WO2024040826A1 - 低温型锂离子电池电解液及其制备方法和锂离子电池 - Google Patents

低温型锂离子电池电解液及其制备方法和锂离子电池 Download PDF

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WO2024040826A1
WO2024040826A1 PCT/CN2022/141945 CN2022141945W WO2024040826A1 WO 2024040826 A1 WO2024040826 A1 WO 2024040826A1 CN 2022141945 W CN2022141945 W CN 2022141945W WO 2024040826 A1 WO2024040826 A1 WO 2024040826A1
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lithium
ion battery
low
electrolyte
battery electrolyte
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French (fr)
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方淳
刘世琦
程方圆
邹雨茜
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Hubei Wanrun New Energy Technology Co Ltd
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Priority to EP22956358.0A priority Critical patent/EP4394989A4/en
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Priority to KR1020247010926A priority patent/KR20240046809A/ko
Priority to JP2024521067A priority patent/JP7777225B2/ja
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • 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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • 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 low-temperature lithium-ion battery electrolytes and preparation methods thereof and lithium-ion batteries.
  • lithium-ion batteries With the increasing application scope of lithium-ion batteries (LIBs), especially in the fields of electric vehicles, aerospace and military industries, there are higher requirements for the low-temperature charge and discharge performance of batteries.
  • carbonate-based commercial electrolytes are easy to solidify at low temperatures and have high impedance, which limits the further application of lithium-ion batteries in the field of low-temperature electric vehicles. Therefore, the optimization of electrolyte has become one of the research hotspots for improving the low-temperature performance of lithium-ion batteries.
  • cathode materials lithium iron phosphate is widely used in the field of electric vehicles due to its high safety performance and low cost. However, due to its low conductivity, its low-temperature performance needs to be improved. Therefore, it has certain market prospects to conduct research on modifying lithium iron phosphate as a lithium ion positive electrode and its adaptability to low-temperature electrolytes.
  • Patent 202111011044.0 discloses a low-temperature lithium-ion battery electrolyte.
  • a low-temperature lithium-ion battery electrolyte For high-nickel ternary positive electrodes, it specifically discloses that it is composed of lithium difluoroxalate borate LiDFOB and a mixed solvent.
  • the concentration of lithium difluoroxalate borate LiDFOB is 0.8 to 1.5 mol/L.
  • the mixed solvent is linear carbonate, cyclic carbonate and ⁇ -butyrolactone.
  • This technical solution reduces the melting point of the electrolyte by adding the low-melting organic solvent ⁇ -butyrolactone to the basic solvent carbonate, thereby improving the low-temperature performance of the lithium-ion battery and improving the battery performance of the lithium-ion battery under low-temperature conditions. Chemical properties, but there is still room for improvement in the low-temperature resistance of lithium ions.
  • the first object of the present invention is to provide a low-temperature lithium-ion battery electrolyte that can effectively improve the discharge specific capacity and capacity retention rate of lithium-ion batteries under low-temperature conditions.
  • the second object of the present invention is to provide a method for preparing the above-mentioned low-temperature lithium-ion battery electrolyte, which method has simple steps, strong operability, and is convenient for practical promotion and large-scale application.
  • the third object of the present invention is to provide a lithium-ion battery, including the above-mentioned low-temperature lithium-ion battery electrolyte, which has excellent electrochemical performance under low-temperature conditions.
  • the invention provides a low-temperature lithium-ion battery electrolyte, including electrolyte salt and organic solvent;
  • the organic solvents include fluorocarboxylic acid esters, fluorocarbonic acid esters and 1,3-dioxacyclo.
  • the fluorocarboxylic acid ester includes diethyl fluoromalonate.
  • the fluorocarbonate includes fluoroethylene carbonate.
  • the electrolyte salt includes lithium bis(trifluoromethanesulfonyl)imide and/or lithium trifluoromethanesulfonyl imide.
  • the electrolyte salt includes lithium bis(trifluoromethanesulfonyl)imide.
  • the volume percentage of fluorocarboxylic acid ester is >40%.
  • the volume percentage of fluorocarboxylate in the low-temperature lithium-ion battery electrolyte is 50% to 70%.
  • volume ratio of the fluorocarboxylate, the fluorocarbonate and the 1,3-dioxane is 90-40:5-50:5-30.
  • the volume ratio of the fluorocarboxylate, the fluorocarbonate and the 1,3-dioxane is 55-65:15-25:15-25.
  • the concentration of the electrolyte salt is 1.0-5.0 mol/L.
  • the concentration of the electrolyte salt in the low-temperature lithium-ion battery electrolyte is 1.5 to 2.5 mol/L.
  • the present invention also provides a method for preparing the low-temperature lithium-ion battery electrolyte as described above.
  • the low-temperature lithium-ion battery electrolyte is obtained by mixing the organic solvent and the electrolyte salt.
  • the present invention also provides a lithium-ion battery, including the low-temperature lithium-ion battery electrolyte as described above.
  • the cathode material of the lithium-ion battery is lithium iron phosphate.
  • the low-temperature lithium-ion battery electrolyte of the present invention uses fluorocarboxylic acid ester as the main solvent, fluorocarbonate and 1,3-dioxacyclo as the eutectic agent, and is combined with bis(trifluoromethanesulfonyl) )Lithium imide; can significantly improve the conductivity of low-temperature lithium ions, which is beneficial to the capacity of lithium-ion batteries at low temperatures.
  • the low-temperature lithium ion battery electrolyte of the present invention can form a stable inorganic component interface phase at the positive electrode by using lithium bis(trifluoromethanesulfonyl)imide as the electrolyte salt; fluorinated ethylene carbonate can form a stable inorganic component interface phase at the negative electrode.
  • the formation of a stable inorganic component interface phase can significantly improve the cycle stability of the battery at low temperatures (-30°C).
  • the low-temperature lithium-ion battery electrolyte of the present invention can significantly improve the discharge specific capacity and capacity retention rate of lithium iron phosphate lithium-ion batteries under low-temperature conditions.
  • the LiFePO 4 /Li battery assembled using it as the electrolyte can - Under a low temperature environment of 30°C, the discharge specific capacity at 0.2C reaches 90mAh/g.
  • Figure 1 is a comparison chart of the discharge specific capacity of batteries prepared by the present invention using the low-temperature lithium-ion battery electrolyte of Example 7 and the lithium-ion battery electrolyte of Comparative Example 5 at a charge and discharge voltage of 2.7-4.2V and -30°C. .
  • a low-temperature lithium-ion battery electrolyte including an electrolyte salt and an organic solvent;
  • Organic solvents include fluorocarboxylic acid esters, fluorocarbonic acid esters, and 1,3-dioxanol.
  • the low-temperature lithium ion battery electrolyte of the present invention can effectively improve the low-temperature lithium ion conductivity by using fluorocarboxylate as the main solvent, fluorocarbonate and 1,3-dioxacyclo as co-solvents, which is beneficial to Capacity performance of lithium-ion batteries at low temperatures.
  • Fluorocarboxylate has a lower melting point, and fluorination can further reduce the freezing point of the carboxylate. Fluorocarboxylate has a lower melting point, which lowers the freezing point of the electrolyte itself; therefore, it can improve the performance of the electrolyte at low temperatures. ionic conductivity, thereby improving the low-temperature performance of the battery; and the introduction of fluorine element is conducive to improving the performance of the interface.
  • fluorocarboxylic acid esters have poor film-forming properties
  • fluorocarbonate is used as a eutectic agent and mixed with fluorocarboxylic acid esters to adjust the film-forming properties of the electrolyte.
  • the impedance of lithium-ion batteries is significantly reduced after the introduction of 1,3-dioxopenta (DOL) with low freezing point and low viscosity. Thereby improving the discharge specific capacity and capacity retention rate of lithium-ion batteries, especially lithium iron phosphate lithium-ion batteries under low temperature conditions.
  • DOL 1,3-dioxopenta
  • the fluorocarboxylate includes diethyl fluoromalonate.
  • Diethyl Fluoromalonate (DEFM) is used as the solvent of the electrolyte.
  • the binding energy between diethyl fluoromalonate and lithium ions is low, which is conducive to the deintercalation process of lithium ions at low temperatures.
  • the fluorocarbonate includes fluoroethylene carbonate (4-Fluoro-1,3-dioxolan-2-one, FEC).
  • the electrolyte salt includes lithium bis(trifluoromethanesulfonyl)imide and/or lithium trifluoromethanesulfonimide; preferably, the electrolyte salt includes bis(trifluoromethanesulfonyl)imide.
  • Lithium amine LiTFSI
  • Lithium bis(trifluoromethanesulfonyl)imide can be dissolved in a solvent at a higher concentration, and it has a higher HOMO energy level and a lower LUMO energy level, and can be charged at the positive electrode/negative electrode during the first charging process. Decomposition occurs at the electrolyte interface to form an interface film with a high content of inorganic components, which can significantly improve the cycle stability of the battery at low temperatures (-30°C).
  • the appropriate concentration of lithium bis(trifluoromethanesulfonyl)imide has high ionic conductivity and can provide a stable fluorine-containing interface film.
  • HOMO is the highest occupied orbit of a molecule.
  • the electrolyte the HOMO energy level can be used to determine the decomposition sequence of each component during the charging process.
  • the LUMO energy level is the lowest unoccupied orbital of the molecule. The lower the LUMO energy level, the easier it is for the substance to obtain electrons.
  • the LUMO energy level can be used to determine the decomposition sequence of each component during the discharge process.
  • the LUMO energy level The lower the component, the easier it is to reduce and form the negative electrolyte interface film. This prevents direct contact between the electrode and the electrolyte during subsequent charging and discharging, and inhibits interface side reactions.
  • the organic solvent of the low-temperature lithium ion battery electrolyte of the present invention is fluorocarboxylate, fluoroethylene carbonate and 1,3-dioxacyclo.
  • Fluorocarboxylate and fluorocarbonate have lower melting points, which can lower the melting point of the electrolyte and increase the ionic conductivity of the electrolyte at low temperatures.
  • LiFSI has a higher HOMO energy level and can preferentially decompose into a film on the surface of the cathode of lithium-ion batteries to improve the stability of the cathode-electrolyte interface.
  • Fluorinated ethylene carbonate has a lower LUMO energy level and can preferentially decompose into a film on the surface of the lithium ion negative electrode to improve the stability of the negative electrode-electrolyte interface. Therefore, the electrolyte of the present invention can improve the specific discharge capacity and capacity retention rate of lithium-ion batteries at low temperatures (-30°C).
  • the low-temperature lithium-ion battery electrolyte includes lithium bis(trifluoromethanesulfonyl)imide, diethyl fluoromalonate, fluoroethylene carbonate, and 1,3-dioxy Five rings.
  • the volume percentage of fluorocarboxylate in the low-temperature lithium-ion battery electrolyte is >40%.
  • the volume percentage of fluorocarboxylate in the low-temperature lithium-ion battery electrolyte is 50% to 70%; typical but not limiting, for example, in the low-temperature lithium-ion battery electrolyte,
  • the volume percentages of fluorocarboxylic acid esters are 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63% , 64%, 65%, 66%, 67%, 68%, 69% or 70%, etc.; preferably, the volume percentage of fluorocarboxylate in the low-temperature lithium-ion battery electrolyte is 55% to 65% ; More preferably, it is 58% to 62%.
  • the volume ratio of fluorocarboxylate, fluorocarbonate and 1,3-dioxane is 90 ⁇ 40:10 ⁇ 50:1 ⁇ 30; typical but not limiting , for example, the volume ratio of fluorocarboxylate, fluorocarbonate and 1,3-dioxane is 80:10:10, 70:15:15, 60:20:20, 50:25:25, 40:30:30, 80:10:5, 70:30:10, 60:10:5, 50:10:20, etc.; preferably, fluorocarboxylates, fluorocarbonates and 1,3-
  • the volume ratio of dioxacyclo is 55-65:15-25:15-25; more preferably, the volume ratio of fluorocarbonate and 1,3-dioxacyclo is 1:1.
  • the concentration of the electrolyte salt in the low-temperature lithium-ion battery electrolyte, is 1.0 to 5.0 mol/L; typically but not limiting, for example, in the low-temperature lithium-ion battery electrolyte, the electrolyte salt concentration The concentration is 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 3.5mol/L, 4.0mol/L, 4.5mol/L or 5.0mol/L, etc.; Preferably, the concentration of the electrolyte salt in the low-temperature lithium-ion battery electrolyte is 1.5 to 2.5 mol/L.
  • a method for preparing the above-mentioned low-temperature lithium-ion battery electrolyte is also provided.
  • the low-temperature lithium-ion battery electrolyte is obtained after mixing the organic solvent and the electrolyte salt.
  • the organic solvent is an anhydrous organic solvent
  • the preparation method of the anhydrous organic solvent includes: adding the organic solvent to a water-removing agent and leaving it standing for 2 to 4 days; preferably, the water-removing agent It is a molecular sieve, model number is and any type.
  • a lithium-ion battery including the above-mentioned low-temperature lithium-ion battery electrolyte.
  • the cathode material of the lithium-ion battery is lithium iron phosphate.
  • a lithium-ion battery includes: a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte;
  • the positive electrode sheet is mainly made of positive electrode active material, conductive agent, binder and dispersant.
  • the positive electrode active material is LiFePO 4 ;
  • the negative electrode piece is a lithium piece
  • the electrolyte is the above-mentioned low-temperature lithium-ion battery electrolyte.
  • the conductive agent includes conductive carbon black.
  • the binder includes polyvinylidene fluoride.
  • the conductive agent includes N-methyl-2-pyrrolidone.
  • the barrier membrane includes a polypropylene microporous membrane.
  • the LiFePO 4 /Li battery assembled using the low-temperature lithium-ion battery electrolyte of the present invention can have a 0.2C discharge specific capacity of 90mAh/g in a low temperature environment of -30°C, and can maintain a stable cycle.
  • the preparation method of the low-temperature lithium-ion battery electrolyte in each embodiment is the same, except that the volume ratio of the solvents DEFM, FEC and DOL used in the low-temperature lithium-ion battery electrolyte is different from that of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • the concentration of LiTFSI is different.
  • the volume ratio of the solvent and the concentration of LiTFSI in each embodiment are shown in Table 1.
  • Example 2 1M 80:10:10 Example 3 1M 60:20:20 Example 4 1M 50:25:25 Example 5 2M 90:5:5 Example 6 2M 80:10:10 Example 7 2M 60:20:20 Example 8 2M 50:25:25 Example 9 3M 90:5:5 Example 10 3M 80:10:10 Example 11 3M 60:20:20 Example 12 3M 50:25:25
  • the preparation method of low-temperature lithium-ion battery electrolyte includes the following steps:
  • the preparation methods of the lithium-ion battery electrolytes in each comparative example are the same. Only the type, volume ratio, type and concentration of the organic solvent used in the lithium-ion battery electrolyte are different, as shown in Table 2.
  • EC is ethylene carbonate
  • DEC diethyl carbonate
  • the preparation method of lithium-ion battery electrolyte includes the following steps:
  • the molecular sieve water removal agent model is Alfa L05335-250g.
  • the low-temperature lithium-ion battery electrolytes of Examples 1 to 12 and the lithium-ion battery electrolytes of Comparative Examples 1 to 5 were respectively used together with the lithium iron phosphate positive electrode and the lithium negative electrode to assemble a battery and conduct electrochemical tests.
  • the test method is as follows:
  • the positive active material is LiFePO 4
  • the conductive agent is conductive carbon black (Super P, Timcal Ltd.)
  • the binder is polyvinylidene fluoride (PVDF, HSV 900, Arkema)
  • the active material on the electrode surface is controlled at 2 ⁇ 4 mg/cm 2 .
  • a button battery was made in a glove box filled with argon, with the negative electrode being a lithium sheet and the polypropylene microporous membrane being the separator. The electrolyte was changed to obtain different batteries for testing.
  • the electrochemical performance test uses Xinwei electrochemical tester. After activating the battery twice at room temperature at 0.2C, place it at -30°C for 2 hours, and then perform low-temperature cycling at a current density of 0.2C. The charge and discharge voltage range is 2.7 ⁇ 4.2V. The test results are as shown in the table 3 shown.
  • the comparison chart of the discharge specific capacity of the battery using the lithium ion battery electrolyte of Example 1 and the lithium ion battery electrolyte of Comparative Example 5 at a charge and discharge voltage of 2.7-4.2V and -30°C is shown in Figure 1, where, The lithium-ion battery electrolyte of Comparative Example 5 is labeled Baseline, and the low-temperature lithium-ion battery electrolyte of Example 7 is labeled LT-Electrolyte.
  • Example 10 Discharge specific capacity (mAh/g) after 50 cycles at -30°C
  • Example 1 61
  • Example 2 69
  • Example 3 77
  • Example 4 73
  • Example 5 81
  • Example 6 85
  • Example 7 90
  • Example 8 81
  • Example 9 71
  • Example 10 69
  • Example 11 78
  • Example 12 72 Comparative example 1 39 Comparative example 2 42 Comparative example 3 34 Comparative example 4 25 Comparative example 5 20
  • the solvent of the electrolyte is a mixed solvent of diethyl fluoromalonate (DEFM), fluorocarbonate (FEC) and 1,3-dioxacyclo (DOL), and the lithium salt is Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) has the highest specific discharge capacity.
  • DEFM diethyl fluoromalonate
  • FEC fluorocarbonate
  • DOL 1,3-dioxacyclo
  • LiTFSI Lithium bis(trifluoromethanesulfonyl)imide
  • Example 7 has the best effect.
  • the specific discharge capacity of LiFePO 4 /Li battery is 90mAh/g, and the capacity retention rate after 50 cycles is close to 100%. Much higher than other comparison ratios.
  • DEFM diethyl fluoromalonate
  • FEC fluoroethylene carbonate
  • DOL 1,3-dioxane

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Abstract

本发明涉及锂离子电池技术领域，尤其是涉及低温型锂离子电池电解液及其制备方法和锂离子电池。本发明的低温型锂离子电池电解液，包括电解质盐和有机溶剂；所述有机溶剂包括氟代羧酸酯、氟代碳酸酯和1,3-二氧五环。氟代羧酸酯凝固点较低，适合作为低温电解液溶剂，氟代碳酸酯作为共熔剂和氟代羧酸酯进行混合调节电解液的低温性能和成膜性，引入低凝固点和低粘度的1,3-二氧五环后电池阻抗明显减小。本发明的低温型锂离子电池电解液可有效改善低温锂离子电导率，有利于锂离子电池在低温下容量的发挥，尤其可提高磷酸铁锂锂离子电池在低温条件下的放电比容量和容量保持率。

Description

低温型锂离子电池电解液及其制备方法和锂离子电池
本申请要求2022年8月24日提交的，申请号为202211016568.3，发明名称为“低温型锂离子电池电解液及其制备方法和锂离子电池”的中国发明专利申请的优先权，该申请的公开内容以引用的方式并入本文。
技术领域
本发明涉及锂离子电池技术领域，尤其是涉及低温型锂离子电池电解液及其制备方法和锂离子电池。
背景技术
随着锂离子电池(LIBs)应用范围的日渐扩大，特别是在电动车、航空航天和军工领域的应用，对电池的低温充放电性能有了更高的要求。然而，提高锂离子电池在低温下的能量存储性能和循环稳定性还存在很多技术性难题。其中，碳酸酯基商用电解液在低温下易凝固、阻抗高限制了锂离子电池在低温电动汽车领域的进一步应用。因此电解液的优化成为改善锂离子电池低温性能的研究热点之一。在众多正极材料当中，磷酸铁锂由于具有较高的安全性能和低廉的成本被广泛应用在电动汽车领域，但由于具有较低的电导率，低温性能有待改善。因此，针对磷酸铁锂作为锂离子正极，对其适配性低温电解液进行改性研究，具有一定的市场前景。
专利202111011044.0公开了低温型锂离子电池电解液，针对高镍三元正极，具体公开了由二氟草酸硼酸锂LiDFOB和混合溶剂组成，二氟草酸 硼酸锂LiDFOB的浓度为0.8～1.5mol/L，所述混合溶剂为线性碳酸酯、环状碳酸酯以及γ-丁内酯。该技术方案通过在基本溶剂碳酸酯中加入低熔点的有机溶剂γ-丁内酯来降低电解液的熔点，使锂离子电池的低温性能得到了改善，提高了锂离子电池在低温条件下的电化学性能，但锂离子的耐低温能力还存在改善空间。
有鉴于此，特提出本发明。
发明内容
本发明的第一目的在于提供一种低温型锂离子电池电解液，可有效改善锂离子电池在低温条件下的放电比容量和容量保持率。
本发明的第二目的在于提供一种上述低温型锂离子电池电解液的制备方法，该方法步骤简单，可操作性强，便于实际推广和大规模应用。
本发明的第三目的在于提供一种锂离子电池，包括上述低温型锂离子电池电解液，其在低温条件下具有优异的电化学性能。
为了实现本发明的上述目的，特采用以下技术方案：
本发明提供了一种低温型锂离子电池电解液，包括电解质盐和有机溶剂；
所述有机溶剂包括氟代羧酸酯、氟代碳酸酯和1,3-二氧五环。
进一步地，所述氟代羧酸酯包括氟代丙二酸二乙酯。
进一步地，所述氟代碳酸酯包括氟代碳酸乙烯酯。
进一步地，所述电解质盐包括双(三氟甲烷磺酰)亚胺锂和/或三氟甲烷磺酰亚胺锂。
优选地，所述电解质盐包括双(三氟甲烷磺酰)亚胺锂。
进一步地，所述低温型锂离子电池电解液中，氟代羧酸酯的体积百分 数＞40％。
优选地，所述低温型锂离子电池电解液中，氟代羧酸酯的体积百分数为50％～70％。
进一步地，所述氟代羧酸酯、所述氟代碳酸酯和所述1,3-二氧五环的体积比为90～40：5～50：5～30。
优选地，所述氟代羧酸酯、所述氟代碳酸酯和所述1,3-二氧五环的体积比为55～65：15～25：15～25。
进一步地，所述低温型锂离子电池电解液中，电解质盐的浓度为1.0～5.0mol/L。
优选地，所述低温型锂离子电池电解液中，电解质盐的浓度为1.5～2.5mol/L。
本发明还提供了如上所述的低温型锂离子电池电解液的制备方法，有机溶剂和电解质盐混匀后得到所述低温型锂离子电池电解液。
本发明还提供了一种锂离子电池，包括如上所述的低温型锂离子电池电解液。
进一步地，所述锂离子电池的正极材料为磷酸铁锂。
与现有技术相比，本发明的有益效果为：
(1)本发明的低温型锂离子电池电解液，以氟代羧酸酯作为主溶剂，氟代碳酸酯及1，3-二氧五环作为共熔剂，并搭配双(三氟甲烷磺酰)亚胺锂；可显著改善低温锂离子电导率，有利于锂离子电池在低温下容量的发挥。
(2)本发明的低温型锂离子电池电解液通过采用双(三氟甲烷磺酰)亚胺锂作为电解质盐，可以在正极形成稳定的无机组分界面相；氟代碳酸乙烯酯可以在负极形成稳定的无机组分界面相，可显著提升电池在低温(-30℃)下的循环稳定性。
(3)本发明的低温型锂离子电池电解液可显著提高磷酸铁锂锂离子电池在低温条件下的放电比容量及容量保持率，采用其作为电解液组装的LiFePO 4/Li电池能够在-30℃的低温环境下，0.2C放电比容量达到90mAh/g。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明分别采用实施例7的低温型锂离子电池电解液与对比例5的锂离子电池电解液制备的电池在2.7～4.2V充放电电压、-30℃下放电比容量的对比图。
具体实施方式
下面将结合附图和具体实施方式对本发明的技术方案进行清楚、完整地描述，但是本领域技术人员将会理解，下列所描述的实施例是本发明一部分实施例，而不是全部的实施例，仅用于说明本发明，而不应视为限制本发明的范围。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
下面对本发明实施例的低温型锂离子电池电解液及其制备方法和锂离子电池进行具体说明。
在本发明的一些实施方式中提供了一种低温型锂离子电池电解液，包括电解质盐和有机溶剂；
有机溶剂包括氟代羧酸酯、氟代碳酸酯和1,3-二氧五环。
本发明的低温型锂离子电池电解液，通过采用氟代羧酸酯作为主溶剂，氟代碳酸酯和1，3-二氧五环作为共溶剂，可有效改善低温锂离子电导率，有利于锂离子电池在低温下容量的发挥。
氟代羧酸酯，羧酸酯熔点较低，氟代可以进一步降低羧酸酯的凝固点，氟代羧酸酯熔点较低，降低了电解液本身的凝固点；因此可以改善电解液在低温下的离子电导率，从而改善电池低温性能；并且氟元素的引入有利于提高界面的性能。
由于氟代羧酸酯成膜性较差，选用氟代碳酸酯作为共熔剂和氟代羧酸酯进行混合调节电解液的成膜性。
引入低凝固点和低粘度的1,3-二氧五环(DOL)后锂离子电池阻抗明显减小。从而提高锂离子电池，尤其是磷酸铁锂锂离子电池在低温条件下的放电比容量及容量保持率。
在本发明的一些实施方式中，氟代羧酸酯包括氟代丙二酸二乙酯。
氟代丙二酸二乙酯(Diethyl Fluoromalonate，DEFM)作为电解液的溶剂，氟代丙二酸二乙酯和锂离子间的结合能较低，利于低温下锂离子的脱嵌过程。
在本发明的一些实施方式中，氟代碳酸酯包括氟代碳酸乙烯酯(4-Fluoro-1,3-dioxolan-2-one，FEC)。
在本发明的一些实施方式中，电解质盐包括双(三氟甲烷磺酰)亚胺锂和/或三氟甲烷磺酰亚胺锂；优选地，电解质盐包括双(三氟甲烷磺酰)亚胺锂(LiTFSI)。
双(三氟甲烷磺酰)亚胺锂，可在溶剂中溶解较高的浓度，且其具有较高的HOMO能级和较低的LUMO能级，能在首次充电过程中在正极/负极-电解液界面处发生分解，形成无机组分含量较多的界面膜，可显著提升电池在低温(-30℃)下的循环稳定性。合适浓度的双(三氟甲烷磺酰)亚胺锂，具有较高的离子电导率，能提供稳定的含氟界面膜。
HOMO是分子的最高占据轨道，HOMO能级越高，该物质越易失去电子。对电解液而言，HOMO能级可以用来判断各组分在充电过程中的分解顺序，HOMO能级越高的组分，意味着越容易氧化形成正极电解液界面膜，从而阻止后续充放电过程中其他组分与电解液的直接接触，抑制正极电解液界面副反应。LUMO能级是分子最低未占据轨道，LUMO能级越低，该物质越易得到电子，对电解液而言，LUMO能级可以用来判断各组分在放电过程中的分解顺序，LUMO能级越低的组分，意味着越容易还原形成负极电解液界面膜。从而阻止后续充放电过程中电极与电解液的直接接触，抑制界面副反应。
本发明的低温型锂离子电池电解液的有机溶剂为氟代羧酸酯、氟代碳酸乙烯酯和1，3-二氧五环。氟代羧酸酯和氟代碳酸酯熔点较低，能降低电解液的熔点，提高低温下电解液的离子电导率。LiFSI的HOMO能级较高，能优先在锂离子电池正极表面分解成膜，改善正极-电解液界面稳定性。氟代碳酸乙烯酯的LUMO能级较低，能优先在锂离子待查你还负极表面分解成膜，改善负极-电解液界面稳定性。因此，本发明的电解液可改善低温下(-30℃)锂离子电池的放电比容量及容量保持率。
在本发明的一些实施中，低温型锂离子电池电解液，包括双(三氟甲烷磺酰)亚胺锂、氟代丙二酸二乙酯、氟代碳酸乙烯酯和1,3-二氧五环。
在本发明的一些实施中，低温型锂离子电池电解液中，氟代羧酸酯的 体积百分数＞40％。
在本发明的一些实施中，低温型锂离子电池电解液中，氟代羧酸酯的体积百分数为50％～70％；典型但非限制性的，例如，低温型锂离子电池电解液中，氟代羧酸酯的体积百分数为50％、51％、52％、53％、54％、55％、56％、57％、58％、59％、60％、61％、62％、63％、64％、65％、66％、67％、68％、69％或者70％等等；优选地，低温型锂离子电池电解液中，氟代羧酸酯的体积百分数为55％～65％；更优选为58％～62％。
在本发明的一些实施方式中，氟代羧酸酯、氟代碳酸酯和1,3-二氧五环的体积比为90～40：10～50：1～30；典型但非限制性的，例如，氟代羧酸酯、氟代碳酸酯和1,3-二氧五环的体积比为80：10：10、70：15：15、60：20：20、50：25：25、40：30：30、80：10：5、70：30：10、60：10：5、50：10：20等等；优选地，氟代羧酸酯、氟代碳酸酯和1,3-二氧五环的体积比为55～65：15～25：15～25；更优选地，氟代碳酸酯和1,3-二氧五环的体积比为1：1。
在本发明的一些实施方式中，低温型锂离子电池电解液中，电解质盐的浓度为1.0～5.0mol/L；典型但非限制性的，例如，低温型锂离子电池电解液中，电解质盐的浓度为1.0mol/L、1.5mol/L、2.0mol/L、2.5mol/L、3.0mol/L、3.5mol/L、4.0mol/L、4.5mol/L或者5.0mol/L等等；优选地，低温型锂离子电池电解液中，电解质盐的浓度为1.5～2.5mol/L。
在本发明的一些实施方式中还提供了上述低温型锂离子电池电解液的制备方法，有机溶剂和电解质盐混匀后得到低温型锂离子电池电解液。
在本发明的一些实施方式中，有机溶剂为无水有机溶剂；无水有机溶剂的制备方法包括：将有机溶剂加入除水剂，静置2～4天制备而成；优选地，除水剂为分子筛，型号为
Figure PCTCN2022141945-appb-000001
和
Figure PCTCN2022141945-appb-000002
型中的任意一种。
在本发明的一些实施方式中还提供了一种锂离子电池，包括上述的低温型锂离子电池电解液。
在本发明的一些实施方式中，锂离子电池的正极材料为磷酸铁锂。
在本发明的一些实施方式中，锂离子电池，包括：正极片、负极片、隔离膜和电解液；
其中，正极片主要由正极活性材料、导电剂、粘结剂和分散剂制得，正极活性材料为LiFePO 4；
负极片为锂片；
电解液为上述低温型锂离子电池电解液。
在本发明的一些实施方式中，导电剂包括导电碳黑。
在本发明的一些实施方式中，粘结剂包括聚偏氟乙烯。
在本发明的一些实施方式中，导电剂包括N-甲基-2-吡咯烷酮。
在本发明的一些实施方式中，隔离膜包括聚丙烯微孔膜。
采用本发明的低温型锂离子电池电解液组装的LiFePO 4/Li电池能够在-30℃的低温环境下，0.2C放电比容量为90mAh/g，且能保持稳定循环。
实施例1～12
各实施例的低温型锂离子电池电解液的制备方法相同，仅低温型锂离子电池电解液中所用溶剂DEFM、FEC和DOL的体积比和双(三氟甲烷磺酰)亚胺锂(LiTFSI)的浓度不同，各实施例的溶剂的体积比和LiTFSI的浓度如表1所示。
表1
  LiTFSI的浓度 DEFM：FEC：DOL(体积比)
实施例1 1M 90：5：5
实施例2 1M 80：10：10
实施例3 1M 60：20：20
实施例4 1M 50：25：25
实施例5 2M 90：5：5
实施例6 2M 80：10：10
实施例7 2M 60：20：20
实施例8 2M 50：25：25
实施例9 3M 90：5：5
实施例10 3M 80：10：10
实施例11 3M 60：20：20
实施例12 3M 50：25：25
低温型锂离子电池电解液的制备方法，包括如下步骤：
在惰性气体保护的手套箱中将氟代丙二酸二乙酯(DEFM)、氟代碳酸酯(FEC)和1，3-二氧五环(DOL)按体积比混合，混合后加入
Figure PCTCN2022141945-appb-000003
分子筛除水剂，静置2天；然后加入双(三氟甲烷磺酰)亚胺锂(LiTFSI)，控制双(三氟甲烷磺酰)亚胺锂(LiTFSI)的浓度，搅拌至澄清透明，混合均匀后即可获得低温型锂离子电池电解液。手套箱中水含量小于0.1ppm，氧含量小于0.1ppm。
Figure PCTCN2022141945-appb-000004
分子筛除水剂型号为Alfa L05335-250g。
对比例1～5
各对比例的锂离子电池电解液的制备方法相同，仅锂离子电池电解液中所用有机溶剂的种类、体积比、电解质盐的种类和浓度不同，具体如表2 所示。
表2
  电解质盐的种类和浓度 有机溶剂的种类和体积比
对比例1 LiPF 6，1M DEFM：FEC：DOL＝60：20：20
对比例2 LiPF 6，2M DEFM：FEC：DOL＝60：20：20
对比例3 LiPF 6，3M DEFM：FEC：DOL＝60：20：20
对比例4 LiTFSI，2M EC：DEC＝50：50
对比例5 LiPF 6，1M EC：DEC＝50：50
其中，EC为碳酸乙烯酯，DEC为碳酸二乙酯。
锂离子电池电解液的制备方法，包括如下步骤：
在惰性气体保护的手套箱中将有机溶剂按体积比混合，混合后加入
Figure PCTCN2022141945-appb-000005
分子筛除水剂，静置2天，然后加入电解质盐，搅拌均匀，控制电解质盐的浓度，搅拌均匀后即可获得锂离子电解质溶液。手套箱中水含量小于0.1ppm，氧含量小于0.1ppm。
Figure PCTCN2022141945-appb-000006
分子筛除水剂型号为Alfa L05335-250g。
试验例1
分别采用实施例1～12的低温型锂离子电池电解液和对比例1～5的锂离子电池电解液与磷酸铁锂正极、锂负极一起组装成为电池，进行电化学测试，测试方法如下：
首先，制备正极片，正极活性材料为LiFePO 4，导电剂为导电碳黑(Super P，Timcal Ltd.)，粘结剂为聚偏氟乙烯(PVDF，HSV 900，Arkema)，分散剂为N-甲基-2-吡咯烷酮(NMP)，按照LiFePO 4：Super P：PVDF＝7：2：1的质量比混合研磨，涂于铝箔上，在经过烘干、辊压、冲片，做成电极片， 电极表面的活性物质控制在2～4mg/cm 2。然后，在充满氩气的手套箱中制作扣式电池，负极为锂片，聚丙烯微孔膜为隔膜，改变电解液获得不同的电池进行测试。
电化学性能测试使用新威电化学测试仪。将电池以0.2C在常温下循环2次进行活化后，置于-30℃下静置2h，然后采用0.2C的电流密度进行低温循环，充放电电压范围为2.7～4.2V，测试结果如表3所示。分别采用实施例1的型锂离子电池电解液与对比例5的锂离子电池电解液电池在2.7-4.2V充放电电压、-30℃下放电比容量的对比图如图1所示，其中，对比例5的锂离子电池电解液电池标记为Baseline，实施例7的低温型锂离子电池电解液记为LT-Electrolyte。
表3
  -30℃循环50次后放电比容量(mAh/g)
实施例1 61
实施例2 69
实施例3 77
实施例4 73
实施例5 81
实施例6 85
实施例7 90
实施例8 81
实施例9 71
实施例10 69
实施例11 78
实施例12 72
对比例1 39
对比例2 42
对比例3 34
对比例4 25
对比例5 20
从图1可以看出，在-30℃低温下，0.2C倍率，50次循环中，采用本发明的低温型锂离子电池电解液组装的电池放电比容量和循环稳定性明显好于对比例5的锂离子电池电解液。
从表1可以看出，电解液的溶剂为氟代丙二酸二乙酯(DEFM)、氟代碳酸酯(FEC)和1，3-二氧五环(DOL)的混合溶剂，锂盐为双(三氟甲烷磺酰)亚胺锂(LiTFSI)时，放电比容量最高。
实施例1～12对比可知，其中，实施例7的效果最好。在-30℃低温下，LiFePO 4/Li电池放电比容量有90mAh/g，50圈容量保持率接近100％。远高于其他对比例。从实施例1～12对比可看出，在溶剂成分为氟代丙二酸二乙酯(DEFM)、氟代碳酸乙烯酯(FEC)和1，3-二氧五环(DOL)的混合溶剂时，氟代碳酸乙烯酯占比为20％和1,3-二氧五环的占比为20％时放电比容量最高，这可能是因为FEC有利于在负极形成富含LiF的无机界面在低温下更稳定，DOL粘度较低有利于减小电解液在低温下的离子电导率。从实施例1～12与对比例1～4的对比可看出锂盐为LiTFSI且浓度为2M时性能最优，这可能是由于LiTFSI优先分解形成含有F的无机组分界面膜更为稳定，且浓度为2M时电解液具有最佳的粘度和电导率。
通过对比例1～4可发现，不含LiTFSI时，溶剂成分为氟代丙二酸二乙酯(DEFM)、氟代碳酸乙烯酯(FEC)和1，3-二氧五环(DOL)的作用效果也优于普通碳酸酯(基础电解液)，这可能是因为上述混合溶剂低温电导率更优且成膜性更好所致。
综上，通过对比发现，与对比例5相比，以双(三氟甲烷磺酰)亚胺锂为电解质盐，氟代丙二酸二乙酯(DEFM)、氟代碳酸乙烯酯(FEC)和1，3-二氧五环(DOL)为溶剂的电解液可以明显改善-30℃低温环境下LiFePO 4/Li电池的放电比容量及容量保持率。其中，DEFM：FEC：DOL＝60：20：20，LiTFSI浓度为2M时电池的放电比容量和循环稳定性最好。组装的LiFePO 4/Li电池在-30℃下放电比容量有90mAh/g且更为稳定。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

  1. 一种低温型锂离子电池电解液，其特征在于，包括电解质盐和有机溶剂；
    所述有机溶剂包括氟代羧酸酯、氟代碳酸酯和1,3-二氧五环。
  2. 根据权利要求1所述的低温型锂离子电池电解液，其特征在于，所述氟代羧酸酯包括氟代丙二酸二乙酯。
  3. 根据权利要求1所述的低温型锂离子电池电解液，其特征在于，所述氟代碳酸酯包括氟代碳酸乙烯酯。
  4. 根据权利要求1所述的低温型锂离子电池电解液，其特征在于，所述电解质盐包括双(三氟甲烷磺酰)亚胺锂和/或三氟甲烷磺酰亚胺锂；
    优选地，所述电解质盐包括双(三氟甲烷磺酰)亚胺锂。
  5. 根据权利要求1所述的低温型锂离子电池电解液，其特征在于，所述低温型锂离子电池电解液中，氟代羧酸酯的体积百分数＞40％；
    优选地，所述低温型锂离子电池电解液中，氟代羧酸酯的体积百分数为50％～70％。
  6. 根据权利要求1所述的低温型锂离子电池电解液，其特征在于，所述氟代羧酸酯、所述氟代碳酸酯和所述1,3-二氧五环的体积比为90～40：5～50：5～30；
    优选地，所述氟代羧酸酯、所述氟代碳酸酯和所述1,3-二氧五环的体积比为55～65：15～25：15～25。
  7. 根据权利要求1所述的，其特征在于，所述低温型锂离子电池电解液中，电解质盐的浓度为1.0～5.0mol/L；
    优选地，所述低温型锂离子电池电解液中，电解质盐的浓度为1.5～2.5mol/L。
  8. 如权利要求1～7任一项所述的低温型锂离子电池电解液的制备方法，其特征在于，有机溶剂和电解质盐混匀后得到所述低温型锂离子电池电解液。
  9. 一种锂离子电池，其特征在于，包括权利要求1～7任一项所述的低温型锂离子电池电解液。
  10. 根据权利要求9所述的锂离子电池，其特征在于，所述锂离子电池的正极材料为磷酸铁锂。
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