CN117219852A - 用于锂二次电池的电解质溶液和包含所述电解质溶液的锂二次电池 - Google Patents
用于锂二次电池的电解质溶液和包含所述电解质溶液的锂二次电池 Download PDFInfo
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- CN117219852A CN117219852A CN202211540691.5A CN202211540691A CN117219852A CN 117219852 A CN117219852 A CN 117219852A CN 202211540691 A CN202211540691 A CN 202211540691A CN 117219852 A CN117219852 A CN 117219852A
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- Prior art keywords
- electrolyte
- secondary battery
- positive electrode
- lithium secondary
- additive
- Prior art date
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 40
- 239000008151 electrolyte solution Substances 0.000 title abstract description 3
- 239000000654 additive Substances 0.000 claims abstract description 51
- 230000000996 additive effect Effects 0.000 claims abstract description 51
- 239000003792 electrolyte Substances 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 18
- -1 1- (3- ((tert-butyldimethylsilyl) oxy) propyl) -5- (4-fluorophenyl) -1H-1,2, 3-triazole-4-carbonitrile Chemical compound 0.000 claims abstract description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 239000013538 functional additive Substances 0.000 claims abstract description 11
- 239000010408 film Substances 0.000 claims description 40
- 239000010409 thin film Substances 0.000 claims description 17
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 7
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- 229910010238 LiAlCl 4 Inorganic materials 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013372 LiC 4 Inorganic materials 0.000 claims description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 3
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 3
- 239000003759 ester based solvent Substances 0.000 claims description 3
- 239000004210 ether based solvent Substances 0.000 claims description 3
- 239000005453 ketone based solvent Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000003660 carbonate based solvent Substances 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 229910010941 LiFSI Inorganic materials 0.000 description 2
- 229910012258 LiPO Inorganic materials 0.000 description 2
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- 239000011149 active material Substances 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 150000001721 carbon Chemical group 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 2
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- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
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- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
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- 235000002639 sodium chloride Nutrition 0.000 description 2
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
-
- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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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- 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
- H01M2300/004—Three solvents
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Abstract
本申请提供了用于锂二次电池的电解质溶液和包含所述电解质溶液的锂二次电池,所述电解质溶液可以提高锂二次电池的寿命和输出特性。用于锂二次电池的电解质包含锂盐、溶剂和功能性添加剂。功能性添加剂包含作为正电极薄膜添加剂的1‑(3‑((叔丁基二甲基甲硅烷基)氧)丙基)‑5‑(4‑氟苯基)‑1H‑1,2,3‑三唑‑4‑甲腈。
Description
技术领域
本申请涉及用于锂二次电池的电解质和包含所述电解质的锂二次电池。更具体地,本申请涉及用于锂二次电池的电解质和包含所述电解质的锂二次电池,所述电解质可以提高高容量锂二次电池的寿命和输出特性。
背景技术
锂二次电池是一种储能系统,其包含正电极、负电极、电解质和隔膜,所述正电极用于在充电时供应锂离子,所述负电极用于接收锂离子,所述电解质用作锂离子传输介质,所述隔膜用于分隔正电极和负电极。当化学电势随着正电极和负电极中的嵌入/脱嵌而变化时,产生并储存电能。
这种锂二次电池已用于移动电子设备,并且如今正迅速扩展其作为已成功实现商业化的电动车辆(EV)和混合动力车辆(HEV)的储能系统的用途。
为了增加电动车辆的行驶里程,研究的重点是提高锂二次电池的能量密度。正电极中高容量的改进能够提高锂二次电池的能量密度。
为了开发具有高能量密度的锂二次电池,需要开发可以克服常规锂二次电池部件(例如正电极、负电极、隔膜和电解质)的性能限制的新型物质。
特别地,电池的能量密度取决于正电极和负电极的特性。因此,应开发适当的电解质,以使这些经开发的正电极物质和负电极物质表现出优异的电化学性能。
当使用片状富镍(Ni)LiNi1-x-yCoxMnyO2(NCM;1-x-y≥0.6)氧化物作为高容量正电极活性材料时,可以通过提高Ni的含量或通过增加充电电压来增加正电极的容量。然而,由于正电极上存在的残余锂组分(Li2CO3和LiOH)促进了电解质的降解并增加了电解质内的界面反应性,从而加速了劣化速率,因此充电/放电性能迅速下降。
因此,正电极-电解质和界面控制技术非常重要。在这个背景下,需要引入能够形成电化学稳定且化学稳定的薄膜的添加剂技术。
背景技术部分中给出的描述仅用于理解本申请的背景,而不应被认为是本领域技术人员已知的现有技术。
发明内容
本申请提供了一种用于锂二次电池的电解质,所述电解质可以提高锂二次电池的寿命和输出特性。本申请还提供了一种包含所述电解质的锂二次电池。
根据本申请的实施方案的用于锂二次电池的电解质包含锂盐、溶剂和功能性添加剂。功能性添加剂包含作为正电极薄膜添加剂的由以下化学式1表示的1-(3-((叔丁基二甲基甲硅烷基)氧)丙基)-5-(4-氟苯基)-1H-1,2,3-三唑-4-甲腈
基于电解质的重量,可以使用0.1重量%至1.0重量%的量的正电极薄膜添加剂。
基于电解质的重量,可以使用0.3重量%至0.5重量%的量的正电极薄膜添加剂。
功能性添加剂还可以包含作为负电极薄膜添加剂的碳酸亚乙烯酯(VC)。
基于电解质的重量,可以使用0.5重量%至3.0重量%的量的碳酸亚乙烯酯(VC)。
锂盐可以包括LiPF6、LiBF4、LiClO4、LiCl、LiBr、LiI、LiB10Cl10、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、LiN(SO2C2F5)2、Li(CF3SO2)2N、LiC4F9SO3、LiB(C6H5)4、Li(SO2F)2N(LiFSI)、(CF3SO2)2NLi或其组合。
溶剂可以包括碳酸酯类溶剂、酯类溶剂、醚类溶剂、酮类溶剂或其组合。
根据本申请的实施方案的锂二次电池包含本文描述的电解质。锂二次电池还可以包含:正电极、负电极和隔膜,所述正电极包含由Ni、Co和Mn构成的正电极活性材料,所述负电极包含含有碳(C)-基材料、硅(Si)-基材料或其组合的负电极活性材料,所述隔膜插入在正电极和负电极之间。
正电极可以包含80重量%或更高的含量的Ni。
附图说明
通过结合附图进行的以下详细描述,本申请的上述方面和其它方面、特征和优点应变得更加明显,在附图中:
图1为使用根据本申请的实施方案的正电极薄膜添加剂清除HF的反应方案;
图2显示了电池初始充电/放电效率随实施例和对比实施例的电解质组成变化的曲线;
图3显示了高温寿命随实施例和对比实施例的电解质组成变化的曲线;以及
图4为倍率性能随实施例和对比实施例的电解质组成变化的图表。
具体实施方式
在下文中,结合所附附图对本申请的实施方案进行详细描述。然而,本申请不限于下文公开的实施方案,而是可以以各种不同形式实施。提供这些实施方案仅仅是为了使本申请完整,并使本申请所属的领域的技术人员能够完全理解本申请的范围。
根据本申请的实施方案的用于锂二次电池的电解质包含锂盐、溶剂和功能性添加剂,其均用于形成适用于锂离子电池的电解质。
锂盐可以包括LiPF6、LiBF4、LiClO4、LiCl、LiBr、LiI、LiB10Cl10、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、LiN(SO2C2F5)2、Li(CF3SO2)2N、LiC4F9SO3、LiB(C6H5)4、Li(SO2F)2N(LiFSI)、(CF3SO2)2NLi或其组合。
锂盐可以以在0.1摩尔至3.0摩尔的范围内或者在0.1摩尔至1.2摩尔的范围内的总浓度存在于电解质中。
溶剂可以包括碳酸酯类溶剂、酯类溶剂、醚类溶剂、酮类溶剂或其组合。
在这方面,碳酸酯类溶剂的示例包括碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(EMC)、碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸丁烯酯(BC)、氟代碳酸乙烯酯(FEC)和碳酸亚乙烯酯(VC)。酯类溶剂可以以γ-丁内酯(GBL)、乙酸正甲酯、乙酸正乙酯、乙酸正丙酯等为示例。作为醚类溶剂,可以使用二丁基醚,但不限于此。
此外,溶剂还可以包含芳族烃类溶剂。芳族烃类溶剂的示例包括苯、氟苯、溴苯、氯苯、环己基苯、异丙基苯、正丁基苯、辛基苯、甲苯、二甲苯、均三甲苯或其组合。
在根据本申请的实施方案的电解质中使用的功能性添加剂可以使用作为正电极薄膜添加剂的由以下化学式1表示的1-(3-((叔丁基二甲基甲硅烷基)氧)丙基)-5-(4-氟苯基)-1H-1,2,3-三唑-4-甲腈(下文称为“CN-12”):
当通过用于比较HOMO和LUMO轨道能级的DFT计算时,正电极薄膜添加剂(1-(3-((叔丁基二甲基甲硅烷基)氧)丙基)-5-(4-氟苯基)-1H-1,2,3-三唑-4-甲腈(CN-12))具有低LUMO能级和高HOMO能级,因此其首先在正电极和负电极的表面上分解以形成CEI层和SEI层,从而抑制与其它溶剂的副反应。
此外,正电极薄膜添加剂CN-12引入了官能团TMSO,以用作酸性组分HF(其作为电池中的老化因子)的清除剂。因此,电解质中HF的降低减少了LiF(其可以作为正电极CEI结构中的电阻组分)的形成,并降低了电池中的超电压,从而改善了倍率性能。
形成了基于三唑(其为正电极薄膜添加剂CN-12的中心部分)的薄膜,以稳定锂盐。占据三唑部分中的氮原子的sp2轨道的未共用的电子对未包含在pi电子云中,因此稳定了水分或酸(特别是PF5),从而防止了LiPF6盐的额外降解。
带有已知对高电压正电极有效的腈基的正电极薄膜添加剂CN-12稳定了过渡金属,从而抑制了正电极上的阳离子混合诱导的相转变。
换言之,腈基在碳原子和氮原子(其中氮原子上未共用的电子对更强烈地吸引电子)之间具有三键,从而与金属形成配位(金属配位络合物)。
锂离子电池中使用的NCM811正电极包含含量高达80%的镍,并存在问题。一个问题是,由于在充电/放电循环中结构稳定性降低,因此当镍迁移至锂层时,会发生阳离子混合。另一个问题是,表面镍层通过接收来自正电极的表面的电子而氧化,因此溶解为镍离子,所述镍离子又移动至负电极的表面以形成氟化镍层,所述氟化镍层作为离子输送的屏障。
已知一种包含在碳原子和氮原子之间具有三键的腈的添加剂,从而形成对于高电压正电极表现出优异的性质的薄膜。正电极薄膜添加剂CN-12对过渡金属(例如镍等)具有亲和力,以防止正电极上过渡金属的洗脱。因此,期望添加剂防止金属沉积到负电极上,并抑制正电极上的阳离子混合导致的相转变,从而减少当正电极完全充电时所产生的热量。
图1为示出使用根据本申请的实施方案的正电极薄膜添加剂(CN-12)清除HF的反应方案。正电极薄膜添加剂(CN-12)的官能团甲硅烷基醚(Si-O)中的硅(Si)元素清除氟(F),同时通过氧(O)除去氢(H)。因此,可以防止CEI破坏和TM洗脱。
此外,正电极薄膜添加剂(CN-12)的腈基通过过渡金属稳定化而有助于正电极的表面上的电荷中和。在这方面,使镍离子稳定化,以抑制正电极上的阳离子混合导致的相转变(层状至尖晶石/岩盐相)。
此外,正电极薄膜添加剂(CN-12)的三唑衍生的结构有助于氮的PF5稳定化,其作为路易斯碱。
基于电解质的总重量,可以添加0.1重量%至1.0重量%或0.1重量%至0.3重量%的量的正电极薄膜添加剂。
当以小于0.1重量%的量添加时,正电极薄膜添加剂的作用很小,因为其不能在正电极活性材料和负电极活性材料的表面上充分地形成表面保护薄膜。大于1.0重量%的正电极薄膜添加剂会导致过度形成表面保护层CEI和SEI,从而增加电池电阻,这会导致寿命降低。
除了正电极薄膜添加剂之外,功能性添加剂还可以包含用于在负电极上形成薄膜的负电极薄膜添加剂。例如,可以使用碳酸亚乙烯酯(下文称为“VC”)作为附加的负电极薄膜添加剂。
基于电解质的重量,可以添加0.5重量%至3.0重量%或1.5重量%至2.5重量%的量的用作负电极薄膜添加剂的VC。
低于负电极薄膜添加剂的下限会降低电池的长期寿命特性。当超过上限时,负电极薄膜添加剂的量会过量地形成表面保护层,并导致电池电阻增加,因此导致电池输出降低。
根据其实施方案,本申请提供了一种锂二次电池,所述锂二次电池包含上述电解质、正电极、负电极和隔膜。
正电极包含由Ni、Co和Mn构成的NCM基正电极活性材料。特别地,根据实施方案的正电极中的正电极活性材料仅由包含80重量%或更高的Ni的NCM基正电极活性材料构成。
负电极包含碳(C)-基负电极活性材料、硅(Si)-基负电极活性材料或其组合。
碳(C)-基负电极活性材料可以包括人造石墨、天然石墨、石墨化碳纤维、石墨化中间相碳微球、富勒烯、无定形碳或其组合。
硅(Si)-基负电极活性材料可以包括氧化硅、硅颗粒、硅合金颗粒或其组合。
对于正电极和负电极,使相应的活性材料与导电材料、粘合剂和溶剂混合以制备电极浆料。将该电极浆料直接施加在集电器上并干燥,以制造正电极或负电极。在这方面,集电器可以由铝(Al)形成,但不限于此。这种电极制造方法是本领域公知的,因此不对其进行详细描述。
粘合剂用于使活性材料颗粒彼此较好地聚集,或者使其牢固地附着至集电器。粘合剂的示例包括但不限于聚乙烯醇、羧甲基纤维素、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧基化聚氯乙烯、聚氟乙烯、带有环氧乙烷的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏氟乙烯、聚乙烯、聚丙烯、苯乙烯丁二烯橡胶、丙烯酸酯化苯乙烯丁二烯橡胶、环氧树脂和尼龙。
导电材料用于赋予电极导电性。只要导电材料具有导电性,而不引起电池中的化学变化,任何导电材料均是可用的。导电材料的示例包括天然石墨、人造石墨、炭黑、乙炔黑、科琴黑、碳纤维、金属粉末或纤维(例如铜、镍、铝、银等)以及金属纤维。此外,还可以使用至少一种导电材料,例如聚亚苯基衍生物。
隔膜防止在正电极和负电极之间形成短路,同时提供锂离子的迁移通道。该隔膜可以是公知的隔膜,例如,聚烯烃膜(例如聚丙烯、聚乙烯、聚乙烯/聚丙烯、聚乙烯/聚丙烯/聚乙烯、聚丙烯/聚乙烯/聚丙烯等)或其多层膜、微孔薄膜、织物或非织造布。供替选地,可以使用涂覆有高度稳定的树脂的多孔聚烯烃薄膜。
在下文中,参考实施例和对比实施例解释本申请。
<测试1>在使用石墨作为负电极时高温(45℃)下的初始电池效率(放电/充电)和
高温寿命特性随正电极薄膜添加剂的量的变化的测试
为了在使用石墨作为负电极时检测初始电池效率和高温寿命特性随电解质中是否存在正电极薄膜添加剂和正电极薄膜添加剂(如果存在)的量的变化,在如下表1所示改变正电极薄膜添加剂CN-12的量的同时在高温(45℃)下测量初始电池效率和100次循环之后的放电保持,其中负电极薄膜添加剂VC的量固定至1.0重量%。结果汇总在表1中,并绘示在图2和图3中。
在这方面,循环在2.5V至4.2V的截止、1C的充电率和45℃的温度的条件下进行。为了制备电解质,使用0.5M LiPF6+0.5LiFSI作为锂盐,并且使用体积比为25:45:30的碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)和碳酸二乙酯(DEC)的混合物作为溶剂。
正电极由NCM811制成,同时负电极为石墨电极。
表1
图2显示了电池初始充电/放电效率随实施例和对比实施例的电解质组成变化的曲线。图3显示了高温寿命随实施例和对比实施例的电解质组成变化的曲线。
如表1及图2和图3所示,与未向电解质中添加正电极薄膜添加剂的对比实施例1相比,在分别添加0.1重量%、0.3重量%和1.0重量%的量的正电极薄膜添加剂(CN-12)的所有实施例1-3中,初始电池效率均得到提高。
此外,电池初始效率与使用0.5重量%的量的LiPO2F2作为负电极薄膜添加剂的对比实施例2的电池初始效率相似。
在高温寿命方面,所有的实施例1-3均与对比实施例1相似或更高。
高温寿命特性与对比实施例2的高温寿命特性相似或更高。
特别地,与对比实施例1相比,实施例2的电池初始效率和高温寿命均得到显著改善。
<测试2>在使用石墨作为负电极时室温(25℃)下的倍率性能随正电极薄膜添加剂
的量的变化的测试
为了在使用石墨作为负电极时检测室温(25℃)下的倍率性能随电解质中是否存在正电极薄膜添加剂和正电极薄膜添加剂(如果存在)的量的变化,在如下表2所示改变正电极薄膜添加剂CN-12的量的同时测量室温(25℃)下的倍率性能,其中负电极薄膜添加剂VC的量固定至1.0重量%。结果汇总在表2中,并绘示在图4中。
在这方面,循环在2.5V至4.2V的截止、0.5C/1.0C/2.0C/3.0C/0.5C的充电率和25℃的温度的条件下进行。为了制备电解质,使用0.5MLiPF6+0.5LiFSI作为锂盐,并且使用体积比为25:45:30的碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)和碳酸二乙酯(DEC)的混合物作为溶剂。
正电极由NCM811制成,同时负电极为石墨电极。
表2
图4为倍率性能随实施例和对比实施例的电解质组成变化的图表。
如表2和图4所示,与未向电解质中添加正电极薄膜添加剂的对比实施例1相比,在分别添加0.1重量%、0.3重量%和1.0重量%的量的正电极薄膜添加剂(CN-12)的所有实施例1-3中,倍率性能相似或得到改善。
此外,倍率性能与使用0.5重量%的量的LiPO2F2作为负电极薄膜添加剂的对比实施例2的倍率性能相似或更高。
特别地,与对比实施例1和2相比,实施例1和2表现出显著改善的倍率性能。
因此,从测试数据可以理解,与不存在本申请的正电极薄膜添加剂(CN-12)相比,在添加0.1重量%至1.0重量%或0.1重量%至0.3重量%的量的本申请的正电极薄膜添加剂(CN-12)时,初始电池效率、高温寿命和倍率性能特性均得到改善。
如上所述,根据本申请的实施方案,电解质可以在正电极活性材料的表面上形成高度离子导电的保护薄膜,以防止电池的降解,从而延长锂二次电池的寿命并增强其输出特性。
此外,电解质保证了高温下的寿命稳定性,从而有助于提高电池的商业价值。
本申请所属的领域的技术人员应理解,本申请可以以其它特定形式实施,而不改变本申请的技术精神和基本特征。因此,应理解,上述实施方案在所有方面均是说明性的,而不是限制性的。本申请的范围由所附权利要求书的范围限定,而不是由具体实施方式限定。应理解,从权利要求书的范围推导出的所有变化形式和修改形式及其等效概念均包含在本申请的范围内。
Claims (10)
1.一种用于锂二次电池的电解质,所述电解质包含:
锂盐;
溶剂;以及
功能性添加剂,所述功能性添加剂包含作为正电极薄膜添加剂的由下式表示的1-(3-((叔丁基二甲基甲硅烷基)氧)丙基)-5-(4-氟苯基)-1H-1,2,3-三唑-4-甲腈
2.根据权利要求1所述的用于锂二次电池的电解质,其中,基于电解质的重量,正电极薄膜添加剂在0.1重量%至1.0重量%的范围内。
3.根据权利要求1所述的用于锂二次电池的电解质,其中,基于电解质的重量,正电极薄膜添加剂在0.1重量%至0.3重量%的范围内。
4.根据权利要求1所述的用于锂二次电池的电解质,其中,功能性添加剂还包含作为负电极薄膜添加剂的碳酸亚乙烯酯。
5.根据权利要求4所述的用于锂二次电池的电解质,其中,基于电解质的重量,碳酸亚乙烯酯在0.5重量%至3.0重量%的范围内。
6.根据权利要求1所述的用于锂二次电池的电解质,其中,锂盐包括LiPF6、LiBF4、LiClO4、LiCl、LiBr、LiI、LiB10Cl10、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、LiN(SO2C2F5)2、Li(CF3SO2)2N、LiC4F9SO3、LiB(C6H5)4、Li(SO2F)2N、(CF3SO2)2NLi或其组合。
7.根据权利要求1所述的用于锂二次电池的电解质,其中,溶剂包括碳酸酯类溶剂、酯类溶剂、醚类溶剂、酮类溶剂或其组合。
8.一种锂二次电池,所述锂二次电池包含电解质,所述电解质包含:
锂盐;
溶剂;以及
功能性添加剂,所述功能性添加剂包含作为正电极薄膜添加剂的由下式表示的1-(3-((叔丁基二甲基甲硅烷基)氧)丙基)-5-(4-氟苯基)-1H-1,2,3-三唑-4-甲腈
9.根据权利要求8所述的锂二次电池,所述锂二次电池还包含:
正电极,所述正电极包含含有Ni、Co和Mn的正电极活性材料;
负电极,所述负电极包含含有碳-基材料、硅-基材料或其组合的负电极活性材料;以及
隔膜,所述隔膜插入在正电极和负电极之间。
10.根据权利要求9所述的锂二次电池,其中,正电极包含80重量%或更高的Ni。
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