WO2022213823A1 - Non-aqueous electrolyte for lithium ion battery and lithium ion battery - Google Patents

Non-aqueous electrolyte for lithium ion battery and lithium ion battery Download PDF

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Publication number
WO2022213823A1
WO2022213823A1 PCT/CN2022/083008 CN2022083008W WO2022213823A1 WO 2022213823 A1 WO2022213823 A1 WO 2022213823A1 CN 2022083008 W CN2022083008 W CN 2022083008W WO 2022213823 A1 WO2022213823 A1 WO 2022213823A1
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Prior art keywords
aqueous electrolyte
lithium ion
carbonate
ion battery
lithium
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PCT/CN2022/083008
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French (fr)
Chinese (zh)
Inventor
曹朝伟
周忠仓
陈雪君
胡时光
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深圳新宙邦科技股份有限公司
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Publication of WO2022213823A1 publication Critical patent/WO2022213823A1/en

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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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of electrochemistry, in particular to a non-aqueous electrolyte for a lithium ion battery and a lithium ion battery.
  • Lithium-ion batteries have made great progress in the field of portable electronic products due to their high operating voltage, high safety, long life, and no memory effect. With the development of new energy vehicles, lithium-ion batteries have great application prospects in power supply systems for new energy vehicles.
  • Lithium-ion battery cells are mainly composed of positive electrode, negative electrode, separator and electrolyte.
  • the electrolyte is the key factor affecting the high temperature performance of the battery.
  • the commonly used electrolyte in lithium-ion batteries is non-aqueous electrolyte, and the additives in non-aqueous electrolyte are particularly important for the high temperature performance of the battery.
  • the lithium ions in the positive electrode material of the battery are deintercalated and intercalated into the carbon negative electrode through the electrolyte.
  • the electrolyte reacts on the surface of the carbon negative electrode to produce compounds such as Li 2 CO 3 , Li 2 O, LiOH, etc., thereby forming a passivation film on the surface of the negative electrode, which is called the solid electrolyte interface film (SEI). ).
  • SEI solid electrolyte interface film
  • the SEI film formed during the initial charging process can prevent the electrolyte from further decomposing on the surface of the carbon negative electrode, and act as a lithium ion tunnel, allowing only lithium ions to pass through.
  • the electrode may change in volume and cause the SEI film to rupture, which may cause the negative electrode of the battery to be exposed again and react with the electrolyte to generate gas at the same time, thereby increasing the internal pressure of the lithium battery and reducing the Cycle life of the battery.
  • the SEI film is more prone to rupture, resulting in a more obvious decrease in the cycle performance of lithium batteries under high temperature conditions. Therefore, the SEI film determines the performance of the lithium-ion battery.
  • the present invention provides a non-aqueous electrolyte for a lithium ion battery, which can improve the high temperature storage and cycle performance of the lithium ion battery.
  • the present invention adopts following technical scheme:
  • a non-aqueous electrolyte for a lithium ion battery comprising a non-aqueous organic solvent, a lithium salt and a spirocyclic ester compound, the spirocyclic ester compound is shown in structural formula 1:
  • R 9 is a halogen atom, a halogenated or non-halogenated alkoxy with 1-10 carbon atoms;
  • the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
  • R 9 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutanoxy, fluoropentanoxy, fluorohexaneoxy, fluoroheptane Oxy, fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, methoxy, ethoxy, propoxy, butyloxy, pentyloxy, hexaneoxy , one of heptalkoxy, octaneoxy, nonalkoxy and decyloxy;
  • R 9 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-6 carbon atoms;
  • the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
  • R 9 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentanoxy, fluorohexaneoxy, methoxy, One of ethoxy, propoxy, butalkoxy, pentalkoxy and hexaneoxy.
  • X 2 is One of the groups;
  • R 10 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-10 carbon atoms;
  • the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
  • R 10 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentanoxy, fluorohexaneoxy, fluoroheptane Oxy, fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, methoxy, ethoxy, propoxy, butyloxy, pentyloxy, hexaneoxy , one of heptalkoxy, octaneoxy, nonalkoxy and decyloxy;
  • R 10 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-6 carbon atoms;
  • the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
  • R 10 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentanoxy, fluorohexaneoxy, methoxy, One of ethoxy, propoxy, butalkoxy, pentalkoxy and hexaneoxy.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen atoms, halogen atoms, halogenated or non-halogenated alkoxy groups of 1-10 carbon atoms A sort of;
  • the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluoro Fluorobutalkoxy, fluoropentanyloxy, fluorohexaneoxy, fluoroheptyloxy, fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, methoxy one of alkoxy group, ethoxy group, propoxy group, butalkoxy group, pentalkoxy group, hexaneoxy group, heptalkoxy group, octaneoxy group, nonalkoxy group and decalkoxy group;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen atoms, halogen atoms, halogenated or non-halogenated alkoxy groups of 1-3 carbon atoms one of the bases;
  • the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from fluoromethoxy, fluoroethoxy, and fluoropropoxy , one of methoxy, ethoxy and propoxy.
  • the spirocyclic ester compound comprises one of categories 1-4:
  • R 9 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-10 carbon atoms;
  • the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
  • R 9 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutanoxy, fluoropentanoxy, fluorohexaneoxy, fluoroheptane Oxy, fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, methoxy, ethoxy, propoxy, butyloxy, pentyloxy, hexaneoxy , one of heptalkoxy, octaneoxy, nonalkoxy and decyloxy;
  • R 9 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-6 carbon atoms;
  • the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
  • R 9 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentanoxy, fluorohexaneoxy, methoxy, One of ethoxy, propoxy, butalkoxy, pentalkoxy and hexaneoxy.
  • X 2 is One of the groups;
  • R 10 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-10 carbon atoms;
  • the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
  • R 10 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentanoxy, fluorohexaneoxy, fluoroheptane Oxy, fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, methoxy, ethoxy, propoxy, butyloxy, pentyloxy, hexaneoxy , one of heptalkoxy, octaneoxy, nonalkoxy and decyloxy;
  • R 10 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-6 carbon atoms;
  • the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
  • R 10 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentanoxy, fluorohexaneoxy, methoxy, One of ethoxy, propoxy, butalkoxy, pentalkoxy and hexaneoxy;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen atoms, halogen atoms, halogenated or non-halogenated alkoxy groups of 1-10 carbon atoms A sort of;
  • the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from fluoromethoxy, fluoroethoxy, and fluoropropoxy , Fluorobutalkoxy, fluoropentalkoxy, fluorohexaneoxy, fluoroheptyloxy, fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, One of Methoxy, Ethoxy, Propoxy, Butyloxy, Pentyloxy, Hexyloxy, Heptyloxy, Octyloxy, Nonalkoxy, Decyloxy ;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen atoms, halogen atoms, halogenated or non-halogenated alkoxy groups of 1-3 carbon atoms one of the bases;
  • the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, methyl One of oxy, ethoxy and propoxy.
  • the spirocyclic ester compound comprises one of compounds 1-65:
  • the mass of the spirocyclic ester compound is 0.01%-5.0% of the total mass of the non-aqueous electrolyte of the lithium ion battery.
  • the mass of the spiro ester compound is less than 0.01% of the total mass of the non-aqueous electrolyte, the content of the compound in the electrolyte is too low to form a complete passivation film on the surface of the negative electrode, so it is difficult to significantly improve the non-aqueous electrolyte battery high temperature performance, and the internal resistance of the battery is not significantly reduced.
  • the mass of the spirocyclic ester compound is higher than 5.0% of the total mass of the non-aqueous electrolyte, an excessively thick SEI passivation film is easily formed on the surface of the negative electrode, which increases the internal resistance of the battery, and the battery capacity retention rate is significantly deteriorated.
  • the mass of the spirocyclic ester compound is 0.5%-3.0% of the total mass of the non-aqueous electrolyte of the lithium ion battery. At this time, the electrochemical performance of the prepared lithium-ion battery is more excellent.
  • non-aqueous electrolyte for the lithium ion battery of the present invention may further contain sulfonate or carbonate.
  • the sulfonate is selected from 1,3-propane sultone (1,3-PS), 1,4-butane sultone (BS), 1,3-propene sultone (PST) one or more of.
  • the carbonate is selected from one or more of vinylene carbonate (VC), ethylene ethylene carbonate (VEC), and fluoroethylene carbonate (FEC).
  • VC vinylene carbonate
  • VEC ethylene ethylene carbonate
  • FEC fluoroethylene carbonate
  • the dosage of the additive is 0.01%-5.0% of the total mass of the non-aqueous electrolyte.
  • the dosage of the additive is 0.2%-3.0% of the total mass of the non-aqueous electrolyte. More preferably, the dosage of the additive is 0.5%-3.0% of the total mass of the non-aqueous electrolyte.
  • the lithium salt is LiPF 6 , LiBOB, LiDFOB, LiBF 4 , LiSbF 6 , LiAsF 6 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiC(SO 2 CF 3 ) 3 Or one or more of LiN(SO 2 F) 2 .
  • the lithium salt is LiPF 6 or a mixture of LiPF 6 and other lithium salts.
  • the mass of the lithium salt is 0.1%-15% of the total mass of the non-aqueous electrolyte.
  • the mass of the lithium salt is 1%-13% of the total mass of the non-aqueous electrolyte.
  • the mass of the lithium salt is 5-13% of the total mass of the non-aqueous electrolyte.
  • the mass of the lithium salt is 10-12% of the total mass of the non-aqueous electrolyte.
  • non-aqueous organic solvent includes at least one cyclic carbonate and at least one chain carbonate.
  • cyclic carbonate includes one or more of ethylene carbonate, propylene carbonate or butylene carbonate.
  • the chain carbonate includes one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate.
  • the present invention also provides a lithium ion battery, comprising the above lithium ion battery non-aqueous electrolyte, a positive electrode, a negative electrode and a separator.
  • the positive electrode includes a positive electrode active material
  • the positive electrode active material includes LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiCo 1-y My O 2 , LiNi 1-y My O 2 , LiMn 2-y My O 4 and one or more of LiNi x Co y Mn z M 1-xyz O 2 , wherein M is selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, One or more of Sr, V or Ti, and 0 ⁇ y ⁇ 1, 0 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, and x+y+z ⁇ 1.
  • the active material of the positive electrode includes LiFe 1-x M x PO 4 , wherein M is selected from Mn, Mg, Co, Ni, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti one or more, and 0 ⁇ x ⁇ 1.
  • the positive electrode further includes a positive electrode current collector for drawing current, and the positive electrode active material is covered on the positive electrode current collector.
  • the negative electrode includes a negative electrode active material
  • the negative electrode active material includes one of a carbon material, a metal alloy, a lithium-containing oxide, and a silicon-containing material.
  • the negative electrode further includes a negative electrode current collector for drawing current, and the negative electrode active material is covered on the negative electrode current collector.
  • the separator is arranged between the positive electrode and the negative electrode, and the separator can be a polyethylene porous film.
  • the spirocyclic ester compound represented by the structural formula 1 in the non-aqueous electrolyte for lithium ion batteries provided by the present invention, by adding the spirocyclic ester compound represented by the structural formula 1 to the electrolyte, the spirocyclic ester compound represented by the structural formula 1 will undergo a reduction reaction on the negative electrode, thereby Cleavage into ring-opened polyvalent anion radicals, and the generated radical end groups will further react to form cross-linked polyvalent salts.
  • This cross-linked polyvalent salt will form a dense network SEI film on the surface of the negative electrode , in addition, the ring tension of the compound represented by the structural formula 1 makes the surface of the SEI film more flexible, and the resistance of the electrode interface film increases relatively slowly even at high temperature, which can effectively reduce the decomposition of the electrolyte solvent on the negative electrode and reduce the gas produced, thereby improving the electrochemical performance of lithium-ion batteries under high temperature conditions.
  • the cross-linked polyvalent salt also has better anti-oxidation properties, slows down the oxidation process of the electrolyte, and can significantly improve the cycle performance and high-temperature storage performance of lithium-ion batteries.
  • the concentration is 1 mol/L, and the total weight of the non-aqueous electrolyte is 100%, and the compound 1 in the mass percentage shown in Example 1 in Table 2 is added.
  • the cathode active material lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 , the conductive carbon black Super-P and the binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 93:4:3, and then they were mixed together. Disperse in N-methyl-2-pyrrolidone (NMP) to obtain a positive electrode slurry. The slurry is evenly coated on both sides of the aluminum foil, dried, calendered and vacuum-dried, and the aluminum lead wires are welded with an ultrasonic welder to obtain a positive electrode plate, the thickness of which is between 120-150 ⁇ m.
  • NMP N-methyl-2-pyrrolidone
  • a three-layer separator with a thickness of 20 ⁇ m was placed between the positive plate and the negative plate, and then the sandwich structure composed of the positive plate, the negative plate and the separator was wound, and then the rolled body was flattened and put into an aluminum foil packaging bag. Vacuum bake for 48h at °C to obtain the cell to be injected.
  • the electrolyte prepared above was injected into the cell, sealed in vacuum, and kept at rest for 24 hours.
  • the routine formation of the first charge is carried out according to the following steps: 0.05C constant current charging for 180min, 0.2C constant current charging to 3.95V, secondary vacuum sealing, and then further charging to 4.2V with 0.2C current constant current, after 24h at room temperature , and discharged to 3.0V at a constant current of 0.2C to obtain a LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite lithium-ion battery.
  • the relevant performance tests of the lithium ion batteries produced in the following examples and comparative examples are carried out below.
  • the performance tested includes high temperature cycle performance test and high temperature storage performance test.
  • the specific test methods are as follows:
  • the lithium-ion batteries produced in the examples and comparative examples were placed in an oven with a constant temperature of 45°C, charged to 4.2V (LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite lithium ion battery) at a constant current of 1C, and then charged at a constant voltage. Charge until the current drops to 0.02C, and then discharge to 3.0V at a constant current of 1C. This cycle is performed to record the first discharge capacity and the last discharge capacity.
  • 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite lithium ion battery
  • Battery capacity retention rate (%) last discharge capacity/first discharge capacity ⁇ 100%.
  • the lithium-ion batteries prepared in the examples and comparative examples were charged to 4.2V (LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite lithium ion battery) at room temperature with 1C constant current and constant voltage after formation, and the initial discharge capacity and The initial battery thickness was then stored at 60°C for 30 days, discharged to 3V at 1C, and the retention and recovery capacity of the battery and the thickness of the battery after storage were measured. Calculated as follows:
  • Battery capacity retention rate (%) retained capacity / initial capacity ⁇ 100%;
  • Thickness expansion ratio (%) (battery thickness after storage ⁇ initial battery thickness)/initial battery thickness ⁇ 100%.
  • Example 1 Compound 1: 1.0% -- Example 2 Compound 3: 1.0% - Example 3 Compound 4: 1.0% - Example 4 Compound 5: 1.0% - Example 5 Compound 6: 1.0% - Example 6 Compound 7: 1.0% - Example 7 Compound 8: 1.0% - Example 8 Compound 9: 1.0% - Comparative Example 1 - - Comparative Example 2 - VC: 1.0% Comparative Example 3 - DTD: 1.0% Comparative Example 4 - PS: 1.0%
  • Comparative Examples 1 to 8 and Comparative Examples 1 and 4 show that, compared with not adding the spirocyclic ester compound of the present invention or adding the sulfuric ester compound of DTD in the electrolyte, adding the non-aqueous electrolyte in the non-aqueous electrolyte.
  • Compounds 1-8 at 1.0% can significantly improve the high-temperature storage and cycle performance of lithium-ion batteries. When stored at 60°C for 30 days, the capacity retention rate and capacity recovery rate of the battery can both reach more than 87%.
  • Example Compound and content Other additives and content Example 9 Compound 1: 0.01% - Example 10 Compound 1: 0.1% - Example 11 Compound 1: 0.5% - Example 12 Compound 1: 2% - Example 13 Compound 1: 3% - Example 14 Compound 1: 5% -
  • adding 0.1%-5.0% of the compound represented by the structural formula 1 to the electrolyte can improve the battery performance.
  • the battery was cycled at 45°C and 1C for 500 cycles, and the capacity retention rate was further improved to more than 90%.
  • the capacity retention rate and capacity of the battery were stored at 60°C for 30 days.
  • the recovery rate can reach more than 90%, and the thickness expansion rate is further reduced. Therefore, the present invention defines the content of the spirocyclic ester compound to be 0.1%-5.0%, preferably 0.5%-3.0%.
  • Example Compound and content Other additives and content Example 15 Compound 1: 0.1% Vinylene carbonate (VC): 1.0% Example 16 Compound 1: 0.5% Vinylene carbonate (VC): 1.0% Example 17 Compound 1: 1.0% Vinylene carbonate (VC): 1.0% Example 18 Compound 1: 5.0% Vinylene carbonate (VC): 1.0% Example 19 Compound 1: 0.1% 1,3-Propane sultone (PS): 1.0% Example 20 Compound 1: 0.5% 1,3-Propane sultone (PS): 1.0% Example 21 Compound 1: 1.0% 1,3-Propane sultone (PS): 1.0% Example 22 Compound 1: 5.0% 1,3-Propane sultone (PS): 1.0%
  • the data of Examples 15-18 relative to Examples 10, 11, 1, 14 and Comparative Example 2 show that adding the compound represented by Structural Formula 1 and VC at the same time, compared with adding the compound represented by Structural Formula 1 or VC alone, the battery's performance is improved. High temperature cycle performance and high temperature storage performance are better.
  • the electrolyte provided in the present invention contains 1% of spirocyclic ester compounds and 1% of vinylene carbonate (VC), so that the capacity retention rate of the assembled battery can reach 92.6% at 45°C and 500 cycles of cycle, and 60 After 30 days of storage at °C, the capacity retention rate can reach 93.5%, the capacity recovery rate can reach 93.8%, and the thickness expansion rate can be reduced to 6.3%.
  • the data of Examples 19-22 relative to Examples 10, 11, 1, 14 and Comparative Example 4 show that adding the compound represented by Structural Formula 1 and PS at the same time, compared with adding the compound represented by Structural Formula 1 or PS alone, the battery has better performance. High temperature cycle performance and high temperature storage performance are better.
  • the electrolyte solution provided in the present invention contains 1% of spirocyclic ester compound and 1% of 1,3-propane sultone (PS), which can make the assembled battery have a capacity retention rate of 500 cycles at 45° C. It reaches 92.8%, the capacity retention rate can reach 93.8% when stored at 60°C for 30 days, the capacity recovery rate can reach 93.9%, and the thickness expansion rate is reduced to 6.0%.
  • the present invention adds spirocyclic ester compounds to the electrolyte, and the prepared electrolyte can ensure that the lithium ion battery can form a stable SEI film during the charging and discharging process, thereby ensuring that the lithium ion battery has excellent electrical properties. chemical properties.

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Abstract

The present invention relates to the technical field of electrochemistry, and specifically relates to a non-aqueous electrolyte for a lithium ion battery and a lithium ion battery. The non-aqueous electrolyte for the lithium ion battery provided by the present invention comprises a non-aqueous organic solvent, a lithium salt and a spirocyclic ester compound. The present invention also provides a lithium ion battery comprising the foregoing non-aqueous electrolyte for the lithium ion battery. The spirocyclic ester compound in the non-aqueous electrolyte for the lithium ion battery provided by the present invention helps the lithium ion battery to form a stable SEI film during charging and discharging processes, so that the prepared lithium ion battery also has an excellent electrochemical performance under high temperature conditions.

Description

一种锂离子电池非水电解液及锂离子电池A lithium ion battery non-aqueous electrolyte and lithium ion battery 技术领域technical field
本发明涉及电化学技术领域，具体涉及一种锂离子电池非水电解液及锂离子电池。The invention relates to the technical field of electrochemistry, in particular to a non-aqueous electrolyte for a lithium ion battery and a lithium ion battery.
背景技术Background technique
锂离子电池因其工作电压高、安全性高、长寿命、无记忆效应等特点，在便携式电子产品领域中取得了长足的发展。随着新能源汽车的发展，锂离子电池在新能源汽车用动力电源系统具有巨大的应用前景。Lithium-ion batteries have made great progress in the field of portable electronic products due to their high operating voltage, high safety, long life, and no memory effect. With the development of new energy vehicles, lithium-ion batteries have great application prospects in power supply systems for new energy vehicles.
锂离子电池电芯主要由正极、负极、隔膜以及电解液组成。其中电解液是影响电池高温性能的关键因素。目前锂离子电池中常用的电解液为非水电解液，非水电解液中的添加剂对电池高温性能的发挥尤其重要。在锂离子电池初始充电过程中，电池正极材料中的锂离子脱嵌出来，通过电解液嵌入碳负极中。由于锂具有高反应性，电解液在碳负极表面反应产生Li 2CO 3、Li 2O、LiOH等化合物，从而在负极表面形成钝化膜，该钝化膜称为固体电解液界面膜(SEI)。在初始充电过程中形成的SEI膜，能够阻止电解液进一步在碳负极表面分解，而且起到锂离子隧道作用，只允许锂离子通过。但是在锂电池的充放电过程中，电极可能会发生体积变化导致SEI膜发生破裂，这可能会致使电池的负极再次暴露并与电解液发生反应同时产生气体，从而增加锂电池的内压，降低电池的循环寿命。电池在高温条件下储存或进行反应时，SEI膜更容易发生破裂，从而导致锂电池在高温条件下循环性能下降更为明显。因此，SEI膜决定了锂离子电池性能的好坏。 Lithium-ion battery cells are mainly composed of positive electrode, negative electrode, separator and electrolyte. The electrolyte is the key factor affecting the high temperature performance of the battery. At present, the commonly used electrolyte in lithium-ion batteries is non-aqueous electrolyte, and the additives in non-aqueous electrolyte are particularly important for the high temperature performance of the battery. During the initial charging of the lithium-ion battery, the lithium ions in the positive electrode material of the battery are deintercalated and intercalated into the carbon negative electrode through the electrolyte. Due to the high reactivity of lithium, the electrolyte reacts on the surface of the carbon negative electrode to produce compounds such as Li 2 CO 3 , Li 2 O, LiOH, etc., thereby forming a passivation film on the surface of the negative electrode, which is called the solid electrolyte interface film (SEI). ). The SEI film formed during the initial charging process can prevent the electrolyte from further decomposing on the surface of the carbon negative electrode, and act as a lithium ion tunnel, allowing only lithium ions to pass through. However, during the charging and discharging process of the lithium battery, the electrode may change in volume and cause the SEI film to rupture, which may cause the negative electrode of the battery to be exposed again and react with the electrolyte to generate gas at the same time, thereby increasing the internal pressure of the lithium battery and reducing the Cycle life of the battery. When the battery is stored or reacted at high temperature, the SEI film is more prone to rupture, resulting in a more obvious decrease in the cycle performance of lithium batteries under high temperature conditions. Therefore, the SEI film determines the performance of the lithium-ion battery.
现有技术中为了提高锂离子电池的各项性能，许多科研者通过往电解液中添加不同的负极成膜添加剂，例如碳酸亚乙烯酯，氟代碳酸乙烯酯，碳酸乙烯亚乙酯，1,3-丙烷磺酸内酯等添加剂来改善SEI膜的质量，从而改善电池的各项性能。但是在电解液中添加上述物质后锂离子电池的高温存储和循环性能仍然较差。因此研发一种能保证锂离子电池在高温下的电化学性能优异的非水电解液至关重要。In order to improve the performance of lithium ion batteries in the prior art, many researchers add different negative electrode film-forming additives to the electrolyte, such as vinylene carbonate, fluoroethylene carbonate, ethylene ethylene carbonate, 1, Additives such as 3-propane sultone to improve the quality of the SEI film, thereby improving the performance of the battery. However, the high-temperature storage and cycle performance of lithium-ion batteries is still poor after adding the above substances to the electrolyte. Therefore, it is very important to develop a non-aqueous electrolyte that can ensure the excellent electrochemical performance of Li-ion batteries at high temperature.
发明内容SUMMARY OF THE INVENTION
为了解决上述技术问题，本发明提供了一种锂离子电池非水电解液，能够改善锂离子电池的高温存储和循环性能。In order to solve the above technical problems, the present invention provides a non-aqueous electrolyte for a lithium ion battery, which can improve the high temperature storage and cycle performance of the lithium ion battery.
本发明采用如下技术方案：The present invention adopts following technical scheme:
一种锂离子电池非水电解液，包括非水有机溶剂、锂盐以及螺环酯类化合物，螺环酯类化合物如结构式1所示：A non-aqueous electrolyte for a lithium ion battery, comprising a non-aqueous organic solvent, a lithium salt and a spirocyclic ester compound, the spirocyclic ester compound is shown in structural formula 1:
Figure PCTCN2022083008-appb-000001
Figure PCTCN2022083008-appb-000001
其中，X 1为
Figure PCTCN2022083008-appb-000002
基团中的一种；R 9为卤素原子、碳原子数为1-10的卤代或非卤代烷氧基的一种； where X 1 is
Figure PCTCN2022083008-appb-000002
One of the groups; R 9 is a halogen atom, a halogenated or non-halogenated alkoxy with 1-10 carbon atoms;
优选的，卤素原子选自氟、氯、溴、碘中的一种；Preferably, the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
优选的，R 9选自氟代甲氧基、氟代乙氧基、氟代丙氧基、氟代丁烷氧基、氟代戊烷氧基、氟代己烷氧基、氟代庚烷氧基、氟代辛烷氧基、氟代壬烷氧基、氟代癸烷氧基、甲氧基、乙氧基、丙氧基、丁烷氧基、戊烷氧基、己烷氧基、庚烷氧基、辛烷氧基、壬烷氧基、癸烷氧基中的一种； Preferably, R 9 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutanoxy, fluoropentanoxy, fluorohexaneoxy, fluoroheptane Oxy, fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, methoxy, ethoxy, propoxy, butyloxy, pentyloxy, hexaneoxy , one of heptalkoxy, octaneoxy, nonalkoxy and decyloxy;
优选的，R 9为卤素原子、碳原子数为1-6的卤代或非卤代烷氧基中的一种； Preferably, R 9 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-6 carbon atoms;
优选的，卤素原子选自氟、氯、溴、碘中的一种；Preferably, the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
优选的，R 9选自氟代甲氧基、氟代乙氧基、氟代丙氧基、氟代丁烷氧基、氟代戊烷氧基、氟代己烷氧基、甲氧基、乙氧基、丙氧基、丁烷氧基、戊烷氧基、己烷氧基中的一种。 Preferably, R 9 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentanoxy, fluorohexaneoxy, methoxy, One of ethoxy, propoxy, butalkoxy, pentalkoxy and hexaneoxy.
X 2为
Figure PCTCN2022083008-appb-000003
基团中的一种；R 10为卤素原子、碳原子数为1-10的卤代或非卤代烷氧基中的一种； X 2 is
Figure PCTCN2022083008-appb-000003
One of the groups; R 10 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-10 carbon atoms;
优选的，卤素原子选自氟、氯、溴、碘中的一种；Preferably, the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
优选的，R 10选自氟代甲氧基、氟代乙氧基、氟代丙氧基、氟代丁烷氧基、氟代戊烷氧基、氟代己烷氧基、氟代庚烷氧基、氟代辛烷氧基、氟代壬烷氧基、氟代癸烷氧基、甲氧基、乙氧基、丙氧基、丁烷氧基、戊烷氧基、己烷氧基、庚烷氧基、辛烷氧基、壬烷氧基、癸烷氧基中的一种； Preferably, R 10 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentanoxy, fluorohexaneoxy, fluoroheptane Oxy, fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, methoxy, ethoxy, propoxy, butyloxy, pentyloxy, hexaneoxy , one of heptalkoxy, octaneoxy, nonalkoxy and decyloxy;
优选的，R 10为卤素原子、碳原子数为1-6的卤代或非卤代烷氧基中的一种； Preferably, R 10 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-6 carbon atoms;
优选的，卤素原子选自氟、氯、溴、碘中的一种；Preferably, the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
优选的，R 10选自氟代甲氧基、氟代乙氧基、氟代丙氧基、氟代丁烷氧基、氟代戊烷氧基、氟代己烷氧基、甲氧基、乙氧基、丙氧基、丁烷氧基、戊烷氧基、己烷氧基中的一种。 Preferably, R 10 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentanoxy, fluorohexaneoxy, methoxy, One of ethoxy, propoxy, butalkoxy, pentalkoxy and hexaneoxy.
R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立的选自氢原子、卤素原子、1-10个碳原子的卤代或非卤代烷氧基中的一种； R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen atoms, halogen atoms, halogenated or non-halogenated alkoxy groups of 1-10 carbon atoms A sort of;
优选的，卤素原子选自氟、氯、溴、碘中的一种；Preferably, the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
优选的，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立的选自氟代甲氧基、氟代乙氧基、氟代丙氧基、氟代丁烷氧基、氟代戊烷氧基、氟代己烷氧基、氟代庚烷氧基、氟代辛烷氧基、氟代壬烷氧基、氟代癸烷氧基、甲氧基、乙氧基、丙氧基、丁烷氧基、戊烷氧基、己烷氧基、庚烷氧基、辛烷氧基、壬烷氧基、癸烷氧基中的一种； Preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluoro Fluorobutalkoxy, fluoropentanyloxy, fluorohexaneoxy, fluoroheptyloxy, fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, methoxy one of alkoxy group, ethoxy group, propoxy group, butalkoxy group, pentalkoxy group, hexaneoxy group, heptalkoxy group, octaneoxy group, nonalkoxy group and decalkoxy group;
优选的，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立的选自氢原子、卤素原子、1-3个碳原子的卤代或非卤代烷氧基中的一种； Preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen atoms, halogen atoms, halogenated or non-halogenated alkoxy groups of 1-3 carbon atoms one of the bases;
优选的，卤素原子选自氟、氯、溴、碘中的一种；Preferably, the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
优选的，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立的选自选自氟代甲氧基、氟代乙氧基、氟代丙氧基、甲氧基、乙氧基、丙氧基中的一种。 Preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from fluoromethoxy, fluoroethoxy, and fluoropropoxy , one of methoxy, ethoxy and propoxy.
进一步的，螺环酯类化合物包含类别1-4中的一种：Further, the spirocyclic ester compound comprises one of categories 1-4:
Figure PCTCN2022083008-appb-000004
Figure PCTCN2022083008-appb-000004
Figure PCTCN2022083008-appb-000005
Figure PCTCN2022083008-appb-000005
其中，X 1为
Figure PCTCN2022083008-appb-000006
基团中的一种；R 9为卤素原子、碳原子数为1-10的卤代或非卤代烷氧基中的一种； where X 1 is
Figure PCTCN2022083008-appb-000006
One of the groups; R 9 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-10 carbon atoms;
优选的，卤素原子选自氟、氯、溴、碘中的一种；Preferably, the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
优选的，R 9选自氟代甲氧基、氟代乙氧基、氟代丙氧基、氟代丁烷氧基、氟代戊烷氧基、氟代己烷氧基、氟代庚烷氧基、氟代辛烷氧基、氟代壬烷氧基、氟代癸烷氧基、甲氧基、乙氧基、丙氧基、丁烷氧基、戊烷氧基、己烷氧基、庚烷氧基、辛烷氧基、壬烷氧基、癸烷氧基中的一种； Preferably, R 9 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutanoxy, fluoropentanoxy, fluorohexaneoxy, fluoroheptane Oxy, fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, methoxy, ethoxy, propoxy, butyloxy, pentyloxy, hexaneoxy , one of heptalkoxy, octaneoxy, nonalkoxy and decyloxy;
优选的，R 9为卤素原子、碳原子数为1-6的卤代或非卤代烷氧基中的一种； Preferably, R 9 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-6 carbon atoms;
优选的，卤素原子选自氟、氯、溴、碘中的一种；Preferably, the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
优选的，R 9选自氟代甲氧基、氟代乙氧基、氟代丙氧基、氟代丁烷氧基、氟代戊烷氧基、氟代己烷氧基、甲氧基、乙氧基、丙氧基、丁烷氧基、戊烷氧基、己烷氧基中的一种。 Preferably, R 9 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentanoxy, fluorohexaneoxy, methoxy, One of ethoxy, propoxy, butalkoxy, pentalkoxy and hexaneoxy.
X 2为
Figure PCTCN2022083008-appb-000007
基团中的一种；R 10为卤素原子、碳原子数为1-10的卤代或非卤代烷氧基中的一种； X 2 is
Figure PCTCN2022083008-appb-000007
One of the groups; R 10 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-10 carbon atoms;
优选的，卤素原子选自氟、氯、溴、碘中的一种；Preferably, the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
优选的，R 10选自氟代甲氧基、氟代乙氧基、氟代丙氧基、氟代丁烷氧基、氟代戊烷氧基、氟代己烷氧基、氟代庚烷氧基、氟代辛烷氧基、氟代壬烷氧基、氟代癸烷氧基、甲氧基、乙氧基、丙氧基、丁烷氧基、戊烷氧基、己烷氧基、庚烷氧基、辛烷氧基、壬烷氧基、癸烷氧基中的一种； Preferably, R 10 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentanoxy, fluorohexaneoxy, fluoroheptane Oxy, fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, methoxy, ethoxy, propoxy, butyloxy, pentyloxy, hexaneoxy , one of heptalkoxy, octaneoxy, nonalkoxy and decyloxy;
优选的，R 10为卤素原子、碳原子数为1-6的卤代或非卤代烷氧基中的一种； Preferably, R 10 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-6 carbon atoms;
优选的，卤素原子选自氟、氯、溴、碘中的一种；Preferably, the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
优选的，R 10选自氟代甲氧基、氟代乙氧基、氟代丙氧基、氟代丁烷氧基、氟代戊烷氧基、氟代己烷氧基、甲氧基、乙氧基、丙氧基、丁烷氧基、戊烷氧基、己烷氧基中的一种； Preferably, R 10 is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentanoxy, fluorohexaneoxy, methoxy, One of ethoxy, propoxy, butalkoxy, pentalkoxy and hexaneoxy;
R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立的选自氢原子、卤素原子、1-10个碳原子的卤代或非卤代烷氧基中的一种； R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen atoms, halogen atoms, halogenated or non-halogenated alkoxy groups of 1-10 carbon atoms A sort of;
优选的，卤素原子选自氟、氯、溴、碘中的一种；Preferably, the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
优选的，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立的选自选自氟代甲氧基、氟代乙氧基、氟代丙氧基、氟代丁烷氧基、氟代戊烷氧基、氟代己烷氧基、氟代庚烷氧基、氟代辛烷氧基、氟代壬烷氧基、氟代癸烷氧基、甲氧基、乙氧基、丙氧基、丁烷氧基、戊烷氧基、己烷氧基、庚烷氧基、辛烷氧基、壬烷氧基、癸烷氧基中的一种； Preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from fluoromethoxy, fluoroethoxy, and fluoropropoxy , Fluorobutalkoxy, fluoropentalkoxy, fluorohexaneoxy, fluoroheptyloxy, fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, One of Methoxy, Ethoxy, Propoxy, Butyloxy, Pentyloxy, Hexyloxy, Heptyloxy, Octyloxy, Nonalkoxy, Decyloxy ;
优选的，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立的选自氢原子、卤素原子、1-3个碳原子的卤代或非卤代烷氧基中的一种； Preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen atoms, halogen atoms, halogenated or non-halogenated alkoxy groups of 1-3 carbon atoms one of the bases;
优选的，卤素原子选自氟、氯、溴、碘中的一种；Preferably, the halogen atom is selected from one of fluorine, chlorine, bromine and iodine;
优选的，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立的选自氟代甲氧基、氟代乙氧基、氟代丙氧基、甲氧基、乙氧基、丙氧基中的一种。 Preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, methyl One of oxy, ethoxy and propoxy.
进一步的，螺环酯类化合物包含化合物1-65中的一种：Further, the spirocyclic ester compound comprises one of compounds 1-65:
Figure PCTCN2022083008-appb-000008
Figure PCTCN2022083008-appb-000008
Figure PCTCN2022083008-appb-000009
Figure PCTCN2022083008-appb-000009
Figure PCTCN2022083008-appb-000010
Figure PCTCN2022083008-appb-000010
Figure PCTCN2022083008-appb-000011
Figure PCTCN2022083008-appb-000011
进一步的，螺环酯类化合物的质量为锂离子电池非水电解液的总质量的0.01％-5.0％。当螺环酯类化合物的质量低于非水电解液的总质量的0.01％时，电解液中的化合物含量过低无法在负极表面形成完整的钝化膜，从而难以明显改善非水电解液电池的高温性能，且电池内阻无明显降低。而当螺环酯类化合物的质量高于非水电解液的总质量的5.0％时，负极表面容易形成过厚的SEI钝化膜，反而增加电池内阻，而且电池容量保持率明显劣化。优选的，螺环酯类化合物的质量为锂离子电池非水电解液的总质量的0.5％-3.0％。此时所制备的锂离子电池的电化学性能更为优异。Further, the mass of the spirocyclic ester compound is 0.01%-5.0% of the total mass of the non-aqueous electrolyte of the lithium ion battery. When the mass of the spiro ester compound is less than 0.01% of the total mass of the non-aqueous electrolyte, the content of the compound in the electrolyte is too low to form a complete passivation film on the surface of the negative electrode, so it is difficult to significantly improve the non-aqueous electrolyte battery high temperature performance, and the internal resistance of the battery is not significantly reduced. When the mass of the spirocyclic ester compound is higher than 5.0% of the total mass of the non-aqueous electrolyte, an excessively thick SEI passivation film is easily formed on the surface of the negative electrode, which increases the internal resistance of the battery, and the battery capacity retention rate is significantly deteriorated. Preferably, the mass of the spirocyclic ester compound is 0.5%-3.0% of the total mass of the non-aqueous electrolyte of the lithium ion battery. At this time, the electrochemical performance of the prepared lithium-ion battery is more excellent.
进一步的，本发明的锂离子电池非水电解液还可以包含磺酸酯或碳酸酯。Further, the non-aqueous electrolyte for the lithium ion battery of the present invention may further contain sulfonate or carbonate.
优选的，所述磺酸酯选自1,3-丙烷磺内酯(1,3-PS)、1,4-丁烷磺内酯(BS)、1,3-丙烯磺内酯(PST)中的一种或多种。Preferably, the sulfonate is selected from 1,3-propane sultone (1,3-PS), 1,4-butane sultone (BS), 1,3-propene sultone (PST) one or more of.
优选的，所述碳酸酯选自碳酸亚乙烯酯(VC)、碳酸乙烯亚乙酯(VEC)、氟代碳酸乙烯酯(FEC)中的一种或多种。Preferably, the carbonate is selected from one or more of vinylene carbonate (VC), ethylene ethylene carbonate (VEC), and fluoroethylene carbonate (FEC).
进一步的，添加剂的用量为非水电解液总质量的0.01％-5.0％。优选的，添加剂的用量为非水电解液总质量的0.2％-3.0％。更优选的，添加剂的用量为非水电解液总质量的0.5％-3.0％。Further, the dosage of the additive is 0.01%-5.0% of the total mass of the non-aqueous electrolyte. Preferably, the dosage of the additive is 0.2%-3.0% of the total mass of the non-aqueous electrolyte. More preferably, the dosage of the additive is 0.5%-3.0% of the total mass of the non-aqueous electrolyte.
进一步的，锂盐为LiPF 6、LiBOB、LiDFOB、LiBF 4、LiSbF 6、LiAsF 6、LiN(SO 2CF 3) 2、LiN(SO 2C 2F 5) 2、LiC(SO 2CF 3) 3或LiN(SO 2F) 2中的一种或多种。 Further, the lithium salt is LiPF 6 , LiBOB, LiDFOB, LiBF 4 , LiSbF 6 , LiAsF 6 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiC(SO 2 CF 3 ) 3 Or one or more of LiN(SO 2 F) 2 .
优选的，锂盐为LiPF 6或LiPF 6与其他锂盐的混合物。 Preferably, the lithium salt is LiPF 6 or a mixture of LiPF 6 and other lithium salts.
进一步的，锂盐的质量为非水电解液总质量的0.1％-15％。Further, the mass of the lithium salt is 0.1%-15% of the total mass of the non-aqueous electrolyte.
优选的，锂盐的质量为非水电解液总质量的1％-13％。Preferably, the mass of the lithium salt is 1%-13% of the total mass of the non-aqueous electrolyte.
优选的，锂盐的质量为非水电解液总质量的5-13％。Preferably, the mass of the lithium salt is 5-13% of the total mass of the non-aqueous electrolyte.
优选的，锂盐的质量为非水电解液总质量的10-12％。Preferably, the mass of the lithium salt is 10-12% of the total mass of the non-aqueous electrolyte.
进一步的，非水有机溶剂包括至少一种环状碳酸酯和至少一种链状碳酸酯。Further, the non-aqueous organic solvent includes at least one cyclic carbonate and at least one chain carbonate.
进一步的，环状碳酸酯包括碳酸乙烯酯、碳酸丙烯酯或碳酸丁烯酯中的一种或多种。Further, the cyclic carbonate includes one or more of ethylene carbonate, propylene carbonate or butylene carbonate.
进一步的，链状碳酸酯包括碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯或碳酸甲丙酯中的一种或多种。Further, the chain carbonate includes one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate.
本发明还提供了一种锂离子电池，包括上述锂离子电池非水电解液、正极、负极以及隔膜。The present invention also provides a lithium ion battery, comprising the above lithium ion battery non-aqueous electrolyte, a positive electrode, a negative electrode and a separator.
进一步的，正极包括正极活性材料，正极活性材料包括LiCoO 2、LiNiO 2、LiMn 2O 4、LiCo 1-yM yO 2、LiNi 1-yM yO 2、LiMn 2-yM yO 4和LiNi xCo yMn zM 1-x-y-zO 2中的一种或多种，其中，M选自Fe、Co、Ni、Mn、Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V或Ti中的一种或多种，且0≤y≤1，0≤x≤1，0≤z≤1，x+y+z≤1。 Further, the positive electrode includes a positive electrode active material, and the positive electrode active material includes LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiCo 1-y My O 2 , LiNi 1-y My O 2 , LiMn 2-y My O 4 and one or more of LiNi x Co y Mn z M 1-xyz O 2 , wherein M is selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, One or more of Sr, V or Ti, and 0≤y≤1, 0≤x≤1, 0≤z≤1, and x+y+z≤1.
进一步的，正极的活性材料包括LiFe 1-xM xPO 4，其中M选自Mn、Mg、Co、Ni、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V或Ti中的一种或多种，且0≤x＜1。 Further, the active material of the positive electrode includes LiFe 1-x M x PO 4 , wherein M is selected from Mn, Mg, Co, Ni, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti one or more, and 0≤x<1.
进一步的，正极还包括用于引出电流的正极集流体，正极活性材料覆盖于正极集流体上。Further, the positive electrode further includes a positive electrode current collector for drawing current, and the positive electrode active material is covered on the positive electrode current collector.
进一步的，负极包括负极活性材料，负极活性材料包括碳材料、金属合金、含锂氧化物及含硅材料中的一种。Further, the negative electrode includes a negative electrode active material, and the negative electrode active material includes one of a carbon material, a metal alloy, a lithium-containing oxide, and a silicon-containing material.
进一步的，负极还包括有用于引出电流的负极集流体，负极活性材料覆盖于负极集流体上。Further, the negative electrode further includes a negative electrode current collector for drawing current, and the negative electrode active material is covered on the negative electrode current collector.
进一步的，隔膜设置在正极和负极之间，隔膜可以为聚乙烯多孔膜。Further, the separator is arranged between the positive electrode and the negative electrode, and the separator can be a polyethylene porous film.
(1)本发明提供的锂离子电池非水电解液，通过在电解液中添加结构式1所示的螺环酯类化合物，结构式1所示的螺环酯类化合物会在负极上发生还原反应从而裂解成为开环状的多价阴离子自由基，产生的自由基端基会进一步发生反应形成交联的多价盐，这种交联的多价盐会在负极表面形成致密的网状结构SEI膜，此外结构式1所示化合物的环张力使SEI膜表面具有较大的柔韧性，即使高温下，电极界面膜阻抗增加也相对比较缓慢，能有效减少电解液溶剂在负极上发生分解，减少气体的产生，从而提高锂离子电池在高温条件下的电化学性能。(1) In the non-aqueous electrolyte for lithium ion batteries provided by the present invention, by adding the spirocyclic ester compound represented by the structural formula 1 to the electrolyte, the spirocyclic ester compound represented by the structural formula 1 will undergo a reduction reaction on the negative electrode, thereby Cleavage into ring-opened polyvalent anion radicals, and the generated radical end groups will further react to form cross-linked polyvalent salts. This cross-linked polyvalent salt will form a dense network SEI film on the surface of the negative electrode , in addition, the ring tension of the compound represented by the structural formula 1 makes the surface of the SEI film more flexible, and the resistance of the electrode interface film increases relatively slowly even at high temperature, which can effectively reduce the decomposition of the electrolyte solvent on the negative electrode and reduce the gas produced, thereby improving the electrochemical performance of lithium-ion batteries under high temperature conditions.
(2)交联的多价盐还具有更加好的抗氧化特性，减缓电解液的氧化进程，能够显著提升锂离子电池的循环性能以及高温储存性能。(2) The cross-linked polyvalent salt also has better anti-oxidation properties, slows down the oxidation process of the electrolyte, and can significantly improve the cycle performance and high-temperature storage performance of lithium-ion batteries.
具体实施方式Detailed ways
下面将结合本发明中的实施例，对本发明实施例中的技术方案进行清楚、完整的描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通的技术人员在没有做出创造性劳动的前提下所获得的所有其它实施例，都属于本发明的保护范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.
实施例1Example 1
1)非水电解液的制备：1) Preparation of non-aqueous electrolyte:
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EC:DEC:EMC＝1:1:1进行混合，然后加入六氟磷酸锂(LiPF 6)至摩尔浓度为1mol/L，以非水电解液的总重量为100％计，加入按表2中实施例1所示质量百分含量的化合物1。 Ethylene carbonate (EC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC) were mixed in a mass ratio of EC:DEC:EMC=1:1:1, and then lithium hexafluorophosphate (LiPF 6 ) was added to mole The concentration is 1 mol/L, and the total weight of the non-aqueous electrolyte is 100%, and the compound 1 in the mass percentage shown in Example 1 in Table 2 is added.
2)正极板的制备：2) Preparation of positive plate:
按93:4:3的质量比混合正极活性材料锂镍钴锰氧化物LiNi 0.5Co 0.2Mn 0.3O 2，导电碳黑Super-P和粘结剂聚偏二氟乙烯(PVDF)，然后将它们分散在N-甲基-2-吡咯烷酮(NMP)中，得到正极浆料。将浆料均匀涂布在铝箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上铝制引出线后得到正极板，极板的厚度在120-150μm之间。 The cathode active material lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 , the conductive carbon black Super-P and the binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 93:4:3, and then they were mixed together. Disperse in N-methyl-2-pyrrolidone (NMP) to obtain a positive electrode slurry. The slurry is evenly coated on both sides of the aluminum foil, dried, calendered and vacuum-dried, and the aluminum lead wires are welded with an ultrasonic welder to obtain a positive electrode plate, the thickness of which is between 120-150 μm.
3)负极板的制备：3) Preparation of negative plate:
按94:1:2.5:2.5的质量比混合负极活性材料人造石墨，导电碳黑Super-P，粘结剂丁苯橡胶(SBR)和羧甲基纤维素(CMC)，然后将它们分散在去离子水中，得到负极浆料。将浆料涂布在铜箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上镍制引出线后得到负极板，极板的厚度在120-150μm之间。Mix the negative active material artificial graphite, conductive carbon black Super-P, binder styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) in a mass ratio of 94:1:2.5:2.5, and then disperse them in the Ionized water to obtain a negative electrode slurry. Coating the slurry on both sides of the copper foil, drying, calendering and vacuum drying, and welding nickel lead wires with an ultrasonic welder to obtain a negative plate with a thickness of 120-150 μm.
4)电芯的制备：4) Preparation of cells:
在正极板和负极板之间放置厚度为20μm的三层隔膜，然后将正极板、负极板和隔膜组成的三明治结构进行卷绕，再将卷绕体压扁后放入铝箔包装袋，在75℃下真空烘烤48h，得到待注液的电芯。A three-layer separator with a thickness of 20 μm was placed between the positive plate and the negative plate, and then the sandwich structure composed of the positive plate, the negative plate and the separator was wound, and then the rolled body was flattened and put into an aluminum foil packaging bag. Vacuum bake for 48h at ℃ to obtain the cell to be injected.
5)电芯的注液和化成：5) Liquid injection and formation of the cell:
在露点控制在-40℃以下的手套箱中，将上述制备的电解液注入电芯中，经真空封装，静止24h。In a glove box with a dew point controlled below -40°C, the electrolyte prepared above was injected into the cell, sealed in vacuum, and kept at rest for 24 hours.
然后按以下步骤进行首次充电的常规化成：0.05C恒流充电180min，0.2C恒流充电至3.95V，二次真空封口，然后进一步以0.2C的电流恒流充电至4.2V，常温搁置24h后，以0.2C的电流恒流放电至3.0V，得到一种LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨锂离子电池。 Then, the routine formation of the first charge is carried out according to the following steps: 0.05C constant current charging for 180min, 0.2C constant current charging to 3.95V, secondary vacuum sealing, and then further charging to 4.2V with 0.2C current constant current, after 24h at room temperature , and discharged to 3.0V at a constant current of 0.2C to obtain a LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite lithium-ion battery.
6)实施例和对比例制作的锂离子电池的性能测试6) Performance test of the lithium ion battery made by the embodiment and the comparative example
为了验证本发明的锂离子电池非水电解液对电池性能的影响，下面对下述实施例及对比例制作的锂离子电池进行相关的性能测试。测试的性能包括高温循环性能测试和高温储存性能测试，具体测试方法如下：In order to verify the influence of the non-aqueous electrolyte of the lithium ion battery of the present invention on the performance of the battery, the relevant performance tests of the lithium ion batteries produced in the following examples and comparative examples are carried out below. The performance tested includes high temperature cycle performance test and high temperature storage performance test. The specific test methods are as follows:
(1)高温循环性能测试(1) High temperature cycle performance test
将实施例及对比例制作的锂离子电池置于恒温45℃的烘箱中，以1C的电流恒流充电至4.2V(LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨锂离子电池)，再恒压充电至电流下降至0.02C，然后以1C的电流恒流放电至3.0V，如此循环，记录第1次的放电容量和最后一次的放电容量。 The lithium-ion batteries produced in the examples and comparative examples were placed in an oven with a constant temperature of 45°C, charged to 4.2V (LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite lithium ion battery) at a constant current of 1C, and then charged at a constant voltage. Charge until the current drops to 0.02C, and then discharge to 3.0V at a constant current of 1C. This cycle is performed to record the first discharge capacity and the last discharge capacity.
按下式计算循环的容量保持率：Calculate the capacity retention of the cycle as follows:
电池容量保持率(％)＝最后一次的放电容量/第1次的放电容量×100％。Battery capacity retention rate (%)=last discharge capacity/first discharge capacity×100%.
(2)高温储存性能测试(2) High temperature storage performance test
将实施例及对比例制作的锂离子电池在化成后在常温下用1C恒流恒压充至4.2V(LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨锂离子电池)，测量电池初始放电容量及初始电池厚度，然后在60℃环境中储存30天后，以1C放电至3V，测量电池的保持容量和恢复容量及储存后电池厚度。计算公式如下： The lithium-ion batteries prepared in the examples and comparative examples were charged to 4.2V (LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite lithium ion battery) at room temperature with 1C constant current and constant voltage after formation, and the initial discharge capacity and The initial battery thickness was then stored at 60°C for 30 days, discharged to 3V at 1C, and the retention and recovery capacity of the battery and the thickness of the battery after storage were measured. Calculated as follows:
电池容量保持率(％)＝保持容量/初始容量×100％；Battery capacity retention rate (%) = retained capacity / initial capacity × 100%;
电池容量恢复率(％)＝恢复容量/初始容量×100％；Battery capacity recovery rate (%)=recovered capacity/initial capacity×100%;
厚度膨胀率(％)＝(储存后电池厚度-初始电池厚度)/初始电池厚度×100％。Thickness expansion ratio (%)=(battery thickness after storage−initial battery thickness)/initial battery thickness×100%.
实施例2Example 2
如表2所示，除了非水电解液的制备中将1.0％的化合物1换成1.0％的化合物3之外，其他与实施例1相同，测试得到的高温性能数据见表3。As shown in Table 2, except that 1.0% of Compound 1 was replaced with 1.0% of Compound 3 in the preparation of the non-aqueous electrolyte, the rest was the same as in Example 1. The high-temperature performance data obtained by testing are shown in Table 3.
实施例3Example 3
如表2所示，除了非水电解液的制备中将1.0％的化合物1换成1.0％的化合物4之外，其他与实施例1相同，测试得到的高温性能数据见表3。As shown in Table 2, except that 1.0% of Compound 1 was replaced with 1.0% of Compound 4 in the preparation of the non-aqueous electrolyte, the rest was the same as that of Example 1. The high-temperature performance data obtained by testing are shown in Table 3.
实施例4Example 4
如表2所示，除了非水电解液的制备中将1.0％的化合物1换成1.0％的化合物5之外，其他与实施例1相同，测试得到的高温性能数据见表3。As shown in Table 2, except that 1.0% of Compound 1 was replaced with 1.0% of Compound 5 in the preparation of the non-aqueous electrolyte, the rest was the same as that of Example 1. The high-temperature performance data obtained by testing are shown in Table 3.
实施例5Example 5
如表2所示，除了非水电解液的制备中将1.0％的化合物1换成1.0％的化合物6之外，其他与实施例1相同，测试得到的高温性能数据见表3。As shown in Table 2, except that 1.0% of Compound 1 was replaced with 1.0% of Compound 6 in the preparation of the non-aqueous electrolyte, the rest was the same as in Example 1. The high-temperature performance data obtained by testing are shown in Table 3.
实施例6Example 6
如表2所示，除了非水电解液的制备中将1.0％的化合物1换成1.0％的化合物7之外，其他与实施例1相同，测试得到的高温性能数据见表3。As shown in Table 2, except that 1.0% of compound 1 is replaced with 1.0% of compound 7 in the preparation of the non-aqueous electrolyte, the rest is the same as that of Example 1, and the high-temperature performance data obtained by testing are shown in Table 3.
实施例7Example 7
如表2所示，除了非水电解液的制备中将1.0％的化合物1换成1.0％的化合物8之外，其他与实施例1相同，测试得到的高温性能数据见表3。As shown in Table 2, except that 1.0% of compound 1 was replaced with 1.0% of compound 8 in the preparation of the non-aqueous electrolyte, the rest was the same as that of Example 1. The high-temperature performance data obtained by testing are shown in Table 3.
实施例8Example 8
如表2所示，除了非水电解液的制备中将1.0％的化合物1换成1.0％的化合物9之外，其他与实施例1相同，测试得到的高温性能数据见表3。As shown in Table 2, except that 1.0% of Compound 1 was replaced with 1.0% of Compound 9 in the preparation of the non-aqueous electrolyte, the rest is the same as that of Example 1. The high-temperature performance data obtained by testing are shown in Table 3.
对比例1Comparative Example 1
如表2所示，除了电解液的制备中不添加1.0％的化合物1之外，其他与实施例1相同，测试得到的高温性能数据见表3。As shown in Table 2, except that 1.0% of compound 1 was not added in the preparation of the electrolyte solution, the rest was the same as that of Example 1. The high temperature performance data obtained by the test are shown in Table 3.
对比例2Comparative Example 2
如表2所示，除了电解液的制备中将1.0％的化合物1换成1.0％的碳酸亚乙烯酯(VC)，其他与实施例1相同，测试得到的高温性能数据见表3。As shown in Table 2, except that 1.0% of compound 1 was replaced with 1.0% of vinylene carbonate (VC) in the preparation of the electrolyte, the rest was the same as that of Example 1. The high-temperature performance data obtained by testing are shown in Table 3.
对比例3Comparative Example 3
如表2所示，除了电解液的制备中将1.0％的化合物1换成1.0％的硫酸乙烯酯(DTD)，其他与实施例1相同，测试得到的高温性能数据见表3。As shown in Table 2, except that 1.0% of compound 1 was replaced by 1.0% of ethylene sulfate (DTD) in the preparation of the electrolyte, the rest is the same as that of Example 1. The high-temperature performance data obtained by testing are shown in Table 3.
对比例4Comparative Example 4
如表2所示，除了电解液的制备中将1.0％的化合物1换成1.0％的1,3-丙烷磺酸内酯(PS)，其他与实施例1相同，测试得到的高温性能数据见表3。As shown in Table 2, except that 1.0% of compound 1 was replaced with 1.0% of 1,3-propane sultone (PS) in the preparation of the electrolyte, the others are the same as in Example 1. For the high-temperature performance data obtained by testing, see table 3.
表1 本发明实施方式中所用螺环酯类化合物1和化合物3-9的结构式Table 1 Structural formulas of spiro ester compound 1 and compound 3-9 used in the embodiment of the present invention
Figure PCTCN2022083008-appb-000012
Figure PCTCN2022083008-appb-000012
Figure PCTCN2022083008-appb-000013
Figure PCTCN2022083008-appb-000013
表2 实施例1-8、对比例1-4中螺环酯类化合物以及其他添加剂的含量Table 2 Contents of spirocyclic ester compounds and other additives in Examples 1-8 and Comparative Examples 1-4
实施例/对比例Example/Comparative Example 化合物及含量Compound and content 其他添加剂及含量Other additives and content
实施例1Example 1 化合物1:1.0％Compound 1: 1.0% ----
实施例2Example 2 化合物3:1.0％Compound 3: 1.0% --
实施例3Example 3 化合物4:1.0％Compound 4: 1.0% --
实施例4Example 4 化合物5:1.0％Compound 5: 1.0% --
实施例5Example 5 化合物6:1.0％Compound 6: 1.0% --
实施例6Example 6 化合物7:1.0％Compound 7: 1.0% --
实施例7Example 7 化合物8:1.0％Compound 8: 1.0% --
实施例8Example 8 化合物9:1.0％Compound 9: 1.0% --
对比例1Comparative Example 1 -- --
对比例2Comparative Example 2 -- VC:1.0％VC: 1.0%
对比例3Comparative Example 3 -- DTD:1.0％DTD: 1.0%
对比例4Comparative Example 4 -- PS:1.0％PS: 1.0%
表3 实施例1-8以及对比例1-4中所制备电池的电化学性能测试结果Table 3 Electrochemical performance test results of batteries prepared in Examples 1-8 and Comparative Examples 1-4
Figure PCTCN2022083008-appb-000014
Figure PCTCN2022083008-appb-000014
Figure PCTCN2022083008-appb-000015
Figure PCTCN2022083008-appb-000015
对比实施例1-8和对比例1、4的测试结果可知，相比在电解液中不添加本发明中的螺环酯类化合物或者添加DTD的硫酸酯类化合物，在非水电解液中添加1.0％的化合物1～8，能够更明显地改善锂离子电池的高温储存和循环性能。在60℃存储30天，电池的容量保持率和容量恢复率均能达到87％以上。The test results of Comparative Examples 1 to 8 and Comparative Examples 1 and 4 show that, compared with not adding the spirocyclic ester compound of the present invention or adding the sulfuric ester compound of DTD in the electrolyte, adding the non-aqueous electrolyte in the non-aqueous electrolyte. Compounds 1-8 at 1.0% can significantly improve the high-temperature storage and cycle performance of lithium-ion batteries. When stored at 60°C for 30 days, the capacity retention rate and capacity recovery rate of the battery can both reach more than 87%.
实施例9Example 9
如表4所示，除了非水电解液的制备中将1.0％的化合物1换成0.01％的化合物1之外，其他与实施例1相同，测试得到的高温性能数据见表5。As shown in Table 4, except that 1.0% of compound 1 is replaced with 0.01% of compound 1 in the preparation of the non-aqueous electrolyte, the rest is the same as that of Example 1. The high-temperature performance data obtained by testing are shown in Table 5.
实施例10Example 10
如表4所示，除了非水电解液的制备中将1.0％的化合物1换成0.1％的化合物1之外，其他与实施例1相同，测试得到的高温性能数据见表5。As shown in Table 4, except that 1.0% of compound 1 is replaced with 0.1% of compound 1 in the preparation of the non-aqueous electrolyte, the rest is the same as that of Example 1, and the high-temperature performance data obtained by testing are shown in Table 5.
实施例11Example 11
如表4所示，除了非水电解液的制备中将1.0％的化合物1换成0.5％的化合物1之外，其他与实施例1相同，测试得到的高温性能数据见表5。As shown in Table 4, except that 1.0% of Compound 1 was replaced with 0.5% of Compound 1 in the preparation of the non-aqueous electrolyte, the rest was the same as in Example 1. The high-temperature performance data obtained by testing are shown in Table 5.
实施例12Example 12
如表4所示，除了非水电解液的制备中将1.0％的化合物1换成2.0％的化合物1之外，其他与实施例1相同，测试得到的高温性能数据见表5。As shown in Table 4, except that 1.0% of Compound 1 was replaced with 2.0% of Compound 1 in the preparation of the non-aqueous electrolyte, the rest is the same as that of Example 1. The high-temperature performance data obtained by testing are shown in Table 5.
实施例13Example 13
如表4所示，除了非水电解液的制备中将1.0％的化合物1换成3.0％的化合物1之外，其他与实施例1相同，测试得到的高温性能数据见表5。As shown in Table 4, except that 1.0% of Compound 1 was replaced with 3.0% of Compound 1 in the preparation of the non-aqueous electrolyte, the rest was the same as that of Example 1. The high-temperature performance data obtained by testing are shown in Table 5.
实施例14Example 14
如表4所示，除了非水电解液的制备中将1.0％的化合物1换成5.0％的化合物1之外，其他与实施例1相同，测试得到的高温性能数据见表5。As shown in Table 4, except that 1.0% of Compound 1 was replaced with 5.0% of Compound 1 in the preparation of the non-aqueous electrolyte, the rest was the same as that of Example 1. The high-temperature performance data obtained by testing are shown in Table 5.
表4 实施例9-14中螺环酯类化合物以及其他添加剂的含量The content of spirocyclic ester compound and other additives in table 4 embodiment 9-14
实施例Example 化合物及含量Compound and content 其他添加剂及含量Other additives and content
实施例9Example 9 化合物1：0.01％Compound 1: 0.01% --
实施例10Example 10 化合物1：0.1％Compound 1: 0.1% --
实施例11Example 11 化合物1：0.5％Compound 1: 0.5% --
实施例12Example 12 化合物1：2％Compound 1: 2% --
实施例13Example 13 化合物1：3％Compound 1: 3% --
实施例14Example 14 化合物1：5％Compound 1: 5% --
表5 实施例9-14所制备电池的电化学性能测试结果Table 5 Electrochemical performance test results of the batteries prepared in Examples 9-14
Figure PCTCN2022083008-appb-000016
Figure PCTCN2022083008-appb-000016
根据实施例根据实施例1、9-14和对比例1中的测试结果可知，在电解液中添加0.1％-5.0％结构式1所示化合物，均可以改善电池性能。当添加0.5％、1.0％、2.0％和3.0％的化合物1电池在45℃，1C条件下循环500周，容量保持率进一步提高至90％以上，60℃储存30天电池的容量保持率、容量恢复率均能达到90％以上，厚度膨胀率进一步降低。因此本发明限定所添加螺环酯类化合物的含量为0.1％-5.0％，优选为0.5％-3.0％。According to the examples According to the test results in Examples 1, 9-14 and Comparative Example 1, adding 0.1%-5.0% of the compound represented by the structural formula 1 to the electrolyte can improve the battery performance. When adding 0.5%, 1.0%, 2.0% and 3.0% of compound 1, the battery was cycled at 45°C and 1C for 500 cycles, and the capacity retention rate was further improved to more than 90%. The capacity retention rate and capacity of the battery were stored at 60°C for 30 days. The recovery rate can reach more than 90%, and the thickness expansion rate is further reduced. Therefore, the present invention defines the content of the spirocyclic ester compound to be 0.1%-5.0%, preferably 0.5%-3.0%.
实施例15Example 15
如表6所示，除了非水电解液的制备中将1.0％的化合物1换成0.1％的化合物1以及1.0％的碳酸亚乙烯酯(VC)之外，其他与实施例1相同，测试得到的高温性能数据见表7。As shown in Table 6, except that 1.0% of compound 1 was replaced with 0.1% of compound 1 and 1.0% of vinylene carbonate (VC) in the preparation of the non-aqueous electrolyte, the rest was the same as in Example 1, and the test results were obtained. The high temperature performance data are shown in Table 7.
实施例16Example 16
如表6所示，除了非水电解液的制备中将1.0％的化合物1换成0.5％的化合物1以及1.0％的碳酸亚乙烯酯(VC)之外，其他与实施例1相同，测试得到的高温性能数据见表7。As shown in Table 6, except that 1.0% of compound 1 was replaced with 0.5% of compound 1 and 1.0% of vinylene carbonate (VC) in the preparation of the non-aqueous electrolyte, the rest was the same as in Example 1, and the test results were obtained. The high temperature performance data are shown in Table 7.
实施例17Example 17
如表6所示，除了非水电解液的制备中将1.0％的化合物1换成1.0％的化合物1以及1.0％的碳酸亚乙烯酯(VC)之外，其他与实施例1相同，测试得到的高温性能数据见表7。As shown in Table 6, except that 1.0% of compound 1 was replaced with 1.0% of compound 1 and 1.0% of vinylene carbonate (VC) in the preparation of the non-aqueous electrolyte, the rest was the same as in Example 1, and the test results were obtained. The high temperature performance data are shown in Table 7.
实施例18Example 18
如表6所示，除了非水电解液的制备中将1.0％的化合物1换成5.0％的化合物1以及1.0％的碳酸亚乙烯酯(VC)之外，其他与实施例1相同，测试得到的高温性能数据见表7。As shown in Table 6, except that 1.0% of compound 1 was replaced with 5.0% of compound 1 and 1.0% of vinylene carbonate (VC) in the preparation of the non-aqueous electrolyte, the rest was the same as in Example 1. The high temperature performance data are shown in Table 7.
实施例19Example 19
如表6所示，除了非水电解液的制备中将1.0％的化合物1换成0.1％的化合物1以及1.0％的碳酸亚乙烯酯(VC)之外，其他与实施例1相同，测试得到的高温性能数据见表7。As shown in Table 6, except that 1.0% of compound 1 was replaced with 0.1% of compound 1 and 1.0% of vinylene carbonate (VC) in the preparation of the non-aqueous electrolyte, the rest was the same as in Example 1, and the test results were obtained. The high temperature performance data are shown in Table 7.
实施例20Example 20
如表6所示，除了非水电解液的制备中将1.0％的化合物1换成0.5％的化合物1以及1.0％的1,3-丙烷磺酸内酯(PS)之外，其他与实施例1相同，测试得到的高温性能数据见表7。As shown in Table 6, except that 1.0% of compound 1 was replaced with 0.5% of compound 1 and 1.0% of 1,3-propane sultone (PS) in the preparation of non-aqueous electrolyte 1 is the same, and the high temperature performance data obtained from the test are shown in Table 7.
实施例21Example 21
如表6所示，除了非水电解液的制备中将1.0％的化合物1换成1.0％的化合物1以及1.0％的1,3-丙烷磺酸内酯(PS)之外，其他与实施例1相同，测试得到的高温性能数据见表7。As shown in Table 6, except that 1.0% of compound 1 was replaced by 1.0% of compound 1 and 1.0% of 1,3-propane sultone (PS) in the preparation of non-aqueous electrolyte 1 is the same, and the high temperature performance data obtained from the test are shown in Table 7.
实施例22Example 22
如表6所示，除了非水电解液的制备中将1.0％的化合物1换成5.0％的化合物1以及1.0％的1,3-丙烷磺酸内酯(PS)之外，其他与实施例1相同，测试得到的高温性能数据见表7。As shown in Table 6, except that 1.0% of compound 1 was replaced by 5.0% of compound 1 and 1.0% of 1,3-propane sultone (PS) in the preparation of non-aqueous electrolyte 1 is the same, and the high temperature performance data obtained from the test are shown in Table 7.
表6 实施例15-22中螺环酯类化合物以及其他添加剂的含量Table 6 Contents of spirocyclic ester compounds and other additives in Examples 15-22
实施例Example 化合物及含量Compound and content 其他添加剂及含量Other additives and content
实施例15Example 15 化合物1:0.1％Compound 1: 0.1% 碳酸亚乙烯酯(VC)：1.0％Vinylene carbonate (VC): 1.0%
实施例16Example 16 化合物1:0.5％Compound 1: 0.5% 碳酸亚乙烯酯(VC)：1.0％Vinylene carbonate (VC): 1.0%
实施例17Example 17 化合物1:1.0％Compound 1: 1.0% 碳酸亚乙烯酯(VC)：1.0％Vinylene carbonate (VC): 1.0%
实施例18Example 18 化合物1:5.0％Compound 1: 5.0% 碳酸亚乙烯酯(VC)：1.0％Vinylene carbonate (VC): 1.0%
实施例19Example 19 化合物1:0.1％Compound 1: 0.1% 1,3-丙烷磺酸内酯(PS)：1.0％1,3-Propane sultone (PS): 1.0%
实施例20Example 20 化合物1:0.5％Compound 1: 0.5% 1,3-丙烷磺酸内酯(PS)：1.0％1,3-Propane sultone (PS): 1.0%
实施例21Example 21 化合物1:1.0％Compound 1: 1.0% 1,3-丙烷磺酸内酯(PS)：1.0％1,3-Propane sultone (PS): 1.0%
实施例22Example 22 化合物1:5.0％Compound 1: 5.0% 1,3-丙烷磺酸内酯(PS)：1.0％1,3-Propane sultone (PS): 1.0%
表7 实施例15-22中所制备的电池的电化学性能测试结果Table 7 Electrochemical performance test results of the batteries prepared in Examples 15-22
Figure PCTCN2022083008-appb-000017
Figure PCTCN2022083008-appb-000017
实施例15-18相对于实施例10、11、1、14和对比例2的数据显示，同时加入结构式1所示化合物和VC，相比于单独加入结构式1所示的化合物或VC，电池的高温循环性能、高温存储性能更优。本发明中所提供的电解液中包含1％的螺环酯类化合物与1％的碳酸亚乙烯酯(VC)可以使所组装电池在45℃，循环500周的容量保持率达到92.6％，60℃存储30天的容量保持率可以到93.5％，容量恢复率可以达到93.8％，厚度膨胀率减小至6.3％。实施例19-22相对于实施例10、11、1、14和对比例4的数据显示，同时加入结构式1所示化合物和PS，相比于单独加入结构式1所示的化合物或PS，电池的高温循环性能、高温存储性能更优。本发明中所提供的电解液中包含1％的螺环酯类化合物与1％的1,3-丙烷磺酸内酯(PS)可以使所组装电池在45℃，循环500周的容量保持率达到92.8％，60℃存储30天的容量保持率可以到93.8％，容量恢复率可以达到93.9％，厚度膨胀率减小至6.0％。The data of Examples 15-18 relative to Examples 10, 11, 1, 14 and Comparative Example 2 show that adding the compound represented by Structural Formula 1 and VC at the same time, compared with adding the compound represented by Structural Formula 1 or VC alone, the battery's performance is improved. High temperature cycle performance and high temperature storage performance are better. The electrolyte provided in the present invention contains 1% of spirocyclic ester compounds and 1% of vinylene carbonate (VC), so that the capacity retention rate of the assembled battery can reach 92.6% at 45°C and 500 cycles of cycle, and 60 After 30 days of storage at ℃, the capacity retention rate can reach 93.5%, the capacity recovery rate can reach 93.8%, and the thickness expansion rate can be reduced to 6.3%. The data of Examples 19-22 relative to Examples 10, 11, 1, 14 and Comparative Example 4 show that adding the compound represented by Structural Formula 1 and PS at the same time, compared with adding the compound represented by Structural Formula 1 or PS alone, the battery has better performance. High temperature cycle performance and high temperature storage performance are better. The electrolyte solution provided in the present invention contains 1% of spirocyclic ester compound and 1% of 1,3-propane sultone (PS), which can make the assembled battery have a capacity retention rate of 500 cycles at 45° C. It reaches 92.8%, the capacity retention rate can reach 93.8% when stored at 60°C for 30 days, the capacity recovery rate can reach 93.9%, and the thickness expansion rate is reduced to 6.0%.
综上所述，本发明在电解液中添加了螺环酯类化合物，所制备的电解液能够保证锂离子电池在充放电过程中能够形成稳定的SEI膜，从而保证锂离子电池具有优异的电化学性能。To sum up, the present invention adds spirocyclic ester compounds to the electrolyte, and the prepared electrolyte can ensure that the lithium ion battery can form a stable SEI film during the charging and discharging process, thereby ensuring that the lithium ion battery has excellent electrical properties. chemical properties.
以上借助具体实施例对本发明做了进一步描述，但是应该理解的是，这里具体的描述，不应理解为对本发明的实质和范围的限定，本领域内的普通技术人员在阅读本说明书后对上述实施例做出的各种修改，都属于本发明所保护的范围。The present invention has been further described above with the help of specific embodiments, but it should be understood that the specific description herein should not be construed as a limitation on the spirit and scope of the present invention. Various modifications made in the embodiments all belong to the protection scope of the present invention.

Claims (10)

  1. 一种锂离子电池非水电解液，其特征在于，包括非水有机溶剂、锂盐以及螺环酯类化合物，所述螺环酯类化合物如结构式1所示：A non-aqueous electrolyte for a lithium ion battery, characterized in that it comprises a non-aqueous organic solvent, a lithium salt and a spiro ester compound, and the spiro ester compound is shown in structural formula 1:
    Figure PCTCN2022083008-appb-100001
    Figure PCTCN2022083008-appb-100001
    其中，X 1为
    Figure PCTCN2022083008-appb-100002
    基团中的一种；R 9为卤素原子、碳原子数为1-10的卤代或非卤代烷氧基中的一种；     where X 1 is
    Figure PCTCN2022083008-appb-100002
    One of the groups; R 9 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-10 carbon atoms;
    X 2为
    Figure PCTCN2022083008-appb-100003
    基团中的一种；R 10为卤素原子、碳原子数为1-10的卤代或非卤代烷氧基中的一种；     X 2 is
    Figure PCTCN2022083008-appb-100003
    One of the groups; R 10 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-10 carbon atoms;
    R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立的选自氢原子、卤素原子、1-10个碳原子的卤代或非卤代烷氧基中的一种。 R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen atoms, halogen atoms, halogenated or non-halogenated alkoxy groups of 1-10 carbon atoms A sort of.
  2. 根据权利要求1所述的锂离子电池非水电解液，其特征在于，所述螺环酯类化合物包含类别1-4中的一种：The non-aqueous electrolyte for lithium ion batteries according to claim 1, wherein the spirocyclic ester compound comprises one of categories 1-4:
    Figure PCTCN2022083008-appb-100004
    Figure PCTCN2022083008-appb-100004
    Figure PCTCN2022083008-appb-100005
    Figure PCTCN2022083008-appb-100005
    其中，R 9为卤素原子、碳原子数为1-10的卤代或非卤代烷氧基中的一种； Wherein, R 9 is a halogen atom, a halogenated or non-halogenated alkoxy group with 1-10 carbon atoms;
    R 10为卤素原子、碳原子数为1-10的卤代或非卤代烷氧基中的一种； R 10 is one of halogen atoms, halogenated or non-halogenated alkoxy groups with 1-10 carbon atoms;
    R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立的选自氢原子、卤素原子、1-10个碳原子的卤代或非卤代烷氧基中的一种。 R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen atoms, halogen atoms, halogenated or non-halogenated alkoxy groups of 1-10 carbon atoms A sort of.
  3. 根据权利要求1或2所述的一种锂离子电池非水电解液，其特征在于，所述卤素原子选自氟、氯、溴、碘；所述1-10个碳原子的卤代或非卤代烷氧基选自氟代甲氧基、氟代乙氧基、氟代丙氧基、氟代丁烷氧基、氟代戊烷氧基、氟代己烷氧基、氟代庚烷氧基、氟代辛烷氧基、氟代壬烷氧基、氟代癸烷氧基、甲氧基、乙氧基、丙氧基、丁烷氧基、戊烷氧基、己烷氧基、庚烷氧基、辛烷氧基、壬烷氧基、癸烷氧基中的一种。The non-aqueous electrolyte for lithium ion batteries according to claim 1 or 2, wherein the halogen atom is selected from the group consisting of fluorine, chlorine, bromine, and iodine; Haloalkoxy is selected from fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutanoxy, fluoropentanoxy, fluorohexaneoxy, fluoroheptyloxy , fluorooctyloxy, fluorononanyloxy, fluorodecyloxy, methoxy, ethoxy, propoxy, butyloxy, pentyloxy, hexaneoxy, heptyl One of alkoxy, octaneoxy, nonalkoxy and decyloxy.
  4. 根据权利要求1所述的锂离子电池非水电解液，其特征在于，所述螺环酯类化合物包含化合物1-65中的一种：The non-aqueous electrolyte for lithium-ion batteries according to claim 1, wherein the spirocyclic ester compound comprises one of compounds 1-65:
    Figure PCTCN2022083008-appb-100006
    Figure PCTCN2022083008-appb-100006
    Figure PCTCN2022083008-appb-100007
    Figure PCTCN2022083008-appb-100007
    Figure PCTCN2022083008-appb-100008
    Figure PCTCN2022083008-appb-100008
    Figure PCTCN2022083008-appb-100009
    Figure PCTCN2022083008-appb-100009
  5. 根据权利要求1所述的锂离子电池非水电解液，其特征在于，所述螺环酯类化合物的质量为锂离子电池非水电解液的总质量的0.01％-5.0％。The non-aqueous electrolyte for lithium ion batteries according to claim 1, wherein the mass of the spirocyclic ester compound is 0.01%-5.0% of the total mass of the non-aqueous electrolyte for lithium ion batteries.
  6. 根据权利要求1所述的锂离子电池非水电解液，其特征在于，还包括磺酸酯或碳酸酯；The non-aqueous electrolyte for lithium ion batteries according to claim 1, further comprising sulfonate or carbonate;
    所述磺酸酯包括1,3-丙烷磺内酯(1,3-PS)、1,4-丁烷磺内酯(BS)、1,3-丙烯磺内酯(PST)中的一种或多种；The sulfonate includes one of 1,3-propane sultone (1,3-PS), 1,4-butane sultone (BS) and 1,3-propene sultone (PST) or more;
    所述碳酸酯包括碳酸亚乙烯酯(VC)、碳酸乙烯亚乙酯(VEC)、氟代碳酸乙烯酯(FEC)中的一种或多种。The carbonate includes one or more of vinylene carbonate (VC), ethylene ethylene carbonate (VEC), and fluoroethylene carbonate (FEC).
  7. 根据权利要求1所述的锂离子电池非水电解液，其特征在于，所述锂盐选自LiPF 6、LiBOB、LiDFOB、 LiBF 4、LiSbF 6、LiAsF 6、LiN(SO 2CF 3) 2、LiN(SO 2C 2F 5) 2、LiC(SO 2CF 3) 3或LiN(SO 2F) 2中的一种或多种。 The non-aqueous electrolyte for lithium ion batteries according to claim 1, wherein the lithium salt is selected from LiPF 6 , LiBOB, LiDFOB, LiBF 4 , LiSbF 6 , LiAsF 6 , LiN(SO 2 CF 3 ) 2 , One or more of LiN(SO 2 C 2 F 5 ) 2 , LiC(SO 2 CF 3 ) 3 or LiN(SO 2 F) 2 .
  8. 根据权利要求1所述的锂离子电池非水电解液，其特征在于，所述非水有机溶剂包括至少一种环状碳酸酯和至少一种链状碳酸酯。The non-aqueous electrolyte for lithium ion batteries according to claim 1, wherein the non-aqueous organic solvent comprises at least one cyclic carbonate and at least one chain carbonate.
  9. 根据权利要求8所述的锂离子电池非水电解液，其特征在于，所述环状碳酸酯包括碳酸乙烯酯、碳酸丙烯酯或碳酸丁烯酯中的一种或多种；所述链状碳酸酯包括碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯或碳酸甲丙酯中的一种或多种。The non-aqueous electrolyte for lithium ion batteries according to claim 8, wherein the cyclic carbonate comprises one or more of ethylene carbonate, propylene carbonate or butylene carbonate; The carbonate includes one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate.
  10. 一种锂离子电池，其特征在于，包括权利要求1-9任一项所述的锂离子电池非水电解液、正极、负极以及隔膜。A lithium-ion battery, characterized in that it comprises the lithium-ion battery non-aqueous electrolyte, a positive electrode, a negative electrode and a separator according to any one of claims 1-9.
PCT/CN2022/083008 2021-04-07 2022-03-25 Non-aqueous electrolyte for lithium ion battery and lithium ion battery WO2022213823A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001351681A (en) * 2000-06-09 2001-12-21 Teijin Chem Ltd Fire retardant electrolyte and nonaqueous secondary cell
CN105655640A (en) * 2016-03-28 2016-06-08 宁德新能源科技有限公司 Non-aqueous electrolyte and lithium-ion battery containing same
JP2019153443A (en) * 2018-03-02 2019-09-12 三井化学株式会社 Nonaqueous electrolyte solution for battery and lithium secondary battery
CN112151751A (en) * 2020-10-15 2020-12-29 宁德新能源科技有限公司 Electrochemical device and electronic device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001351681A (en) * 2000-06-09 2001-12-21 Teijin Chem Ltd Fire retardant electrolyte and nonaqueous secondary cell
CN105655640A (en) * 2016-03-28 2016-06-08 宁德新能源科技有限公司 Non-aqueous electrolyte and lithium-ion battery containing same
JP2019153443A (en) * 2018-03-02 2019-09-12 三井化学株式会社 Nonaqueous electrolyte solution for battery and lithium secondary battery
CN112151751A (en) * 2020-10-15 2020-12-29 宁德新能源科技有限公司 Electrochemical device and electronic device

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