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 claims description 4
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002001 electrolyte material Substances 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004334 fluoridation Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 20
- 239000002904 solvent Substances 0.000 abstract description 14
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 7
- 159000000002 lithium salts Chemical class 0.000 abstract description 7
- 238000009835 boiling Methods 0.000 abstract description 5
- 239000013538 functional additive Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 150000005677 organic carbonates Chemical group 0.000 abstract description 4
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 25
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical group Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000005046 Chlorosilane Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 239000006183 anode active material Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 5
- 125000005336 allyloxy group Chemical group 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 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
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- DZVMPZZLNXJNLL-UHFFFAOYSA-N difluoro(methyl)silane Chemical group C[SiH](F)F DZVMPZZLNXJNLL-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002555 ionophore Substances 0.000 description 1
- 230000000236 ionophoric effect Effects 0.000 description 1
- 239000007788 liquid 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
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 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
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/122—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/123—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-halogen linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0031—Chlorinated solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0034—Fluorinated solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
Abstract
本发明提供了一类卤硅烷功能化碳酸酯电解质材料,其制备方法及在锂电池中的应用。其化学结构如式1所示,式1化合物含卤硅烷基团和有机碳酸酯基团,分子结构中含有机碳酸酯部分有助于锂离子的离解和传导,有机硅功能团能改进电极的表面性能和提高材料的界面性能。本发明所述的卤硅烷功能化碳酸酯电解质材料可用作功能添加剂或共溶剂应用于锂离子电池,电解液包括锂盐,高介电常数溶剂或低沸点的有机溶剂,和化学结构如式1所示的化合物。该类材料也可以应用于其它电化学储能器件。
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,尤其是涉及一类含卤硅烷功能化碳酸酯电解质材料,其制备方法及在锂离子电池电解液功能添加剂(或共溶剂)中的应用。
技术背景
锂离子电池具有开路电压高、比容量大、循环寿命长、安全性能好、自放电小、应用范围宽、无记忆效应、无污染等优点,作为新型绿色电池,目前已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。
电解液是锂离子电池的重要组成部分,是在电池正、负极之间起传导作用的离子导体,是连接正、负极材料之间的桥梁,它本身的性能及其与正负极形成的界面状况很大程度上影响电池的性能。选择合适的电解液是获得高能量密度和功率密度、长循环寿命和安全性良好的锂离子电池的关键因素之一。目前商业电解液主要是由多种有机碳酸酯溶剂混合组成,但是这类电解液易燃、易挥发,导致了锂离子电池的安全事故频频发生;此外,有机碳酸酯类电解液还存在高低温性能、安全性、大容量和高倍率放电不足等缺点。当在锂离子电池有机电解液中添加少量的功能添加剂时,电池的电化学性能如电导率、循环效率和可逆容量等能够得到明显的改善。它们具有“用量小、见效快”的特点,操作简单,可直接加入到有机电解液中。在基本不增加电池成本的基础上,就能显著改善电池的性能。因此,设计开发高安全性和高性能的新型电解液添加剂是锂离子电池材料的研究热点。
有机硅电解质材料具有优良的热稳定性和低温离子传导性能、高电导率、无毒性、低可燃性和高分解电压等优点,与碳基类似物相比具有更高的电化学稳定性(4.5V以上),应用小分子有机硅电解液的锂电池也表现出优良的充放电循环性能,高能量密度和较高的功率密 度。取代基对有机硅电解质材料的影响也有相关的计算报道,吸电子基团取代可以提高有机硅化合物的电化学窗口(J.Phys.Chem.C.2011,115,12216)。而实验报道的卤硅烷化合物用于锂离子电池中却很少,在先专利有报道通过有机硅化合物与含氟碱金属盐的反应生成的氟硅烷对电池阻抗性能的影响(CN102113164),也有提及有机氟硅烷存在应用于锂电池添加剂的潜在可能性(US2009/0197167A1)。虽然卤硅烷化合物用于锂电池的电解质材料或添加剂的研究不多,但开发新型卤硅烷化合物应用于锂离子电池有着重要的研究和实际意义。
发明内容
本发明的目的是提供一类应用范围广的含卤硅烷基团和有机碳酸酯基团的卤硅烷功能化碳酸酯电解质材料,并提供了其制备方法以及用作功能添加剂或共溶剂在锂离子电池中的应用。
本发明卤硅烷功能化碳酸酯电解质材料,其化学结构如式1示:
式1
其中R1选自如下结构单元:亚甲基[-(CH2)m-,m=1~3]或含醚链[-(CH2)mO(CH2)n-,m,n=1~3]的基团;R2,R3,R4选自烷基[-(CH2)mCH3,m=0~3],芳基(或取代芳基),或X(卤素)取代;且R2,R3,R4至少有一个X取代基团,所述卤素优选为-Cl,-F。式1化合物含卤硅烷基团和有机碳酸酯基团,有机硅基团为卤硅烷基团,有机碳酸酯基团为4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮或4-乙基-1,3-二氧戊环-2-酮。其中所述卤硅烷基团可为单卤代或二卤代、三卤代硅烷化合物,可为氯硅烷基团或氟硅烷基团。分子结构中含有机碳酸酯部分有助于锂离子的离解和传导,有机硅功能团能改进电极的表面性能和提高材料的界面性能。
本发明还提供了上述卤硅烷功能化碳酸酯电解质材料的制备方法,该方法包括如下步骤: (1)双键取代的碳酸酯与卤代硅氢烷或烷氧基硅氢烷通过硅氢化反应,制备相应的卤硅烷或烷氧基硅烷取代的碳酸酯;(2)步骤(1)产物与氟化试剂反应生成相应的氟硅烷取代的碳酸酯。
所述双键取代的碳酸酯为4-[(烯丙氧基)甲基]-1,3-二氧戊环-2-酮或4-乙烯基-1,3-二氧戊环-2-酮;卤代硅氢烷为氯代硅氢烷;烷氧基硅氢烷为甲氧基取代硅氢烷或乙氧基取代硅氢烷;并且上述双键取代碳酸酯与硅氢烷的摩尔比为1:1.0~1.5。
所述硅氢化反应催化剂选自:氯铂酸,二氧化铂,或Karstedt′s催化剂,并且其加入的量为0.1~1mol%(相对于双键碳酸酯);所述氟化试剂包括:三氟化硼·乙醚、三氟化锑、氟化钾、或氟化锂,所述氟化试剂与卤硅烷或烷氧基硅烷取代的碳酸酯的摩尔比为3~1:1。
反应在惰性气体保护环境下进行的;硅氢化反应的温度为30~80度,反应时间是2~24小时;氟化反应的温度为30~80度,反应时间是2~24小时。
本发明还提供了式1所示的卤硅烷功能化碳酸酯电解质材料在锂离子电池中的应用。所述卤硅烷功能化碳酸酯电解质材料可作为功能添加剂或共溶剂应用于锂离子电池的电解液中。所述锂离子电池电解液包括式1所示的有机化合物,还包括锂盐,高介电常数溶剂或低沸点的有机溶剂。
本发明有机硅功能化碳酸酯电解质材料也可以作为电解质材料应用于其它电化学储能器件(如燃料电池、电解电容和超级电容)及其它光电器件(如有机太阳能电池等)。
附图说明:
图1为本发明实施例1化合物的核磁氢谱和碳谱图。
图2为本发明实施例2化合物的核磁氢谱和碳谱图。
图3为本发明实施例3化合物的核磁氢谱和碳谱图。
图4为本发明实施例4化合物的核磁氢谱和碳谱图。
图5为本发明实施例5化合物的核磁氢谱和碳谱图。
图6为本发明实施例6化合物的核磁氢谱和碳谱图。
图7为本发明实施例4化合物(MFGC)的电化学窗口图。
图8为本发明实施例4化合物(MFGC)的离子电导率图。
图9为本发明实施例4化合物(MFGC)添加于商业电解液(1M LiPF6 EC/DMC/DEC=1:1:1)的电池性能测试图。
具体实施方式
下面结合附图和实施例对本发明内容作进一步说明。
本发明卤硅烷功能化碳酸酯电解质材料的制备路线具体有以下两种:
方法一:(1)4-[(烯丙氧基)甲基]-1,3-二氧戊环-2-酮或4-乙烯基-1,3-二氧戊环-2-酮与烷氧基硅氢烷通过硅氢化反应制备烷氧基硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮或烷氧基硅烷取代的4-乙基-1,3-二氧戊环-2-酮;(2)烷氧基硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮或烷氧基硅烷取代的4-乙基-1,3-二氧戊环-2-酮与氟化试剂(包括三氟化硼·乙醚、三氟化锑、含氟的碱金属盐)反应制备相应的氟硅烷功能化碳酸酯电解质材料。具体合成路线如下所示。
上述反应的具体步骤如下:(1)烷氧基硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮 或烷氧基硅烷取代的4-乙基-1,3-二氧戊环-2-酮的制备:在室温条件下,将烷氧基硅氢烷(1.1eq.)缓慢滴入加有0.1~1mol%的铂催化剂的4-[(烯丙氧基)甲基]-1,3-二氧戊环-2-酮或4-乙烯基-1,3-二氧戊环-2-酮中,待滴加完毕,反应体系升温至85度后反应12小时,通过蒸馏可得到烷氧基硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮或烷氧基硅烷取代的4-乙基-1,3-二氧戊环-2-酮。(2)卤硅烷功能化碳酸酯电解质材料的制备:在氩气保护下,将三氟化硼乙醚溶液(三氟化硼·乙醚与烷氧基硅烷取代的碳酸酯的摩尔比为3~1:1)滴入烷氧基硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮或烷氧基硅烷取代的4-乙基-1,3-二氧戊环-2-酮的甲苯溶液中,加热反应过夜,旋蒸溶剂,然后将所得反应混合物通过减压蒸馏得目标产物。
方法二:(1)4-[(烯丙氧基)甲基]-1,3-二氧戊环-2-酮或4-乙烯基-1,3-二氧戊环-2-酮与氯代硅氢烷通过硅氢化反应制备氯硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮或氯硅烷取代的4-乙基-1,3-二氧戊环-2-酮;(2)氯硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮或氯硅烷取代的4-乙基-1,3-二氧戊环-2-酮与氟化试剂(包括三氟化硼·乙醚、三氟化锑、含氟的碱金属盐)反应制备相应的氟硅烷功能化碳酸酯电解质材料。具体合成路线如下所示。
上述反应的方法二具体步骤如下:(1)氯代硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮或氯硅烷取代的4-乙基-1,3-二氧戊环-2-酮的制备:在室温条件下,将氯代硅氢烷(1.1eq.)缓慢滴入加有0.1~1mol%的铂催化剂的4-[(烯丙氧基)甲基]-1,3-二氧戊环-2-酮或4-乙烯基 -1,3-二氧戊环-2-酮中,待滴加完毕,反应体系升温至85度后反应12小时,可得到相应硅氢化产物。(2)氟硅烷功能化碳酸酯电解质材料的制备:在氩气保护下,将氟化钾(氟化钾与氯硅烷取代的碳酸酯的摩尔比为3~1:1)加入氯代硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮或氯硅烷取代的4-乙基-1,3-二氧戊环-2-酮的乙腈溶液中,室温搅拌反应过夜,旋蒸溶剂,然后将所得反应混合物通过减压蒸馏得目标产物。
实施例1-6化合物的结构式如下所示:
实施例1:三氟硅烷取代4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮的合成(TFGC)
在氩气保护下,取4-[(烯丙氧基)甲基]-1,3-二氧戊环-2-酮(0.1mol)和三乙氧基硅烷(0.11mol)在氯铂酸(0.4%mol)催化的条件下,反应体系升温至85度后反应12小时,然后蒸馏可得三乙氧基硅烷取代的烯丙基甘油碳酸酯化合物。将三氟化硼·乙醚(0.1mol)滴加至三乙氧基硅烷取代的烯丙基甘油碳酸酯(0.05mol)的甲苯溶液中,加热至80度后反应2小时,将溶剂旋蒸,后减压蒸馏得三氟硅烷取代烯丙基甘油碳酸酯,对其进行核磁表征,核磁谱图如附图1所示:
1H NMR(600MHz,CDCl3):δ=1.05(m,2H,SiCH2CH2),1.84(m,2H,SiCH2CH2),3.54(m,2H,SiCH2CH2CH2),3.68(m,2H,OCH2CH),4.36(m,1H,CH2),4.50(m,1H,CH2),4.84(m,1H,CH).
13C NMR(150.9MHz,CDCl3):3.77,3.88,4.00,4.14,21.71,66.36,69.99,72.20,74.79, 154.86.
实施例2:三氟硅烷取代4-乙基-1,3-二氧戊环-2-酮的合成(TFVEC)
用4-乙烯基-1,3-二氧戊环-2-酮为反应物,采用实施例1相同的合成方法,通过减压蒸馏得目标产物。对其进行核磁表征,核磁谱图如附图2所示:
1H NMR(600MHz,CDCl3):δ=1.10(m,1H,SiCH2CH2),1.25(m 1H,SiCH2CH2),1.97(m,2H,SiCH2CH2),4.09(t,3J=8.4Hz,1H,CH2),4.57(m,1H,3J=8.4Hz,CH2),4.71(m,1H,CH).
13C NMR(150.9MHz,CDCl3):2.20,25.76,68.62,76.79,154.32.
实施例3:一甲基二氟硅烷取代4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮的合成(DFGC)
用二乙氧基硅烷为反应物,采用实施例1相同的合成方法,通过减压蒸馏得目标产物。
也可以用本专利所描述的方法二:4-[(烯丙氧基)甲基]-1,3-二氧戊环-2-酮(0.2mol)与一甲基二氯硅氢烷(0.2mol)在氯铂酸(0.4%mol)催化的条件下反应制备一甲基二氯硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮;一甲基二氯硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮与氟化钾在乙腈溶液中反应制备相应的一甲基二氟硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮。
对其进行核磁表征,核磁谱图如附图3所示:
1H NMR(600MHz,CDCl3):δ=0.34(t,3H,3J=6.0Hz,SiCH3),0.82(m,2H,SiCH2CH2),1.73(m,2H,SiCH2CH2),3.50(t,2H,3J=6.0Hz,SiCH2CH2CH2),3.60(dq,2H,3J=10.8Hz,OCH2CH),4.37(dd,1H,3J=10.8Hz,CH2),4.49(dd,1H,3J=10.8Hz,CH2),4.80(m,1H,CH).
13C NMR(150.9MHz,CDCl3):-4.34(t,3J=16.05),9.82(t,3J=15.45),21.74,66.21,69.78,73.20,75.01,154.95.
实施例4:二甲基一氟硅烷取代4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮的合成(MFGC)
4-[(烯丙氧基)甲基]-1,3-二氧戊环-2-酮(0.2mol)与二甲基一氯硅氢烷(0.2mol)在氯铂酸(0.4%mol)催化的条件下反应制备二甲基一氯硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮;二甲基一氯硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮与氟化钾在乙腈溶液中反应制备相应的二甲基一氟硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮。
也可以用本专利所描述的方法一:用一乙氧基甲基硅烷为反应物,采用实施例1相同的合成方法,通过减压蒸馏得目标产物。对其进行核磁表征,核磁谱图如附图4所示:
1H NMR(600MHz,CDCl3):δ=0.10(s,3H,SiCH3),0.59(t,2H,SiCH2CH2),1.19(t,6H,Si(OCH2H3)2),1.63(m,2H,SiCH2CH2),3.46(m,2H,SiCH2CH2CH2),3.62(dq,2H,3J=10.8Hz,OCH2CH),3.74(q,4H,3J=7.2Hz,Si(OCH2H3)2),4.38(dd,1H,3J=6.0Hz,CH2),4.47(dd,1H, 3J=6.0Hz,CH2),4.78(m,1H,CH).
13C NMR(150.9MHz,CDCl3):-5.0,9.7,18.3,22.9,58.1,66.2,69.5,74.3,75.0,154.9.
实施例5:二甲基一氯硅烷取代4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮的合成(MCGC)
4-[(烯丙氧基)甲基]-1,3-二氧戊环-2-酮(0.2mol)与二甲基一氯硅氢烷(0.2mol)在氯铂酸(0.4%mol)催化的条件下反应制备一甲基二氯硅烷取代的4-[(丙氧基)甲基]-1,3-二氧戊环-2-酮。通过减压蒸馏得目标产物。对其进行核磁表征,核磁谱图如附图5所示:
1H NMR(600MHz,CDCl3):δ=0.42(s,6H,Si(CH3)2),0.83(m,2H,SiCH2CH2),1.70(m,2H,SiCH2CH2),3.52(m,2H,SiCH2CH2CH2),3.65(dq,2H,3J=10.8Hz,OCH2CH),4.40(t,1H,3J=8.4Hz,CH2),4.50(t,1H,3J=8.4Hz,CH2),4.80(m,1H,CH).
13C NMR(150.9MHz,CDCl3):1.57,14.97,23.11,66.24,69.68,73.90,75.00,154.86.
实施例6:一甲基二氯硅烷取代4-乙基-1,3-二氧戊环-2-酮的合成(DCVEC)
4-乙烯基-1,3-二氧戊环-2-酮(0.2mol)与一甲基二氯硅氢烷(0.2mol)在氯铂酸(0.4%mol)催化的条件下反应制备一甲基二氯硅烷取代的4-乙基-1,3-二氧戊环-2-酮。通过减压蒸馏得目标产物。对其进行核磁表征,核磁谱图如附图6所示:
1H NMR(600MHz,CDCl3):δ=0.83(s,3H,SiCH3),1.23(m,2H,SiCH2CH2),1.95(m,2H,SiCH2CH2),4.10(t,3J=8.4Hz,1H,CH2),4.56(m,1H,3J=8.4Hz,CH2),4.73(m,1H,CH).
13C NMR(150.9MHz,CDCl3):5.08,16.04,27.10,68.74,76.79,154.60.
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。
高介电常数溶剂不特别限制,通常为电池领域常用的溶剂,例如,环状碳酸酯如碳酸亚乙酯、碳酸亚丙酯,或γ-丁内酯等。低沸点的有机溶剂也不特别限制,可为碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯二甲氧乙烷,或脂肪酸酯衍生物等。高介电常数溶剂和低沸点的有机溶剂的体积比可为1:1至1:9,高介电常数溶剂和低沸点的有机溶剂也可以单独使用。锂盐可为在锂电池中通常使用的的锂盐。例如,锂盐可选包括LiClO4、LiCF3SO3、LiPF6、LiN(CF3SO2)2、LiBF4、Li(BC4O8)和LiN(C2F5SO2)2等锂盐中的至少一种。有机电解液中锂盐的浓度可为0.5-2.0M。
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。将正极活性材料组合物直接涂覆在铝集电体上并干燥以制备正极板。或者,将正极活性材料组合物在独立的基板上流延,并将从其获得的膜层压在铝集电体上以制备正极板。
正极活性材料可为本领域中通常使用的任何含锂的金属氧化物。含锂的金属氧化物的实例包括LiCoO2、LiMnxO2x(其中x=1、2)、LiNi1-xMnxO2(其中0<x<1)和LiNi1-x-yCoxMnyO2(其中0≤x≤0.5,0≤y≤0.5)和LiFePO4。
炭黑可用作导电剂。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。溶剂可选自N-甲基吡咯烷酮(NMP)、丙酮、水等。正极活性材料、导电剂、粘合剂和溶剂的量可采用现有技术在锂电池中通常使用的用量。
硅金属、硅薄膜、锂金属、锂合金、碳质材料或石墨可用作负极活性材料。负极活性材料组合物中的导电剂、粘结剂和溶剂可与正极活性材料组合物中的那些相同。如果需要,可将增塑剂加入正极活性材料组合物和负极活性材料组合物中以在电极板中产生孔。
隔膜可由在锂电池中通常使用的任何材料构成。可使用对电解质的离子的移动具有低阻抗和具有良好的吸收电解液的能力的材料。例如,该材料可为选自玻璃纤维、聚酯、特氟隆(Teflon)、聚乙烯、聚丙烯、聚四氟乙烯(PTFE)及其组合的无纺物或纺织物。更具体地,锂离子电池可选用包括聚乙烯、聚丙烯等可卷绕的隔膜,和锂离子电池可使用具有优异的浸渍有机电解液的能力的隔膜。
在所进行的实验中,所使用的电解液和LiPF6来自东莞杉杉有限公司,锂片来自中国锂能,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99.9999%)气氛下进行。
将LiPF6溶解于碳酸亚乙酯,碳酸二甲酯,和碳酸二乙酯(EC:DMC:DEC=1:1:1)中配成浓度为1M的电解液,向此电解液中加入2vol.%的MFGC。利用LiCoO2和Li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3.0V-4.3V。
附图7为本发明实施例4化合物(MFGC)的电化学窗口图,其氧化电位大于5V。附图8为本发明实施例4化合物(MFGC)的离子电导率图,溶有1M的LiTFSI。表1为本发明实施例化合物的粘度和介电常数表,从中可以看出,该类化合物表现出较高的介电常数。附图9为本发明实施例4化合物添加于电池中的循环性能曲线,相比于普通电解液的电池,添加有有机硅功能化碳酸酯的电池表现出更高的容量保持率。
表1:
粘度(cP) | 介电常数 | |
MFGC | 16.6 | 49.2 |
DFGC | 20.0 | 53.5 |
TFGC | 22.7 | -- |
对比例1:
为做对比,使用商业电解液(1M LiPF6 EC:DMC:DEC=1:1:1),按与实施例7相同的方法组装硬币式电池(2025),然后按实施例7相同的方法进行充/放电比较测试。
Claims (7)
1.一种卤硅烷功能化碳酸酯电解质材料,其化学结构如式1所示:
R1选自如下基团:[-(CH2)m-,m=1~3]或[-(CH2)mO(CH2)n-,m,n=1~3];R2,R3,R4选自如下基团:[-(CH2)mCH3,m=0~3],或卤素取代基,且R2,R3,R4至少有一个为卤素取代基团,且R1选自-(CH2)3O(CH2)-,R2选自CH3时,R3或R4不能同时选自氯。
2.如权利要求1所述的卤硅烷功能化碳酸酯电解质材料的制备方法,其特征在于包括如下步骤:(1)双键取代的碳酸酯化合物与卤代硅氢烷或烷氧基硅氢烷通过硅氢化反应,制备相应的卤硅烷或烷氧基硅烷取代的碳酸酯;或(2)步骤(1)产物与氟化试剂反应生成相应的氟硅烷取代的碳酸酯。
3.根据权利要求2所述的卤硅烷功能化碳酸酯电解质材料的制备方法,其特征在于:所述双键取代的碳酸酯为4-[(烯丙氧基)甲基]-1,3-二氧戊环-2-酮或4-乙烯基-1,3-二氧戊环-2-酮;卤代硅氢烷为氯代硅氢烷;烷氧基硅氢烷为甲氧基取代硅氢烷或乙氧基取代硅氢烷;并且上述双键取代碳酸酯与硅氢烷的摩尔比为1:1.0~1.5。
4.根据权利要求2所述的卤硅烷功能化碳酸酯电解质材料的制备方法,其特征在于:所述硅氢化反应催化剂选自:氯铂酸,二氧化铂,或Karstedt's催化剂,并且其加入的量为双键取代的碳酸酯化合物的0.1~1mol%;所述氟化试剂包括:三氟化硼·乙醚、三氟化锑、氟化钾、或氟化锂,所述氟化试剂与卤硅烷或烷氧基硅烷取代的碳酸酯的摩尔比为3~1:1。
5.根据权利要求2或4之任一所述的卤硅烷功能化碳酸酯电解质材料的制备方法,其特征在于:反应在惰性气体保护环境下进行的;硅氢化反应的温度为30~80度,反应时间是2~24小时;氟化反应的温度为30~80度,反应时间是2~24小时。
6.权利要求1所述的卤硅烷功能化碳酸酯电解质材料在锂离子电池中的应用。
7.如权利要求6所述的卤硅烷功能化碳酸酯电解质材料在锂离子电池中的应用,其特征在于式1所述含卤硅烷功能化碳酸酯电解质材料作为电解质添加剂或共溶剂应用于锂离子电池的电解液中。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210358351.0A CN102964372B (zh) | 2012-09-24 | 2012-09-24 | 卤硅烷功能化碳酸酯电解质材料,其制备方法及在锂离子电池电解液中的应用 |
PCT/CN2012/084205 WO2014043981A1 (zh) | 2012-09-24 | 2012-11-07 | 卤硅烷功能化碳酸酯电解质材料,其制备方法及在锂离子电池电解液中的应用 |
US14/430,480 US20150270574A1 (en) | 2012-09-24 | 2012-11-07 | Halogenosilane functionalized carbonate electrolyte material, preparation method thereof and use in electrolyte for lithium ion battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210358351.0A CN102964372B (zh) | 2012-09-24 | 2012-09-24 | 卤硅烷功能化碳酸酯电解质材料,其制备方法及在锂离子电池电解液中的应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102964372A CN102964372A (zh) | 2013-03-13 |
CN102964372B true CN102964372B (zh) | 2015-09-30 |
Family
ID=47794832
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201210358351.0A Active CN102964372B (zh) | 2012-09-24 | 2012-09-24 | 卤硅烷功能化碳酸酯电解质材料,其制备方法及在锂离子电池电解液中的应用 |
Country Status (3)
Country | Link |
---|---|
US (1) | US20150270574A1 (zh) |
CN (1) | CN102964372B (zh) |
WO (1) | WO2014043981A1 (zh) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104752766B (zh) * | 2013-12-30 | 2017-05-31 | 比亚迪股份有限公司 | 电解液添加剂、含该添加剂的电解液及使用电解液的锂离子电池 |
WO2016054621A1 (en) | 2014-10-03 | 2016-04-07 | Silatronix, Inc. | Functionalized silanes and electrolyte compositions and electrochemical devices containing them |
CN105514487A (zh) * | 2015-12-30 | 2016-04-20 | 中国科学院广州能源研究所 | 一种有机硅电解液和硅基电极材料配合使用的方法 |
CN106252727A (zh) * | 2016-11-03 | 2016-12-21 | 深圳市沃特玛电池有限公司 | 一种锂离子电池电解液、锂离子电池 |
CN109768319B (zh) * | 2017-11-09 | 2021-05-14 | 深圳新宙邦科技股份有限公司 | 锂离子电池非水电解液及使用该电解液的锂离子电池 |
CN109786834B (zh) * | 2019-01-25 | 2021-01-12 | 宁德新能源科技有限公司 | 电解液及电化学装置 |
EP4156366A1 (en) * | 2020-05-19 | 2023-03-29 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous electrolytic solution battery |
CN112582674B (zh) * | 2020-09-30 | 2022-02-11 | 骆驼集团新能源电池有限公司 | 一种12v启停锂离子电池电解液 |
CN112652818A (zh) * | 2021-01-12 | 2021-04-13 | 东莞维科电池有限公司 | 锂离子电池用电解液及锂离子电池 |
CN113140794B (zh) * | 2021-03-30 | 2022-07-12 | 山东海容电源材料有限公司 | 一种电解液成膜添加剂及含该添加剂的锂离子电池电解液 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4939068A (en) * | 1987-12-01 | 1990-07-03 | Basf Aktiengesellschaft | Anodic oxidation of the surface of aluminum or aluminum alloys |
CN1501539A (zh) * | 2002-11-16 | 2004-06-02 | ����Sdi��ʽ���� | 非水电解液及使用它的锂电池 |
US20120135313A1 (en) * | 2004-02-04 | 2012-05-31 | West Robert C | Electrolyte including silane for use in electrochemical devices |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6120940A (en) * | 1996-10-30 | 2000-09-19 | The Johns Hopkins University | Electrochemical storage cell containing at least one electrode formulated from a phenylene-thienyl based polymer |
JP4063384B2 (ja) * | 1998-03-02 | 2008-03-19 | ダウ・コ−ニング・コ−ポレ−ション | ハイドロカーボンオキシシリル官能性ポリマーの製造方法 |
US20070065728A1 (en) * | 2003-03-20 | 2007-03-22 | Zhengcheng Zhang | Battery having electrolyte with mixed solvent |
JP4656312B2 (ja) * | 2005-09-13 | 2011-03-23 | 信越化学工業株式会社 | 環状カーボネート変性有機ケイ素化合物を含有する非水電解液並びに二次電池及びキャパシタ |
WO2008032539A1 (fr) * | 2006-09-13 | 2008-03-20 | Kaneka Corporation | POLYMÈRE DURCISSABLE À L'HUMIDITÉ COMPORTANT UN GROUPE SiF ET COMPOSITION DURCISSABLE CONTENANT UN TEL POLYMÈRE |
US20110136018A1 (en) * | 2008-08-06 | 2011-06-09 | Mitsui Chemicals, Inc. | Non-aqueous electrolytic solution, lithium secondary battery and method for producing same, and mixed-type non-aqueous electrolytic solution |
US8492033B2 (en) * | 2009-06-18 | 2013-07-23 | Uchicago Argonne, Llc | Fast cure gel polymer electrolytes |
JP5694833B2 (ja) * | 2010-09-22 | 2015-04-01 | 富士フイルム株式会社 | 非水二次電池用電解液及びリチウム二次電池 |
-
2012
- 2012-09-24 CN CN201210358351.0A patent/CN102964372B/zh active Active
- 2012-11-07 WO PCT/CN2012/084205 patent/WO2014043981A1/zh active Application Filing
- 2012-11-07 US US14/430,480 patent/US20150270574A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4939068A (en) * | 1987-12-01 | 1990-07-03 | Basf Aktiengesellschaft | Anodic oxidation of the surface of aluminum or aluminum alloys |
CN1501539A (zh) * | 2002-11-16 | 2004-06-02 | ����Sdi��ʽ���� | 非水电解液及使用它的锂电池 |
US20120135313A1 (en) * | 2004-02-04 | 2012-05-31 | West Robert C | Electrolyte including silane for use in electrochemical devices |
Non-Patent Citations (3)
Title |
---|
Silicon-Containing Carbonates—Synthesis, Characterization, and Additive Effects for Silicon-Based Polymer Electrolytes;Nicholas A. A. Rossi等;《Silicon》;20101110;第2卷(第4期);第205页左栏方案2方程式 * |
Synthesis and dielectric constants of polymers with cyclic carbonate pendant groups;Andrew P Purdy等;《Polymer Preprints》;20031231;第44卷(第1期);第854页左栏倒数第2段 * |
锂离子电池有机硅电解液;秦雪英等;《化学进展》;20120531;第24卷(第5期);第3454-3459页 * |
Also Published As
Publication number | Publication date |
---|---|
CN102964372A (zh) | 2013-03-13 |
US20150270574A1 (en) | 2015-09-24 |
WO2014043981A1 (zh) | 2014-03-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102964372B (zh) | 卤硅烷功能化碳酸酯电解质材料,其制备方法及在锂离子电池电解液中的应用 | |
Wang et al. | A fluorinated polycarbonate based all solid state polymer electrolyte for lithium metal batteries | |
KR101650851B1 (ko) | 비수전해액 전지용 전해액 및 이것을 이용한 비수전해액 전지 | |
Wang et al. | Exploring polymeric lithium tartaric acid borate for thermally resistant polymer electrolyte of lithium batteries | |
Wu et al. | High-energy density Li metal dual-ion battery with a lithium nitrate-modified carbonate-based electrolyte | |
CN102924495B (zh) | 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 | |
Sångeland et al. | Stable cycling of sodium metal all-solid-state batteries with polycarbonate-based polymer electrolytes | |
CN102723528B (zh) | 两性离子液体电解质材料及其制备与在锂电池电解液中的应用 | |
CN104022310B (zh) | 锂离子二次电池及含有该电解液的锂离子电池 | |
CN103094611B (zh) | 一种制备离子液体凝胶电解质的方法 | |
CN109103488B (zh) | 一种聚合物钠电池及其制备方法和应用 | |
US9130240B2 (en) | Ionic liquid, lithium secondary battery electrolyte comprising the ionic liquid, and lithium secondary battery comprising the electrolyte | |
Amine et al. | Novel silane compounds as electrolyte solvents for Li-ion batteries | |
Feng et al. | A highly soluble dimethoxybenzene derivative as a redox shuttle for overcharge protection of secondary lithium batteries | |
CN101882696A (zh) | 一种含氟磺酰亚胺基锂盐的非水电解质材料及其应用 | |
CN105742077A (zh) | 电力存储装置、锂离子二次电池、双电层电容器和锂离子电容器 | |
CN108242563B (zh) | 耐高电压的固态锂电池聚合物电解质及其制备和应用 | |
CN105977534A (zh) | 一种二次锂硫电池用功能电解液及其制备方法 | |
Wang et al. | Fluorosilane compounds with oligo (ethylene oxide) substituent as safe electrolyte solvents for high-voltage lithium-ion batteries | |
CN102746330A (zh) | 有机硅功能化碳酸酯电解质材料,其制备方法及在锂电池电解液中的应用 | |
Almazrou et al. | Electrochemical Performance of Highly Ion-Conductive Polymer Electrolyte Membranes Based on Polyoxide-tetrathiol Conetwork for Lithium Metal Batteries | |
Wang et al. | Study on the Mixed Electrolyte of N, N-Dimethylacetamide/Sulfolane and Its Application in Aprotic Lithium–Air Batteries | |
US8936882B2 (en) | Electrolyte compositions for lithium and lithium-ion batteries | |
Liu et al. | Mechanism of Bilayer Polymer-Based Electrolyte with Functional Molecules in Enhancing the Capacity and Cycling Stability of High-Voltage Lithium Batteries | |
Patra et al. | Charge–Discharge Behavior of Lithium-Ion Batteries Using a Polymer Electrolyte Bearing High-Density Functional Groups |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |