WO2018006563A1 - 一种锂离子电池非水电解液及锂离子电池 - Google Patents

一种锂离子电池非水电解液及锂离子电池 Download PDF

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WO2018006563A1
WO2018006563A1 PCT/CN2016/113008 CN2016113008W WO2018006563A1 WO 2018006563 A1 WO2018006563 A1 WO 2018006563A1 CN 2016113008 W CN2016113008 W CN 2016113008W WO 2018006563 A1 WO2018006563 A1 WO 2018006563A1
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ion battery
lithium ion
sulfone compound
compound
lithium
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PCT/CN2016/113008
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French (fr)
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林木崇
石桥
曾长安
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深圳新宙邦科技股份有限公司
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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
    • 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
    • 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
    • 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 present application relates to the field of lithium ion battery electrolytes, and in particular to a lithium ion battery non-aqueous electrolyte and a lithium ion battery.
  • lithium-ion batteries Compared with other batteries, lithium-ion batteries have the advantages of light weight, small size, high operating voltage, high energy density, high output power, high charging efficiency, no memory effect and long cycle life. Used in the 3C consumer electronics market. And with the development of new energy vehicles, non-aqueous electrolyte lithium-ion batteries are becoming more and more popular as power supply systems for automobiles. With the continuous improvement of the cruising range requirements of new energy vehicles, the high energy density of power lithium-ion batteries is increasingly required.
  • the ternary nickel-cobalt-manganese cathode material has become a research hotspot of new energy power battery cathode materials due to its high energy density, low cost, excellent performance and relatively good safety, and with the continuous energy density of power batteries. Improvement, ternary nickel-cobalt-manganese material power battery is moving toward high voltage.
  • the ternary nickel-cobalt-manganese material has the disadvantage of insufficient high-temperature performance as a positive electrode material.
  • the nickel element has a strong catalytic effect on the electrolyte, which catalyzes the decomposition of the electrolyte, thereby reducing the discharge capacity.
  • the accumulation of decomposition products leads to a significant increase in internal resistance; this condition becomes particularly severe under conditions of high voltage, high temperature and high nickel content, which greatly deteriorates battery performance and hinders high voltage ternary nickel cobalt manganese.
  • Material batteries are put to practical use in the field of power batteries.
  • the electrolyte is a key factor affecting the overall performance of the battery.
  • the additives in the electrolyte are particularly important for the performance of the battery. Therefore, in order to give full play to the performance of the power battery of the ternary nickel-cobalt-manganese material, the matching of the electrolyte is the key.
  • the currently practical lithium ion battery electrolyte is a non-aqueous electrolyte added with a conventional film-forming additive such as vinylene carbonate (abbreviation VC) or fluoroethylene carbonate (abbreviated as FEC), and the battery is excellent by the addition of VC and FEC. Cyclic performance.
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • Patent application No. 201410534841.0 discloses a novel film-forming additive for a phosphate compound containing a triple bond, which not only improves high temperature cycle performance, but also significantly improves storage performance.
  • Sulfone compounds have also been reported very early in the literature (Journal of Power Sources 179 (2008) 770–779), mainly to improve the stability of high-voltage batteries and improve cycle performance.
  • the scientific and technological workers in the field found that the passivation film formed by the three-bond phosphate ester additive at the electrode interface is poor in conductivity, resulting in a large interface impedance, which significantly degrades the low temperature performance, and is particularly likely to cause the battery to be at a low temperature.
  • Lithium-deposited lithium is used to suppress the application of non-aqueous lithium-ion batteries under low temperature conditions.
  • the purpose of the present application is to provide a new lithium ion battery non-aqueous electrolyte and a lithium ion battery.
  • An aspect of the present application discloses a lithium ion battery non-aqueous electrolyte comprising unsaturated phosphate esters and a sulfone compound, and the sulfone compound includes a cyclic sulfone compound and/or a linear sulfone compound;
  • the unsaturated phosphate compound has the structure shown in Formula 1,
  • R1, R2, and R3 are each independently selected from a hydrocarbon group having 1-4 carbon atoms, and at least one of R1, R2, and R3 is an unsaturated hydrocarbon group having a double bond or a hydrazone bond;
  • the cyclic sulfone compound has a structure represented by Formula 2
  • the linear sulfone compound has a structure represented by Formula 3
  • R 4 , R 5 , R 6 and R 7 are each independently selected from a hydrogen atom, a halogen or an alkyl group having 1 to 5 carbon atoms, and A is a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms.
  • the functional group substituted may be a halogen or an alkyl group having 1 to 3 carbon atoms.
  • the sulfone compound may be a cyclic sulfone compound or a linear sulfone compound, or may be used in combination.
  • the application of the sulfone compound to the electrolyte solution is not proposed in the present application.
  • the present application has been extensively studied and tested to find that the sulfone compound and the above unsaturated phosphate compound can be used together to obtain a better one.
  • the present application is made by high and low temperature performance and cycle performance. It is to be understood that the present application is based on the patent application No. 201410534841 and the priority of the patent application No. 201510397735.7, the related technical content and terminology of the above two patent applications are applicable to the present application.
  • the key to the present application is to use a sulfone compound in combination with the above unsaturated phosphate compound.
  • the unsaturated phosphate compound of the present application is at least one selected from the group consisting of the compounds of the structural formula shown in Table 1, that is, the unsaturated phosphate compound is at least one selected from the group consisting of Compound 1 to Compound 6.
  • the unsaturated phosphate compound shown in Formula 1, or the unsaturated phosphate compound of Compound 1 to Compound 6, is a preferred technical solution of the present application, and does not exclude other compounds having similar physical and chemical properties. Saturated phosphate compounds.
  • the cyclic sulfone compound is at least one of the structural compounds represented by Formula 4 and/or Formula 5,
  • R8 to R16 are each independently selected from a hydrogen atom, a halogen or an alkyl group having 1 to 5 carbon atoms.
  • the sulfone compound is selected from the group consisting of sulfolane, 3-methylsulfolane, 3,3,4,4-tetrafluorosulfolane, cyclopentanesulfone, dimethylsulfone, methylethylsulfone and diethylsulfone. At least one.
  • sulfone compound represented by the formula II to formula V or the specifically defined sulfone compound, is a preferred technical solution of the present application, and other sulfone compounds having similar physical and chemical properties are not excluded.
  • the unsaturated phosphate compound occupies the non-aqueous battery of the lithium ion battery. 0.1% to 2% of the total weight of the electrolyte.
  • the unsaturated phosphate compound accounts for 0.2% to 1% of the total weight of the nonaqueous electrolyte of the lithium ion battery.
  • the sulfone compound accounts for 0.1% to 30% of the total weight of the nonaqueous electrolyte of the lithium ion battery.
  • the sulfone compound accounts for 0.1% to 10% of the total weight of the nonaqueous electrolyte of the lithium ion battery.
  • the sulfone compound accounts for 0.5 to 10% by weight based on the total weight of the lithium ion battery nonaqueous electrolyte.
  • the sulfone compound accounts for 1 to 10% of the total weight of the nonaqueous electrolyte of the lithium ion battery.
  • the film forming effect of the positive and negative electrodes is poor, and the effect of improving the performance is not obtained; and when the amount thereof is too high, When it is more than 2%, the film thickness at the electrode interface is increased, the battery resistance is increased, and the battery performance is deteriorated.
  • the sulfone compound when the content of the sulfone compound is less than 0.1%, the sulfone compound cannot function effectively; when the content of the sulfone compound is more than 10%, in fact, within a certain range, for example, 30% or less, the comparison can still be exhibited. Good performance. When the content of the sulfone compound is more than 30%, the viscosity of the electrolyte is excessively large, and the film formation at the electrode interface is thick, the battery impedance is increased, and the battery performance is deteriorated.
  • the key of the present application is to use an unsaturated phosphate compound in combination with a sulfone compound to improve high and low temperature performance and cycle performance; it can be understood that the change in the amount of the two will inevitably directly affect the performance of the electrolyte. Thereby affecting the high and low temperature performance and cycle performance of the battery. Therefore, in the preferred embodiment of the present application, the amount of both is particularly limited in order to secure the performance of the electrolyte and the battery.
  • the configured non-aqueous electrolyte has good high-low temperature performance and cycle performance; if it exceeds the range, its corresponding performance is inevitably affected, but for some requirements relatively Low or lower usage requirements can also improve the high and low temperature performance or cycle performance of the battery to some extent.
  • the weight ratio of the sulfone compound to the unsaturated phosphate compound is greater than or equal to 0.2.
  • the content of the unsaturated phosphate compound is high and the content of the sulfone compound is low, the low temperature performance is remarkably insufficient.
  • the organic solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and methyl propyl carbonate. At least one.
  • the lithium salt is selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium difluorooxalate borate, lithium bis(trifluoromethylsulfonyl)imide and difluorosulfonate. At least one of the lithium imide salts.
  • the other side of the application discloses a lithium ion battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte solution, wherein the electrolyte solution is the lithium ion battery non-aqueous electrolyte solution of the present application.
  • the charge cutoff voltage of the lithium ion battery of the present application is greater than or equal to 4.35V.
  • the positive electrode is selected from the group consisting of LiCoO2, LiNiO2, LiMn2O4, LiCo1-yMyO2, At least one of LiNi1-yMyO2, LiMn2-yMyO4, and LiNixCoyMnzM1-xy-zO2; wherein, M is selected from the group consisting of Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr At least one of V and Ti, and 0 ⁇ y ⁇ 1, 0 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, x + y + z ⁇ 1.
  • non-aqueous electrolyte of the present application has been developed for a lithium ion battery, and thus can be applied to various lithium ion batteries including, but not limited to, the types listed in the present application.
  • the unsaturated phosphate compound and the sulfone compound are combined and added to the electrolyte to form a protective film having a uniform composition, a moderate thickness, and a good density at the electrode interface;
  • the use of the electrolyte can make the electrolyte have good stability on the positive electrode, so that the battery obtains excellent high temperature performance and cycle performance, and can maintain the battery with low impedance and excellent low temperature performance of the battery.
  • the non-aqueous electrolyte of the present application lays a foundation for preparing a high-quality power battery.
  • the key point of the present application is that the unsaturated phosphate compound represented by Formula 1 and the sulfone compound are combined and added to the non-aqueous electrolyte to keep the battery low while not affecting high temperature performance and cycle performance.
  • the internal resistance gives the battery excellent low temperature performance.
  • the unsaturated phosphate compound represented by Formula 1 can form a stable passivation film on the surface of the negative electrode, and can prevent the reductive decomposition of the electrolyte to a large extent.
  • the unsaturated phosphate compound can also form a protective film on the surface of the positive electrode, which can further prevent the electrolyte from being oxidatively decomposed on the surface of the positive electrode and suppress the elution of the positive metal ion, especially when the charging voltage is equal to or greater than 4.35V.
  • the effect is more obvious, and the high-temperature performance and cycle performance of the lithium battery can be significantly improved, but the addition of the unsaturated-phosphate compound also causes an increase in internal resistance, thereby deteriorating the low-temperature performance.
  • the present application adds a sulfone compound to the unsaturated phosphate compound shown in Formula One. Since the oxidation potential of the sulfone compound is low, a protective film having a small thickness, a uniform composition, and a good density can be formed on the positive electrode. The denseness of the protective film can effectively improve the decomposition reaction of the electrolyte in the positive electrode, prevent the dissolution of the positive electrode metal ions; the thickness of the protective film and the uniformity of the composition can effectively reduce the impedance; and the reduction of the impedance can make the battery obtain an excellent low temperature. performance.
  • the unsaturated phosphate ester compound can form a uniform dense passivation film on the positive electrode, so that the electrolyte has good stability, so that the battery has excellent high temperature performance and cycle performance.
  • the sulfone compound can also be formed on the electrode, and the resulting film composition is uniform and dense, so that the battery has a lower impedance, so that the battery has excellent low temperature performance.
  • the amount of the monounsaturated phosphate compound and the sulfone compound is limited in the present application.
  • the sulfone compound accounts for 0.5% to 30% of the total weight of the nonaqueous electrolyte of the lithium ion battery, preferably 1 to 10% of the total weight of the nonaqueous electrolyte of the lithium ion battery, which is to obtain more in the electrolyte. High chemical stability and full performance of the electrolyte.
  • a cyclic sulfone compound and a chain sulfone compound are simultaneously added, and the two synergistically react, and the content of the cyclic sulfone compound is 1-3 of the total weight of the electrolyte. %, the content of the chain sulfone compound is 1-2% of the total weight of the electrolyte, and the synergistic effect of the two is that the thickness of the protective film formed on the positive electrode is relatively uniform, and the compactness is good, the impedance can be effectively reduced, and the performance of the battery is improved.
  • the preparation method of the lithium ion battery of the present invention comprises a positive electrode preparation step, a negative electrode preparation step, an electrolyte preparation step, a separator preparation step, and a battery assembly step. details as follows:
  • the positive electrode preparation step is: mixing the positive active material LiNi0.5Co0.2Mn0.3O2, the conductive carbon black and the binder polyvinylidene fluoride according to the mass ratio of 96.8:2.0:1.2, and dispersing in N-methyl-2-pyrrolidone
  • the positive electrode slurry is obtained, and the positive electrode slurry is uniformly coated on both sides of the aluminum foil, dried, calendered and vacuum dried, and the aluminum lead wire is welded by an ultrasonic welding machine to obtain a positive electrode plate, and the thickness of the electrode plate is 120- Between 150 ⁇ m.
  • the preparation step of the negative electrode is: mixing graphite, conductive carbon black, binder styrene butadiene rubber and carboxymethyl cellulose in a mass ratio of 96:1:1.2:1.8, dispersing in deionized water to obtain a negative electrode slurry, and the negative electrode slurry
  • the material is coated on both sides of the copper foil, dried, calendered and vacuum dried, and the nickel lead wire is welded by an ultrasonic welder to obtain a negative electrode plate having a thickness of 120-150 ⁇ m.
  • the separator preparation step is as follows: a three-layer separator of polypropylene, polyethylene and polypropylene is used, and the thickness is 20 ⁇ m.
  • the battery assembly step is: placing a three-layer separator having a thickness of 20 ⁇ m between the positive electrode plate and the negative electrode plate, and then winding the sandwich structure composed of the positive electrode plate, the negative electrode plate and the separator, and then squashing the wound body and placing it
  • the lead wires of the positive and negative electrodes are respectively welded to the corresponding positions of the cover plate, and the cover plate and the metal shell are welded together by a laser welding machine to obtain the battery core to be injected;
  • the electrolyte is injected into the cell through the injection hole, and the amount of the electrolyte is required to fill the gap in the cell.
  • the lithium ion battery prepared in this example was tested as follows:
  • the 300th cycle capacity retention ratio (%) (300th cycle discharge capacity / first cycle discharge capacity) ⁇ 100%.
  • 500th cycle capacity retention rate (%) (500th cycle discharge capacity / first cycle discharge capacity) ⁇ 100%;
  • High-temperature storage performance The battery after the formation is charged to 4.35V at a normal temperature with a constant current of 1C, and the initial discharge capacity of the battery is measured, and then stored at 60 ° C for 30 days, discharged at 1 C to 3.0 V, and the battery is measured. Maintain capacity and recover capacity. Calculated as follows:
  • Battery capacity retention rate (%) retention capacity / initial capacity ⁇ 100%;
  • Battery capacity recovery rate (%) recovery capacity / initial capacity ⁇ 100%.
  • the low temperature discharge efficiency value of -20 ° C 1 C discharge capacity (-20 ° C) / 1 C discharge capacity (25 ° C).
  • Charge DCIR value slope value of a linear plot of different charge currents and corresponding cutoff voltages.
  • Discharge DCIR value slope value of a linear plot of different discharge currents and corresponding cutoff voltages.
  • Example 2 the same procedures as in Example 1 were carried out except for the specific compounds of the sulfone compound and the unsaturated phosphate compound, and the amounts thereof.
  • the specific compounds of the respective examples, and the amounts thereof are shown in Table 2, wherein the amounts are calculated as a percentage of the total weight of each of the nonionic electrolytes of the lithium ion battery.
  • the present application also designed six comparative examples, namely, Comparative Examples 1-6.
  • the six comparative examples are only different from the specific compounds and amounts added in the first embodiment or other examples, and the others are different. The same as in the first embodiment.
  • the specific compounds of the respective comparative examples, and the amounts thereof are shown in Table 2, and the amounts thereof are calculated as a percentage of the added matter to the total weight of the nonaqueous electrolyte of the lithium ion battery.
  • Example 1 0.1 0.5
  • Example 2 0.5 1
  • Example 3 1 5
  • Example 4 1 10
  • Example 5 1 30
  • Example 6 2
  • Example 7 0.5
  • Example 8 1 5
  • Example 9 1 10
  • Example 10 1 5
  • Example 11 1
  • Example 12 1 5 5
  • Example 13 1 5 5
  • Example 14 0.1 0.5 Example 15 0.5 1
  • Example 16 1 5 Example 17 1 10
  • Example 19 10
  • Example 20 2
  • Comparative example 1 Comparative example 2
  • Comparative example 3 Comparative example 4
  • Comparative example 5 Comparative example 6 1
  • the blank indicates that the corresponding substance or the comparative example was not added, and the tripropargyl phosphate was the compound 1 in Table 1, and the diallylethyl phosphate was the compound 4 in Table 1.
  • the present application combines an unsaturated phosphate compound and a sulfone compound, and at a suitable ratio, the battery can obtain excellent high temperature performance and cycle performance as well as good low temperature performance.
  • the amount of the phosphate ester is 0.1% to 2%, and the amount of the sulfone compound is 0.1% to 30%, which can improve the high-temperature performance and the cycle performance; and the amount of the unsaturated phosphate is 0.2% to 1%, and the sulfone compound
  • the dosage is 1 to 10%, the effect is better.

Abstract

一种锂离子电池非水电解液及锂离子电池。所述锂离子电池非水电解液，包括不饱和磷酸酯类化合物和砜类化合物，砜类化合物包括环状砜类化合物和/或直链砜类化合物；不饱和磷酸酯类化合物具有式一所示结构；环状砜类化合物具有式二所示结构，直链砜类化合物具有式三所示结构。所述非水电解液，将不饱和磷酸酯类化合物和砜类化合物同时添加到电解液中，在电极界面形成一层成份均匀、厚薄适中，且致密性好的保护膜；两者配合使用，使得电解液在正极具有较好稳定性，可使电池获得优良高温性能和循环性能，而且，两者组合可以使电池保持较低阻抗，进而使电池获得优良的低温性能。所述电解液为制备高品质动力电池奠定了基础。

Description

一种锂离子电池非水电解液及锂离子电池 技术领域
本申请涉及锂离子电池电解液领域，特别是涉及一种锂离子电池非水电解液及锂离子电池。
背景技术
锂离子电池与其它电池相比，具有质量轻、体积小、工作电压高、能量密度高、输出功率大、充电效率高、无记忆效应和循环寿命长等优点，目前已经越来越多的被用于3C消费类电子产品市场。并且随着新能源汽车的发展，非水电解液锂离子电池作为汽车的动力电源***也越来越普及。随着新能源汽车续航里程要求的不断提高，越来越要求动力锂离子电池的高能量密度化。三元镍钴锰正极材料因其较高的能量密度、低成本、性能优良、安全性相对较好等优势，成为目前新能源动力电池正极材料的研究热点，且随着动力电池能量密度的不断提高，三元镍钴锰材料动力电池正朝着高电压的方向发展。
但是三元镍钴锰材料作为正极材料存在高温性能不足的缺点，在三元镍钴锰材料中，镍元素对电解液具有很强的催化作用，会催化电解液的分解，从而降低放电容量，并且分解产物的积累会导致明显的内阻增长；这种情况在高电压、高温和镍含量较高的条件下，会变得尤为严重，从而大大劣化电池性能，阻碍高电压三元镍钴锰材料电池在动力电池领域的实用化。
电解液是影响电池综合性能的关键因素，特别地，电解液中的添加剂对电池的各项性能的发挥尤其重要。因此，要充分发挥三元镍钴锰材料的动力电池的性能，电解液的匹配是关键。目前实用化的锂离子电池电解液是添加传统的成膜添加剂如碳酸亚乙烯酯(缩写VC)或氟代碳酸乙烯酯(缩写FEC)的非水电解液，通过VC和FEC的添加保障电池优异的循环性能。但VC的高电压稳定性较差，FEC高温下容易分解产气。因此，在高电压高温条件下，这些添加剂很难满足高温循环的性能要求。
专利申请201410534841.0中公开了一种含三键的磷酸酯化合物新型成膜添加剂，其不仅可以改善高温循环性能，还能明显改善储存性能。砜类化合物也很早见于文献报道(Journal of Power Sources 179(2008)770–779)，主要是提高高电压电池的稳定性，改善循环性能。但本领域的科技工作者在研究中发现，三键的磷酸酯添加剂在电极界面所形成的钝化膜导电性较差，导致界面阻抗较大，明显劣化了低温性能，特别容易导致电池在低温下充电析锂，抑制了非水锂离子电池在低温条件下的应用。
发明内容
本申请的目的是提供一种新的锂离子电池非水电解液及锂离子电池。
为了实现上述目的，本申请采用了以下技术方案：
本申请的一方面公开了一种锂离子电池非水电解液，包括不饱和磷酸酯类和砜类化合物，砜类化合物包括环状砜类化合物和/或直链砜类化合物；
不饱和磷酸酯类化合物具有式一所示结构，
Figure PCTCN2016113008-appb-000001
其中，R1、R2、R3分别独立地选自碳原子数为1-4的烃基，且R1、R2、R3中至少一个为含有双键或叁键的不饱和烃基；
环状砜类化合物具有式二所示结构，所述直链砜类化合物具有式三所示结构，
Figure PCTCN2016113008-appb-000002
其中，R4、R5、R6、R7分别独立地选自氢原子、卤素或碳原子数为1-5的烷基，A是包括2～6个碳原子数的取代或非取代的亚烷基，其取代的官能团可以是卤素或碳原子数为1-3的烷基。
需要说明的是，本申请的关键在于，在锂离子电池非水电解液中同时添加了上述不饱和磷酸酯类化合物和砜类化合物，克服了单独添加不饱和磷酸酯类化合物所导致的界面阻抗大、低温下充电析锂等缺陷。其中，砜类化合物可以是环状砜类化合物或直链砜类化合物，也可以是两者混合使用。
还需要说明的是，砜类化合物应用于电解液并非本申请率先提出的，本申请经过大量的研究和试验发现，将砜类化合物和上述不饱和磷酸酯类化合物配合使用，能够获得更好的高低温性能和循环性能，从而提出了本申请。可以理解，本申请是在专利申请201410534841的基础上，并以专利申请201510397735.7为优先权而提出的，因此，以上两件专利申请中的相关技术内容和术语适用于本申请。此外，本申请的关键在于将砜类化合物和上述不饱和磷酸酯类化合物配合使用，至于具体的砜类化合物和上述不饱和磷酸酯类化合物，可以采用现有的实验室常用或不常用的化合物；但是，为了保障非水电解液的性能，本申请优选的方案中，对砜类化合物和上述不饱和磷酸酯类化合物的具体类型，甚至具体化合物进行了说明和限定，这将在后面的技术方案中详细介绍。
优选的，本申请的不饱和磷酸酯类化合物选自表1所示结构式的化合物中的至少一种，即不饱和磷酸酯类化合物选自化合物1至化合物6中的至少一种。
表1 用于锂离子电池非水电解液的不饱和磷酸酯类化合物
Figure PCTCN2016113008-appb-000003
可以理解，无论是式一所示的不饱和磷酸酯类化合物，还是化合物1到化合物6的不饱和磷酸酯类化合物，都是本申请的优选的技术方案，不排除其它具有相似理化特性的不饱和磷酸酯类化合物。
更优选的，环状砜类化合物为式四和/或式五所示结构化合物的至少一种，
Figure PCTCN2016113008-appb-000004
其中，R8-R16分别独立地选自氢原子、卤素或碳原子数为1-5的烷基。
更优选的，砜类化合物选自环丁砜、3-甲基环丁砜、3,3,4,4-四氟环丁砜、环戊砜、二甲基砜、甲基乙基砜和二乙基砜中的至少一种。
可以理解，无论是式二至式五所示的砜类化合物，还是具体限定的几种砜类化合物，都是本申请的优选的技术方案，不排除其它具有相似理化特性的砜类化合物。
优选的，本申请的锂离子电池非水电解液中，不饱和磷酸酯类化合物占锂离子电池非水 电解液总重量的0.1％～2％。
优选的，本申请的锂离子电池非水电解液中，不饱和磷酸酯类化合物占锂离子电池非水电解液总重量的0.2％～1％。
优选的，本申请的锂离子电池非水电解液中，砜类化合物占锂离子电池非水电解液总重量的0.1％～30％。
优选的，砜类化合物占锂离子电池非水电解液总重量的0.1％～10％。
进一步优选的，砜类化合物占锂离子电池非水电解液总重量的0.5～10％。
更优选的，砜类化合物占锂离子电池非水电解液总重量的1～10％。
本申请的锂离子电池非水电解液中，当不饱和磷酸酯类化合物的用量小于0.1％时，正负极成膜效果差，且起不到改善性能的效果；而当其用量过高，大于2％时，会使电极界面的成膜厚，增大电池阻抗，劣化电池性能。
同时，当砜类化合物的含量小于0.1％时，砜类化合物无法有效发挥作用；当砜类化合物的含量大于10％时，事实上，在一定范围内，例如30％以下，仍能体现出较好的性能。当砜类化合物的含量大于30％时，会导致电解液粘度过大，同时在电极界面成膜较厚，增大电池阻抗，劣化电池性能。
需要说明的是，本申请的关键在于将不饱和磷酸酯类化合物与砜类化合物配合使用，从而改善高低温性能和循环性能；可以理解，两者的用量变化必然会直接影响电解液的性能，从而影响电池的高低温性能和循环性能。因此，在本申请的优选方案中，为了保障电解液和电池的性能，对两者的用量进行了特别限定。可以理解，在本申请所限定的范围内，所配置的非水电解液具有良好的高低温性能和循环性能；如果超出该范围，其相应的性能必然会受影响，但是，对于一些要求相对较低或者较次的使用需求中，同样可以在一定程度上改善电池的高低温性能或循环性能。
进一步的，本申请的锂离子电池非水电解液中，砜类化合物与不饱和磷酸酯类化合物的重量比大于或等于0.2。当不饱和磷酸酯类化合物的含量高而砜类化合物含量较低时，低温性能明显不足。
优选的，本申请的非水电解液中，有机溶剂选自碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯和碳酸甲丙酯中的至少一种。
优选的，本申请的非水电解液中，锂盐选自六氟磷酸锂、高氯酸锂、四氟硼酸锂、双氟草酸硼酸锂、二(三氟甲基磺酰)亚胺锂和双氟磺酰亚胺锂盐中的至少一种。
本申请的另一面公开了一种锂离子电池，包括正极、负极、置于正极与负极之间的隔膜，以及电解液，其中，电解液为本申请的锂离子电池非水电解液。
本申请的锂离子电池的充电截止电压大于或等于4.35V。
优选的，本申请的锂离子电池中，正极选自LiCoO2、LiNiO2、LiMn2O4、LiCo1-yMyO2、 LiNi1-yMyO2、LiMn2-yMyO4和LiNixCoyMnzM1-x-y-zO2中的至少一种；，其中，M选自Fe、Co、Ni、Mn、Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V和Ti中的至少一种，且0≤y≤1，0≤x≤1，0≤z≤1，x+y+z≤1。
需要说明的是，本申请的非水电解液，是针对锂离子电池而研制的，因此，可以适用于各种锂离子电池，包括但不仅限于本申请所列举的类型。
由于采用以上技术方案，本申请的有益效果在于：
本申请的非水电解液，将上述不饱和磷酸酯类化合物和砜类化合物配合，同时添加到电解液中，在电极界面形成一层成份均匀、厚薄适中，且致密性好的保护膜；两者配合使用，可以使得电解液在正极具有良好的稳定性，使得电池获得优良高温性能和循环性能，而且，可以使得电池保持较低的阻抗、使电池获得优良的低温性能。本申请的非水电解液为制备高品质的动力电池奠定了基础。
具体实施方式
本申请的关键在于，将式一所示的不饱和磷酸酯类化合物和砜类化合物配合，加入到的非水电解液中，在不影响高温性能和循环性能的同时，可以使得电池保持较低的内阻，进而使电池获得优良的低温性能。
其中，式一所示的不饱和磷酸酯类化合物能够在负极表面形成稳定的钝化膜，可较大程度阻止电解液的还原分解。此外，不饱和磷酸酯类化合物也能在正极表面形成保护膜，可以进一步阻止电解液在正极表面被氧化分解，同时抑制正极金属离子的溶出，尤其是在充电电压等于或大于4.35V时，其效果更加明显，可以明显提高锂电池的高温性能和循环性能，但是式一不饱和磷酸酯化合物的添加同时也引起内阻增大，从而低温性能变差的问题。
针对上述问题，本申请在添加式一所示不饱和磷酸酯类化合物的基础上，加入砜类化合物。由于砜类化合物的氧化电位较低，可以在正极形成一层厚度较薄、成分均匀、致密性好的保护膜。保护膜的致密性好可以有效改善电解液在正极的分解反应，阻止正极金属离子的溶出；保护膜的厚度及成分均匀的性质，可以有效降低阻抗；而阻抗的降低可以使得电池获得优良的低温性能。
因此，本申请的锂离子电池非水电解液的有益效果在于：
(1)不饱和磷酸酯类化合物可以在正极形成一致密钝化膜，使得电解液具有较好的稳定性，从而使得电池具有优良的高温性能和循环性能。砜类化合物也可以在电极成膜，所成的膜组分均匀，致密，使得电池具有较低的阻抗，从而使得电池具有优良的低温性能。
(2)将式一所示不饱和磷酸酯类化合物和砜类化合物配合，同时添加到电解液中，在电极界面形成一层成份均匀、厚薄适中，且致密性好的保护膜；两者配合使用，可以使电池获 得优良高温性能和循环性能，而且，两者组合可以使电池保持较低的阻抗，进而使电池获得优良的低温性能。
此外，为了保障非水电解液的性能，本申请对式一不饱和磷酸酯类化合物、砜类化合物的用量进行了限定。其中，砜类化合物占锂离子电池非水电解液总重量的0.5％～30％，优选的，占锂离子电池非水电解液总重量的1～10％，这是为了在电解液中获得更高的化学稳定性，充分发挥电解液的性能。并且，在本申请的一种优选的实现方式中，同时添加了环状砜类化合物和链状砜类化合物，两者协同作用，环状砜类化合物的含量为电解液总重量的1-3％，链状砜类化合物的含量为电解液总重量的1-2％，两者的协同作用在正极形成的保护膜厚度较为均匀，且致密性良好，能有效降低阻抗，并改善电池的性能。
下面通过具体实施例和附图对本申请作进一步详细说明。以下实施例仅对本申请进行进一步说明，不应理解为对本申请的限制。
实施例1
本例锂离子电池的制备方法，包括正极制备步骤、负极制备步骤、电解液制备步骤、隔膜制备步骤和电池组装步骤。具体如下：
正极制备步骤为：按96.8:2.0:1.2的质量比混合正极活性材料LiNi0.5Co0.2Mn0.3O2、导电碳黑和粘结剂聚偏二氟乙烯，分散在N-甲基-2-吡咯烷酮中，得到正极浆料，将正极浆料均匀涂布在铝箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上铝制引出线后得到正极板，极板的厚度在120-150μm之间。
负极制备步骤为：按96:1:1.2:1.8的质量比混合石墨、导电碳黑、粘结剂丁苯橡胶和羧甲基纤维素，分散在去离子水中，得到负极浆料，将负极浆料涂布在铜箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上镍制引出线后得到负极板，极板的厚度在120-150μm之间。
电解液制备步骤为：将碳酸乙烯酯、碳酸甲乙酯和碳酸二乙酯按体积比为EC:EMC:DEC＝3:3:4进行混合，混合后加入浓度为1.0mol/L的六氟磷酸锂，加入基于电解液总重量的0.1wt％的三炔丙基磷酸酯和0.5wt％的环丁砜。
隔膜制备步骤为：采用聚丙烯、聚乙烯和聚丙烯三层隔离膜，厚度为20μm。
电池组装步骤为：在正极板和负极板之间放置厚度为20μm的三层隔离膜，然后将正极板、负极板和隔膜组成的三明治结构进行卷绕，再将卷绕体压扁后放入方形铝制金属壳中，将正负极的引出线分别焊接在盖板的相应位置上，并用激光焊接机将盖板和金属壳焊接为一体，得到待注液的电芯；将上述制备的电解液通过注液孔注入电芯中，电解液的量要保证充满电芯中的空隙。
然后按以下步骤进行首次充电的常规化成：0.05C恒流充电3min，0.2C恒流充电5min，0.5C恒流充电25min，搁置1h，整形、补注液、封口，然后进一步以0.2C的电流恒流充电至4.2V，常温搁置24h后，0.2C恒流恒压充电至4.2V，然后以0.2C的电流恒流放电至3.0V。获得本例的锂离子电池。
对本例制备的锂离子电池进行如下测试：
(1)高温循环性能测试：在45℃下，将化成后的电池用1C恒流恒压充至4.35V，然后用1C恒流放电至3.0V。充/放电300次循环后，计算第300次循环容量的保持率，以评估其高温循环性能。计算公式如下：
第300次循环容量保持率(％)＝(第300次循环放电容量/第一次循环放电容量)×100％。
(2)常温循环性能测试：在25℃下，将化成后的电池用1C恒流恒压充至4.35V，然后用1C恒流放电至3.0V。充/放电500次循环后计算第500次循环容量的保持率，以评估其常温循环性能。计算公式如下：
第500次循环容量保持率(％)＝(第500次循环放电容量/第一次循环放电容量)×100％；
(3)高温储存性能：将化成后的电池在常温下用1C恒流恒压充至4.35V，测量电池初始放电容量，然后在60℃储存30天后，以1C放电至3.0V，测量电池的保持容量和恢复容量。计算公式如下：
电池容量保持率(％)＝保持容量/初始容量×100％；
电池容量恢复率(％)＝恢复容量/初始容量×100％。
(4)低温放电性能测试：在25℃下，将化成后的电池用1C恒流恒压充至4.35V，然后用1C恒流放电至3.0V，记录放电容量。然后1C恒流恒压充满，置于-20℃的环境中搁置12h后，1C恒流放电至3.0V，记录放电容量。
-20℃的低温放电效率值＝1C放电容量(-20℃)/1C放电容量(25℃)。
(5)常低温直流阻抗(DCIR)性能测试：在25℃下，将化成后的电池1C充电到半电状态，分别用0.1C，0.2C，0.5C，1C和2C充放十秒，分别记录充放电截止电压。然后，以不同倍率的充放电电流为横坐标(单位：A)，以充放电电流所对应的截止电压为纵坐标，做线性关系图(单位：mV)。
充电DCIR值＝不同充电电流与相应截止电压的线性图的斜率值。
放电DCIR值＝不同放电电流与相应截止电压的线性图的斜率值。
(6)另外，对将化成后的电池在0℃用0.3C充电后，测量负极的析锂程度，并采用5分制进行评估，分数越低，说明析锂越严重。具体的，5分表示不析锂、4表示较轻微析锂、3表示一般析锂、2表示较严重析锂、1表示严重析锂。
本例的所有测试结果如表3所示。
实施例2-20
实施例2-20中，除了砜类化合物和不饱和磷酸酯类化合物的具体化合物，及其用量不同以外，其它均与实施例1相同。各实施例的具体化合物，及其用量如表2所示，其中用量是按照各物质占锂离子电池非水电解液总重量的百分比计算的。
另外，本申请还设计了6个对比例，即对比例1-6，同样的，6个对比例与实施例1或其它实施例相比，也仅仅是添加的具体化合物和用量不同，其它均与实施例1相同。各对比例的具体化合物，及其用量如表2所示，同样的，其中用量是按照添加的物质占锂离子电池非水电解液总重量的百分比计算的。
表2 各实施例和对比例的物质及其用量
实施例 三炔丙基磷酸酯 二烯丙基乙基磷酸酯 环丁砜 甲基乙基砜 二甲基砜 VC
实施例1 0.1   0.5      
实施例2 0.5   1      
实施例3 1   5      
实施例4 1   10      
实施例5 1   30      
实施例6 2   10      
实施例7 0.5   10      
实施例8 1     5    
实施例9 1     10    
实施例10 1       5  
实施例11 1       10  
实施例12 1   5 5    
实施例13 1   5   5  
实施例14   0.1 0.5      
实施例15   0.5 1      
实施例16   1 5      
实施例17   1 10      
实施例18   1 30      
实施例19   2 10      
实施例20 2   0.3      
对比例1 1          
对比例2     5      
对比例3       5    
对比例4         5  
对比例5           1
对比例6   1        
表中，空白表示相应的实施例或对比例没有添加该对应的物质，三炔丙基磷酸酯即表1中的化合物1，二烯丙基乙基磷酸酯即表1中的化合物4。
实施例1-20和对比例1-6的测试结果如表3所示。
表3 各实施例和对比例的测试结果
Figure PCTCN2016113008-appb-000005
Figure PCTCN2016113008-appb-000006
表2中，0℃0.3C充电，负极析锂程度测试中，5表示不析锂、4表示较轻微析锂、3表示一般析锂、2表示较严重析锂、1表示严重析锂。
通过对比例1-6的测试结果对比，可以发现不饱和磷酸酯类化合物单独使用时，循环性能和高温存储较好，低温性能很差。砜类化合物单独使用时，循环性能和高温存储性能较差，低温性能较好。
而本申请的实施例1-20的测试结果中，通过对比例1和实施例3-5、8-13的对比，可以发现在不饱和磷酸酯类化合物基础上，添加砜类化合物，不仅仅低温性能能得到明显改善，同时循环性能和高温性能也有较明显改善。
同时，本申请的实施例1-20的测试结果中，相对于对比例1-6，可以发现同时包含不饱和磷酸酯类化合物和砜类化合物的所有实施例的高温性能和低温性能都有所改善。通过实施例4、6、7对比，17和19对比，随着不饱和磷酸酯类化合物的增加，其高温性能有所提高，但是低温性能相对下降，特别是阻抗，随着用量的增加，阻抗也随之增大。尤其当不饱和磷酸酯类化合物的含量高而砜类化合物含量较低时，低温性能明显不足。
综上所述，本申请将不饱和磷酸酯类化合物和砜类化合物配合使用，在合适的比例下，可以使电池获得优良的高温性能和循环性能以及良好的低温性能。其中，在用量方面，不饱 和磷酸酯类用量0.1％～2％，砜类化合物用量0.1％～30％都可以起到改善高低温性能和循环性能的效果；而在不饱和磷酸酯用量0.2％～1％、砜类化合物用量1～10％的情况下，效果更佳。
以上内容是结合具体的实施方式对本申请所作的进一步详细说明，不能认定本申请的具体实施只局限于这些说明。对于本申请所属技术领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本申请的保护范围。

Claims (9)

  1. 一种锂离子电池非水电解液，其特征在于：包括不饱和磷酸酯类化合物和砜类化合物，所述砜类化合物包括环状砜类化合物和/或直链砜类化合物；
    所述不饱和磷酸酯类化合物具有式一所示结构，
    Figure PCTCN2016113008-appb-100001
    其中，R1、R2、R3分别独立地选自碳原子数为1-4的烃基，且R1、R2、R3中至少一个为含有双键或叁键的不饱和烃基；
    所述环状砜类化合物具有式二所示结构，所述直链砜类化合物具有式三所示结构，
    Figure PCTCN2016113008-appb-100002
    其中，R4、R5、R6、R7分别独立地选自氢原子、卤素或碳原子数为1-5的烷基，A是包括2～6个碳原子数的取代或非取代的亚烷基，其取代的官能团为卤素或碳原子数为1-3的烷基。
  2. 根据权利要求1所述的锂离子电池非水电解液，其特征在于：所述环状砜类化合物为式四和/或式五所示结构化合物的至少一种，
    Figure PCTCN2016113008-appb-100003
    其中，R8-R16分别独立地选自氢原子、卤素或碳原子数为1-5的烷基。
  3. 根据权利要求1所述的锂离子电池非水电解液，其特征在于：所述砜类化合物选自环丁砜、3-甲基环丁砜、3,3,4,4-四氟环丁砜、环戊砜、二甲基砜、甲基乙基砜和二乙基砜中的至少一种。
  4. 根据权利要求1-3任一项所述的锂离子电池非水电解液，其特征在于：所述不饱和磷酸酯类化合物占锂离子电池非水电解液总重量的0.1％～2％，优选的，占锂 离子电池非水电解液总重量的0.2％～1％。
  5. 根据权利要求1-3任一项所述的锂离子电池非水电解液，其特征在于：所述砜类化合物占锂离子电池非水电解液总重量的0.1％～30％，优选的，占锂离子电池非水电解液总重量的0.1～10％，进一步优选的，占锂离子电池非水电解液总重量的0.5～10％，更优选的，占锂离子电池非水电解液总重量的1～10％。
  6. 根据权利要求1-3任一项所述的锂离子电池非水电解液，其特征在于：所述砜类化合物与所述不饱和磷酸酯类化合物的重量比大于或等于0.2。
  7. 一种锂离子电池，包括正极、负极、置于正极与负极之间的隔膜，以及电解液，其特征在于：所述电解液为权利要求1-6任一项所述的锂离子电池非水电解液。
  8. 根据权利要求7所述的锂离子电池，其特征在于：所述正极选自LiCoO2、LiNiO2、LiMn2O4、LiCo1-yMyO2、LiNi1-yMyO2、LiMn2-yMyO4和LiNixCoyMnzM1-x-y-zO2中的一种或两种以上，其中，M选自Fe、Co、Ni、Mn、Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V和Ti中的一种或两种以上，且0≤y≤1，0≤x≤1，0≤z≤1，x+y+z≤1。
  9. 根据权利要求7所述的锂离子电池，其特征在于：所述锂离子电池的充电截止电压大于或等于4.35V。
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