CN105591156A - Electrolyte containing tricyanobenzene and lithium ion secondary battery containing electrolyte - Google Patents

Electrolyte containing tricyanobenzene and lithium ion secondary battery containing electrolyte Download PDF

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CN105591156A
CN105591156A CN 201610009642 CN201610009642A CN105591156A CN 105591156 A CN105591156 A CN 105591156A CN 201610009642 CN201610009642 CN 201610009642 CN 201610009642 A CN201610009642 A CN 201610009642A CN 105591156 A CN105591156 A CN 105591156A
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vinegar
carbonate
electrolyte
containing
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王再盛
仰永军
李斌
万华平
许梦清
李伟善
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东莞市凯欣电池材料有限公司
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0567Liquid materials characterised by the additives
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/0025Organic electrolyte

Abstract

The invention discloses an electrolyte containing 1,3,5-tricyanobenzene. The electrolyte comprises an organic solvent, conductive lithium salt and an additive, wherein the additive is 1,3,5-tricyanobenzene; the organic solvent is selected from more than one of cyclic carbonate and linear carbonate; the use mass of the additive is equivalent to 0.1%-10% of the total mass of the lithium salt and the organic solvent. Tricyanobenzene and transition metal have higher complexation, dissolving out of transition metal of a positive plate can be effectively inhibited, the transition metal can be enriched on the surface of the positive plate to form a protecting film, catalytic decomposition of electrolyte components on the surface of the positive plate is inhibited, and the high-temperature storage performance of the secondary battery is improved.

Description

一种含有苯三腈的电解液及含有该电解液的锂离子二次电池技术领域本发明设计锂离子电池制备领域,具体涉及一种含有苯三腈的电解液及含有该电解液的锂离子二次电池。 Electrolyte solution containing trimesic carbonitrile and lithium ion secondary batteries Technical Field of the electrolyte containing the present invention is designed to prepare a lithium ion battery art, particularly, to a nitrile trimesic electrolyte containing lithium ions and the electrolyte solution containing secondary battery. 背景技术锂离子电池因其比能量高、体积小、质量轻、无记忆效应、循环寿命长等优点广泛应用于便携式电子设备中。 BACKGROUND ART Lithium ion batteries because of its high specific energy, small volume, light weight, no memory effect, long cycle life and other advantages are widely used in portable electronic devices. 但是,随着便携式电子产品的快速发展,对锂离子的比能量提出越来越高的要求。 However, with the rapid development of portable electronic products, higher and higher requirements for specific energy of lithium ions. 但是在充满电状态下,锂离子二次电池的整个化学体系具有极高的化学活性。 However, in the fully charged state, the lithium ion secondary battery of the entire chemical system having a high chemical activity. 当电子产品持续使用或环境温度升高时,都可能使锂离子二次电池处于高温状态,这时作为正极活性材料的金属氧化物显示出非常强的氧化性,容易与电解液发生氧化反应,导致电解液分解。 When the continuous use electronic products or environmental temperature, can make a lithium ion secondary battery in a high temperature state, at this time showed a very strong oxidizing metal oxide as a positive electrode active material, the reaction with the electrolyte is easily oxidized, leading to decomposition of the electrolyte. 此外,随着锂离子二次电池的高电压话,电解液在正极表面的氧化分解会加剧,导致锂离子二次电池的储存性能下降。 Further, if a high voltage as the lithium ion secondary battery, the electrolytic solution in the positive electrode surface oxidation decomposition exacerbated, resulting in storage performance lithium ion secondary battery decreases. 因此,抑制电解液和正极活性材料之前的氧化反应是防止锂离子二次电池高温储存性能恶化的关键。 Thus, the key to high temperature storage lithium ion secondary battery electrolyte and suppress performance deterioration of the oxidation reaction before the positive active material is prevented. 目前为了提高锂离子二次电池的能量密度,主要采用一些镍元素含量加高的正极活性材料,如镍钴铝氧化物、锂镍钴锰氧化物等。 Currently, to increase the energy density of the lithium ion secondary battery, the positive electrode active material mainly nickel element content of some heightening, such as nickel cobalt aluminum oxide, a lithium nickel cobalt manganese oxide and the like. 但是高镍含量的正极活性材料在充电截止电压较高时,会提高正极片的氧化嗯呢管理,造成电解液的氧化问题更严重。 However, a high nickel content of the positive electrode active material during charge-cutoff voltage is higher, the oxidation of the positive electrode plate will increase management ah it, causing more serious problem of oxidation of the electrolytic solution. 因此对于这种高能量的正极活性材料或当锂离子二次电池在高电压使用时,解决电解液的分解尤为迫切。 Thus the decomposition of the electrolytic solution is urgent for this high-energy cathode active material or lithium ion secondary battery when used in a high voltage, solution. 发明内容鉴于背景技术所存在的问题,本发明的目的在于提供一种用于锂离子电池的电解液, 其工作电压在4.2V以上时,能够有效地抑制电解液的氧化并改善锂离子二次电池的高温储存性能,解决锂离子二次电池在高压高温储存是造成的电解液的分解及由此导致的锂离子二次电池气胀的问题。 In view of the problems of the background art, an object of the present invention to provide an electrolyte for a lithium ion battery, when the operating voltage 4.2V or more, can be effectively suppressed oxidation of the electrolytic solution and improves lithium ion secondary high-temperature storage performance of the battery, lithium ion secondary batteries solution stored at high pressure and temperature and the decomposition is a problem lithium ion secondary battery electrolyte resulting bloating caused. 本发明通过以下技术方案实现: 一种含有苯三腈的电解液,包括有机溶剂、导电锂盐和添加剂,其中:所述有机溶剂选为环状碳酸酯和线性碳酸酯的一种以上,所述的添加剂结构式(1)如下: The present invention is achieved by the following technical solution: an electrolyte containing a nitrile trimesic, including organic solvent, a conductive lithium salt and an additive, wherein: the organic solvent is preferably one cyclic carbonate and linear carbonate above, the additives described formula (1) as follows:

Figure CN105591156AD00031

所述添加剂的使用质量相当于所述锂盐和所述有机溶剂总质量的0.1%~10%。 The use of additives corresponding to 0.1% by mass of the lithium salt and 10% of the total mass of the organic solvent. 所述有机溶剂包括环状碳酸酯溶剂和线型碳酸酯溶剂,环状碳酸酯溶剂和线型碳酸酯溶剂的配比为质量比为1:1~3:2,导电锂盐的终浓度为0.8~1.5mol/L。 The organic solvent comprises a cyclic carbonate solvent, and the ratio of the linear carbonate solvent, an ester solvent, a cyclic carbonate and linear carbonate solvents to mass ratio of 1: 1 to 3: 2, the final concentration of the conductive lithium salt is 0.8 ~ 1.5mol / L. 所述的环状碳酸酯溶剂为碳酸乙烯酯、碳酸丙烯酯、氟代碳酸乙烯酯、γ-丁内酯和γ-戊内酯中的一种以上。 The solvent is a cyclic carbonate as ethylene carbonate, propylene carbonate, fluoroethylene carbonate, ethylene carbonate, [gamma] -butyrolactone and [gamma] -valerolactone in one or more. 所述的线型碳酸酯溶剂为碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯或碳酸甲丙酯中的至少一种。 The linear carbonate is dimethyl carbonate as solvent, at least one carbonate, ethylmethyl carbonate, diethyl carbonate, methyl or propylparaben. 所述的导电锂盐为六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、二草酸硼酸锂(LiBOB)、 二氟草酸硼酸锂(LiDFOB)、三氟甲基磺酸锂(LiSO3CF3)、高氯酸锂(LiCKk)、六氟砷酸锂(LiAsF 6)、双三氟甲基磺酰亚胺锂(Li (CF3SO2)2N)中的至少一种。 Said conductive lithium salt is lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium trifluoromethanesulfonate (LiSO3CF3), perchlorate lithium (LiCKk), lithium hexafluoroarsenate (LiAsF 6), at least one bistrifluoromethylsulfonyl imide (Li (CF3SO2) 2N) in. 所述电解液还包含常用的添加剂,所述的常用添加剂为碳酸亚乙烯酯、碳酸乙烯亚乙酯、丙磺酸内酯、丁磺酸内酯、硫酸乙烯酯、己二腈、丁二腈、LiB0B、LiDF0B、中的一种以上, 所述的常用添加剂占非水电解液总质量的0.1-5.0%。 The electrolytic solution further comprises usual additives, the conventional additives vinylene carbonate, vinyl ethylene carbonate, propane sultone, butane sultone, vinyl sulfate, adiponitrile, succinonitrile a LiB0B, LiDF0B, in the above, the usual additives comprise 0.1-5.0% of the total mass of the nonaqueous electrolytic solution. 本发明的另一目的在于提供所述用于锂离子二次电池的含有苯三腈的电解液的制备方法。 Another object of the present invention to provide a method of preparing the electrolyte solution for a lithium ion secondary battery comprising trimellitic nitrile. 一种电解液的制备方法: (1) 将有机溶剂按比例混合后用5 A分子筛、氢化钙、氢化锂纯化除杂、除水; (2) 在室温条件下,将导电锂盐溶解在上述有机溶剂中,并搅拌均匀; (3) 加入常用添加剂,并搅拌均匀;加入添加剂,制得本发明的含有苯三腈的电解液。 A method of preparing the electrolytic solution: (1) The ratio of the organic solvent by mixing with a 5 A molecular sieve, calcium hydride, lithium hydride impurity purification, water removal; (2) at room temperature, a conductive lithium salt dissolved in the above an organic solvent, and stir; (3) common additives added, and uniformly stirred; additives to prepare an electrolytic solution containing trimesic nitrile of the present invention. 一种锂离子二次电池,包括包括正极活性材料、负极活性材料和隔膜,还包括本发明的含有苯三腈的电解液。 A lithium ion secondary battery comprising a positive electrode comprising active material, a negative electrode active material and a separator, further comprising an electrolyte containing a nitrile trimesic present invention. 所述正极活性材料为一种含锂过渡金属氧化物,正极活性材料为以下物质的一种以上:LiCo〇2、LiNi〇2、LiMn〇2、LiMn2〇4、Li(NiaC〇bMnc)〇2(0〈a〈l,0〈b〈l,0〈C〈l,a+b+C=l)、 LiNii-yMny〇2、LiNii-yMny〇2(〇SzS2)、LiM x(P04)y(]\C%Ni、Co、Mn、Ti、V,〇SxS5,〇SyS5); 负极活性材料为可嵌入/脱出锂离子的碳材料、锂金属、硅或锡及其氧化物中的一种以上; 隔膜为自织布、无纺布、合成树脂微多孔膜的任一种。 The positive electrode active material is a lithium-containing transition metal oxide positive electrode active material is more than one of the following substances: LiCo〇2, LiNi〇2, LiMn〇2, LiMn2〇4, Li (NiaC〇bMnc) 〇2 (0 <a <l, 0 <b <l, 0 <C <l, a + b + C = l), LiNii-yMny〇2, LiNii-yMny〇2 (〇SzS2), LiM x (P04) y (] \ C% Ni, Co, Mn, Ti, V, 〇SxS5, 〇SyS5); a negative electrode active material may intercalation / deintercalation of lithium ions, a carbon material, lithium metal, silicon or tin oxide, and above; septum is self woven fabric, a nonwoven fabric, a synthetic resin according to any microporous membrane. 本发明的优点在于: 所述的苯三腈与过渡金属有较强的络合作用,能够有效地抑制正极片过渡金属的溶出,能够在正极片表面富集,形成一层保护膜,抑制电解液组分在正极片表面的催化分解, 从而改善二次电池的高温储存性能。 Advantage of the present invention is that: the nitrile-benzenetricarboxylic the transition metal complexation strong, positive electrode sheet can be effectively suppressed elution of the transition metal, can be enriched at the surface of the positive electrode sheet, a protective film is formed to suppress electrolytic fluid catalytic component decomposition of the positive electrode sheet surface, thereby improving the high-temperature storage performance of the secondary battery.

具体实施方式以下实施例进一步详细的说明本发明,但本发明并不局限于这种实施例。 DETAILED DESCRIPTION The following examples further illustrate the present invention in detail, but the present invention is not limited to such embodiments. 下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。 Below in connection with embodiments of the present invention will be described in further detail, but the embodiment of the present invention is not limited thereto. 实施例1 (1) 将环状碳酸酯溶剂碳酸乙烯酯(EC)和线型碳酸酯溶剂碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按质量比EC: EMC: DEC = 3:5:2混合,并采用分子筛、氢化钙、氢化锂纯化除杂、除水; (2) 在室温条件下,将导电锂盐LiPF6溶解在步骤(1)得到的溶剂中,终浓度为I.Omol/ L,搅拌均匀,得到普通电解液; (3) 在步骤(2)制备的普通电解液中添加入三氟甲磺酸三氟乙酯,用量为电解液质量的1.5% ;得到用于锂离子电池的高压电解液。 Example 1 (1) the cyclic carbonate ester solvent of ethylene carbonate (EC) and linear carbonate solvents ethylmethyl carbonate (EMC), diethyl carbonate (DEC) mass ratio of EC: EMC: DEC = 3: 5: 2 mixed, and molecular sieve, calcium hydride, lithium hydride impurity purification, water removal; (2) at room temperature, the conductive lithium salt is LiPF6 dissolved in step (1) in a solvent to give a final concentration of I. Omol / L, stirring uniformly, ordinary electrolytic solution; (3) added to trifluoromethanesulfonic acid trifluoroethyl electrolytic solution in an ordinary step (2) was prepared in an amount of 1.5% by mass of the electrolytic solution; obtained for high pressure electrolyte lithium ion battery. 实施例2 (1) 将环状碳酸酯溶剂碳酸乙烯酯(EC)和线型碳酸酯溶剂碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按质量比EC: EMC: DEC = 3:5:2混合,采用分子筛、氢化钙、氢化锂纯化除杂、除水; (2) 在室温条件下,将导电锂盐LiPF6溶解在步骤(1)得到的溶剂中,终浓度为lmol/L, 搅拌均匀,配成普通电解液; (3) 在步骤(2)制备的普通电解液中添加三氟甲磺酸三氟乙酯,用量为电解液质量的0.5%;得到用于锂离子电池的高压功能电解液。 Example 2 (1) the cyclic carbonate ester solvent of ethylene carbonate (EC) and linear carbonate solvents ethylmethyl carbonate (EMC), diethyl carbonate (DEC) mass ratio of EC: EMC: DEC = 3: 5: 2 mixture, molecular sieve, calcium hydride, lithium hydride impurity purification, water removal; (2) at room temperature, the conductive lithium salt is LiPF6 dissolved in step (1) in a solvent to give a final concentration of lmol / L , stir, dubbed ordinary electrolytic solution; (3) was added trifluoromethanesulfonic acid trifluoroethyl electrolytic solution in an ordinary step (2) was prepared in an amount of 0.5% by mass of the electrolytic solution; for lithium ion batteries obtained high pressure electrolyte function. 实施例3 (1) 将环状碳酸酯溶剂碳酸乙烯酯(EC)和线型碳酸酯溶剂碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按质量比EC: EMC: DEC = 3:5:2混合,采用分子筛、氢化钙、氢化锂纯化除杂、除水; (2) 在室温条件下,将导电锂盐LiPF6溶解在步骤(1)得到的溶剂中,终浓度为I.Omol/ L,搅拌均匀,配成普通电解液; (3) 在步骤(2)制备的普通电解液中添加三氟甲磺酸三氟乙酯,用量为电解液质量的1% ;得到用于锂离子电池的含硼成膜功能电解液。 Example 3 (1) the cyclic carbonate ester solvent of ethylene carbonate (EC) and linear carbonate solvents ethylmethyl carbonate (EMC), diethyl carbonate (DEC) mass ratio of EC: EMC: DEC = 3: 5: 2 mixture, molecular sieve, calcium hydride, lithium hydride impurity purification, water removal; (2) at room temperature, the conductive lithium salt is LiPF6 dissolved in step (1) in a solvent to give a final concentration of I.Omol / L, stir, dubbed ordinary electrolytic solution; (3) was added trifluoromethanesulfonic acid trifluoroethyl electrolytic solution in an ordinary step (2) was prepared in an amount of 1% by mass of the electrolytic solution; obtained for a lithium boron-ion battery electrolyte forming function. 实施例4 (1) 将环状碳酸酯溶剂碳酸乙烯酯(EC)和线型碳酸酯溶剂碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按质量比EC: EMC: DEC = 3:5:2混合,采用分子筛、氢化钙、氢化锂纯化除杂、除水; (2) 在室温条件下,将导电锂盐LiClO4溶解在步骤(1)得到的溶剂中,终浓度为I.Omol/ L,搅拌均匀,配成普通电解液; (3) 在步骤(2)制备的普通电解液中添加三氟甲磺酸三氟乙酯,用量为电解液质量的2% ;得到用于锂离子电池的高压电解液。 Example 4 (1) the cyclic carbonate ester solvent of ethylene carbonate (EC) and linear carbonate solvents ethylmethyl carbonate (EMC), diethyl carbonate (DEC) mass ratio of EC: EMC: DEC = 3: 5: 2 mixture, molecular sieve, calcium hydride, lithium hydride impurity purification, water removal; (2) at room temperature, the conductive lithium salt is LiClO4 dissolved in step (1) in a solvent to give a final concentration of I.Omol / L, stir, dubbed ordinary electrolytic solution; (3) was added trifluoromethanesulfonic acid trifluoroethyl electrolytic solution in an ordinary step (2) was prepared in an amount of 2% by mass of the electrolytic solution; obtained for a lithium high pressure electrolyte ion battery. 实施例5 (1) 将环状碳酸酯溶剂碳酸乙烯酯(EC)和线型碳酸酯溶剂碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按质量比EC: EMC: DEC = 3:5:2混合,采用分子筛、氢化钙、氢化锂纯化除杂、除水; (2) 在室温条件下,将导电锂盐LiAsF6溶解在步骤(1)得到的溶剂中,终浓度为1.2mol/ L,搅拌均匀,配成普通电解液; Example 5 (1) the cyclic carbonate ester solvent of ethylene carbonate (EC) and linear carbonate solvents ethylmethyl carbonate (EMC), diethyl carbonate (DEC) mass ratio of EC: EMC: DEC = 3: 5: 2 mixture, molecular sieve, calcium hydride, lithium hydride impurity purification, water removal; (2) at room temperature, LiAsF6 conductive lithium salt dissolved in step (1) in a solvent to give a final concentration of 1.2mol / L, stir, dubbed common electrolyte;

[0049] (3)在步骤(2)制备的普通电解液中添加三氟甲磺酸三氟乙酯,用量为电解液质量的2% ;得到用于锂离子电池的高压电解液。 [0049] (3) adding electrolyte in the normal step (2) Preparation of trifluoroethyl trifluoromethanesulfonate, in an amount of 2% by mass of the electrolytic solution; obtained high pressure electrolyte for a lithium ion battery. 实施例6 (1) 将环状碳酸酯溶剂碳酸乙烯酯(EC)和线型碳酸酯溶剂碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按质量比EC: EMC: DEC = 3:5:2混合,采用分子筛、氢化钙、氢化锂纯化除杂、除水; (2) 在室温条件下,将导电锂盐Li(CF3SO2)2N溶解在步骤(1)得到的溶剂中,终浓度为1.2mol/L,搅拌均匀,配成普通电解液; (3) 在步骤(2)制备的普通电解液中添加三氟甲磺酸三氟乙酯,用量为电解液质量的1.5% ;得到用于锂离子电池的高压电解液。 Example 6 (1) the cyclic carbonate ester solvent of ethylene carbonate (EC) and linear carbonate solvents ethylmethyl carbonate (EMC), diethyl carbonate (DEC) mass ratio of EC: EMC: DEC = 3: 5: 2 mixture, molecular sieve, calcium hydride, lithium hydride impurity purification, water removal; (2) at room temperature, a conductive lithium salt Li (CF3SO2) 2N dissolved in step (1) in a solvent to give a final concentration was 1.2mol / L, stir, dubbed ordinary electrolytic solution; (3) was added trifluoromethanesulfonic acid trifluoroethyl electrolytic solution in an ordinary step (2) was prepared in an amount of 1.5% by mass of the electrolytic solution; obtained electrolyte for a high voltage lithium ion battery. 实施例7 (1)将环状碳酸酯溶剂碳酸乙烯酯(EC)和线型碳酸酯溶剂碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按质量比EC: EMC: DEC = 3:5:2混合,采用分子筛、氢化钙、氢化锂纯化除杂、除水; ⑵在室温条件下,将导电锂盐LiC(CF3SO2)3溶解在步骤(1)得到的溶剂中,终浓度为1.2mol/L,搅拌均匀,配成普通电解液; (3)在步骤(2)制备的普通电解液中添加三氟甲磺酸三氟乙酯,用量为电解液质量的0.5%;得到用于锂离子电池的高压电解液。 Example 7 (1) the cyclic carbonate ester solvent of ethylene carbonate (EC) and linear carbonate solvents ethylmethyl carbonate (EMC), diethyl carbonate (DEC) mass ratio of EC: EMC: DEC = 3: 5: 2 mixture, molecular sieve, calcium hydride, lithium hydride impurity purification, water removal; ⑵ at room temperature, a conductive lithium salt LiC (CF3SO2) 3 was dissolved in step (1) in a solvent to give a final concentration of 1.2 mol / L, mixing evenly, dubbed ordinary electrolytic solution; (3) was added trifluoromethanesulfonic acid trifluoroethyl electrolytic solution in an ordinary step (2) was prepared in an amount of 0.5% by mass of the electrolytic solution; obtained for high pressure electrolyte lithium ion battery. 将实施例1-7所制备的锂离子电池的高压电解液和普通电解液装配成锂二次电池,性能如下表 The high pressure electrolyte lithium ion battery prepared in Examples 1-7 and assembled into common electrolyte lithium secondary battery, the performance of the following table

Figure CN105591156AD00061

上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。 The above-described preferred embodiment of the present invention embodiment, but the embodiment of the present invention is not limited to the above embodiments, changes made to any other without departing from the spirit and principle of the present invention, modifications, substitutions, combinations, simplified equivalent effect replacement method, are included within the scope of the present invention.

Claims (10)

  1. 1. 一种含有I,3,5-苯S腊的电解液,包括有机溶剂、导电裡盐和添加剂,其中:所述有机溶剂选为环状碳酸醋和线性碳酸醋的一种W上,所述的添加剂结构式(1)如下: A containing I, 3,5- benzene wax S electrolyte comprising an organic solvent, and salt in the conductive additive, wherein: the organic solvent is preferably one kind of W on the cyclic carbonate and linear carbonate vinegar vinegar, the additive of formula (1) as follows:
    Figure CN105591156AC00021
  2. 2. 根据权利要求1所述的含有1,3,5-苯S腊的电解液,所述添加剂的使用质量占所述裡盐和所述有机溶剂总质量的百分比为0.1 %~10%。 2. The electrolytic solution containing trimesic S of the wax according to claim 1, the use of additives to the mass percentage of salt in the total mass of the organic solvent and 0.1 to 10%.
  3. 3. 根据权利要求1所述的含有1,3,5-苯=腊的电解液,所述有机溶剂包括环状碳酸醋溶剂和线型碳酸醋溶剂,环状碳酸醋溶剂和线型碳酸醋溶剂的配比为质量比为1:1~3:2, 导电裡盐的终浓度为0.8~1.5mol/L。 3. The electrolyte trimesic = wax, the organic solvent comprises a cyclic carbonate and linear carbonate solvents vinegar vinegar solvent, cyclic carbonate and linear carbonate solvents vinegar vinegar in claim 1 comprising the solvent ratio is the mass ratio of 1: 1 to 3: 2, in a final concentration of conductive salt is 0.8 ~ 1.5mol / L.
  4. 4. 根据权利要求2所述的含有1,3,5-苯S腊的电解液,所述的环状碳酸醋溶剂为碳酸乙締醋、碳酸丙締醋、氣代碳酸乙締醋、丫-下内醋和丫-戊内醋中的一种W上。 4. The electrolytic solution contains the 1,3,5-benzenetricarboxylic S December 2, wherein said solvent is a cyclic carbonate, ethyl carbonate vinegar association vinegar, vinegar association propyl carbonate, ethyl carbonate, associated gas substituting vinegar, Ah - the lower and vinegar Ah - vinegar on a W valerolactam.
  5. 5. 根据权利要求2所述的含有1,3,5-苯S腊的电解液,所述的线型碳酸醋溶剂为碳酸二甲醋、碳酸甲乙醋、碳酸二乙醋或碳酸甲丙醋中的至少一种。 The electrolytic solution containing trimesic S of the wax according to claim 2, the linear carbonate is dimethyl carbonate solvent vinegar vinegar, vinegar, methylethyl carbonate, diethyl carbonate, methylpropyl carbonate vinegar or vinegar at least one.
  6. 6. 根据权利要求1所述的含有1,3,5-苯=腊的电解液,所述的导电裡盐为六氣憐酸裡化iPFs)、四氣棚酸裡化iBF4)、二草酸棚酸裡化iBOB)、二氣草酸棚酸裡化iDFOB)、S氣甲基横酸裡化iS化CF3)、高氯酸裡化iCl〇4)、六氣神酸裡化iAsFs)、双S氣甲基横酷亚胺裡化i (C的S化)2N)中的至少一种。 According to claim 1 containing a wax trimesic = electrolyte, said conductive salt in six of the gas in the ipfs pity acid), in four of the acid gas shed iBF4), bisoxalate acid in the shed of iBOB), two gas oxalic acid in the shed of iDFOB), S in the acid gas of a cross-methyl iS oriented CF3), of perchlorate in iCl〇4), six gas in God acid of iAsFs), bis cool air cross-S-methyl imide of at least one in the I (C S of the) 2N).
  7. 7. 根据权利要求1所述的含有1,3,5-苯S腊的电解液,所述电解液还包含常用的添加剂,所述的常用添加剂为碳酸亚乙締醋、碳酸乙締亚乙醋、丙横酸内醋、下横酸内醋、硫酸乙締醋、己二腊、下二腊、LiB0B、LiDF0B、中的一种W上,所述的常用添加剂占非水电解液总质量的0.1-10.0%。 The electrolytic solution containing trimesic S December according to claim 1, the electrolyte further comprises usual additives, said additives commonly associated vinegar ethylene carbonate, ethylene carbonate, ethyl association vinegar, the cross-propionic acid acetate, acetic acid on the inner bottom rail, vinegar acetic acid association, adipic wax, the wax two, LiB0B, LiDF0B, in a W, the usual additives accounts for the total mass of the nonaqueous electrolyte of 0.1 to 10.0%.
  8. 8. -种电解液的制备方法: (1) 将有机溶剂按比例混合后用5分子筛、氨化巧、氨化裡纯化除杂、除水; (2) 在室溫条件下,将导电裡盐溶解在上述有机溶剂中,并揽拌均匀; (3) 加入常用添加剂,并揽拌均匀;加入添加剂,制得权利要求1-7任一项所述的含有1, 3,5-苯=腊的电解液。 8. - The method of producing the electrolytic solution: (1) The ratio of the organic solvent by mixing with 5 molecular sieves, Qiao amide, amide impurity in the purified water removal; (2) at room temperature, in the conductive salt is dissolved in the organic solvent, and mix well embrace; (3) common additives added, uniformly mixed and embrace; additives, prepared according to any of claims 1-7 containing 1, 3,5-benzene = La electrolyte.
  9. 9. 一种裡离子二次电池,包括正极活性材料、负极活性材料和隔膜,还包括权利要求1-7任一项所述的含有苯=腊的电解液。 A in ion secondary battery comprising a positive electrode active material, a negative electrode active material and a separator, further comprising an electrolyte containing benzene = wax according to any one of claims 1-7.
  10. 10. 根据权利要求9所述的裡离子二次电池,所述正极活性材料为一种含裡过渡金属氧化物,正极活性材料为W 下物质的一种W 上:LiCo〇2、LiNi〇2、LiMn〇2、LiMn2〇4、Li(NiaC〇bMnc) 〇2(0<a<l,0<b<l,0<C<l,a+b+C=l)、LiNii-yMny〇2、LiNh-yMny〇2(0^z^2)、LiMx(P04)y(M 为Ni、Co、Mn、Ti、V,0^x刮,0奪y刮);负极活性材料为可嵌入/脱出裡离子的碳材料、裡金属、娃或锡及其氧化物中的一种W上;隔膜为自织布、无纺布、合成树脂微多孔膜的任一种。 10. The ion secondary battery in accordance with claim 9, the active material is a positive electrode containing a transition metal oxide in the positive electrode active material is the substance on to give a W W: LiCo〇2, LiNi〇2 , LiMn〇2, LiMn2〇4, Li (NiaC〇bMnc) 〇2 (0 <a <l, 0 <b <l, 0 <C <l, a + b + C = l), LiNii-yMny〇2 , LiNh-yMny〇2 (0 ^ z ^ 2), LiMx (P04) y (M is Ni, Co, Mn, Ti, V, 0 ^ x scraping blade y 0 wins); negative active material may be embedded / carbon material in the extrusion ions in metal, tin, and baby or W is an oxide of one; of the separator from the woven fabric, a nonwoven fabric, a synthetic resin according to any microporous membrane.
CN 201610009642 2016-01-04 2016-01-04 Electrolyte containing tricyanobenzene and lithium ion secondary battery containing electrolyte CN105591156A (en)

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JPH0477481A (en) * 1990-07-19 1992-03-11 Elna Co Ltd 1,3,5-tricyanobenzene-tetrathiafulvalene complex and its production
US6004698A (en) * 1997-08-21 1999-12-21 The United States Of America As Represented By The United States Department Of Energy Solid polymer electrolyte electrochemical storage cell containing a redox shuttle additive for overcharge protection
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