CN105789696B - 一种含有新型硼酸锂的电解液及使用该锂盐的电池 - Google Patents
一种含有新型硼酸锂的电解液及使用该锂盐的电池 Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 32
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 239000011258 core-shell material Substances 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000007767 bonding agent Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-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
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 229910013098 LiBF2 Inorganic materials 0.000 claims description 2
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 claims description 2
- 229910013874 LiPF2O2 Inorganic materials 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 238000005087 graphitization Methods 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000003780 insertion Methods 0.000 claims description 2
- 230000037431 insertion Effects 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 150000002642 lithium compounds Chemical class 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 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
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000002931 mesocarbon microbead Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920000447 polyanionic polymer Polymers 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims 1
- 229910006095 SO2F Inorganic materials 0.000 claims 1
- 239000011149 active material Substances 0.000 claims 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims 1
- BKIWAQYWKUFSRE-UHFFFAOYSA-N prop-1-ene;sulfuric acid Chemical group CC=C.OS(O)(=O)=O BKIWAQYWKUFSRE-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000006259 organic additive Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 150000003459 sulfonic acid esters Chemical class 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical group O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910013188 LiBOB Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- -1 propene sultone Chemical class 0.000 description 2
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013426 LiN(SO2F)2 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- DWJFPXCDDHKKKI-UHFFFAOYSA-N S1(=O)OCC(C)CCO1.S(O)(O)(=O)=O Chemical compound S1(=O)OCC(C)CCO1.S(O)(O)(=O)=O DWJFPXCDDHKKKI-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BZWQNMUGNDAMBX-UHFFFAOYSA-N butyl butane-1-sulfonate Chemical compound CCCCOS(=O)(=O)CCCC BZWQNMUGNDAMBX-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004804 winding Methods 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
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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
- H01M10/052—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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- 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
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Abstract
本发明公开了一种含有新型硼酸锂的电解液及使用该锂盐的电池,一种含有新型硼酸锂的电解液,包括电解质锂盐、新型硼酸锂、非水有机溶剂和添加剂,新型硼酸锂结构式中含有磺酸酯基团,电解液中使用含有磺酸酯基团的新型硼酸锂具有良好的高温特性,同时这种添加剂不会增加电池的内阻,因此使得锂离子电池在低温下也具有较好的性能表现。
Description
技术领域
本发明涉及锂离子电池领域,具体涉及一种含有新型硼酸锂的电解液及使用该锂盐的电池。
背景技术
锂二次电池具有工作电压高、比能量密度大、循环寿命长、自放电率低、无记忆效应以及环境污染小等优点,已经广泛应用于各类电子消费品市场,也是未来电动车辆和各种电动工具的理想动力源。目前技术市场上,负极材料主要由石墨负极垄断,电解液普遍采用环状和线状混合的碳酸酯体系以兼顾粘度、溶解性和电导率等性质,再兼以各类功能性添加剂来满足锂离子电池的综合性能。
功能性添加剂包括成膜添加剂,抗过充添加剂,稳定剂,阻燃添加剂等,其中磺酸酯类添加剂,包括丙磺酸内酯,丙烯磺酸内酯,丁磺酸内酯,亚硫酸酯等在目前商品电解液中广泛应用,主要改善锂离子电池下高温的存储,循环性能,对抑制电池胀气方面也体现出良好的效果。主要机理是磺酸酯类的添加剂除了在负极具有成膜特性以外,在正极表面同样具有钝化活性位的作用。但是磺酸酯类添加剂在电解液中过多使用,往往导致电池内阻增大,对倍率型电池带来较大的负面影响。
发明内容
本发明针对以上背景技术,目的是提供一种可以有效兼顾锂离子电池高低温性能的含有新型硼酸锂的电解液,因为新型硼酸锂含有磺酸酯基团,所以电解液中使用含有磺酸酯基团的新型硼酸锂具有良好的高温特性,同时不会增加电池的内阻,因此使得锂离子电池在低温下也具有较好的性能表现。
为了实现上述目的,本发明通过以下技术方案来实现:
一种含有新型硼酸锂的电解液,包括电解质锂盐、新型硼酸锂、非水有机溶剂和添加剂,所述新型硼酸锂的结构式为如下(I):
其中n为1-5的整数。
所述电解质锂盐在电解液中的浓度为0.5~2mol/L。
所述电解质锂盐为LiBF4、LiPF6、LiPF2O2、LiAsF6、LiClO4、LiSO3CF3、LiB(C2O4)2、LiBF2C2O4、LiN(SO2CF3)2、LiN(SO2F)2的一种及以上。
所述新型硼酸锂在电解液中的质量百分含量为0.1-10%。
非水有机溶剂包括碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、γ-丁内酯(GBL)、乙酸甲酯(EM)、乙酸乙酯(EA)、乙酸丙酯(EP)、乙酸丁酯(EB)、丙酸甲酯(PA)、丙酸乙酯(PE)、丙酸丙酯(PP)、丙酸丁酯(PB)、丁酸甲酯(BA)、丁酸乙酯(BE)、丁酸丙酯(BP)中的一种及以上。
所述添加剂为碳酸亚乙烯酯(VC),碳酸乙烯亚乙酯(VEC),氟代碳酸乙烯酯(FEC),1,3-丙磺酸内酯(PS),1,4-丁磺酸内酯(BS),硫酸乙烯酯(DTD),硫酸丙烯酯,亚硫酸乙烯酯和亚硫酸丙烯酯中的一种及以上。
所述添加剂在电解液中的质量百分含量为0.5%~10%。
一种锂二次电池,包括正极片、负极片、隔膜以及本发明的锂离子电池电解液;正极片包括嵌入/脱嵌锂离子的正极活性材料、导电剂、集流体、将所述正极活性材料和导电剂与所述集流体结合的结合剂;负极片包括可嵌入或者脱嵌锂离子的负极活性材料、导电剂、集流体、将所述负极活性材料和导电剂与所述集流体结合的结合剂。
所述正极活性材料包括锂的金属氧化物和金属元素Mg、Al、Ti、Sn、V、Ge、Ga、B、Zr、Cr、Fe、Sr以及稀土元素中的一种以上;所述负极活性材料包括锂金属、锂合金、结晶碳、无定型碳、碳纤维、硬碳和软碳。
所述正极活性材料还包括聚阴离子锂化合物LiMx(PO4)y,其中0≤x≤5,0≤y≤5,M为Ni、Co、Mn、Fe、Ti和V的任一种;所述负极活性材料中的结晶碳包括天然石墨、石墨化焦炭、石墨化MCMB、石墨化中间相沥青碳纤维中的一种及以上。
本发明的优点在于:
含有磺酸酯基团的硼酸锂同时具有磺酸内酯和LiBOB的化学结构,在负极和正极表面有利于形成更稳定的钝化膜,具体体现于电池在高温下具有良好的循环性能和容量恢复率,同时较低的内阻增长率。
具体实施方式
下面通过示例性的实施例对本发明进行进一步的阐述;但本发明的范围不应局限于实施例的范围,任何不偏离本发明主旨的变化或改变能够为本领域的技术人员所理解,都在本发明的保护范围以内。
实施例1
(1)电解液的制备
在氩气氛围的手套箱中(H2O<1ppm),将有机溶剂按质量比为EC(碳酸乙烯酯)∶EMC(碳酸甲乙酯):DEC(碳酸二乙酯)=30∶40:30与LiPF6(1.0M)混合,加入总质量1%的碳酸亚乙烯酯(VC),2%的氟代碳酸乙烯酯(FEC),1.5%的丁二腈(SN),0.5%的乙磺酸硼酸锂。充分搅拌均匀,即得到本发明所述的锂二次电池电解液(游离酸<15ppm,水分<10ppm)。
(3)正极极片的制备
将质量百分比为3%的聚偏氟乙烯(PVDF)溶解于1-甲基-2-吡咯烷酮溶液中,将质量百分比94%的LiCoO2和3%的导电剂炭黑加入上述溶液并混合均匀,将混制的浆料涂布在铝箔的两面后,烘干、滚压后得到正极极片。
(4)负极极片的制备
将质量百分比为4%的SBR粘结剂,质量百分比为1%的CMC增稠剂溶于水溶液中,将质量百分比为95%的石墨加入上述溶液,混合均匀,将混制的浆料涂布在铜箔的两面后,烘干、滚压后得到负极极片。
(5)锂二次电池的制备
将上述制备的正极极片、负极极片和隔离膜以卷绕方式制成方形电芯,采用聚合物包装,灌注上述制备的电解液,经化成等工艺后制成容量为1600mAh的锂二次电池。
(6)电池性能测
循环性能测试,以0.5/0.5C充放电的倍率对电池进行充放电循环测试,截止电压区间为3.0~4.35V。高温储存性能测试,首先将化成完毕的电池在常温状态下以0.5C充放电一次,再以0.5C将电池充满电后测试内阻,进行高温保存,待电池完全冷却后,将取出的电池测试内阻,以0.5C进行放电测试。
实施例2-8
除下表参数外,其他参数及制备方法同实施例2。
表1实施例3-8
表2实施例和对比例的测试结果
从实施例1~8,对比例2~6和对比例1的结果可知,添加剂对电池的循环性能和高温性能影响较大,从对比例2~4和对比例6的结果可知,磺酸酯类添加剂有助于改善电池的高温性能,但同时增加电池的内阻变化。从对比例5和对比例6的结果可知,LiBOB作为添加剂使用同样可以改善电池的高温性能,但同时导致电池内助增大。从实施例1~8,对比例2~6的结果可知,在硼酸盐的结构中引入磺酸酯基团能够有效提升电池在高温存储后的容量保持力和恢复力,同时显著降低电池的内阻。
以上仅是针对本发明的可行实施例的具体说明,但该实施例并非用以限制本发明的专利范围,凡未脱离本发明思路所为的等效实施或变更,均应包含于本发明的专利范围中。
Claims (10)
1.一种含有新型硼酸锂的电解液,其特征在于,包括电解质锂盐、新型硼酸锂、非水有机溶剂和添加剂,所述新型硼酸锂的结构式为如下(I):
(I)
其中n为1-5的整数。
2.根据权利要求1所述的含有新型硼酸锂的电解液,其特征在于,所述电解质锂盐在电解液中的浓度为0.5~2 mol/L。
3.根据权利要求1所述的含有新型硼酸锂的电解液,其特征在于,所述电解质锂盐为LiBF4、LiPF6、LiPF2O2、LiAsF6、LiClO4、LiSO3CF3、LiB(C2O4)2、LiBF2C2O4、LiN(SO2CF3)2、LiN(SO2F)2的一种及以上。
4.根据权利要求1所述的含有新型硼酸锂的电解液,其特征在于, 所述新型硼酸锂在电解液中的质量百分含量为0.1-10%。
5.根据权利要求1所述的含有新型硼酸锂的电解液,其特征在于,非水有机溶剂包括碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、γ-丁内酯(GBL)、乙酸甲酯(EM)、乙酸乙酯(EA)、乙酸丙酯(EP)、乙酸丁酯(EB)、丙酸甲酯(PA)、丙酸乙酯(PE)、丙酸丙酯(PP)、丙酸丁酯(PB)、丁酸甲酯(BA)、丁酸乙酯(BE)、丁酸丙酯(BP)中的一种及以上。
6.根据权利要求1所述的含有新型硼酸锂的电解液,其特征在于,所述添加剂为碳酸亚乙烯酯(VC),碳酸乙烯亚乙酯(VEC),氟代碳酸乙烯酯(FEC),1, 3-丙磺酸内酯(PS),1, 4-丁磺酸内酯(BS),硫酸乙烯酯(DTD),硫酸丙烯酯,亚硫酸乙烯酯和亚硫酸丙烯酯中的一种及以上。
7.根据权利要求6所述的含有新型硼酸锂的电解液,其特征在于,所述添加剂在电解液中的质量百分含量为0.5%~10%。
8.一种锂二次电池,包括正极片、负极片、隔膜以及权利要求1-7任意一项所述的含有新型硼酸锂的电解液;正极片包括嵌入/脱嵌锂离子的正极活性材料、导电剂、集流体、将所述正极活性材料和导电剂与所述集流体结合的结合剂;负极片包括可嵌入或者脱嵌锂离子的负极活性材料、导电剂、集流体、将所述负极活性材料和导电剂与所述集流体结合的结合剂。
9.根据权利要求8所述的锂二次电池,所述正极活性材料包括锂的金属氧化物,还包括金属元素Mg、Al、Ti、Sn、V、Ge、Ga、Zr、Cr、Fe、Sr的一种以上以及稀土元素中的一种以上;所述负极活性材料包括金属锂、锂合金、结晶碳、无定型碳。
10.根据权利要求9所述的锂二次电池,所述正极活性材料还包括聚阴离子锂化合物LiMx(PO4)y,其中0≤ x ≤ 5,0 ≤ y ≤ 5, M为Ni、Co、Mn、Fe、Ti和V的任一种;所述负极活性材料中的结晶碳包括天然石墨、石墨化焦炭、石墨化MCMB、石墨化中间相沥青碳纤维中的一种及以上。
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