CN116417665A - 非水电解液及锂离子电池 - Google Patents
非水电解液及锂离子电池 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 48
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 25
- -1 hexafluorophosphate Chemical compound 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- ACKHWUITNXEGEP-UHFFFAOYSA-N aluminum cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Co+2].[Ni+2] ACKHWUITNXEGEP-UHFFFAOYSA-N 0.000 claims description 3
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-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
- 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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 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
- 150000005678 chain carbonates Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 abstract description 11
- 239000004332 silver Substances 0.000 abstract description 11
- 150000002500 ions Chemical group 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
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- 238000002360 preparation method Methods 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 3
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- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 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
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XACUEDCHPANNRH-UHFFFAOYSA-L [Ag+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F Chemical compound [Ag+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F XACUEDCHPANNRH-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000011572 manganese Substances 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
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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
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- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
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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
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Abstract
本发明公开了一种非水电解液及含该非水电解液的锂离子电池,该非水电解液包括锂盐、非水有机溶剂和添加剂,添加剂如结构式1所示的化合物,AgxM结构式1其中,M表示六氟磷酸根、四氟硼酸根、草酸根、高氯酸根、硝酸根、氟阴离子、双三氟甲基磺酸根中的任意一种,x表示阴离子的化学价态。本发明的添加剂AgxM中的负离子结构能够改善高电压下的电池的循环性能,而银正离子能够优化固体电解质界面膜的成分,通过银离子的吸附作用,形成一定程度的吸附,进而提升了电池的高温循环性能。因此,采用本发明的非水电解液制得的锂离子电池具有良好的高温存储性能、高温循环性能及低温放电性能。
Description
技术领域
本发明属于锂离子电池技术领域,尤其涉及一种非水电解液及锂离子电池。
背景技术
锂离子电池由于具有高比能量、无记忆效应、循环寿命长等优点被广泛应用于3C数码、电动工具、航天、储能、动力汽车等领域。现有的钴酸锂和三元材料由于拥有较高的能量密度和质量能量密度,成为锂离子电池的正极活性材料的首选材料。为了满足大型移动式用电设备的需求,发展大比容量的锂离子电池已经迫在眉睫。最常见的方法就是提升锂离子电池的电压,但是所有的高电压正极材料都面临一个共性的问题:电解液在高电压下出现分解,例如在4.535V的高压下,常规的电解液在电池正极表面氧化分解更快,特别在高温条件下,会进一步加速电解液的氧化分解,同时促使正极材料的恶化反应。目前,改变这一现状的技术思路主要集中在电解液添加剂的结构设计,例如:中国专利CN114597490A,设计了一种硫酸酯类的物质,显著改善了锂电池三元和磷酸铁锂电池的高温存储性能和高温循环性能。这些技术方案主要集中在有机类电解液添加剂的研发,而无机盐类的电解液添加剂开发比较少,因为无机盐类的物质在碳酸酯类的溶解度较低,此外,目前为止,无机盐类的电解液添加剂改善效果有限。对此,如何开发出适用高电压下电解液的无机盐类添加剂任重而道远。
发明内容
本发明的目的是提供一种非水电解液,可提高锂离子电池于高电压(尤其是4.535V时)体系下的高温存储性能和高温循环性能,同时还可改善锂离子电池的低温放电性能。
为了实现以上目的,本发明提供了一种非水电解液,包括锂盐、非水有机溶剂和添加剂,所述添加剂如结构式1所示的化合物,
AgxM结构式1
其中,M表示六氟磷酸根、四氟硼酸根、草酸根、高氯酸根、硝酸根、氟阴离子、双三氟甲基磺酸根中的任意一种,x表示阴离子的化学价态。
与现有技术相比,本发明的非水电解液,包括锂盐、非水有机溶剂和添加剂,添加剂为AgxM,M为六氟磷酸根、四氟硼酸根、草酸根、高氯酸根、硝酸根、氟阴离子、双三氟甲基磺酸根,这些负离子结构能够改善高电压下的电池的循环性能,而银正离子能够优化固体电解质界面膜的成分,通过银离子的吸附作用,形成一定程度的吸附,进而提升了锂离子电池的高温循环性能。同时,该正、负离子配合形成的添加剂AgxM,可优化正极/电解液界面,降低电极的表面活性从而抑制电解液的氧化分解,使得电解液在持续高电压下保持稳定,进而提升锂离子电池于高电压(尤其是4.535V时)体系下的高温存储性能和高温循环性能,同时,银离子具有强电化学导电性且随价位升高,表现出更高的氧化还原性,AgxM的添加可以显著提高电解液的离子电导,所以在作为锂离子电池电解液应用过程中可提高循环性能和库伦效率,该添加剂的加入还可改善锂离子电池的低温放电性能。
在有的实施例中,添加剂AgxM为四氟硼酸银、草酸银、硝酸银、双三氟甲基磺酸银中的一种。其中,为了使锂离子电池获得较好的高温存储性能,添加剂AgxM采用硝酸银,而为了使锂离子电池获得较好的高温循环性能,添加剂AgxM采用草酸银。
在有的实施例中,本发明的添加剂于非水电解液中的质量百分比为0.1~3%,优选为,添加剂于非水电解液中的质量百分比为0.1~2%,作为示例地,添加剂于非水电解液中的质量百分比可为但不限于为0.1%、0.2%、0.5%、1%、1.5%、2%。
在有的实施例中,本发明的锂盐于非水电解液中的质量百分比为6.5~15.5%,作为示例地,锂盐于非水电解液中的质量百分比可为但不限于为6.5%、7%、8%、9%、10%、12%、12.5%、13%、14%、15%。
在有的实施例中,本发明的锂盐选自六氟磷酸锂(LiPF6)、高氯酸锂、四氟硼酸锂、三氟甲基磺酸锂、双三氟甲基磺酰亚胺锂、双草酸硼酸锂(LiBOB)、二氟磷酸锂、二氟草酸硼酸锂、二氟二草酸磷酸锂和双氟磺酰亚胺锂中的至少一种。作为示例地,锂盐为六氟磷酸锂(LiPF6)或双草酸硼酸锂(LiBOB),在一个优选的实施例中,锂盐为两种以上化合物的混合物,比如,锂盐为六氟磷酸锂(LiPF6)和双草酸硼酸锂(LiBOB)的混合物,或锂盐为六氟磷酸锂和三氟甲基磺酸锂的混合物,可以获得更佳优异的高温循环性能。
在有的实施例中,本发明的非水有机溶剂为链状碳酸酯、环状碳酸酯和羧酸酯中的至少一种。进一步地,非水有机溶剂选自碳酸乙烯酯(EC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸丙烯酯(PC)、乙酸丁酯(n-Ba)、γ-丁内酯(γ-Bt)、丙酸丙酯(n-PP)、丙酸乙酯(EP)和丁酸乙酯(Eb)中的至少一种。
在有的实施例中,本发明的非水有机溶剂于非水电解液中的质量百分比为60~90%,优选地,非水有机溶剂于非水电解液中的质量百分比为70~88%,更为优选地,非水有机溶剂于非水电解液中的质量百分比为80~88%。作为示例地,非水有机溶剂于非水电解液中的质量百分比可为但不限于为80%、82%、85%、86%、87%、88%。
对应地,本发明还提供了一种锂离子电池,包括正极材料、负极材料及上述非水电解液,因该锂离子电池含该非水电解液,具有良好的高温存储性能和高温循环性能,及低温放电性能。
在有的实施例中,所述正极材料含钴元素,优选地,所述正极材料为钴酸锂、镍钴锰氧化物或镍钴铝氧化物中的至少一种。这些正极材料均含钴离子,具备催化性能,能大幅提高与银离子的吸附作用,形成较强的吸附,进而大幅提高电池的高温循环性能。
其中,镍钴锰氧化物的化学式为LiNixCoyMnzM(1-x-y-z)O2;镍钴铝氧化物的化学式为LiNixCoyAlzN(1-x-y-z)O2,其中M、N各自独立地选自Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V和Ti中的至少一种,0<x<1,0<y<1,0<z<1,x+y+z≤1;钴酸锂的化学式为LiCoO2。
在有的实施例中,本发明的负极材料选自人造石墨、天然石墨、钛酸锂、硅碳复合材料和氧化亚硅中的至少一种。
具体实施方式
为更好地说明本发明的目的、技术方案和有益效果,下面通过具体实施例来进一步说明本发明的目的、技术方案及有益效果,但不构成对本发明的任何限制,实施例中未注明具体条件者,可按照常规条件或制造商建议的条件进行,所用试剂或仪器未注明生产厂商者,均为可通过市售而获得的常规产品。
实施例1
(1)制备非水电解液
在充满氩气的手套箱(O2<1ppm,H2O<1ppm)中,将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照重量比为EC:EMC:DEC=1:1:1进行混合,制得87g非水有机溶剂,接着加入0.5g四氟硼酸银作为添加剂,溶解并充分搅拌后加入12.5g六氟磷酸锂,混合均匀后获得非水电解液。
(2)制备正极
将LiCoO2、粘接剂PVDF和导电剂SuperP按质量比95:1:4混合均匀制成一定粘度的锂离子电池正极浆料,将混制的浆料涂布在铝箔的两面后,烘干、辊压后得到正极片。
(3)制备负极
将人造石墨与导电剂SuperP、增稠剂CMC、粘接剂SBR(丁苯橡胶乳液)按质量比95:1.5:1.0:2.5的比例制成浆料,混合均匀,用混制的浆料涂布在铜箔的两面后,烘干、辊压后得到负极片。
(4)制备隔膜
将单层PE多孔聚合物薄膜作为隔离膜(S),其厚度为5微米,孔隙率为39%,无机涂层为Al2O3,有机颗粒为聚偏二氟乙烯。
(5)制备锂离子电池
将正极、隔膜以及负极以卷绕的方式制成软包电芯,采用聚合物铝塑膜包装,灌装上述制备的锂离子电池非水电解液,经化成、分容等工序后制成容量为4000mAh的锂离子电池。
实施例2~7和对比例1的非水电解液配方如表1所示,配制电解液及制备电池的步骤同实施例1。
表1非水电解液的配方
将实施例1~7和对比例1制成的锂离子电池分别进行低温放电性能测试、高温存储测试和高温循环测试,具体测试条件如下,性能测试结果如表2所示。
锂离子电池低温放电性能测试
在常温(25℃)条件下,对锂离子电池进行一次0.5C/0.5C充电和放电(放电容量记为C0),上限电压为4.535V,然后在0.5C恒流恒压条件下将电池充电至4.535V,将锂离子电池置于-20℃低温箱中搁置4h,在-20℃下进行0.5C放电(放电容量记为C1),利用下面公式计算锂离子电池的低温放电率:
低温放电率=(C1/C0)*100%
锂离子电池高温存储性能测试
在常温(25℃)条件下,对锂离子电池进行一次0.3C/0.3C充电和放电(电池放电容量记录为C0),上限电压为4.535V;将电池放置于60℃烘箱中搁置7d,取出电池,将电池放置于25℃环境中,进行0.3C放电,放电容量记录为C1;然后对锂离子电池进行一次0.3C/0.3C充电和放电(电池放电容量记录为C2),利用下面公式计算锂离子电池的容量保持率和容量恢复率:
容量保持率=(C1/C0)*100%
容量恢复率=(C2/C0)*100%
锂离子电池高温循环性能测试
将锂离子电池置于45℃恒温箱中,静置30分钟,使锂离子电池达到恒温。以1C恒流充电至电压为4.535V,然后以4.535V恒压充电至电流为0.05C,接着以1C恒流放电至电压为3.0V,记录电池的首圈放电容量为C0。此为一个充放电循环。然后在45℃条件下进行1C/1C充电和放电300周,放电容量记为C1,利用下面公式计算锂离子电池的容量保持率。
容量保持率=(C1/C0)*100%
表2锂离子电池性能测试结果
由表2的结果可知,实施例1~7的锂离子电池的高温存储性能、高温循环性能、低温放电性能皆优于对比例1,其中实例1~3做含量梯度添加,实验数据差异并不明显,表明在添加0.5g四氟硼酸银时上述实施例1所述非水有机电解液里银离子含量已达饱和状态。本发明的非水电解液采用了添加剂为AgxM,M为六氟磷酸根、四氟硼酸根、草酸根、高氯酸根、硝酸根、氟阴离子、双三氟甲基磺酸根,这些负离子结构能够改善高电压下的电池的循环性能,而银正离子能够优化固体电解质界面膜的成分,通过银离子的吸附作用,形成一定程度的吸附,进而提升了电池的高温循环性能。同时,该正、负离子配合形成的添加剂AgxM,可优化正极/电解液界面,降低电极的表面活性从而抑制电解液的氧化分解,使得电解液在持续高电压下保持稳定,进而提升锂离子电池于高电压(尤其是4.535V时)体系下的高温存储性能和高温循环性能,同时,在实际研发过程中还发现,该添加剂的加入还可改善锂离子电池的低温放电性能。
实施例5的数据说明,添加剂AgxM采用硝酸银,电池的高温循环循环容量保持率高于其他实施例,银离子溶于上述实施例1所述非水电解液后,银离子可提前氧化参与形成致密均匀的SEI膜,平坦、无锂枝晶的表面,这得益于硝酸根的作用,能够降快充性能条件下析锂的风险,减少了金属锂与电解液溶剂EC等环状分子的催化反应,同时阳离子银离子能够改变锂离子进入正极界面位置的溶剂化效应,降低电解液界面位置的位阻,另一方面银离子本征的吸附效应,使得钴酸锂在高电压循环过程中钴离子的溶出到电解液中会降低,加强了CEI界面的稳定性,间接提升了电池界面稳定性,综合硝酸银两方面的作用机制使得锂离子电池能获得较好的高温循环和高温存储性能。
最后应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种非水电解液,其特征在于,包括锂盐、非水有机溶剂和添加剂,所述添加剂如结构式1所示的化合物,
AgxM结构式1
其中,M表示六氟磷酸根、四氟硼酸根、草酸根、高氯酸根、硝酸根、氟阴离子、双三氟甲基磺酸根中的任意一种,x表示阴离子的化学价态。
2.如权利要求1所述的非水电解液,其特征在于,所述添加剂于所述非水电解液中的质量百分比为0.1~2%。
3.如权利要求1所述的非水电解液,其特征在于,所述锂盐于所述非水电解液中的质量百分比为6.5~15.5%。
4.如权利要求1所述的非水电解液,其特征在于,所述锂盐选自六氟磷酸锂、高氯酸锂、四氟硼酸锂、三氟甲基磺酸锂、双三氟甲基磺酰亚胺锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸硼酸锂、二氟二草酸磷酸锂和双氟磺酰亚胺锂中的至少一种。
5.如权利要求1所述的非水电解液,其特征在于,所述非水有机溶剂为链状碳酸酯、环状碳酸酯和羧酸酯中的至少一种。
6.如权利要求5所述的非水电解液,其特征在于,所述非水有机溶剂选自碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸丙烯酯、乙酸丁酯、γ-丁内酯、丙酸丙酯、丙酸乙酯和丁酸乙酯中的至少一种。
7.一种锂离子电池,包括正极材料、负极材料,其特征在于,还包括如权利要求1~6任意一项所述的非水电解液。
8.如权利要求7所述的锂离子电池,其特征在于,所述正极材料含钴元素。
9.如权利要求8所述的锂离子电池,其特征在于,所述正极材料为钴酸锂、镍钴锰氧化物或镍钴铝氧化物中的至少一种。
10.如权利要求7所述的锂离子电池,其特征在于,所述锂离子电池的最高充电电压为4.535V。
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