WO2025007922A1 - 一种电解液及包括该电解液的电池 - Google Patents

一种电解液及包括该电解液的电池 Download PDF

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WO2025007922A1
WO2025007922A1 PCT/CN2024/103625 CN2024103625W WO2025007922A1 WO 2025007922 A1 WO2025007922 A1 WO 2025007922A1 CN 2024103625 W CN2024103625 W CN 2024103625W WO 2025007922 A1 WO2025007922 A1 WO 2025007922A1
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substituted
negative electrode
unsubstituted
lithium
alkyl
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French (fr)
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刘建奇
何柳青
方嘉琳
李素丽
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Zhuhai Cosmx Battery Co Ltd
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Zhuhai Cosmx Battery Co Ltd
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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
    • 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 belongs to the technical field of electrolytes, and in particular relates to an electrolyte and a battery including the electrolyte.
  • Lithium-ion batteries are considered suitable power sources in mobile electronic devices, electric vehicles, and large-scale energy storage systems due to their high energy density and long cycle life.
  • LIBs Lithium-ion batteries
  • researchers have developed electrode materials with high reversible capacity, including high-voltage cathode materials and low-operating potential anode materials close to 0 V (vs. Li/Li+).
  • Silicon (Si) is considered to be the most promising anode material for next-generation lithium-ion batteries due to its high theoretical capacity.
  • the silicon particles will break and new active surface sites will be generated, which may lead to further irreversible electrolyte decomposition.
  • fluoroethylene carbonate (FEC) is used as an efficient reducible additive introduced into batteries with silicon anode systems. Previous studies have shown that FEC as an additive can effectively change the properties of the SEI layer on the surface of the anode and improve the electrochemical performance of anodes such as graphite and silicon.
  • FEC plays a positive role in improving the electrochemical performance of silicon anode, it decomposes to produce hydrofluoric acid (HF) under high temperature environment, which destroys the positive electrode material and reacts with some organic salts to cause thermal failure of the battery. Therefore, it becomes crucial to seek improved FEC.
  • HF hydrofluoric acid
  • the purpose of this application is to provide an electrolyte and a battery including the electrolyte.
  • This application further improves the high temperature performance of the battery by adding steric hindering groups and/or electron donating groups in FEC molecules to reduce the reaction between fluoroethylene carbonate molecules and LiPF 6 , thereby producing less HF acid, while also overcoming the problem that existing fluoroethylene carbonate may cause thermal failure of the battery in a high temperature environment, and further improving the electrochemical performance and safety performance of lithium-ion batteries in a high temperature environment.
  • the electrolyte is expected to provide lithium-ion batteries with higher electrochemical performance and safety performance for electric vehicles, mobile electronic devices, and large-scale energy storage systems, thereby promoting further development in these fields.
  • An electrolyte comprises an organic solvent, an electrolyte lithium salt and an additive; the additive comprises an R group-modified fluoroethylene carbonate compound; the R group is a steric hindrance group and/or an electron-donating group.
  • the electron donating group refers to a group that can increase the electron cloud density on the ethylene carbonate ring.
  • the steric hindering group refers to a group that causes mutual repulsion of the internal molecular structure of fluoroethylene carbonate in spatial arrangement.
  • the additive is selected from at least one of the compounds shown in Formula I:
  • R is defined as above.
  • the additive is selected from at least one of the compounds represented by Formula 1 to Formula 5:
  • the electrolyte lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ) or a combination of lithium hexafluorophosphate (LiPF 6 ) and at least one of the following electrolyte lithium salts: lithium difluorophosphate (LiPO 2 F 2 ), lithium difluorooxalatoborate (LiDFOB), lithium bis(trifluoromethylsulfonylimide), lithium difluorobis(oxalatophosphate), lithium tetrafluoroborate, lithium bis(oxalatoborate), lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium bis(trifluoromethylsulfonyl)imide, lithium bis(pentafluoroethylsulfonyl)imide, tris(trifluoromethylsulfonyl)methyllithium, and lithium bis(trifluoromethylsulf
  • the organic solvent is selected from carbonates and/or carboxylates
  • the carbonate is selected from at least one of ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethyl methyl carbonate
  • the carboxylate is selected from at least one of propyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, propyl propionate (PP), ethyl propionate (EP), methyl butyrate and ethyl butyrate.
  • the weight of the additive is 5% to 20% of the total weight of the organic solvent in the electrolyte, preferably 10% to 15%, for example 10%, 12%, 13%, 14% or 15%.
  • the electrolyte is used in a battery, preferably a lithium-ion battery.
  • the present application also provides a battery, which includes the above-mentioned electrolyte.
  • the battery further includes a positive electrode sheet containing a positive electrode active material, a negative electrode sheet containing a negative electrode active material, and a separator.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer coated on one side or both sides of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material, a conductive agent and a binder.
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer coated on one side or both sides of the negative electrode current collector, and the negative electrode active material layer includes a negative electrode active material, a conductive agent and a binder.
  • the mass percentage of each component in the positive electrode active material layer is The composition comprises: 80-99.8 wt % of positive electrode active material, 0.1-10 wt % of conductive agent, and 0.1-10 wt % of binder.
  • the mass percentage of each component in the positive electrode active material layer is: 90-99.6wt% of positive electrode active material, 0.2-5wt% of conductive agent, and 0.2-5wt% of binder.
  • the mass percentage of each component in the negative electrode active material layer is: 80-99.8wt% of negative electrode active material, 0.1-10wt% of conductive agent, and 0.1-10wt% of binder.
  • the mass percentage of each component in the negative electrode active material layer is: 90-99.6wt% of negative electrode active material, 0.2-5wt% of conductive agent, and 0.2-5wt% of binder.
  • the conductive agent is selected from at least one of conductive carbon black, acetylene black, Ketjen black, conductive graphite, conductive carbon fiber, carbon nanotubes, metal powder, and carbon fiber.
  • the binder is selected from at least one of sodium carboxymethyl cellulose, styrene-butadiene latex, polytetrafluoroethylene, and polyethylene oxide.
  • the negative electrode active material includes a carbon-based negative electrode material and/or a silicon-based negative electrode material.
  • the silicon-based negative electrode material is selected from at least one of nano-silicon, silicon-oxygen negative electrode material (SiO x (0 ⁇ x ⁇ 2)) or silicon-carbon negative electrode material.
  • the carbon-based negative electrode material is selected from at least one of artificial graphite, natural graphite, mesophase carbon microbeads, hard carbon, and soft carbon.
  • the mass ratio of the silicon-based negative electrode material to the carbon-based negative electrode material in the negative electrode active material is 9:1 to 1:9, for example, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2 or 9:1.
  • the positive electrode active material is selected from one or more of lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate, and ternary materials.
  • the battery satisfies at least one of the following relationships:
  • the mass ratio of the additive in the battery to the mass ratio of the lithium cobalt oxide is in the range of 0.01352-0.1352, and the preferred mass ratio is 0.027;
  • the mass ratio of the additive in the battery to the carbon-based negative electrode material is in the range of 0.025-0.25, and the preferred mass ratio is 0.049;
  • the mass ratio of the additive in the battery to the silicon-based negative electrode material is in the range of 0.02-0.3, and the preferred mass ratio is 0.049;
  • the mass ratio of the additive in the battery to the total mass of the carbon-based negative electrode material and the silicon-based negative electrode material is between 0.034 and 0.34, and the preferred mass ratio is 0.068.
  • the present application provides an electrolyte and a battery including the electrolyte.
  • the electrolyte of the present application can solve the problem of thermal failure of the battery in a high temperature environment and bring at least one of the following beneficial effects to the lithium-ion battery:
  • R-group modified fluoroethylene carbonate compounds help reduce the risk of thermal failure of batteries in high temperature environment. This beneficial effect is particularly important for battery systems operating in harsh environments, such as electric vehicles and large-scale energy storage systems.
  • R-group modified fluoroethylene carbonate compounds help maintain the battery's cycle performance and capacity retention in high temperature environments, thereby improving the overall performance of lithium-ion batteries. This is of great significance for meeting the demand for high-performance batteries, such as mobile electronic devices and electric vehicles.
  • the R-group-modified fluoroethylene carbonate compounds of the present application can be applied to silicon-based negative electrode materials and/or carbon-based negative electrode materials to improve their electrochemical performance. This means that the present application has a wide range of application potentials and can be used in various types of lithium-ion batteries.
  • This application provides important support for the technological progress and market development of electric vehicles, mobile electronic devices and large-scale energy storage systems by providing a lithium-ion battery with higher electrochemical performance and safety performance.
  • the electrolyte of this application not only solves the problem of thermal failure of batteries in high temperature environments, but also makes important contributions to improving the electrochemical performance and safety performance of lithium-ion batteries. This will help meet the growing demand for high-performance batteries and promote the development of related fields.
  • FIG1 is a comparison chart of the cycle capacity retention rates of the batteries of Comparative Example 1 and Examples 1-2.
  • FIG2 is a comparison diagram of the impedance of the batteries of Example 1 and Examples 1-2 after 200 cycles.
  • FIG3 is a comparison chart of the cycle capacity retention rates of the batteries of Comparative Example 1 and Examples 3-5.
  • FIG4 is a comparison diagram of the impedance of the batteries of Example 1 and Examples 3-5 after 200 cycles.
  • the additives represented by Formula 1 to Formula 5 of the present application can be prepared by methods known in the art, or can be prepared by the following method:
  • a fluorinated epoxy compound is prepared by a nucleophilic epoxidation reaction.
  • X in the general formula (1) can be a group having a certain degree of steric hindrance such as tetraphenylmethoxy, sulfonimide, cyclopentadienyl, tert-butyl, or a group having a certain degree of electron donating property such as aldehyde, alcohol, benzyl, amino, methylthio, formamide, formyloxy, pyridyl, acetamido, etc.
  • steric hindrance such as tetraphenylmethoxy, sulfonimide, cyclopentadienyl, tert-butyl
  • electron donating property such as aldehyde, alcohol, benzyl, amino, methylthio, formamide, formyloxy, pyridyl, acetamido, etc.
  • Synthesis route Take a certain amount of the compound represented by general formula (1) and dissolve it in DMF. Use 0.3 mol/L hydrogen peroxide or tert-butyl peroxide alkaline solution catalyst, stir and add it dropwise into the above solution. Maintain the temperature at about 80°C and react for 12 hours to obtain general formula (2).
  • Dissolve the general formula (2) in ethyl acetate add an appropriate amount of AlCl 3 catalyst, introduce carbon dioxide, keep the temperature at 80°C, react for 12 hours, add water to reduce the reaction temperature to room temperature, extract the dissolved The target product is extracted in ethyl acetate, and finally a relatively pure additive is obtained by centrifugation, washing and centrifugation.
  • the lithium ion batteries of Examples 1-10 and Comparative Example 1 were prepared by the following steps:
  • the positive electrode active materials lithium cobalt oxide (LiCoO 2 ), polyvinylidene fluoride (PVDF), and conductive carbon black (super P) are mixed in a mass ratio of 7:1:2, and N-methylpyrrolidone (NMP) is added and stirred under the action of a vacuum mixer until the mixed system becomes a positive electrode active slurry with uniform fluidity; the positive electrode active slurry is evenly coated on both surfaces of a 10 ⁇ m thick aluminum foil; the coated aluminum foil is placed in an oven at 60°C and dried for 24 hours, and then rolled and cut to obtain the desired positive electrode sheet.
  • NMP N-methylpyrrolidone
  • Silicon-carbon negative electrode active material, artificial graphite, conductive carbon black (SP) and styrene-butadiene rubber (SBR) are mixed in a mass ratio of 2:6:1:1, deionized water is added, and a negative electrode active slurry is obtained under the action of a vacuum mixer; the negative electrode active slurry is evenly coated on both surfaces of an 8 ⁇ m thick copper foil; the coated copper foil is dried at room temperature, then transferred to a 60°C oven for drying for 24 hours, and then cold pressed and cut to obtain a negative electrode sheet.
  • EC/DMC were mixed uniformly at a volume ratio of 1:1, and then fully dried lithium hexafluorophosphate (LiPF 6 ) was quickly added thereto to form a concentration of 1 mol/L. After dissolution, additives accounting for Xwt% of the total mass of the organic solvent were added and mixed uniformly to prepare the electrolytes of the examples and comparative examples.
  • the positive electrode sheet of step 1), the negative electrode sheet of step 2) and the separator are stacked in the order of positive electrode sheet, separator and negative electrode sheet, and then wound to obtain a battery cell; the battery cell is placed in an outer packaging aluminum foil, and the electrolyte of step 3) is injected into the outer packaging, and a lithium-ion battery is obtained after vacuum packaging, standing, forming, shaping, sorting and other processes.
  • the injection amount of the electrolyte is 9.5g
  • the addition amount of lithium cobalt oxide is 35.34g
  • the total mass of the carbon-based negative electrode material and the silicon-based negative electrode material is 13.9g
  • the mass ratio of the additive to the mass of the lithium cobalt oxide is shown in Table 1; the mass ratio of the additive to the total mass of the carbon-based negative electrode material and the silicon-based negative electrode material is shown in Table 1.
  • Capacity retention rate 45°C constant temperature for 30min, 1C constant current charging to 4.5V, 4.5V constant voltage charging, 0.3C cut-off; 0.7C discharge to 3V. Perform charging cycles 200 times according to this charging system and calculate the capacity retention rate.
  • Furnace temperature Place the fully charged battery in the test chamber, and heat up the chamber at a rate of 5°C/min. When the temperature inside the chamber reaches 130°C ⁇ 2°C, keep the temperature constant for 60 minutes. If the battery does not fail at 130°C, heat it at a rate of 1°C/min until the temperature of the battery body changes suddenly.
  • the battery was disassembled after 200 cycles, and the electrolyte was obtained and the free HF acid content in the electrolyte was titrated with sodium formate.
  • the preparation process of the lithium-ion battery of this embodiment is substantially the same as that of Embodiment 1, except that the injection amount of the electrolyte is 19.08 g.
  • the preparation process of the lithium-ion battery of this embodiment is substantially the same as that of Embodiment 1, except that the injection amount of the electrolyte is 9.5 g.
  • the preparation process of the lithium ion battery in this embodiment is substantially the same as that in embodiment 1, except that the electrolysis
  • the amount of liquid injected was 9.54 g.
  • the results in Table 1 show that the furnace failure temperatures of Examples 1-2 are higher than those of Comparative Example 1, indicating that after the introduction of sulfonyl imide and cyclopentadienyl into FEC, the furnace failure temperatures are significantly increased, proving that the increase in steric hindrance caused by sulfonyl imide and cyclopentadienyl can effectively enhance the thermal stability of the battery.
  • the furnace failure temperatures of Examples 3-5 are higher than those of Comparative Example 1, indicating that the introduction of electron-donating groups at the ortho position of the F element can effectively reduce the electron density of ortho hydrogen atoms, reduce their acidity, and make it more difficult to escape to form HF acid, thereby improving the furnace temperature performance of the battery.
  • the HF content of Examples 1-2 is significantly lower than that of Comparative Example 1, indicating that the addition of a large sterically hindered group can block the attack of Lewis acid on F and H.
  • the HF content of Examples 3-5 is significantly lower than that of Comparative Example 1, indicating that the addition of an electron-donating group can reduce the possibility of FEC escaping hydrofluoric acid.
  • FIG1 is a comparison chart of the cycle capacity retention rates of the batteries of comparative example 1 and examples 1-2, specifically a cycle capacity curve of the battery at 45° C.
  • the capacity retention rates of examples 1 and 2 are significantly higher than those of comparative example 1, indicating that the introduction of sulfonyl imide and cyclopentadienyl can effectively prevent the capacity decay problem caused by the side reactions brought by FEC.
  • Figure 2 is a fully charged EIS graph of the battery of Example 1 and Example 1-2 after 200 cycles.
  • the membrane impedance and charge transfer impedance of the battery of Example 1-2 are significantly smaller than the impedance of the battery of Comparative Example 1, indicating that the introduction of sulfonimide and cyclopentadienyl can form a SEI film with lower impedance.
  • FIG3 is a comparison chart of the cycle capacity retention rates of the batteries of Example 1 and Examples 3-5, specifically a cycle capacity curve of the battery at 45° C.
  • the capacity retention rates of the batteries of Examples 3-5 are all higher than that of Comparative Example 1, indicating that the introduction of aldehyde, formamide, pyridine and acetamide groups at the adjacent carbon positions can prevent their rapid decomposition through the electron-donating effect, thereby improving the capacity retention rate during the cycle.
  • Figure 4 is a fully charged EIS graph of the battery of Example 1 and Examples 3-5 after 200 cycles.
  • the membrane impedance and charge transfer impedance of the battery of Examples 3-5 are significantly smaller than the impedance of the battery of Comparative Example 1, indicating that the introduction of aldehyde groups, formamide groups, pyridine groups and acetamide groups can form a SEI film with lower impedance and reduce the charge transfer impedance at the same time.

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Abstract

提供一种电解液及包括该电解液的电池。通过在FEC分子中添加位阻基团和/或供电子基团以降低氟代乙烯碳酸酯分子与LiPF 6的反应，从而产生更少的HF酸，进一步提高电池的高温性能，同时还能够克服现有氟代乙烯碳酸酯在高温环境下可能导致电池热失效的问题，并进一步提高锂离子电池的在高温环境下的电化学性能和安全性能。所述电解液有望为电动汽车、移动电子设备和大规模能源存储系统提供更高电化学性能和安全性能的锂离子电池，从而推动这些领域的进一步发展。

Description

一种电解液及包括该电解液的电池
本申请要求于2023年07月04日提交中国专利局、申请号为2023108124444、申请名称为“一种电解液及包括该电解液的电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
本申请要求于2023年08月23日提交中国专利局、申请号为2023110677987、申请名称为“一种电解液及包括该电解液的电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于电解液技术领域，具体涉及一种电解液及包括该电解液的电池。
背景技术
锂离子电池(LIBs)由于其高能量密度和长循环寿命，在移动电子设备、电动汽车和大规模能源存储系统中被认为是合适的电源。为了提高锂离子电池的能量密度，研究人员已经开发了具有高可逆容量的电极材料，包括高电压正极材料和接近0V(相对于Li/Li+)的低工作电位负极材料。
然而，电极-电解质界面的劣化会导致电池循环性能不佳。为了稳定电极-电解质界面，人们提出了诸如电极材料表面涂层和使用电解质添加剂等各种方法。通过使用可还原和可氧化化合物形成人工固态电解质界面(SEI)是改善电极-电解质界面稳定性的最有效策略之一。
硅(Si)被认为是下一代锂离子电池中最有前景的负极材料，因为其具有高理论容量。然而，由于在循环过程中硅负极会发生巨大的体积变化，导致硅颗粒破裂并产生新的活性表面位点，从而可能导致进一步的不可逆电解质分解。为了提高硅负极的电化学性能，氟乙烯碳酸酯(FEC)被用作一种高效的可还原添加剂引入到硅负极体系的电池中。已有研究表明，FEC作为添加剂能有效改变负极表面SEI层的性质，并提高如石墨和硅等负极的电化学性能。
尽管FEC对负极具有有益的影响，但其分解机制仍在研究之中。FEC可 以分解成乙烯基碳酸酯(VC)、氢氟酸(HF)等成分。然而，有研究报道，FEC衍生的SEI膜在某些电池系统中可能对电化学性能产生不良影响。Koeun Kim等人研究了FEC和EC基电解液对LCO-NCM/Si-C电极循环性能的影响，结果表明FEC在60℃下的容量损失要比EC基电解液的损失大。他们认为在高温下，FEC会与六氟磷酸锂发生反应，产生比较多的氢氟酸，导致正极金属离子的溶出，最终导致容量下降。
因此，尽管FEC在改善硅负极电化学性能方面具有积极作用，但由于其在高温环境下会分解产生氢氟酸(HF)，在破坏正极材料的同时与一些有机盐反应导致电池热失效的问题，寻求改进的FEC变得至关重要。
发明内容
为了改善氟代乙烯碳酸酯(FEC)在高温环境下可能导致电池热失效的问题，本申请的目的是提供一种电解液及包括该电解液的电池。本申请通过在FEC分子中添加位阻基团和/或供电子基团以降低氟代乙烯碳酸酯分子与LiPF6的反应，从而产生更少的HF酸，进一步提高电池的高温性能，同时还能够克服现有氟代乙烯碳酸酯在高温环境下可能导致电池热失效的问题，并进一步提高锂离子电池在高温环境下的电化学性能和安全性能。所述电解液有望为电动汽车、移动电子设备和大规模能源存储系统提供更电化学高性能和安全性能的锂离子电池，从而推动这些领域的进一步发展。
本申请目的是通过如下技术方案实现的：
一种电解液，所述电解液包括有机溶剂、电解质锂盐以及添加剂；所述添加剂包括R基团改性的氟代碳酸乙烯酯类化合物；所述R基团为位阻基团和/或供电子基团。
根据本申请的实施方式，所述供电子基团是指可以使得碳酸乙烯酯环上电子云密度升高的基团。
根据本申请的实施方式，所述位阻基团是指在空间排布造成氟代碳酸乙烯酯内部分子结构的相互排斥作用的基团。
根据本申请的实施方式，所述R基团选自-CHO、-OH、-NR1R2、-S(＝O)NR1R2、-S(＝O)2NR1R2、-CONR1R2、-OC(＝O)H、-NHCOH、取代或未取代的-S-C1-12烷基、取代或未取代的-OC(＝O)C1-12烷基、取代或未取代的 -NHCOC1-12烷基、取代或未取代的C1-12烷基、取代或未取代的C6-12芳基、取代或未取代的C2-12烯基、取代或未取代的5-12元杂芳基；若为取代时，取代基为C1-12烷基；R1和R2相同或不同，彼此独立地选自H、C1-12烷基。
根据本申请的实施方式，所述R基团选自-CHO、-OH、-NR1R2、-S(＝O)NR1R2、-S(＝O)2NR1R2、-CONR1R2、-OC(＝O)H、-NHCOH、取代或未取代的-S-C1-6烷基、取代或未取代的-OC(＝O)C1-6烷基、取代或未取代的-NHCOC1-6烷基、取代或未取代的C1-6烷基、取代或未取代的C6-8芳基、取代或未取代的C2-6烯基、取代或未取代的5-8元杂芳基；若为取代时，取代基为C1-6烷基；R1和R2相同或不同，彼此独立地选自H、C1-6烷基。
根据本申请的实施方式，所述R基团选自-CHO、-OH、-NR1R2、-S(＝O)NR1R2、-S(＝O)2NR1R2、-CONR1R2、-OC(＝O)H、-NHCOH、取代或未取代的-S-C1-3烷基、取代或未取代的-OC(＝O)C1-3烷基、取代或未取代的-NHCOC1-3烷基、取代或未取代的C3-6烷基、取代或未取代的C6-7芳基、取代或未取代的C3-6烯基、取代或未取代的5-6元杂芳基；若为取代时，取代基为C1-3烷基；R1和R2相同或不同，彼此独立地选自H、C1-3烷基。
根据本申请的实施方式，所述R基团选自-CHO、-OH、-NH2、-S(＝O)NH2、-S(＝O)2N(CH3)2、-CONH2、-OC(＝O)H、-NHCOH、-S-CH3、-OC(＝O)CH3、-NHCOCH3、叔丁基、苄基、环戊二烯基、吡啶基。
根据本申请的实施方式，所述添加剂选自具有式I所示的化合物中的至少一种：
其中，R的定义如上所述。
根据本申请的实施方式，所述添加剂选自式1～式5所示的化合物中的至少一种：

根据本申请的实施方式，所述电解质锂盐选自六氟磷酸锂(LiPF6)或者选自六氟磷酸锂(LiPF6)与下述电解质锂盐中的至少一种的组合：二氟磷酸锂(LiPO2F2)、二氟草酸硼酸锂(LiDFOB)、双三氟甲基磺酰亚胺锂、二氟双草酸磷酸锂、四氟硼酸锂、双草酸硼酸锂、六氟锑酸锂、六氟砷酸锂、二(三氟甲基磺酰)亚胺锂、二(五氟乙基磺酰)亚胺锂、三(三氟甲基磺酰)甲基锂、二(三氟甲基磺酰)亚胺锂。
根据本申请的实施方式，所述有机溶剂选自碳酸酯和/或羧酸酯，所述碳酸酯选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)和碳酸甲乙酯中的至少一种；所述羧酸酯选自乙酸丙酯、乙酸正丁酯、乙酸异丁酯、乙酸正戊酯、乙酸异戊酯、丙酸丙酯(PP)、丙酸乙酯(EP)、丁酸甲酯和正丁酸乙酯中的至少一种。
根据本申请的实施方式，所述添加剂的重量为所述电解液中有机溶剂总重量的5％～20％，优选为10％～15％，例如为10％、12％、13％、14％或15％。
根据本申请的实施方式，所述电解液用于电池，优选为用于锂离子电池。
本申请还提供一种电池，所述电池包括上述的电解液。
根据本申请的实施方式，所述电池还包括含有正极活性物质的正极片、含有负极活性物质的负极片、隔离膜。
根据本申请的实施方式，所述正极片包括正极集流体和涂覆在正极集流体一侧或两侧表面的正极活性物质层，所述正极活性物质层包括正极活性物质、导电剂和粘结剂。
根据本申请的实施方式，所述负极片包括负极集流体和涂覆在负极集流体一侧或两侧表面的负极活性物质层，所述负极活性物质层包括负极活性物质、导电剂和粘结剂。
根据本申请的实施方式，所述正极活性物质层中各组分的质量百分含量 为：80～99.8wt％的正极活性物质、0.1～10wt％的导电剂、0.1～10wt％的粘结剂。
优选地，所述正极活性物质层中各组分的质量百分含量为：90～99.6wt％的正极活性物质、0.2～5wt％的导电剂、0.2～5wt％的粘结剂。
根据本申请的实施方式，所述负极活性物质层中各组分的质量百分含量为：80～99.8wt％的负极活性物质、0.1～10wt％的导电剂、0.1～10wt％的粘结剂。
优选地，所述负极活性物质层中各组分的质量百分含量为：90～99.6wt％的负极活性物质、0.2～5wt％的导电剂、0.2～5wt％的粘结剂。
根据本申请的实施方式，所述导电剂选自导电炭黑、乙炔黑、科琴黑、导电石墨、导电碳纤维、碳纳米管、金属粉、碳纤维中的至少一种。
根据本申请的实施方式，所述粘结剂选自羧甲基纤维素钠、丁苯胶乳、聚四氟乙烯、聚氧化乙烯中的至少一种。
根据本申请的实施方式，所述负极活性物质包括碳基负极材料和/或硅基负极材料。
根据本申请的实施方式，所述硅基负极材料选自纳米硅、硅氧负极材料(SiOx(0<x<2))或者硅碳负极材料中的至少一种。
根据本申请的实施方式，所述碳基负极材料选自人造石墨、天然石墨、中间相碳微球、硬碳、软碳中的至少一种。
根据本申请的实施方式，所述负极活性物质中硅基负极材料和碳基负极材料的质量比为9:1～1:9，例如为1:9、2:8、3:7、4:6、5:5、6:4、7:3、8:2或9:1。
根据本申请的实施方式，所述正极活性物质选自钴酸锂、锰酸锂、磷酸铁锂、三元材料中的一种或几种。
根据本申请的实施方式，所述电池满足如下关系中的至少一种：
(1)若所述正极活性物质为钴酸锂时，电池中添加剂的质量与钴酸锂的质量比在0.01352-0.1352范围内，优选质量比为0.027；
(2)若所述负极活性物质为碳基负极材料时，电池中添加剂的质量与碳基负极材料的质量比在0.025-0.25范围内，优选质量比为0.049；
(3)若所述负极活性物质为硅基负极材料时，电池中添加剂的质量与硅基负极材料的质量比在0.02-0.3范围内，优选质量比为0.049；
(4)若所述负极活性物质为碳基负极材料和硅基负极材料时，电池中添加剂的质量与碳基负极材料和硅基负极材料总质量的质量比在0.034-0.34之间，优选质量比为0.068。
本申请的有益效果：
本申请提供了一种电解液及包括该电解液的电池。本申请的电解液能够解决高温环境下可能导致电池热失效问题的同时为锂离子电池带来了以下有益效果中的至少一项：
1.提高电池安全性：通过降低FEC在高温环境下产生HF的可能性，R基团改性的氟代碳酸乙烯酯类化合物有助于减少电池在高温环境下热失效的风险。这一有益效果对于在恶劣环境下运行的电池系统尤为重要，如电动汽车和大规模能源存储系统。
2.增强电池性能：R基团改性的氟代碳酸乙烯酯类化合物有助于在高温环境下保持电池的循环性能和容量保持，从而提高锂离子电池的整体性能。这对于满足对高性能电池的需求，如移动电子设备和电动汽车等应用具有重要意义。
3.优化固态电解质界面(SEI)层：本申请的R基团改性的氟代碳酸乙烯酯类化合物有助于形成更稳定的SEI层，从而在高温环境下保持电池的电化学性能和安全性能。这对于提高锂离子电池的循环寿命和耐久性具有积极影响。
4.适用于多种负极材料：本申请的R基团改性的氟代碳酸乙烯酯类化合物可应用于硅基负极材料和/或碳基负极材料，提高它们的电化学性能。这意味着本申请具有广泛的应用潜力，可以用于各种类型的锂离子电池。
5.推动相关领域的发展：本申请通过提供一种具有更高电化学性能和安全性能的锂离子电池，为电动汽车、移动电子设备和大规模能源存储系统的技术进步和市场发展提供了重要支持。
总之，本申请的电解液不仅解决了高温环境下可能导致电池热失效的问题，还为提高锂离子电池的电化学性能和安全性能做出了重要贡献。这将有助于满足不断增长的高性能电池的需求，并推动相关领域的发展。
附图说明
图1是对比例1与实施例1-2的电池的循环容量保持率对比图。
图2是对比例1与实施例1-2的电池循环200圈后的阻抗对比图。
图3是对比例1与实施例3-5的电池的循环容量保持率对比图。
图4是对比例1与实施例3-5的电池循环200圈后的阻抗对比图。
具体实施方式
为了便于理解本申请，下面将对本申请进行更详细的描述。但是，应当理解，本申请可以以许多不同的形式来实现，并不限于本文所描述的实施方式或实施例。相反地，提供这些实施方式或实施例的目的是使对本申请的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施方式或实施例的目的，不是旨在于限制本申请。
本申请的式1～式5所示添加剂可以是采用本领域已知的方法制备得到的，也可以是通过如下方法制备得到的：
两步法制备：
(1)从通式(1)出发利用亲核环氧化反应制备氟代环氧化合物。
通式(1)中的X可以四苯基甲氧基、磺酰亚胺、环戊二烯基、叔丁基等具有一定位阻的基团，也可以是醛基、醇基、苄基、氨基、甲硫基、甲酰胺基、甲酰氧基、吡啶基、乙酸胺基等具有一定给电子性的基团。
合成路线：取一定量的通式(1)所示化合物溶解在DMF中，使用0.3mol/L过氧化氢或过氧化叔丁醇碱性溶液催化剂，搅拌并逐滴加入上述溶液中，温度维持在80℃左右，反应12h获得通式(2)。
(2)通式(2)与二氧化碳反应形成氟代饱和环状碳酸酯。
将通式(2)溶解在乙酸乙酯，加入适量的AlCl3催化剂中，通入二氧化碳，将温度保持在80℃中，反应12h后，加入水将反应温度降至室温，萃取将溶解 在乙酸乙酯的中的目标产物提取，最后通过离心，洗涤，离心获得较纯净的添加剂。
下文将结合具体实施例对本申请做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本申请，而不应被解释为对本申请保护范围的限制。凡基于本申请上述内容所实现的技术均涵盖在本申请旨在保护的范围内。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。
实施例1-10和对比例1的锂离子电池通过以下步骤制备得到：
1)正极片制备
将正极活性材料钴酸锂(LiCoO2)、聚偏氟乙烯(PVDF)、导电炭黑(super P)按照7:1:2的质量比进行混合，加入N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌，直至混合体系成均一流动性的正极活性浆料；将正极活性浆料均匀涂覆于10μm厚的铝箔的两个表面；将涂覆好的铝箔置于60℃的烘箱中干燥24h，然后经过辊压、分切得到所需的正极片。
2)负极片制备
将硅碳负极活性材料、人造石墨、导电炭黑(SP)和丁苯橡胶(SBR)按照质量比2:6:1:1进行混合，加入去离子水，在真空搅拌机作用下获得负极活性浆料；将负极活性浆料均匀涂覆在8μm厚的铜箔的两个表面；将涂覆好的铜箔在室温下晾干，随后转移至60℃烘箱干燥24h，然后经过冷压、分切得到负极片。
3)电解液的制备
在充满氩气的手套箱中(H2O<0.1ppm，O2<0.1ppm)，将EC/DMC按照体积比1:1混合均匀，然后往其中快速加入充分干燥的六氟磷酸锂(LiPF6)形成1mol/L的浓度，溶解后加入占有机溶剂总质量Xwt％的添加剂，混合均匀后制备得到实施例和对比例的电解液。
4)锂离子电池的制备
将步骤1)的正极片、步骤2)的负极片和隔离膜按照正极片、隔离膜和负极片的顺序层叠设置后，再进行卷绕得到电芯；将电芯置于外包装铝箔中，将步骤3)的电解液注入外包装中，经过真空封装、静置、化成、整形、分选等工序，获得锂离子电池。所述锂离子电池中，电解液的注入量为9.5g，钴酸锂的添加量为35.34g，碳基负极材料和硅基负极材料总质量为13.9g，添加剂的质量与钴酸锂的质量比如表1所示；添加剂的质量与碳基负极材料和硅基负极材料总质量的质量比如表1所示。
5)性能测试
容量保持率：45℃恒温30min，1C恒流充电至4.5V，4.5V恒压充电，0.3C截止；0.7C放电至3V。按此充电制度进行充电循环200次，计算容量保持率。
炉温：将满电的电池放入试验箱中，试验箱以5℃/min的升温速率进行升温，当箱内温度达到130℃±2℃后恒温持续60min，若达到130℃未失效，则以1℃/min的速率升温，直到电池本体温度发生突变。
酸度：对循环200圈后的电池进行拆解，获得电解液并用甲酸钠滴定电解液中游离的HF酸含量。
实施例11
本实施例的锂离子电池的制备工艺与实施例1大致相同，不同的是，电解液的注入量为19.08g。
实施例12
本实施例的锂离子电池的制备工艺与实施例1大致相同，不同的是，电解液的注入量为9.5g。
实施例13
本实施例的锂离子电池的制备工艺与实施例1大致相同，不同的是，电解 液的注入量为9.54g。
表1实施例和对比例的电池的性能测试结果
从表1的结果显示，实施例1-2的炉温失效温度要比对比例1的高，说明在FEC中引入磺酰亚胺和环戊二烯基后，炉温失效温度明显提升，证明磺酰亚胺和环戊二烯基引起空间位阻的增大可以有效增强电池的热稳定性。实施例3-5的炉温失效温度要比对比例1的高，说明在F元素的邻位引入供电子基团可以有效降低提高邻位氢原子的电子密度，降低其酸性，使其更难脱出形成HF酸，从而提高电池的炉温性能。
对循环200圈后的电池进行拆解，获得电解液并用甲酸钠滴定电解液中游离的HF酸含量，结果如表1所示，实施例1-2的HF含量明显低于对比例1中HF酸的含量，说明加入空间位阻大的基团可以阻挡路易斯酸对F和H的进攻。实施例3-5的HF含量明显低于对比例1中HF酸的含量，说明加入供电子基团可以降低FEC脱出氢氟酸的可能性。
图1是对比例1与实施例1-2的电池的循环容量保持率对比图，具体是电池在45℃的循环容量曲线图。从图1中可以看出，当电池循环200圈以后，实施例1和实施例2的容量保持率显著高于对比例1，说明磺酰亚胺和环戊二烯基的引入可以有效防止FEC带来的副反应导致的容量衰退问题。
图2是对比例1与实施例1-2的电池循环200圈结束后满电的EIS图。从图2中可以看出，实施例1-2的电池的膜阻抗和传荷阻抗要明显比对比例1的电池的阻抗小，说明磺酰亚胺和环戊二烯基的引入可以形成阻抗更低的SEI膜。
图3是对比例1与实施例3-5的电池的循环容量保持率对比图，具体是电池在45℃的循环容量曲线图。从图3中可以看出，当电池循环200圈以后，实施例3-5的电池的容量保持率均要比对比例1高，说明醛基、甲酰胺基、吡啶基和乙酸胺基在邻碳位置的引入能够通过给电子效应防止其快速分解，提高其循环过程中的容量保持率。
图4是对比例1与实施例3-5的电池循环200圈结束后满电的EIS图。从图4中可以看出，实施例3-5的电池的膜阻抗和传荷阻抗要明显比对比例1的电池的阻抗小，说明醛基、甲酰胺基、吡啶基和乙酸胺基的引入可以形成阻抗更低的SEI膜，同时降低传荷阻抗。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。

Claims (13)

  1. 一种电解液，其中，所述电解液包括有机溶剂、电解质锂盐以及添加剂；所述添加剂包括R基团改性的氟代碳酸乙烯酯类化合物；所述R基团为位阻基团和/或供电子基团。
  2. 根据权利要求1所述的电解液，其中，所述R基团选自-CHO、-OH、-NR1R2、-S(＝O)NR1R2、-S(＝O)2NR1R2、-CONR1R2、-OC(＝O)H、-NHCOH、取代或未取代的-S-C1-12烷基、取代或未取代的-OC(＝O)C1-12烷基、取代或未取代的-NHCOC1-12烷基、取代或未取代的C1-12烷基、取代或未取代的C6-12芳基、取代或未取代的C2-12烯基、取代或未取代的5-12元杂芳基；若为取代时，取代基为C1-12烷基；R1和R2相同或不同，彼此独立地选自H、C1-12烷基。
  3. 根据权利要求2所述的电解液，其中，所述R基团选自-CHO、-OH、-NR1R2、-S(＝O)NR1R2、-S(＝O)2NR1R2、-CONR1R2、-OC(＝O)H、-NHCOH、取代或未取代的-S-C1-6烷基、取代或未取代的-OC(＝O)C1-6烷基、取代或未取代的-NHCOC1-6烷基、取代或未取代的C1-6烷基、取代或未取代的C6-8芳基、取代或未取代的C2-6烯基、取代或未取代的5-8元杂芳基；若为取代时，取代基为C1-6烷基；R1和R2相同或不同，彼此独立地选自H、C1-6烷基。
  4. 根据权利要求3所述的电解液，其中，所述R基团选自-CHO、-OH、-NR1R2、-S(＝O)NR1R2、-S(＝O)2NR1R2、-CONR1R2、-OC(＝O)H、-NHCOH、取代或未取代的-S-C1-3烷基、取代或未取代的-OC(＝O)C1-3烷基、取代或未取代的-NHCOC1-3烷基、取代或未取代的C3-6烷基、取代或未取代的C6-7芳基、取代或未取代的C3-6烯基、取代或未取代的5-6元杂芳基；若为取代时，取代基为C1-3烷基；R1和R2相同或不同，彼此独立地选自H、C1-3烷基。
  5. 根据权利要求1-4任一项所述的电解液，其中，所述R基团选自-CHO、-OH、-NH2、-S(＝O)NH2、-S(＝O)2N(CH3)2、-CONH2、-OC(＝O)H、-NHCOH、-S-CH3、-OC(＝O)CH3、-NHCOCH3、叔丁基、苄基、环戊二烯基、吡啶基。
  6. 根据权利要求1-5任一项所述的电解液，其中，所述添加剂选自具有式I所示的化合物中的至少一种：
    其中，R的定义如权利要求1-5任一项所述。
  7. 根据权利要求1-6任一项所述的电解液，其中，所述添加剂选自式1～式5所示的化合物中的至少一种：

  8. 根据权利要求1-7任一项所述的电解液，其中，所述电解质锂盐选自六氟磷酸锂(LiPF6)或者选自六氟磷酸锂(LiPF6)与下述电解质锂盐中的至少一种的组合：二氟磷酸锂(LiPO2F2)、二氟草酸硼酸锂(LiDFOB)、双三氟甲基磺酰亚胺锂、二氟双草酸磷酸锂、四氟硼酸锂、双草酸硼酸锂、六氟锑酸锂、六氟砷酸锂、二(三氟甲基磺酰)亚胺锂、二(五氟乙基磺酰)亚胺锂、三(三氟甲基磺酰)甲基锂、二(三氟甲基磺酰)亚胺锂。
  9. 根据权利要求1-8任一项所述的电解液，其中，所述添加剂的重量为所述电解液中有机溶剂总重量的5％～20％。
  10. 根据权利要求9所述的电解液，其中，所述添加剂的重量为所述电解液中有机溶剂总重量的10％～15％。
  11. 一种电池，所述电池包括权利要求1-10任一项所述的电解液。
  12. 根据权利要求11所述的电池，其中，所述电池还包括含有正极活性物质的正极片、含有负极活性物质的负极片、隔离膜；
    所述负极活性物质包括碳基负极材料和/或硅基负极材料，所述硅基负极材料选自纳米硅、硅氧负极材料(SiOx(0<x<2))或者硅碳负极材料中的至少一种，所述碳基负极材料选自人造石墨、天然石墨、中间相碳微球、硬碳、软碳中的至少一种；
    所述正极活性物质选自钴酸锂、锰酸锂、磷酸铁锂、三元材料中的一种或几种。
  13. 根据权利要求10或11所述的电池，其中，所述电池满足如下关系中的至少一种：
    (1)若所述正极活性物质为钴酸锂时，电池中添加剂的质量与钴酸锂的质量比在0.01352-0.1352范围内；
    (2)若所述负极活性物质为碳基负极材料时，电池中添加剂的质量与碳基负极材料的质量比在0.025-0.25范围内；
    (3)若所述负极活性物质为硅基负极材料时，电池中添加剂的质量与硅基负极材料的质量比在0.02-0.3范围内；
    (4)若所述负极活性物质为碳基负极材料和硅基负极材料时，电池中添加剂的质量与碳基负极材料和硅基负极材料总质量的质量比在0.034-0.34之间。
PCT/CN2024/103625 2023-07-04 2024-07-04 一种电解液及包括该电解液的电池 Ceased WO2025007922A1 (zh)

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