CN114243112A - 一种阻燃电解液及其应用 - Google Patents
一种阻燃电解液及其应用 Download PDFInfo
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- CN114243112A CN114243112A CN202111577037.7A CN202111577037A CN114243112A CN 114243112 A CN114243112 A CN 114243112A CN 202111577037 A CN202111577037 A CN 202111577037A CN 114243112 A CN114243112 A CN 114243112A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 52
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000003063 flame retardant Substances 0.000 title claims abstract description 21
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 37
- -1 fluorosulfonyl Chemical group 0.000 claims description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 28
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 19
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 13
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 claims description 12
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 6
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- WXBWKMLIVXELSF-UHFFFAOYSA-N 2,2,2-trifluoro-n,n-dimethylacetamide Chemical compound CN(C)C(=O)C(F)(F)F WXBWKMLIVXELSF-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- MPDOUGUGIVBSGZ-UHFFFAOYSA-N n-(cyclobutylmethyl)-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC=CC(NCC2CCC2)=C1 MPDOUGUGIVBSGZ-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 3
- 239000002904 solvent Substances 0.000 abstract description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 9
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 239000007983 Tris buffer Substances 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
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- 239000011889 copper foil Substances 0.000 description 1
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- FNNQVYCCWJJBHH-UHFFFAOYSA-N difluoro methyl phosphate Chemical compound COP(=O)(OF)OF FNNQVYCCWJJBHH-UHFFFAOYSA-N 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- 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
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- Chemical & Material Sciences (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
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Abstract
本发明提供了一种阻燃电解液及其应用;包括:锂盐、添加剂A、非水有机溶剂和其他添加剂。本发明还涉及前述阻燃电解液的应用。本发明所用原料添加剂A在受热气化时能释放出含磷自由基,可与电解液中的氢自由基结合,可有效地阻止有机溶剂的燃烧或爆炸,极大提升锂离子电池的安全性;其次,其结构中包含大量氟元素,故能提升电解液的闪点,进而提升电解液的阻燃效果。由于本发明提供的由添加剂A和其他组分组成的电解液,用于制备离子电池时能在电极表面形成稳定致密的保护膜,阻止高温下电极材料和电解液溶剂的副反应,避免电池热失控的发生。
Description
技术领域
本发明涉及锂电池技术领域;尤其涉及一种阻燃电解液及其应用。
背景技术
锂离子电池凭借其高性能、低成本、高功率、清洁环保等诸多优点,已然成为人们在新能源方向的首选,其在移动电源、储能、消费电子、动力电池等领域都有很好的发展。随着锂离子电池在各个领域的不断普及,其本身暴露出的安全性问题也越来越多,诸如冒烟、起火甚至爆炸等情况也屡见不鲜。尤其是近几年电动汽车和储能行业的快速发展,锂离子电池的安全事故频频爆出,这引起了人们对锂电池安全性的广泛关注。
锂离子电池热失控很大程度上是因为在高温或者高倍率充放电条件下,电极材料和电解液溶剂温度进一步升高,导致电极表面固体电解质界面层溶解,溶剂直接暴露于电极表面并和电极材料反应而放出大量的热,最终引发电池的起火、爆炸等问题。而且锂离子电池电解液溶剂大多具有低沸点、易燃易爆的性质,致使电解液本身也具备易燃易爆特点。因此开发一款锂离子电池阻燃电解液显得尤为重要。
发明内容
本发明的目的是提供了一种阻燃电解液及其应用。
本发明是通过以下技术方案实现的:
本发明提供一种阻燃电解液,包括以下重量百分比的各组分:
优选地,所述添加剂A的结构通式为:
其中,式中R1、R2、R3、R4分别为氰基、碳原子数为1-6的烷基、三甲基硅基中的至少一种。
优选地,所述烷基和三甲基硅基中的一个或多个氢原子为以下取代基所取代:氟、三氟甲基、氟磺酰基、三氟甲磺酰基、磺酸锂基、氟(磺酰亚胺锂基)磺酰基、三氟甲基(磺酰亚胺锂基)磺酰基、氟苯基、三氟甲基苯基、氟磺酰基苯基、三氟甲磺酰基苯基、磺酸锂基苯基、氟(磺酰亚胺锂基)磺酰基苯基、三氟甲基(磺酰亚胺锂基)磺酰基苯基。
优选地,所述锂盐为六氟磷酸锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸硼酸锂、双(氟磺酰)亚胺锂、双(三氟甲基磺酰)亚胺锂、三氟甲磺酸锂、四氟硼酸锂、高氯酸锂、(氟磺酰)三氟甲基磺酰亚胺锂、四氯铝酸锂、六氟砷酸锂中的至少一种。
优选地,所述非水有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、γ-丁内酯、二氧五环、四氢呋喃、二甲基三氟乙酰胺、二甲基亚砜中的至少一种。
优选地,所述其他添加剂为双草酸硼酸锂、二氟磷酸锂、二氟草酸硼酸锂、二氟二草酸硼酸锂、四氟草酸磷酸锂、碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、1,4-丁烷磺酸内酯中的至少一种。
本发明还涉及前述的阻燃电解液的应用,用于锂离子电池的制备,锂电池包括正极、负极、隔膜和所述电解液。
本发明具有以下优点:
(1)本发明所用的原料添加剂A为磷酸酯类添加剂;一方面,在受热气化时能释放出含磷自由基,可与电解液中的氢自由基结合,可有效地阻止有机溶剂的燃烧或爆炸,极大提升锂离子电池的安全性;另一方面,结构中包含大量氟元素,故能提升电解液的闪点,进而提升电解液的阻燃效果。
(2)本发明提供的添加剂A引入大量含Si基团,在电池燃烧时能生成含有Si-O键的无机绝热层,能隔绝氧气使电池自熄。
(3)本发明提供的由添加剂A和其他组分组成的电解液,用于制备离子电池时能在电极表面形成稳定致密的保护膜,阻止高温下电极材料和电解液溶剂的副反应,避免电池热失控的发生。
具体实施方式
下面结合具体实施例对本发明进行详细说明。应当指出的是,以下的实施实例只是对本发明的进一步说明,但本发明的保护范围并不限于以下实施例。
实施例
本实施例涉及一种阻燃电解液,包括:锂盐、添加剂A、非水有机溶剂和其他添加剂;
其中R1、R2、R3、R4分别为氰基、碳原子数为1-6的烷基、三甲基硅基中的至少一种。
所述烷基和三甲基硅基中的一个或多个氢原子可被如下基团中的至少一种取代:氟、三氟甲基、氟磺酰基、三氟甲磺酰基、磺酸锂基、氟(磺酰亚胺锂基)磺酰基、三氟甲基(磺酰亚胺锂基)磺酰基、氟苯基、三氟甲基苯基、氟磺酰基苯基、三氟甲磺酰基苯基、磺酸锂基苯基、氟(磺酰亚胺锂基)磺酰基苯基、三氟甲基(磺酰亚胺锂基)磺酰基苯基。
1、电解液的制备
实施例1-14、对比例1-4所涉及的电解液均按照以下方法进行配制:
将碳酸乙烯酯(EC,溶剂)、碳酸二甲酯(DMC,溶剂)、碳酸甲乙酯(EMC,溶剂)按照质量比EC:DMC:EMC=2:3:5混合均匀,加入六氟磷酸锂(锂盐)至锂盐浓度为1mol/L,加入添加剂A和其他添加剂(其两者的用量wt%见表1),溶解搅拌均匀即制得所需电解液。
实施例1-14及对比例1-4中添加剂种类及用量如表1所示。
表1
编号 | 添加剂A/用量(wt%) | 其他添加剂/用量(wt%) |
实施例1 | 结构1,1% | 碳酸亚乙烯酯,2% |
实施例2 | 结构1,2% | 碳酸亚乙烯酯,2% |
实施例3 | 结构1,3% | 碳酸亚乙烯酯,2% |
实施例4 | 结构1,4% | 碳酸亚乙烯酯,2% |
实施例5 | 结构1,5% | 碳酸亚乙烯酯,2% |
实施例6 | 结构110% | 碳酸亚乙烯酯2% |
实施例7 | 结构120% | 碳酸亚乙烯酯2% |
实施例8 | 结构21% | 碳酸亚乙烯酯2%氟代碳酸乙烯酯1% |
实施例9 | 结构2,2% | 碳酸亚乙烯酯,2%;氟代碳酸乙烯酯,1% |
实施例10 | 结构2,3% | 碳酸亚乙烯酯,2%;氟代碳酸乙烯酯,1% |
实施例11 | 结构2,4% | 碳酸亚乙烯酯,2%;氟代碳酸乙烯酯,1% |
实施例12 | 结构2,5% | 碳酸亚乙烯酯,2%;氟代碳酸乙烯酯,1% |
实施例13 | 结构1,10% | 碳酸亚乙烯酯,2%;氟代碳酸乙烯酯,1% |
实施例14 | 结构1,20% | 碳酸亚乙烯酯,2%;氟代碳酸乙烯酯,1% |
对比例1 | / | / |
对比例2 | 碳酸亚乙烯酯,2% | |
对比例3 | / | 氟代碳酸乙烯酯,1% |
对比例4 | / | 碳酸亚乙烯酯,2%;氟代碳酸乙烯酯,1% |
表1中,结构2对应的添加剂A为((氟磺酰亚胺锂基磺酰基)二氟甲基(磺酸锂基)二氟甲基(三氟甲基磺酰苯基)二氟甲基)硅基氰基五氟乙基(三氟甲基磺酰亚胺锂基磺酰基)二氟甲基磷酸四酯锂,其结构式为:
2、正极片的制备
将正极材料镍钴锰酸锂(LiNi0.5Co0.2Mn0.3)、导电剂Super P、碳纳米管、聚偏氟乙烯按照质量比95.5:1.5:1.5:1.5均匀分散在N,N-二甲基吡咯烷酮溶剂中,制成正极浆料;将分散好的浆料均匀涂覆在厚度为14μm的铝箔上,置于80℃鼓风烘箱中烘干,辊压、模切后制成正极片。
3、负极片的制备
将石墨、导电剂Super P、羧甲基纤维素、丁苯橡胶按照质量比94:3:2:1均匀分散在去离子水中,制成负极浆料;将分散好的负极浆料涂敷在厚度为10μm的铜箔上,置于80℃鼓风烘箱中烘干,辊压、模切后制成负极片。
4、锂离子电池的制备
将正极片、负极片、隔膜(正极片、负极片、隔膜和电解液)按照叠片工艺制成极芯,将极芯装入铝塑膜中,经历顶侧封、烘烤、注液、化成等工序制成软包电池。
5、性能测试
1)电解液阻燃性测试
将上述实施例1-14和对比例1-4制备的电解液按如下方法进行阻燃性测试:
使用直径约为0.5cm的玻璃纤维棉球在待测电解液中充分浸泡,然后将该玻璃纤维棉球安置在前端折成“O”型的细铁丝上,并用气体点火装置点燃,记录点火装置移开后至火焰自动熄灭的时间,该段时间称为自熄时间,以单位质量电解液的自熄时间来比较不同电解液的可燃性。
2)电池耐高温安全性能测试(热冲击试验)
将上述实施例1-5、实施例8-12和对比例1-4的软包电池在25℃,以1C恒流充电至电压4.6V,再以4.6V恒压充电至电流为0.05C,即为满电状态。
将上述满电状态的软包电池放入热冲击试验箱中,以5℃/min升温速率进行升温,当试验箱内的温度达到130℃时保持恒温,并持续30min,观察电池是否出现热失控现象。
上述实施例1-14和对比例1-4制备的锂离子电池耐高温安全性能和电解液的自熄时间的测试结果见表2。
表2
从实施例1-10和对比例1-4的电池测试结果来看,本发明所提供的电解液具有更短的自熄时间,能使电解液具有阻燃甚至不燃性;本发明所提供的电解液能降低电池热失控的风险,使电池在130℃热冲击试验时不发生起火、爆炸等热失控现象。进而佐证了本发明所用原料添加剂A在受热气化时能释放出含磷自由基,可与电解液中的氢自由基结合,可有效地阻止有机溶剂的燃烧或爆炸,极大提升锂离子电池的安全性;其次,其结构中包含大量氟元素,故能提升电解液的闪点,进而提升电解液的阻燃效果。由于本发明提供的由添加剂A和其他组分组成的电解液,用于制备离子电池时能在电极表面形成稳定致密的保护膜,阻止高温下电极材料和电解液溶剂的副反应,避免电池热失控的发生。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (7)
3.如权利要求2所述的阻燃电解液,其特征在于,所述烷基和三甲基硅基中的一个或多个氢原子为以下取代基所取代:氟、三氟甲基、氟磺酰基、三氟甲磺酰基、磺酸锂基、氟(磺酰亚胺锂基)磺酰基、三氟甲基(磺酰亚胺锂基)磺酰基、氟苯基、三氟甲基苯基、氟磺酰基苯基、三氟甲磺酰基苯基、磺酸锂基苯基、氟(磺酰亚胺锂基)磺酰基苯基、三氟甲基(磺酰亚胺锂基)磺酰基苯基。
4.如权利要求1所述的阻燃电解液,其特征在于,所述锂盐为六氟磷酸锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸硼酸锂、双(氟磺酰)亚胺锂、双(三氟甲基磺酰)亚胺锂、三氟甲磺酸锂、四氟硼酸锂、高氯酸锂、(氟磺酰)三氟甲基磺酰亚胺锂、四氯铝酸锂、六氟砷酸锂中的至少一种。
5.如权利要求1所述的阻燃电解液,其特征在于,所述非水有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、γ-丁内酯、二氧五环、四氢呋喃、二甲基三氟乙酰胺、二甲基亚砜中的至少一种。
6.如权利要求1所述的阻燃电解液,其特征在于,所述其他添加剂为双草酸硼酸锂、二氟磷酸锂、二氟草酸硼酸锂、二氟二草酸硼酸锂、四氟草酸磷酸锂、碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、1,4-丁烷磺酸内酯中的至少一种。
7.一种如权利要求1所述的阻燃电解液的应用,其特征在于,用于锂离子电池的制备,锂电池包括正极、负极、隔膜和所述电解液。
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