WO2024099053A1 - 电解液及锂离子电池 - Google Patents

电解液及锂离子电池 Download PDF

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WO2024099053A1
WO2024099053A1 PCT/CN2023/125698 CN2023125698W WO2024099053A1 WO 2024099053 A1 WO2024099053 A1 WO 2024099053A1 CN 2023125698 W CN2023125698 W CN 2023125698W WO 2024099053 A1 WO2024099053 A1 WO 2024099053A1
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electrolyte
lithium
substituted
additive
carbonate
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PCT/CN2023/125698
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English (en)
French (fr)
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刘欣
梁大宇
李道聪
杨茂萍
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合肥国轩高科动力能源有限公司
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Publication of WO2024099053A1 publication Critical patent/WO2024099053A1/zh

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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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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 invention relates to the technical field of lithium ion batteries, and in particular to an electrolyte and a lithium ion battery.
  • Lithium-ion batteries have the advantages of high energy density, long cycle life, and no memory effect, and are widely studied and applied.
  • the cathode materials of commercial high-capacity lithium-ion batteries mainly include lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese oxide, and ternary materials.
  • lithium-ion batteries are required to have high energy density, high specific energy density, and long cycle life.
  • the main ways to increase energy density currently include using positive and negative active materials with high specific capacity, adding additives, and increasing the operating voltage of lithium-ion batteries.
  • the operating voltage of lithium-ion batteries is increased, the oxidation of the positive active materials will increase, which will make the electrolyte more easily oxidized and decomposed, not only producing a large amount of gas byproducts causing battery swelling, but also solid byproducts deposited on the surface of the positive electrode material, causing the battery interface impedance to increase sharply and the battery performance to deteriorate rapidly.
  • currently commercial additives can only improve the high or low temperature performance of the battery, and there are few additives that can take both high and low temperatures into account.
  • the main purpose of the present invention is to provide an electrolyte and a lithium ion battery to solve the problem that lithium ion batteries in the prior art are difficult to have excellent electrical properties such as cycle capacity retention rate at both high and low temperatures.
  • an electrolyte comprising an organic solvent, LiPF 6 and an additive, the additive comprising heptamethyldisilazane and a cyanosilane compound, the cyanosilane compound having the following structural formula:
  • R1, R2, and R3 are independently selected from any one or more of C 1 to C 10 substituted or unsubstituted alkyl, C 1 to C 10 substituted or unsubstituted alkoxy, C 2 to C 10 substituted or unsubstituted alkynyl, C 6 to C 12 substituted or unsubstituted alkylaryl, (R4) 3 SiO-, and R4 is selected from C 1 to C 10 substituted or unsubstituted alkyl Any one of .
  • n is any integer from 1 to 3, preferably R1, R2, and R3 are independently selected from any one or more of C 1 to C 4 substituted or unsubstituted alkyl, C 1 to C 4 substituted or unsubstituted alkoxy, C 2 to C 4 substituted or unsubstituted alkynyl, substituted or unsubstituted phenyl, (R4) 3 SiO-, and R4 is selected from any one of C 1 to C 4 substituted or unsubstituted alkyl; preferably R1, R2, and R3 are independently selected from any one or more of methyl, ethyl, methoxy, ethoxy, ethynyl, phenyl, (CH 3 ) 3 SiO-, (CH 3 CH 2 ) 3 SiO-, and preferably the cyanosilane compound is selected from
  • the mass of the above-mentioned heptamethyldisilazane is 0.1-5wt% of the total mass of the electrolyte, preferably 0.5-3wt%
  • the mass of the cyanosilane compound is 0.1-5wt% of the total mass of the electrolyte, preferably 0.5-3wt%
  • the mass ratio of heptamethyldisilazane to cyanosilane compound is preferably 1:4-2:1.
  • the organic solvent is selected from any one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl acetate, ⁇ -butyrolactone, propyl propionate, ethyl propionate, 1,3-dioxymethane, and diethylene glycol dimethyl ether.
  • the organic solvent is a combination of ethyl methyl carbonate, ethylene carbonate, and diethyl carbonate.
  • the volume ratio of ethyl methyl carbonate, ethylene carbonate, and diethyl carbonate is 5 to 8:3 to 5:2 to 4.
  • the electrolyte further comprises a lithium salt additive, preferably the concentration of the lithium salt additive is 0.1 to 5 wt %, and the lithium salt additive is preferably selected from lithium hexafluoroarsenate, lithium perchlorate, lithium tetrafluoroborate, lithium methanesulfonate, lithium trifluoromethanesulfonate, bis(trifluoromethyl)sulfonate, lithium tetrafluoroborate, lithium tetrafluoromethane ... Any one or more of lithium methylsulfonyl imide and lithium bis(oxalatoborate).
  • the lithium salt additive is preferably lithium tetrafluoroborate and/or lithium bis(trifluorosulfonyl imide).
  • the concentration of the above-mentioned LiPF 6 is 0.5 to 1.5 mol/L.
  • the above-mentioned electrolyte also includes functional additives, preferably the functional additives are 0.1 to 5wt% of the total mass of the electrolyte, further, the functional additives are preferably selected from any one or more of circulation additives, low-temperature additives, high-temperature additives, flame retardant additives, and anti-overcharge additives, and further, the functional additives are preferably selected from any one or more of vinylene carbonate, fluoroethylene carbonate, vinyl sulfate, tris(trimethylsilane) phosphate, 1,3-propane sultone, methanedisulfonic acid methylene ester, 1,3,6-hexanetrinitrile, tris(pentafluorophenyl)borane, lithium difluorophosphate, 3-hexylthiophene, hexafluorocyclotriphosphazene, and tris(hexafluoroisopropyl) phosphate.
  • the functional additives
  • the electrolyte includes ethyl methyl carbonate, ethylene carbonate, diethyl carbonate, LiPF 6 , vinylene carbonate, heptamethyldisilazane and Among them, heptamethyldisilazane is 2wt% of the electrolyte, 1wt% of the electrolyte; or heptamethyldisilazane is 1wt% of the electrolyte, For electrolysis 2wt% of the electrolyte; or heptamethyldisilazane is 0.6wt% of the electrolyte, is 2.4wt% of the electrolyte; or the cyanosilane compound is And heptamethyldisilazane is 2wt% of the electrolyte, It is 1wt% of the electrolyte.
  • a lithium-ion battery comprising a positive electrode sheet, a negative electrode sheet and an electrolyte, wherein the electrolyte is the electrolyte described above.
  • the above-mentioned positive electrode sheet includes a positive electrode active material, and the positive electrode active material is preferably selected from any one or more of lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese oxide, nickel cobalt lithium manganese oxide, and lithium-rich lithium manganese oxide.
  • the negative electrode sheet preferably includes a negative electrode active material, and the negative electrode active material is preferably selected from any one or more of natural graphite, artificial graphite, silicon, and lithium titanate.
  • a part of heptamethyldisilazane can combine with HF to form a stable amine salt compound, effectively removing HF, while the remaining heptamethyldisilazane is oxidized on the positive electrode surface before the solvent to form a CEI film, thereby improving the problems of gas production and transition metal dissolution under high voltage, and further improving the high temperature cycle performance of lithium-ion batteries.
  • Cyanosilane compounds are both oxidized and reduced before the solvent, and can form SEI films and CEI films on the positive and negative electrode surfaces.
  • the CEI film containing Si-C ⁇ N structure has higher conductivity, which is more helpful to reduce impedance, and then reduce the low-temperature DC internal resistance of lithium-ion batteries.
  • amine salt compounds can participate in the process of cyanosilane compounds forming SEI film and CEI film and serve as a part of SEI film and CEI film, which is not only conducive to improving the conductivity of SEI film and CEI film, but also the SEI film and CEI film obtained by the synergistic effect of heptamethyldisilazane and cyanosilane compounds are thinner, more uniform and denser, which can further reduce the low-temperature DC internal resistance of lithium-ion batteries, improve the cycle performance of lithium-ion batteries, reduce the growth rate of DC internal resistance during the cycle, and effectively improve the stability and safety of lithium-ion batteries as a whole.
  • lithium-ion batteries in the prior art have difficulty in having excellent electrical properties such as cycle capacity retention rate at both high and low temperatures.
  • the present invention provides an electrolyte and a lithium-ion battery.
  • an electrolyte comprising an organic solvent, LiPF 6 and an additive, the additive comprising heptamethyldisilazane and a cyanosilane compound, the cyanosilane compound having the following structural formula:
  • R1, R2, and R3 are each independently selected from any one or more of C1 - C10 substituted or unsubstituted alkyl, C1 - C10 substituted or unsubstituted alkoxy, C2 - C10 substituted or unsubstituted alkynyl, C6 - C12 substituted or unsubstituted alkylaryl, and (R4) 3SiO- ; and R4 is selected from any one of C1 - C10 substituted or unsubstituted alkyl.
  • a portion of heptamethyldisilazane can combine with HF to form a stable amine salt compound, effectively removing HF.
  • the remaining heptamethyldisilazane is oxidized on the positive electrode surface before the solvent to form a CEI film, thereby improving the problems of gas production and transition metal dissolution under high voltage, and further improving the high-temperature cycle performance of lithium-ion batteries.
  • Cyanosilane compounds are both oxidized and reduced before the solvent, and can form SEI films and CEI films on the positive and negative electrode surfaces.
  • the CEI film containing the Si-C ⁇ N structure has a higher conductivity, which is more helpful to reduce impedance, thereby reducing the low-temperature DC internal resistance of lithium-ion batteries.
  • amine salt compounds can participate in the process of cyanosilane compounds forming SEI films and CEI films and serve as a part of SEI films and CEI films, which is not only beneficial to improve the conductivity of SEI films and CEI films, but also the SEI films and CEI films obtained by the synergistic effect of heptamethyldisilazane and cyanosilane compounds are thinner, more uniform, and more dense, which can further reduce the lithium-ion battery.
  • the low-temperature DC internal resistance of the battery improves the cycle performance of the lithium-ion battery, reduces the growth rate of the DC internal resistance during the cycle, and effectively improves the stability and safety of the lithium-ion battery as a whole.
  • n is any integer from 1 to 3, preferably R1, R2, and R3 are independently selected from any one or more of C 1 to C 4 substituted or unsubstituted alkyl, C 1 to C 4 substituted or unsubstituted alkoxy, C 2 to C 4 substituted or unsubstituted alkynyl, substituted or unsubstituted phenyl, (R4) 3 SiO-, and R4 is selected from any one of C 1 to C 4 substituted or unsubstituted alkyl; preferably R1, R2, and R3 are independently selected from any one or more of methyl, ethyl, methoxy, ethoxy, ethynyl, phenyl, (CH 3 ) 3 SiO-, (CH 3 CH 2 ) 3 SiO-, and preferably the cyanosilane compound is selected from Any one or more of .
  • the SEI film and CEI film formed by the above-mentioned types of cyanosilane compounds are more uniform and denser.
  • the mass of the heptamethyldisilazane is 0.1-5wt% of the total mass of the electrolyte, preferably 0.5-3wt%, and the mass of the cyanosilane compound is 0.1-5wt% of the total mass of the electrolyte, preferably 0.5-3wt%. It is preferred that the mass ratio of the heptamethyldisilazane to the cyanosilane compound is 1:4-2:1, which is more conducive to the synergistic effect of heptamethyldisilazane and cyanosilane compounds.
  • the organic solvent is preferably selected from any one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl acetate, ⁇ -butyrolactone, propyl propionate, ethyl propionate, 1,3-dioxymethane, and diethylene glycol dimethyl ether.
  • the organic solvent is preferably a combination of ethyl methyl carbonate, ethylene carbonate and diethyl carbonate, and the volume ratio of ethyl methyl carbonate, ethylene carbonate and diethyl carbonate is preferably 5-8:3-5:2-4.
  • the above-mentioned types of organic solvents can better avoid the damage of water to the electrolyte, and at the same time help to promote the more complete dissolution of the components in the electrolyte, thereby improving the synergy between the components and obtaining an electrolyte with excellent electrical properties.
  • the above-mentioned electrolyte preferably also includes a lithium salt additive, and the concentration of the lithium salt additive is preferably 0.1-5wt%.
  • the lithium salt additive is preferably selected from any one or more of lithium hexafluoroarsenate, lithium perchlorate, lithium tetrafluoroborate, lithium methanesulfonate, lithium trifluoromethylsulfonate, lithium bistrifluoromethylsulfonyl imide, and lithium bis(trifluoromethyl)borate.
  • the lithium salt additive is preferably lithium tetrafluoroborate and/or lithium bis(trifluorosulfonyl)imide salt.
  • the above-mentioned electrolyte preferably also includes a functional additive, and the functional additive is preferably 0.1 to 5wt% of the total mass of the electrolyte. Further, the functional additive is preferably selected from any one or more of a circulation additive, a low-temperature additive, a high-temperature additive, a flame retardant additive, and an anti-overcharge additive.
  • the functional additive is preferably selected from any one or more of vinylene carbonate, fluoroethylene carbonate, vinyl sulfate, tris(trimethylsilane) phosphate, 1,3-propane sultone, methanedisulfonic acid methylene ester, 1,3,6-hexanetrinitrile, tris(pentafluorophenyl)borane, lithium difluorophosphate, 3-hexylthiophene, hexafluorocyclotriphosphazene, and tris(hexafluoroisopropyl) phosphate.
  • the electrolyte includes ethyl methyl carbonate, ethylene carbonate, diethyl carbonate, LiPF 6 , vinylene carbonate, heptamethyldisilazane and Among them, heptamethyldisilazane is 2wt% of the electrolyte, 1wt% of the electrolyte; or Disilazane is 1wt% of the electrolyte, 2wt% of the electrolyte; or heptamethyldisilazane is 0.6wt% of the electrolyte, is 2.4wt% of the electrolyte; or the cyanosilane compound is And heptamethyldisilazane is 2wt% of the electrolyte, 1wt% of the electrolyte is more conducive to obtaining excellent comprehensive performance Further, preferably, the mass ratio of ethyl methyl carbonate, ethylene carbonate and diethyl carbonate is 5:3:2, the concentration of LiPF
  • a lithium-ion battery comprising a positive electrode sheet, a negative electrode sheet and an electrolyte, wherein the electrolyte is the aforementioned electrolyte.
  • the lithium-ion battery using the above electrolyte has a lower impedance, which can significantly reduce the low-temperature DC internal resistance of the lithium-ion battery, improve the cycle performance of the lithium-ion battery, reduce the growth rate of the DC internal resistance during the cycle, and effectively improve the stability and safety of the lithium-ion battery as a whole.
  • the above-mentioned positive electrode sheet preferably includes a positive electrode active material, and the positive electrode active material is preferably selected from any one or more of lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese oxide, nickel cobalt lithium manganese oxide, and lithium-rich lithium manganese oxide.
  • the negative electrode sheet preferably includes a negative electrode active material, and the negative electrode active material is preferably selected from any one or more of natural graphite, artificial graphite, silicon, and lithium titanate.
  • Ethylene carbonate (EC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC) are mixed in a mass ratio of 5:3:2, and after mixing, 1 mol of lithium hexafluorophosphate (LiPF 6 ) electrolyte (100 g), 0.5 wt % of heptamethyldisilazane (based on the total mass of the electrolyte), 0.5 wt % of cyanosilane compound 2 (based on the total mass of the electrolyte), and then 1 wt % of vinylene carbonate (based on the total mass of the electrolyte) and 1 wt % of lithium tetrafluoroborate are added.
  • LiPF 6 lithium hexafluorophosphate
  • Nickel cobalt lithium manganese oxide ternary material LiNi 0.7 Co 0.1 Mn 0.2 O 2 , conductive agent Super P, adhesive PVDF and carbon nanotubes (CNT) are mixed evenly at a mass ratio of 97.5:0.5:1:1 to prepare a lithium ion battery positive electrode slurry of a certain viscosity, which is coated on aluminum foil for current collector with a coating amount of 360 g/m 2 , dried at 85°C and then cold pressed; then striped and sliced, and then baked at 85°C in vacuum for 4 hours to prepare a lithium ion battery positive electrode sheet that meets the requirements.
  • lithium-ion batteries The positive electrode sheet, negative electrode sheet and separator (polyethylene film coated ceramic separator) prepared according to the above process are made into a lithium-ion battery with a thickness of 0.5 mm, a width of 8 mm, and a length of 10 mm through a lamination process.
  • the capacity is 3Ah, and the battery is vacuum-baked at 85°C for 48 hours, and the above-mentioned electrolyte is injected.
  • the production of 3Ah soft-pack lithium-ion batteries is completed through the processes of packaging, shelving, formation, aging, secondary packaging and capacity division.
  • Comparative Example 1 and Comparative Example 2 changed the ratio and type of specific substances in the electrolyte, and obtained a lithium ion battery with reference to the preparation method of Example 1.
  • the electrolyte formula is shown in Table 1 below.
  • Example 10 The difference between Example 10 and Example 4 is that
  • the cyanosilane compound is cyanosilane compound 1, and a 3Ah soft-pack lithium-ion battery is finally obtained.
  • Example 11 The difference between Example 11 and Example 4 is that,
  • the cyanosilane compound is cyanosilane compound 3, and a 3Ah soft-pack lithium-ion battery is finally obtained.
  • Example 12 The difference between Example 12 and Example 4 is that,
  • the cyanosilane compound is cyanosilane compound 4, and a 3Ah soft-pack lithium-ion battery is finally obtained.
  • Example 14 The difference between Example 14 and Example 4 is that the lithium salt additive is lithium methane sulfonate, and a 3Ah soft-pack lithium-ion battery is finally obtained.
  • the lithium salt additive is lithium methane sulfonate, and a 3Ah soft-pack lithium-ion battery is finally obtained.
  • Example 15 The difference between Example 15 and Example 4 is that bistrifluorosulfonyl imide lithium salt with a concentration of 1 wt % is used as a conventional lithium salt additive, and a 3Ah soft-pack lithium-ion battery is finally obtained.
  • the 3Ah soft-pack lithium-ion batteries prepared in Examples 1 to 15 and Comparative Examples 1 and 2 were cycled at a charge and discharge current of 1C/1C, with a test voltage range of 3.0 to 4.5V.
  • the initial capacity and initial internal resistance of the battery cells are shown in Table 2.
  • High voltage and high temperature cycle experiment Take the above 3Ah soft pack lithium ion battery, charge it to 4.5V limit voltage at 0.5C, then change to constant voltage charging until the charging current is ⁇ cut-off current, let it stand for 30 minutes, then discharge it to 2.8V cut-off voltage at 0.5C, let it stand for 30 minutes, and perform charge and discharge experiments according to the above process, and perform low temperature DCR, high temperature cycle and high temperature shelf performance tests, and test its DC internal resistance DCR during the cycle. Calculate the low temperature DCR and capacity retention rate of the battery cell at high voltage, and the results are shown in Table 2.
  • a portion of heptamethyldisilazane can combine with HF to form a stable amine salt compound, effectively removing HF.
  • the remaining heptamethyldisilazane is oxidized on the positive electrode surface before the solvent to form a CEI film, thereby improving the problems of gas production and transition metal dissolution under high voltage, and further improving the high-temperature cycle performance of lithium-ion batteries.
  • Cyanosilane compounds are both oxidized and reduced before the solvent, and can form SEI films and CEI films on the positive and negative electrode surfaces.
  • the CEI film containing the Si-C ⁇ N structure has a higher conductivity, which is more helpful to reduce impedance, thereby reducing the low-temperature DC internal resistance of lithium-ion batteries.
  • amine salt compounds can participate in the process of cyanosilane compounds forming SEI films and CEI films and serve as a part of SEI films and CEI films, which is not only beneficial to improve the conductivity of SEI films and CEI films, but also the combination of heptamethyldisilazane and cyanosilane compounds can also improve the conductivity of SEI films and CEI films.
  • the SEI film and CEI film obtained by the synergistic effect of the substances are thinner, more uniform and denser, which can further reduce the low-temperature DC internal resistance of the lithium-ion battery, improve the cycle performance of the lithium-ion battery, reduce the growth rate of the DC internal resistance during the cycle, and effectively improve the stability and safety of the lithium-ion battery as a whole.

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Abstract

提供了一种电解液及锂离子电池。该电解液包括有机溶剂、LiPF 6以及添加剂，添加剂包括七甲基二硅氮烷和氰硅烷类化合物，氰硅烷类化合物具有以下结构式：式（I）其中，n为1至6中的任意一个整数，R1、R2、R3各自独立的地选自C 1～C 10的取代或非取代的烷基、C 1～C 10的取代或非取代的烷氧基、C 2～C 10的取代或非取代的炔基、C 6～C 12的取代或非取代的烷基芳基、(R4) 3SiO-中的任意一种或多种，R4选自C 1～C 10的取代或非取代的烷基中的任意一种。电解液可以降低锂离子电池的低温直流内阻，提升锂离子电池的循环性能、降低循环过程中直流内阻的增长率，在整体上有效提高锂离子电池的稳定性与安全性。

Description

电解液及锂离子电池
本申请是以CN申请号为202211402785.6，申请日为2022年11月10日的中国申请为基础，并主张其优先权，该CN申请的公开内容再次作为整体引入本申请中。
技术领域
本发明涉及锂离子电池技术领域，具体而言，涉及一种电解液及锂离子电池。
背景技术
锂离子电池具有能量密度高、循环寿命长、无记忆效应等优点，被广泛的研究与应用。目前商品化的高容量锂离子电池的正极材料主要有钴酸锂、锰酸锂、镍锰酸锂、三元材料等，为了满足便携式电子产品以及电动汽车可持续工作的需求，需要锂离子电池具有高能量密度、高比能量密度以及长循环寿命。
当前提高能量密度的主要途径包括使用具有高比容量的正、负极活性材料、添加添加剂以及提高锂离子电池的工作电压。其中，当提高锂离子电池的工作电压后会导致正极活性材料氧化性增加，进而导致电解液更容易氧化分解，不仅产生大量气体副产物造成电池鼓胀，而且固态副产物沉积在正极材料的表面，导致电池界面阻抗急剧升高，电池的性能迅速劣化。另外，目前商业化的添加剂只能改善电池的高温或者低温性能，很少有高低温兼顾的添加剂。
发明内容
本发明的主要目的在于提供一种电解液及锂离子电池，以解决现有技术中的锂离子电池难以在高温与低温下兼具优良的循环容量保持率等电性能的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种电解液，该电解液包括有机溶剂、LiPF6以及添加剂，添加剂包括七甲基二硅氮烷和氰硅烷类化合物，氰硅烷类化合物具有以下结构式：
其中，n为1至6中的任意一个整数，R1、R2、R3各自独立的地选自C1～C10的取代或非取代的烷基、C1～C10的取代或非取代的烷氧基、C2～C10的取代或非取代的炔基、C6～C12的取代或非取代的烷基芳基、(R4)3SiO-中的任意一种或多种，R4选自C1～C10的取代或非取代的烷基中 的任意一种。
进一步地，上述n为1至3中的任意一个整数，优选R1、R2、R3各自独立的地选自C1～C4的取代或非取代的烷基、C1～C4的取代或非取代的烷氧基、C2～C4的取代或非取代的炔基、取代或非取代的苯基、(R4)3SiO-中的任意一种或多种，R4选自C1～C4的取代或非取代的烷基中的任意一种；优选R1、R2、R3各自独立的地选自甲基、乙基、甲氧基、乙氧基、乙炔基、苯基、(CH3)3SiO-、(CH3CH2)3SiO-中的任意一种或多种，优选氰硅烷类化合物选自
中的任意一种或多种。
进一步地，上述七甲基二硅氮烷的质量为电解液总质量的0.1～5wt％，优选为0.5～3wt％，氰硅烷类化合物的质量为电解液总质量的0.1～5wt％，优选为0.5～3wt％，优选七甲基二硅氮烷和氰硅烷类化合物的质量比为1:4～2:1。
进一步地，上述有机溶剂选自碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、乙酸乙酯、γ-丁内酯、丙酸丙酯、丙酸乙酯、1,3-二氧甲烷、二甘醇二甲醚中的任意一种或多种，优选有机溶剂为碳酸甲乙酯、碳酸乙烯酯和碳酸二乙酯的组合，优选碳酸甲乙酯、碳酸乙烯酯和碳酸二乙酯的体积比为5～8:3～5:2～4。
进一步地，上述电解液还包括锂盐添加剂，优选锂盐添加剂的浓度为0.1～5wt％，优选锂盐添加剂选自六氟砷酸锂、高氯酸锂、四氟硼酸锂、甲基磺酸锂、三氟甲基磺酸锂、双三氟 甲基磺酰亚胺锂、双草酸硼酸酯锂中的任意一种或多种，进一步地，优选锂盐添加剂为四氟硼酸锂和/或双三氟磺酰亚胺锂盐。
进一步地，上述LiPF6的浓度为0.5～1.5mol/L。
进一步地，上述电解液还包括功能添加剂，优选功能添加剂为电解液总质量的0.1～5wt％，进一步地，优选功能添加剂选自循环添加剂、低温添加剂、高温添加剂、阻燃添加剂、防过充添加剂中的任意一种或多种，更进一步地，优选功能添加剂选自碳酸亚乙烯酯、氟代碳酸乙烯酯、硫酸乙烯酯、三(三甲基硅烷)磷酸酯、1,3-丙烷磺内酯、甲烷二磺酸亚甲酯、1,3,6-己烷三腈、三(五氟苯基)硼烷、二氟磷酸锂、3-己基噻吩、六氟环三磷腈、三(六氟异丙基)磷酸酯中的任意一种或多种。
进一步地，上述电解液包括碳酸甲乙酯、碳酸乙烯酯和碳酸二乙酯、LiPF6、碳酸亚乙烯酯、七甲基二硅氮烷和其中，七甲基二硅氮烷为电解液的2wt％，为电解液的1wt％；或七甲基二硅氮烷为电解液的1wt％，为电解 液的2wt％；或七甲基二硅氮烷为电解液的0.6wt％，为电解液的2.4wt％；或氰硅烷类化合物为且七甲基二硅氮烷为电解液的2wt％，为电解液的1wt％。
根据本发明的另一方面，提供了一种锂离子电池，包括正极片、负极片以及电解液，该电解液为上述的电解液。
进一步地，上述正极片包括正极活性物质，优选正极活性物质选自钴酸锂、锰酸锂、镍锰酸锂、镍钴锰酸锂、富锂锰酸锂中的任意一种或多种，优选负极片包括负极活性物质，优选负极活性物质选自天然石墨、人造石墨、硅、钛酸锂中的任意一种或多种。
应用本发明的技术方案，一部分七甲基二硅氮烷能够与HF结合形成稳定的胺盐类化合物，有效去除HF，同时剩余的七甲基二硅氮烷在正极表面优先于溶剂被氧化，形成CEI膜，从而改善了高电压下产气与过渡金属溶出的问题，进而提高了锂离子电池的高温循环性能。氰硅烷类化合物既优先于溶剂氧化又优先于溶剂还原，可以在正负极表面成SEI膜和CEI膜， 含Si-C≡N结构的CEI膜具有更高的电导率，从而更有助于降低阻抗，进而降低锂离子电池的低温直流内阻。此外，胺盐类化合物能够参与到氰硅烷类化合物成SEI膜和CEI膜的过程中并作为SEI膜和CEI膜的一部分，不仅有利于提高SEI膜和CEI膜的导电性，而且七甲基二硅氮烷与氰硅烷类化合物协同作用得到的SEI膜和CEI膜更薄、更均匀、更致密，从而可以进一步地降低锂离子电池的低温直流内阻，提升锂离子电池的循环性能、降低循环过程中直流内阻的增长率，在整体上有效提高锂离子电池的稳定性与安全性。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
如背景技术所分析的，现有技术中的锂离子电池难以在高温与低温下兼具优良的循环容量保持率等电性能的问题，为解决该问题，本发明提供了一种电解液及锂离子电池。
在本申请的一种典型的实施方式中，提供了一种电解液，该电解液包括有机溶剂、LiPF6以及添加剂，添加剂包括七甲基二硅氮烷和氰硅烷类化合物，氰硅烷类化合物具有以下结构式：
其中，n为1至6中的任意一个整数，R1、R2、R3各自独立的地选自C1～C10的取代或非取代的烷基、C1～C10的取代或非取代的烷氧基、C2～C10的取代或非取代的炔基、C6～C12的取代或非取代的烷基芳基、(R4)3SiO-中的任意一种或多种，R4选自C1～C10的取代或非取代的烷基中的任意一种。
一部分七甲基二硅氮烷能够与HF结合形成稳定的胺盐类化合物，有效去除HF，同时剩余的七甲基二硅氮烷在正极表面优先于溶剂被氧化，形成CEI膜，从而改善了高电压下产气与过渡金属溶出的问题，进而提高了锂离子电池的高温循环性能。氰硅烷类化合物既优先于溶剂氧化又优先于溶剂还原，可以在正负极表面成SEI膜和CEI膜，含Si-C≡N结构的CEI膜具有更高的电导率，从而更有助于降低阻抗，进而降低锂离子电池的低温直流内阻。此外，胺盐类化合物能够参与到氰硅烷类化合物成SEI膜和CEI膜的过程中并作为SEI膜和CEI膜的一部分，不仅有利于提高SEI膜和CEI膜的导电性，而且七甲基二硅氮烷与氰硅烷类化合物协同作用得到的SEI膜和CEI膜更薄、更均匀、更致密，从而可以进一步地降低锂离子电 池的低温直流内阻，提升锂离子电池的循环性能、降低循环过程中直流内阻的增长率，在整体上有效提高锂离子电池的稳定性与安全性。
在本申请的一种实施例中，上述n为1至3中的任意一个整数，优选R1、R2、R3各自独立的地选自C1～C4的取代或非取代的烷基、C1～C4的取代或非取代的烷氧基、C2～C4的取代或非取代的炔基、取代或非取代的苯基、(R4)3SiO-中的任意一种或多种，R4选自C1～C4的取代或非取代的烷基中的任意一种；优选R1、R2、R3各自独立的地选自甲基、乙基、甲氧基、乙氧基、乙炔基、苯基、(CH3)3SiO-、(CH3CH2)3SiO-中的任意一种或多种，优选氰硅烷类化合物选自 中的任意一种或多种。
上述种类的氰硅烷类化合物形成的SEI膜和CEI膜更均匀、更致密。
为了进一步地提高七甲基二硅氮烷与氰硅烷类化合物的作用效果，优选上述七甲基二硅氮烷的质量为电解液总质量的0.1～5wt％，优选为0.5～3wt％，氰硅烷类化合物的质量为电解液总质量的0.1～5wt％，优选为0.5～3wt％。优选上述七甲基二硅氮烷和氰硅烷类化合物的质量比为1:4～2:1，更有利于发挥七甲基二硅氮烷与氰硅烷类化合物的协同增效作用。
在本申请的一种实施例中，优选上述有机溶剂选自碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、乙酸乙酯、γ-丁内酯、丙酸丙酯、丙酸乙酯、1,3-二氧甲烷、二甘醇二甲醚中的任意一种或多种，优选有机溶剂为碳酸甲乙酯、碳酸乙烯酯和碳酸二乙酯的组合，优选碳酸甲乙酯、碳酸乙烯酯和碳酸二乙酯的体积比为5～8:3～5:2～4。
上述种类的有机溶剂可以更好地规避水对电解液的破坏，同时有利于促进电解液中的各组分更充分的进行溶解，从而提高各组分之间的协同性，得到电学性能优良的电解液。
为增强锂盐添加剂与锂盐以及添加剂之间的配合作用，从而提高电解液的综合性能，优选上述电解液还包括锂盐添加剂，优选锂盐添加剂的浓度为0.1～5wt％，优选锂盐添加剂选自六氟砷酸锂、高氯酸锂、四氟硼酸锂、甲基磺酸锂、三氟甲基磺酸锂、双三氟甲基磺酰亚胺锂、双草酸硼酸酯锂中的任意一种或多种，进一步地，优选锂盐添加剂为四氟硼酸锂和/或双三氟磺酰亚胺锂盐。
为进一步地改善电解液，得到综合性能更优良的锂离子电池，优选上述电解液还包括功能添加剂，优选功能添加剂为电解液总质量的0.1～5wt％，进一步地，优选功能添加剂选自循环添加剂、低温添加剂、高温添加剂、阻燃添加剂、防过充添加剂中的任意一种或多种，更进一步地，优选功能添加剂选自碳酸亚乙烯酯、氟代碳酸乙烯酯、硫酸乙烯酯、三(三甲基硅烷)磷酸酯、1,3-丙烷磺内酯、甲烷二磺酸亚甲酯、1,3,6-己烷三腈、三(五氟苯基)硼烷、二氟磷酸锂、3-己基噻吩、六氟环三磷腈、三(六氟异丙基)磷酸酯中的任意一种或多种。
优选上述电解液包括碳酸甲乙酯、碳酸乙烯酯和碳酸二乙酯、LiPF6、碳酸亚乙烯酯、七甲基二硅氮烷和其中，七甲基二硅氮烷为电解液的2wt％，为电解液的1wt％；或七甲 基二硅氮烷为电解液的1wt％，为电解液的2wt％；或七甲基二硅氮烷为电解液的0.6wt％，为电解液的2.4wt％；或氰硅烷类化合物为且七甲基二硅氮烷为电解液的2wt％，为电解液的1wt％，更有利于得到综合性能优良 的锂离子电池。进一步地，优选其中的碳酸甲乙酯、碳酸乙烯酯和碳酸二乙酯的质量比为5:3:2，LiPF6的浓度为1mol/L，碳酸亚乙烯酯为电解液的1wt％。
在本申请的另一种典型的实施方式中，提供了一种锂离子电池，包括正极片、负极片以及电解液，该电解液为前述的电解液。
采用上述电解液的锂离子电池具有较低的阻抗，可以明显降低锂离子电池的低温直流内阻，提升锂离子电池的循环性能、降低循环过程中直流内阻的增长率，在整体上有效提高锂离子电池的稳定性与安全性。
为提高电解液与正极片的配合作用，优选上述正极片包括正极活性物质，优选正极活性物质选自钴酸锂、锰酸锂、镍锰酸锂、镍钴锰酸锂、富锂锰酸锂中的任意一种或多种，优选负极片包括负极活性物质，优选负极活性物质选自天然石墨、人造石墨、硅、钛酸锂中的任意一种或多种。
以下将结合具体实施例和对比例，说明本申请的有益技术效果。
实施例1
电解液的制备：将碳酸乙烯酯(EC)、碳酸二乙酯(DEC)和碳酸甲乙酯(EMC)按质量比为5:3:2进行混合，混合后加入1mol的六氟磷酸锂(LiPF6)的电解液(100g)、0.5wt％的七甲基二硅氮烷(以电解液总质量计)，0.5wt％的氰硅烷类化合物2(以电解液总质量计)，再加入1wt％的碳酸亚乙烯酯(以电解液总质量计)，浓度为1wt％的四氟硼酸锂。
正极片的制备：将镍钴锰酸锂三元材料LiNi0.7Co0.1Mn0.2O2、导电剂Super P、粘接剂PVDF和碳纳米管(CNT)按质量比97.5:0.5:1:1混合均匀制成一定粘度的锂离子电池正极浆料，涂布在集流体用铝箔上，其涂布量为360g/m2，在85℃下烘干后进行冷压；然后进行分条，切片，然后在真空85℃烘4h，制成满足要求的锂离子电池正极片。
负极片的制备：将人造石墨与导电剂Super P、增稠剂CMC、粘接剂SBR(丁苯橡胶乳液)按质量比95:1.5:1.0:2.5的比例制成浆料，混合均匀，用混制的浆料涂布在铜箔的两面后，烘干、辊压后得到负极片，然后在真空85℃烘4h制成满足要求的锂离子电池负极片。
锂离子电池的制备：将根据上述工艺制备的正极片、负极片和隔膜(聚乙烯膜涂陶瓷隔膜)经叠片工艺制作成厚度为0.5mm，宽度为8mm，长度为10的锂离子电池，容量为3Ah，在85℃下真空烘烤48小时，注入上述电解液，经封装、搁置、化成、老化、二次封装和分容等工序完成3Ah软包锂离子电池的制作。
实施例2至9、对比例1、对比例2改变电解液中具体物质的配比和种类，并参考实施例的1制备方法得到锂离子电池，电解液配方如下表1所示。
表1
实施例10
实施例10与实施例4的区别在于，
氰硅烷类化合物为氰硅烷类化合物1，最终得到3Ah软包锂离子电池。
实施例11
实施例11与实施例4的区别在于，
氰硅烷类化合物为氰硅烷类化合物3，最终得到3Ah软包锂离子电池。
实施例12
实施例12与实施例4的区别在于，
氰硅烷类化合物为氰硅烷类化合物4，最终得到3Ah软包锂离子电池。
实施例13
实施例13与实施例4的区别在于，溶剂为EC:EMC:DMC＝5:3:2，最终得到3Ah软包锂离子电池。
实施例14
实施例14与实施例4的区别在于，锂盐添加剂为甲基磺酸锂，最终得到3Ah软包锂离子电池。
实施例15
实施例15与实施例4的区别在于，浓度为1wt％的双三氟磺酰亚胺锂盐作为常规锂盐添加剂，最终得到3Ah软包锂离子电池。

分别将实施例1～15和对比例1、对比例2制成的3Ah软包锂离子电池按照1C/1C充放电电流进行循环，测试电压范围3.0～4.5V，电芯的首次容量和电芯初始内阻如表2所示。
分别对上述实施例1～15和对比例1、对比例2组装的3Ah软包锂离子电池进行高电压高温性能检测，具体检测方法如下：
高电压高温循环实验：取上述3Ah软包锂离子电池，以0.5C充电至4.5V限制电压后改为恒压充电，至充电电流≤截止电流，静置30min，然后0.5C放电至截止电压2.8V，静置30min，按上述工序进行充放电实验，并进行低温DCR、高温循环及高温搁置性能测试，并在循环过程中测试其直流内阻DCR。计算电池电芯高电压下的低温DCR及容量保持率，结果如表2所示。
表2
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：
一部分七甲基二硅氮烷能够与HF结合形成稳定的胺盐类化合物，有效去除HF，同时剩余的七甲基二硅氮烷在正极表面优先于溶剂被氧化，形成CEI膜，从而改善了高电压下产气与过渡金属溶出的问题，进而提高了锂离子电池的高温循环性能。氰硅烷类化合物既优先于溶剂氧化又优先于溶剂还原，可以在正负极表面成SEI膜和CEI膜，含Si-C≡N结构的CEI膜具有更高的电导率，从而更有助于降低阻抗，进而降低锂离子电池的低温直流内阻。此外，胺盐类化合物能够参与到氰硅烷类化合物成SEI膜和CEI膜的过程中并作为SEI膜和CEI膜的一部分，不仅有利于提高SEI膜和CEI膜的导电性，而且七甲基二硅氮烷与氰硅烷类化合 物协同作用得到的SEI膜和CEI膜更薄、更均匀、更致密，从而可以进一步地降低锂离子电池的低温直流内阻，提升锂离子电池的循环性能、降低循环过程中直流内阻的增长率，在整体上有效提高锂离子电池的稳定性与安全性。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (12)

  1. 一种电解液，其特征在于，所述电解液包括有机溶剂、LiPF6以及添加剂，所述添加剂包括七甲基二硅氮烷和氰硅烷类化合物，所述氰硅烷类化合物具有以下结构式：
    其中，n为1至6中的任意一个整数，
    R1、R2、R3各自独立的地选自C1～C10的取代或非取代的烷基、C1～C10的取代或非取代的烷氧基、C2～C10的取代或非取代的炔基、C6～C12的取代或非取代的烷基芳基、(R4)3SiO-中的任意一种或多种，R4选自C1～C10的取代或非取代的烷基中的任意一种。
  2. 根据权利要求1所述的电解液，其特征在于，所述n为1至3中的任意一个整数，所述R1、所述R2、所述R3各自独立的地选自C1～C4的取代或非取代的烷基、C1～C4的取代或非取代的烷氧基、C2～C4的取代或非取代的炔基、取代或非取代的苯基、(R4)3SiO-中的任意一种或多种，所述R4选自C1～C4的取代或非取代的烷基中的任意一种。
  3. 根据权利要求2所述的电解液，其特征在于，所述R1、所述R2、所述R3各自独立的地选自甲基、乙基、甲氧基、乙氧基、乙炔基、苯基、(CH3)3SiO-、(CH3CH2)3SiO-中的任意一种或多种。
  4. 根据权利要求3所述的电解液，其特征在于，所述氰硅烷类化合物选自 中的任意一种或多种。
  5. 根据权利要求1至4中任一项所述的电解液，其特征在于，所述七甲基二硅氮烷的质量为所述电解液总质量的0.1～5wt％，和/或所述氰硅烷类化合物的质量为所述电解液总质量的0.1～5wt％，和/或所述七甲基二硅氮烷和所述氰硅烷类化合物的质量比为1∶4～2∶1。
  6. 根据权利要求1至4中任一项所述的电解液，其特征在于，所述有机溶剂选自碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、乙酸乙酯、γ-丁内酯、丙酸丙酯、丙酸乙酯、1，3-二氧甲烷、二甘醇二甲醚中的任意一种或多种。
  7. 根据权利要求1至4中任一项所述的电解液，其特征在于，所述电解液还包括锂盐添加剂，所述锂盐添加剂的浓度为0.1～5wt％，所述锂盐添加剂选自六氟砷酸锂、高氯酸锂、四氟硼酸锂、甲基磺酸锂、三氟甲基磺酸锂、双三氟甲基磺酰亚胺锂、双草酸硼酸酯锂中的任意一种或多种。
  8. 根据权利要求1至4中任一项所述的电解液，其特征在于，所述LiPF6的浓度为0.5～1.5mol/L。
  9. 根据权利要求1至4中任一项所述的电解液，其特征在于，所述电解液还包括功能添加剂，所述功能添加剂为所述电解液总质量的0.1～5wt％，所述功能添加剂选自循环添加剂、低温添加剂、高温添加剂、阻燃添加剂、防过充添加剂中的任意一种或多种，所述功能添加剂选自碳酸亚乙烯酯、氟代碳酸乙烯酯、硫酸乙烯酯、三(三甲基硅烷)磷酸酯、1，3-丙烷磺内酯、甲烷二磺酸亚甲酯、1，3，6-己烷三腈、三(五氟苯基)硼烷、二氟磷酸锂、3-己基噻吩、六氟环三磷腈、三(六氟异丙基)磷酸酯中的任意一种或多种。
  10. 根据权利要求9所述的电解液，其特征在于，所述电解液包括碳酸甲乙酯、碳酸乙烯酯和碳酸二乙酯、所述LiPF6、碳酸亚乙烯酯、七甲基二硅氮烷和 其中，所述七甲基二硅氮烷为所述电解液的2wt％，所述为所述电解液的1wt％；或所述七甲基二硅氮烷为所述电解液的1wt％，所述为所述电解液的2wt％；或所述七甲基二硅氮烷为所述电解液的0.6wt％，所述为所述电解液的2.4wt％；或所述氰硅烷类化合物为 且所述七甲基二硅氮烷为所述电解液的2wt％，所述为所述电解液的1wt％。
  11. 一种锂离子电池，包括正极片、负极片以及电解液，其特征在于，所述电解液为权利要求1至10中任一项所述的电解液。
  12. 根据权利要求11所述的锂离子电池，其特征在于，所述正极片包括正极活性物质，所述正极活性物质选自钴酸锂、锰酸锂、镍锰酸锂、镍钴锰酸锂、富锂锰酸锂中的任意一种或多种，所述负极片包括负极活性物质，所述负极活性物质选自天然石墨、人造石墨、硅、钛酸锂中的任意一种或多种。
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