WO2015003560A1 - 电解液添加剂及含该添加剂的电解液及锂离子电池 - Google Patents

电解液添加剂及含该添加剂的电解液及锂离子电池 Download PDF

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WO2015003560A1
WO2015003560A1 PCT/CN2014/081142 CN2014081142W WO2015003560A1 WO 2015003560 A1 WO2015003560 A1 WO 2015003560A1 CN 2014081142 W CN2014081142 W CN 2014081142W WO 2015003560 A1 WO2015003560 A1 WO 2015003560A1
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Prior art keywords
electrolyte
group
additive
electrolyte additive
ion battery
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PCT/CN2014/081142
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English (en)
French (fr)
Inventor
杨聚平
何向明
王莉
李建军
尚玉明
高剑
王要武
郭建伟
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江苏华东锂电技术研究院有限公司
清华大学
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Priority to JP2016526420A priority Critical patent/JP6143401B2/ja
Publication of WO2015003560A1 publication Critical patent/WO2015003560A1/zh
Priority to US14/983,501 priority patent/US9923241B2/en

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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
    • 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
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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

Definitions

  • the invention relates to an electrolyte additive, an electrolyte solution using the additive, and a lithium ion battery. Background technique
  • Lithium-ion batteries are the highest voltage and highest energy density of batteries that have been commercialized to date, and have good development prospects.
  • lithium-ion batteries there is a higher demand for operating voltage and energy density of lithium-ion batteries.
  • a lithium ion battery is mainly composed of an electrode, a separator, and an electrolyte.
  • the electrolyte is an important part of the battery, and its stable performance is the guarantee for the normal operation of the lithium ion battery.
  • the electrochemical window of a conventional lithium ion battery electrolyte can only reach about 4.5V, that is, oxidative decomposition occurs after a charging voltage exceeding 4.5V, making it difficult to use under higher voltage conditions.
  • An electrolyte additive selected from the group consisting of a maleimide derivative, a bismaleimide derivative, and a combination of the two, the maleimide derivative, the bismaleimide derivative
  • the structural formulas are as shown in Equations I and II: Formula T
  • R 1 , ⁇ 2 may be selected from a hydrogen atom and a halogen atom
  • R 3 may be selected from a silicon-containing group, a nitrogen-containing group, a fluorine-containing group, a phosphorus-containing group, and a repeating unit containing a vinyl group.
  • An electrolyte comprising: an alkali metal salt electrolyte; a non-aqueous solvent; and the above electrolysis agent.
  • a lithium ion battery comprising: a positive electrode; a negative electrode; a separator; and the above electrolyte.
  • the electrolyte additive of the embodiment of the invention only needs to add a maleimide derivative, a bismaleimide derivative or a combination of the two in the electrolyte, without adding additional materials. That is, the electrochemical window of the electrolyte can be made to about 5V, and further, the electrolyte can be used under higher voltage conditions, thereby improving the application range. At the same time, the electrolyte additive can also improve the high pressure cycle performance and capacity retention of the lithium ion battery.
  • 1 is a linear potential sweep curve of an electrolyte in an embodiment of the present invention.
  • FIG. 2 is a comparison diagram of a charge and discharge cycle test of a lithium ion battery according to a comparative example and an embodiment of the present invention.
  • Figure 3 is a graph showing the discharge capacity of the lithium ion battery of the comparative example and the embodiment at different currents.
  • Figure 4 is a graph showing the discharge curves of the lithium ion battery of the comparative example and the embodiment at different temperatures.
  • Embodiments of the present invention provide a lithium ion battery comprising: a positive electrode, a negative electrode, a separator, and an electrolyte.
  • the positive electrode includes a positive current collector and a positive material layer disposed on the surface of the positive current collector.
  • the material of the cathode current collector may be selected from aluminum, titanium or stainless steel.
  • the positive electrode material layer includes a positive active material, a conductive agent, and a binder.
  • the positive active material may be LiCo0 2 , LiNi0 2 , LiFeP0 4 or other positive electrode materials.
  • the conductive agent may be one or more of a carbon material such as carbon black, a conductive polymer, acetylene black, carbon fiber, carbon nanotubes, and graphite.
  • the binder may be one of polyvinylidene fluoride (PVDF), poly(vinylidene fluoride), polytetrafluoroethylene (PTFE), fluorine rubber, ethylene propylene diene monomer, and styrene butadiene rubber (SBR). Or a variety.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • the negative electrode may include a negative electrode current collector and a negative electrode material layer disposed on the surface of the negative electrode current collector.
  • the material of the anode current collector may be selected from copper, nickel or stainless steel.
  • the negative electrode material layer includes a negative electrode active material, a conductive agent, and a binder.
  • the negative electrode active material may be metallic lithium, lithium intercalated carbon material, lithium alloy or the like.
  • the conductive agent and the binder for the negative electrode are the same as the conductive agent and the binder for the positive electrode.
  • the separator may be a polyolefin microporous membrane, a modified polypropylene felt, a polyethylene felt, a glass fiber felt, an ultrafine glass fiber paper vinylon felt or a nylon felt and a wettable polyolefin microporous film welded or bonded.
  • a composite film may be a polyolefin microporous membrane, a modified polypropylene felt, a polyethylene felt, a glass fiber felt, an ultrafine glass fiber paper vinylon felt or a nylon felt and a wettable polyolefin microporous film welded or bonded.
  • a composite film may be a polyolefin microporous membrane, a modified polypropylene felt, a polyethylene felt, a glass fiber felt, an ultrafine glass fiber paper vinylon felt or a nylon felt and a wettable polyolefin microporous film welded or bonded.
  • the electrolyte includes an alkali metal salt electrolyte, a non-aqueous solvent, and an electrolyte additive.
  • the alkali metal salt electrolyte may be LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiC10 4 , LiAlCl 4 , LiGaCl 4 , LiN0 3 , LiC(S0 2 CF 3 ) 3 , LiN(S0 2 CF 3 ) 2 , LiSCN, Li0 3 SCF 2 CF 3 , LiC 6 F 5 S0 3 , Li0 2 CCF 3 , LiS0 3 F, Li(C 6 H 5 ) 4 or LiCF 3 S0 3 .
  • the nonaqueous solvent may be ethylene carbonate, propylene carbonate, butylene carbonate, Y-butyrolactone, dipropyl carbonate, N-decyl pyrrolidone, N-mercaptocarboxamide, N-mercaptoethyl Amide, bis-indenyl amide, diethyl phthalamide, acetonitrile, succinonitrile, adiponitrile, glutaronitrile, disulfoxide, dinonyl sulfite, vinylene carbonate, cesium carbonate, carbonic acid Diterpene ester, diethyl carbonate, fluoroethylene carbonate, propyl chlorocarbonate, acid anhydride, sulfolane, decyl sulfonyl sulfone, tetrahydrofuran, 2-mercaptotetrahydrofuran, propylene oxide, decyl acetate, acetic acid Ester, decyl butyrate,
  • the electrolyte additive may be a maleimide organism, a bismaleimide organism, or a combination thereof.
  • the mass of the electrolyte additive is from 0.1% to 30% by mass of the electrolyte.
  • the mass of the electrolyte additive is from 0.1% to 10% by mass of the electrolyte.
  • R 1 , R 2 are selected from a hydrogen atom and a halogen atom
  • R 3 is selected from the group consisting of a silicon-containing group, a nitrogen-containing group, a fluorine-containing group, a phosphorus-containing group, and a repeating unit containing a vinyl group.
  • the maleimide staining organism can be obtained by reacting 3,4-bis[3 ⁇ 4 generation maleic anhydride with the corresponding substituted amine or its hydrochloride (R 3 NH ); or by N-substituted maleic acid ⁇ alkylene amine with an acid halide (eg: S0Br 2, S0C1 2, S0I 2) reaction. It will be appreciated that one skilled in the art can also prepare the maleimide derivative by other methods.
  • the bismaleimide derivative can be prepared by the following method: using terpene benzene, dichloroethane and DMF (dimercapto phthalamide) as a mixed solvent, and sodium benzene sulfonate as a dehydrating agent, at a higher Dehydration cyclization at a temperature to obtain a bismaleimide derivative; or using sodium acetate or nickel acetate as a catalyst, diamine and MA (decyl acrylate) are first reacted in a solvent to form BMIA; then dehydrated with acetic anhydride Agent, BMIA dehydration cyclization to form bismaleimide. It will be appreciated that those skilled in the art may also prepare the bismaleimide derivative by other methods.
  • R is an alkyl group
  • ⁇ is an integer greater than or equal to 3 and less than or equal to 8.
  • the nitrogen-containing group may be -ROOCHN-R-NH-C-, wherein R is an alkyl group.
  • R is an alkyl group.
  • the vinyl-containing repeating unit is fCH 2 CH 2 0 ⁇ n , wherein n is greater than or equal to 1 and less than An integer of 30.
  • FIG. 1 is a linear potential scanning curve of the electrolyte solution obtained by the linear potential scanning method.
  • the electrochemical window of the electrolyte in the present embodiment can reach about 5 V, which is larger than At present, the conventional electrolyte can reach the electrochemical window, that is, about 4.5V.
  • Fig. 2 is a comparison diagram of charge and discharge cycles of an electrolyte battery containing an additive in an electrolyte battery containing no additive as a comparative example and the present embodiment.
  • the charge and discharge cycle conditions are: 25 °C, with 0.2C charge and discharge cycle, the charge and discharge voltage range is 2.75-4.5V. It can be seen from Figure 2 that under these conditions, the capacity of the lithium ion battery containing the additive is relatively stable, and the battery capacity attenuation ratio is small.
  • FIG. 3 is a diagram showing the discharge capacity of the electrolyte battery containing no additive as a comparative example and the electrolyte battery containing the additive in this example at different currents.
  • the test conditions are: 25 °C, charging to 4.2V at 0.2C, leaving lOmin, and then discharging to 2.75V with 0.2C 0.5C 1C 3C 3C 5C 7C IOC (same current discharge cycle 5 times), recording discharge capacity . It can be seen from Fig. 3 that as the current increases, the discharge specific capacity of the electrolyte battery containing no additive and the electrolyte battery containing the additive are lowered.
  • FIG. 4 is a graph showing discharge curves of an electrolyte battery containing no additive as a comparative example and an electrolyte battery containing an additive in this example at different temperatures.
  • the test conditions are: 25 °C, charge to 4.2V at 0.2C, leave lOmin, then discharge at 55 °C 0 °C and -20 °C, 0.2C to 2.75V, record the discharge capacity, from the figure 4 can be seen: As the temperature decreases, The discharge specific capacity of the electrolyte battery containing no additive and the electrolyte battery containing the additive are both lowered.
  • the electrolyte battery containing no additive and the electrolyte battery containing the additive had no significant difference in discharge specific capacity at various temperatures. It shows that the lithium ion battery can work normally in the temperature range of -20 ° C to 55 ° C.
  • the electrolyte additive of the invention can make the electrochemical window of the electrolyte reach about 5V, and further, the electrolyte can be used under higher voltage conditions, thereby improving the application range; the electrolyte additive can also improve the high pressure cycle of the lithium ion battery. Performance and capacity retention rate; in addition, the electrolyte additive does not reduce the rate discharge performance of the lithium ion battery at different currents and different temperatures, and the lithium ion battery containing the additive of the invention can be at a temperature of -20 ° C to 55 ° C Working within the scope.

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Abstract

一种电解液添加剂，该电解液添加剂包括：马来酰亚胺衍生物、双马来酰亚胺衍生物或两者的组合，所述马来酰亚胺衍生物、双马来酰亚胺衍生物的结构式分别为：式（Ｉ）、式（ＩＩ）。其中，R1和R2均可选自氢原子以及卤素原子，R3可选自含硅基团、含氮基团、含氟基团、含磷基团、含乙烯氧基重复单元。还提供应用该电解液添加剂的电解液及锂离子电池。

Description

电解液添加剂及含该添加剂的电解液及锂离子电池 技术领域
本发明涉及一种电解液添加剂，及应用该添加剂的电解液、锂离子电池。 背景技术
目前， 随着电动汽车及便携式电子设备如手机、 数码相机和笔记本电脑 等的迅猛发展， 市场对高功率、 高能量密度电池的需求越来越大。 锂离子电 池是迄今为止已经商业化的电池中电压最高、 能量密度最大的电池， 具有良 好的发展前景。 但是， 随着锂离子电池在电动汽车、 混合动力汽车、 无绳电 动工具及军事上的应用增多，对锂离子电池的工作电压和能量密度有了更高 的要求。
锂离子电池主要由电极、 隔离膜以及电解液构成。 电解液是电池的一个 重要组成部分， 其稳定的性能是锂离子电池正常工作的保证。 目前常规的锂 离子电池电解液的电化学窗口只能达到 4.5V左右， 即， 在超过 4.5V的充电 电压之后发生氧化分解， 使其难以在更高电压条件下使用。
现有技术中，有大量研究通过在电解液中加入添加剂改善电解液的功用 及性能，然而现有技术在电解液中加入添加剂通常是为了改善电池的高压循 环性能和容量保持率。 因此， 未发现有通过在电解液中加入添加剂提高电解 液电化学窗口的 4艮道。 发明内容
有鉴于此，确有必要提供一种可以提高锂离子电池电解液的电化学窗口 的电解液添加剂， 及应用该电解液添加剂的电解液、 锂离子电池。
一种电解液添加剂， 其选自马来酰亚胺衍生物、 双马来酰亚胺衍生物以 及两者的组合， 所述马来酰亚胺衍生物、 双马来酰亚胺衍生物的结构式分别 如式 I及式 II所示：
Figure imgf000004_0001
式 T 式 π
其中， R1, ^2均可选自氢原子以及卤素原子， R3可选自含硅基团、 含氮 基团、 含氟基团、 含磷基团、 含乙烯氧基重复单元。
一种电解液， 其包括： 一碱金属盐电解质； 一非水溶剂； 以及上述电解 ^力口剂。
一种锂离子电池， 其包括： 一正极； 一负极； 一隔离膜； 以及上述电解 液。
相较于现有技术， 本发明实施例的电解液添加剂只需在电解液中加入马 来酰亚胺衍生物、 双马来酰亚胺衍生物或两者的组合物， 无需添加额外的材 料， 即可以使电解液的电化学窗口达到 5V左右， 进而， 使该电解液可以在 更高电压条件下使用， 提高应用范围。 同时， 该电解液添加剂还可以提高锂 离子电池的高压循环性能和容量保持率。 附图说明
图 1为本发明实施例中电解液的线性电势扫描曲线。
图 2为本发明对比例与实施例锂离子电池充放电循环测试比较图。
图 3为本发明对比例与实施例锂离子电池在不同电流下的放电容量图。 图 4为本发明对比例与实施例锂离子电池在不同温度下的放电曲线图。 如下具体实施方式将结合上述附图进一步说明本发明。 具体实施方式
本发明实施例提供一种锂离子电池， 其包括： 一正极、 一负极、 一隔离 膜以及一电解液。
所述正极包括一正极集流体及一设置于该正极集流体表面的正极材料 层。 该正极集流体的材料可以选自铝、 钛或不锈钢。 该正极材料层包括一正 极活性材料、 一导电剂以及一粘结剂。 该正极活性材料可以为 LiCo02、 LiNi02、 LiFeP04或其它正极材料。 该导电剂可以为碳素材料， 如碳黑、 导 电聚合物、 乙炔黑、 碳纤维、 碳纳米管及石墨中的一种或多种。 该粘结剂可 以是聚偏氟乙烯 (PVDF)、 聚偏（二）氟乙烯、 聚四氟乙烯 (PTFE)、 氟类橡胶、 三元乙丙橡胶及丁苯橡胶 (SBR)中的一种或多种。
所述负极可包括一负极集流体及一设置于该负极集流体表面的负极材 料层。 该负极集流体的材料可以选自铜、 镍或不锈钢。 该负极材料层包括一 负极活性材料、 一导电剂以及一粘结剂。 该负极活性材料可为金属锂、 嵌锂 的碳材料或锂合金等。 所述负极用的导电剂及粘结剂与所述正极用的导电剂 及粘结剂相同。
所述隔离膜可以为聚烯烃微多孔膜、 改性聚丙烯毡、 聚乙烯毡、 玻璃纤 维毡、超细玻璃纤维纸维尼纶毡或尼龙毡与可湿性聚烯烃微孔膜经焊接或粘 接而成的复合膜。
所述电解液包括一碱金属盐电解质、 一非水溶剂以及一电解液添加剂。 所述碱金属盐电解质可以为 LiPF6、 LiBF4、 LiAsF6、 LiSbF6、 LiC104、 LiAlCl4、 LiGaCl4、 LiN03、 LiC(S02CF3)3、 LiN(S02CF3)2、 LiSCN、 Li03SCF2CF3、 LiC6F5S03、 Li02CCF3、 LiS03F、 Li(C6H5)4或 LiCF3S03。
所述非水溶剂可以为碳酸亚乙酯、 碳酸丙烯酯、 碳酸丁烯酯、 Y -丁内 酯、 碳酸二丙酯、 N-曱基吡咯烷酮、 N-曱基曱酰胺、 N-曱基乙酰胺、 二曱基 曱酰胺、 二乙基曱酰胺、 乙腈、 丁二腈、 己二腈、 戊二腈、 二曱亚砜、 亚硫 酸二曱酯、 碳酸亚乙烯酯、 碳酸曱乙酯、 碳酸二曱酯、 碳酸二乙酯、 氟代碳 酸乙烯酯、 氯代碳酸丙烯酯、 酸酐、 环丁砜、 曱氧基曱基砜、 四氢呋喃、 2- 曱基四氢呋喃、 环氧丙烷、 乙酸曱酯、 乙酸乙酯、 丁酸曱酯、 丙酸乙酯、 丙 酸曱酯、 1,3-二氧戊烷、 1,2-二乙氧基乙烷、 1,2-二曱氧基乙烷、 或 1,2-二丁 氧基中的一种或几种的组合。
所述电解液添加剂可以为马来酰亚胺 生物、 双马来酰亚胺 生物或其 组合。 所述电解液添加剂的质量占电解液质量的百分比为 0.1% ~ 30%。 优选 地， 所述电解液添加剂的质量占电解液质量的百分比为 0.1% ~ 10%。
其中， 马来酰亚胺衍生物、 双马来酰亚胺衍生物的结构式分别为：
Figure imgf000006_0001
, 其中， R1, R2选自氢原子以及卤 素原子， R3选自含硅基团、 含氮基团、 含氟基团、 含磷基团以及含乙烯氧基 重复单元。
所述马来酰亚胺^汙生物可通过 3, 4—二 [¾代马来酸酐与相应的取代胺 或其盐酸盐 （R3NH )反应得到； 或通过 N—取代马来酰亚胺与亚^ 酸卤（如： S0Br2、 S0C12、 S0I2)反应得到。 可以理解， 本领域技术人员也可釆用其他方 法制备所述马来酰亚胺衍生物。
所述双马来酰亚胺衍生物可通过以下方法制备： 以曱苯、 二氯乙烷和 DMF (二曱基曱酰胺）为混合溶剂， 对曱苯磺酸钠为脱水剂， 在较高温度下 进行脱水环化得到双马来酰亚胺衍生物； 或以乙酸钠或乙酸镍作为催化剂， 二元胺与 MA (丙烯酸曱酯 ) 在溶剂中反应首先生成 BMIA; 然后以乙酸酐 为脱水剂， BMIA脱水环化生成双马来酰亚胺。 可以理解， 本领域技术人员 也可釆用其他方法制备所述双马来酰亚胺衍生物。
Figure imgf000006_0002
, 其中， R为烷基， η为大于等于 3小于等于 8 的整数。
所述含氮基团可以为 -ROOCHN-R-NH-C -, 其中， R为烷基。
Figure imgf000006_0003
中 R为烷基。
所述含乙烯氧基重复单元为 fCH2CH20}n, 其中， n为大于等于 1小于等 于 30的整数。
实施例
取 1.0mol/L的 LiPF6溶于碳酸乙烯酯 (EC)、 碳酸二乙酯 (DEC)、 碳酸曱 乙酉^ EMC)混合溶剂（体积比 EC/DEC/EMC=1/1/1 ), 加入 1% (质量百分比 )
Figure imgf000007_0001
充分搅拌使之均勾， 并进行脱泡， 得到电解液， 将该电解液注入由正极材料 （LiCo02 )、 负极材料 （Li ) 和隔离膜组成的电 芯中配置成锂离子电池。
请参阅图 1 , 图 1是用线性电势扫描法得到的本实施例中电解液的线性 电势扫描曲线， 从图 1可以看出， 本实施中的电解液的电化学窗口可以达到 5V左右， 大于目前常规的电解液的所能达到电化学窗口， 即， 4.5V左右。
请一并参阅图 2, 图 2为以未含有添加剂的电解液电池作为比较例与本 实施例含有添加剂的电解液电池充放电循环对比图。 其中， 充放电循环条件 为： 25 °C , 以 0.2C充放电循环， 充放电电压范围是 2.75-4.5V。 从图 2可以 看出： 此条件下， 含有添加剂的锂离子电池的容量比较稳定， 且电池容量衰 减比例较小。
请一并参阅图 3 , 图 3为以未含有添加剂的电解液电池作为比较例与本 例含有添加剂的电解液电池在不同电流下的放电容量图。其中，测试条件为： 25 °C , 以 0.2C充电至 4.2V, 搁置 lOmin, 然后分别以 0.2C 0.5C 1C 3C 3C 5C 7C IOC (相同电流放电循环 5次）放电至 2.75V, 记录放电容量。 从图 3可以看出： 随着电流的增加， 未含有添加剂的电解液电池与含有添加 剂的电解液电池的放电比容量均降低。 在各个电流下， 未含有添加剂的电解 液电池与含有添加剂的电解液电池的放电容量无明显差别。 因此， 可以确定 该添加剂的加入在降低电池容量衰减的同时， 不会降低锂离子电池的倍率放 电性能。
请参阅图 4, 图 4为以未含有添加剂的电解液电池作为比较例与本例含 有添加剂的电解液电池在不同温度下的放电曲线图。 其中， 测试条件为： 25 °C , 以 0.2C充电至 4.2V, 搁置 lOmin, 然后分别在 55 °C 0 °C以及 -20 °C , 以 0.2C放电至 2.75V, 记录放电容量， 从图 4可以看出： 随着温度的降低， 未含有添加剂的电解液电池与含有添加剂的电解液电池的放电比容量均降 低。 而且未含有添加剂的电解液电池与含有添加剂的电解液电池在各个温度 下， 放电比容量无明显差别。 说明该锂离子电池可在 -20°C至 55°C的温度范 围内正常工作。
本发明的电解液添加剂可以使电解液的电化学窗口达到 5V左右，进而， 使该电解液可以在更高电压条件下使用， 提高应用范围； 该电解液添加剂还 可以提高锂离子电池的高压循环性能和容量保持率； 另外， 该电解液添加剂 不会降低锂离子电池不同电流和不同温度下的倍率放电性能， 且含有本发明 添加剂的锂离子电池可在 -20°C至 55°C的温度范围内正常工作。
另外， 本领域技术人员还可在本发明精神内做其它变化， 当然， 这些依 据本发明精神所做的变化， 都应包含在本发明所要求保护的范围之内。

Claims

权 利 要 求 书
1. 一种电解液添加剂， 其选自马来酰亚胺衍生物、 双马来酰亚胺衍生物以及两 者的组合， 所述马来酰亚胺衍生物、 双马来酰亚胺衍生物的结构式分别如式 I 及式 II所示：
Figure imgf000009_0001
式 I 式 π
其中， R^ R2选自氢原子以及卤素原子， R3选自含硅基团、 含氮基团、 含氟 基团、 含磷基团以及含乙烯氧基重复单元。
2. 如权利要求 1所述的电解液添加剂， 其特征在于， 所述含硅基团为
Figure imgf000009_0002
, 其中， R为烷基， n为大 于等于 3小于等于 8的整数。
3. 如权利要求 1所述的电解液添加剂， 其特征在于， 所述含氮基团为
-ROOCHN-R-NH-COOR- , 其中， R为烷基。
4. 如权利要求 1所述的电解液添加剂， 其特征在于， 所述含氟基团选自
以及
Figure imgf000009_0003
o I I
5. 如权利要求 1所述的电解液添加剂， 其特征在于， 所述含碑基团为 I , 其中 R为烷基。
6. 如权利要求 1所述的电解液添加剂， 其特征在于， 所述含乙烯氧基重复单元 为 fCH2CH20}n, 其中， n为大于等于 1小于等于 30的整数。
7. 一种电解液， 其包括： 一碱金属盐电解质；
一非水溶剂； 及
如权利要求 1至 6中任一项所述的电解液添加剂。
8. 如权利要求 7所述的电解液， 其特征在于， 所述电解液添加剂的质量占电解 液质量的百分比为 0.1% ~ 30%。
9. 如权利要求 7所述的电解液， 其特征在于， 所述电解液添加剂的质量占电解 液质量的百分比为 0.1% ~ 10%。
10. 一种锂离子电池， 其包括：
一正极；
一负极；
一隔离膜； 以及
如权利要求 7所述的电解液。
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